Chemical in The Laboratory PDF

Chemistry in the Laboratory
John }. Alexander
University of Cincinnati
Margaret }.
Steffel
The Ohio State University Marion Campus
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HARCOURT
BRACE
JOVANOVICH,
Austin
PUBLISHERS
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Preface
The collection of experiments, some classical, some new, in Chemistry in the Laboratory emphasizes the accumulation and interpretation of numerical data. Even in the qualitative experiments, students are often requested to draw semiquantitative conclusions. Most of the experiments in this manual have been class tested for several years at b o t h the University of Cincinnati and The O h i o State University Marion Campus. Many experimentsespecially those in the qualitative analysis sectionrequire more than one three-hour laboratory period to complete. In a d d i t i o n , more than one experiment pertaining to a specific subject (for example, e q u i l i b r i u m ) is often presented. We have designed the experiments in Chemistry in the Laboratory in the belief that an instructive experience in the laboratory is possible o n l y if students carefully prepare for their w o r k and keep complete records of their data in a laboratory notebook. We are grateful for the useful suggestions c o n t r i b u t e d by many teaching assistants and students. We especially wish to thank Sam Lucas, T i m Becker, Ralph Brewer, and Ed Schroer, all of the University of C i n c i n n a t i . A n d to K a t h y Bailey, who accurately and cheerfully typed several early drafts of the manual. Finally, we wish to acknowledge w i t h gratitude the encouragement of Thomas B. Cameron, late o f the University o f C i n c i n n a t i . The authors welcome comments and suggestions f r o m the users of this manual. John Alexander Margaret J. Steffel
Contents
Introduction Experiment 1 Experiment 2 Experiment 3 Experiment 4 Experiment 5 Experiment 6 Experiment 7 Experiment 8 Experiment 9
1 The Use of Balances: Hydrated Compounds 29 Properties of Substances Compound Stoichiometry Stoichiometry of a Reaction Synthesis of Co(NH ) C/
3 6 3
39 49 55 61 69 79
Line Spectra of Elements
A Simple Covalent Compound: Synthesis and Properties Salt Identification Using Visible and Infrared Spectra 87 Synthesis of Coordination Compounds and Their Identification Using Spectrophotometry 105 Vaporization of a Liquid: Vapor Pressure and Heat of Vaporization 119 Molar Weight by Vapor Density 127 "Molecular Interactions in Solution Freezing Point Lowering 143 Chemical Kinetics: Oxidation of Ethanol by Chromium( VI) 151 A Complete Rate Law Chemical Equilibrium 163 169 135
Experiment 10
Experiment 11 Experiment 12 Experiment 13 Experiment 14
Experiment 15 Experiment 16 Experiment 17
Spectropliotometric Determination of an Equilibrium Constant 181 Enthalpy of Reaction 191 201 213
Experiment 18 Experiment 19 Experiment 20 Experiment 21 Experiment 22 Experiment 23 Experiment 24 Experiment 25 Experiment 26

vii
Solubility of an Electrolyte
Gravimetric Determination of Iron Acid-Base Titration Antacids 229 221
Acidic and Basic Salts 235 Electrochemistry: Voltaic Cells 243 Electrochemistry: An Electrolytic Cell An Oxidation-Reduction Titration 259 253
viii
Contents
Experiment 27 Metal Chelate Complexes
267 277
Experiment 28 Synthesis of an Organo metallic Compound Introduction II Inorganic Qualitative Analysis 285
Experiment 29 Qualitative Analysis of the Group I Cations Experiment 30 Qualitative Analysis of the Croup II Cations Experiment 3 1 Qualitative Analysis of the Group III Cations Experiment 32 Qualitative Analysis of the Group IV Cations Experiment 33 Experiment 34 Qualitative Analysis of the Group V Cations Qualitative Analysis of Anions 345 351
293 301 319 331 339
Experiment 35 Analysis of a General Unknown Appendix I Appendix II Appendix I I I Appendix IV Appendix V
Sample Laboratory Report: Density Determination Graphing Experimental Data Infrared Spectrophotometers 367 373 375
365
Visible and Ultraviolet Spectrophotometers
Reagents and Constants for Qualitative Analysis
378
Introduction
Why Have a Chemistry Laboratory?
Y o u r faculty requires y o u to spend time each week w o r k i n g in a chemistry laboratory. If y o u have no intention of becoming a practicing chemist, y o u may wonder why there is this insistence on performing laboratory experiments. After all, you d o n ' t have to write a novel when y o u take a course in literature. Why isn't just learning about chemistry sufficient'' Why must y o u actually carry out experiments in a laboratory? There are at least three important reasons w h y students who are preparing for careers in medicine, biology, physics, or chemistry must have actual experience w i t h scientific experimentation. First, chemistry (like other natural sciences) is based on experiment. Scientific conclusions arc reached by carefully studying the results of experimental observationsnot by making plausible conjectures. To illustrate this p o i n t , consider a simple example. Someone might wonder whether iron chloride w i l l react w i t h iodine. A balanced equation for a possible reaction can easily be w r i t t e n FeCl + I
2
Fel + Cl
2
But does this plausible equation represent the way nature really behaves? The way to find out is to / r y the reaction to see if it w o r k s ! ( I t doesn't.) I n f o r m a t i o n in your text has resulte"d from experiments of many scientists. What y o u do in the laboratory should make y o u personally aware that scientific knowledge is based as solidly on experimentation as it is on reasoning. Second, y o u should begin to develop some manipulative skills in performing quantitative experiments. G o o d laboratory technique becomes increasingly essential as y o u progress to more advanced scientific courses and w i l l , o f course, be mandatory when y o u u l t i m a t e l y practice y o u r profession. T h i r d , y o u need to develop the ability to keep careful records of your experimental observations and to communicate, b o t h verbally and in w r i t i n g , w i t h others about these observations and the conclusions y o u draw from them. These functions are served by the laboratory notebook and the Report Sheets described later in the I n t r o d u c t i o n .
WHAT Y O U ' L L DO IN THE L A B O R A T O R Y
Even though one purpose of the laboratory is to make y o u aware that chemistry is an experimental science, it w o u l d be impossible for y o u to repeat all of the i m p o r t a n t chemical experiments ever conducted. Obviously, we can select only a reasonable number of projects to complete in the laboratory this year. Each of these has been chosen w i t h one (or all) of the f o l l o w i n g criteria in m i n d : 1. To show the relationship between experimental measurement and chemical theory. Sometimes this involves c o n f i r m i n g the results that y o u have already
Introduction
2. 3. 4.
read about in the t e x t ; at other times, y o u w i l l be asked to design simple experiments to test various theoretical possibilities. To teach basic laboratory technique. To help y o u learn to manipulate and interpret numerical data. To give y o u an idea of what a chemist's actual w o r k entails. )
In all of y o u r laboratory w o r k , y o u should make a special effort to develop the ability to observe what is actually happening in an experiment - n o t what y o u t h i n k should be happening. Most successful scientific experiments are usually designed w i t h some n o t i o n o f what w i l l occur. However, i f preconceived expectations are not realized, it does not always mean that the experiment has failed. It may only mean that the scientist overlooked or did not eompletely understand some theoretical principle or some aspect of experimental design. The scientist's task then is to t r y to explain what happenednot to be disappointed because what was expected to happen d i d n ' t occur. Y o u should do the same thing in the laboratory: first observe what happens and then try to understand and explain i t . The content o f lecture and laboratory sessions will probably not be correlated completely. Several ideas already discussed in lectures are usually applied to a single laboratory problem. A few experiments may involve material that has not yet been covered in a lecture. To some people, this might appear to be a case of p u t t i n g "the cart before the horse." However, y o u should be able to learn new chemical concepts in the laboratory just as you do in a lecture.
_ _ _
YOUR LABORATORY RESPONSIBILITIES
1. It is impossible to overemphasize the importance of preparation prior to the laboratory period. V i r t u a l l y every bad t r i p in the laboratory is due to an ''underdose" of preparation! If you are going to complete all of the necessary laboratory w o r k w i t h i n the time allotted, y o u must be prepared when y o u come to class. This means that y o u should study the experiment in advance and have a plan for carrying out y o u r work efficiently. The laboratory instructor w i l l answer any questions y o u may have, but this will not help y o u i f y o u are not familiar enough w i t h the material to k n o w what questions to ask. 2. Y o u will be expected to keep a laboratory notebook. Reserve a notebook exclusively for chemistry laboratory, and bring it to each laboratory session or to any other class meeting in which laboratory w o r k is to be discussed. Y o u should make several kinds of appropriate entries in your notebook. First, y o u may need to prepare a w o r k outline or set up a data table before y o u come to the laboratory. Or y o u may need to calculate the weight or the volume of a particular reagent that y o u w i l l need. A n y preparatory material o f this kind should be recorded in your notebook. Second, y o u w i l l want to note y o u r qualitative observations describing what happens and how things look while y o u carry o u t an experiment. For example, the colors of starting materials and products, the texture of a precipitate, or whether or not a reaction evolves heat cottlcl be recorded. Y o u should also note any mistakes or difficulties that might cause y o u to question the results in any part of an experi-
Safety in the L a b o r a t o r y
ment. For example', using the w r o n g concentration of a solution, spilling some of a carefully measured substance, or using too m u c h of a particular reagent may affect' the accuracy o f your results. I f y o u record an error when y o u make it, y o u w i l l remember it and this may help y o u to explain w h y y o u r results are incorrect. T h i r d , all numerical data should be carefully and completely recorded in y o u r \ notebook. Be certain to label all numbers w i t h the appropriate units. A good way organize y o u r data w o u l d be to make a data table in y o u r notebook similar to the one on the Report Sheet for each experiment and then to enter numerical data in the appropriate places as y o u obtain them. The purpose of keeping a laboratory notebook is not to provide a w o r k of art for your instructor to admire. Do not record data on scraps of paper and copy them in your notebook laterand perhaps more neatly. Have y o u r notebook w i t h y o u at all times and record data as you obtain them. If, for any reason, y o u decide later that y o u are not going to use a piece of data, you can simply draw a line through i t . But d o n ' t run the risk of losing i m p o r t a n t data just to keep y o u r records neat. A l l types of practicing technicians and scientists record data and observations this way. Learn ami practice proper recording of data from the start. 3. The experiments in this manual require y o u to submit w r i t t e n reports. Unless your instructor's procedures differ, each report will be due at the beginning o f the next laboratory meeting after the experiment has been performed. Almost every experiment in this manual contains a Report Sheet to guide y o u in preparing your report. The "Results and Discussion" section at the end of each experiment tells y o u how to treat y o u r data when filling out the Report Sheet. Questions w h i c h should serve to stimulate y o u r t h i n k i n g about experimental results are also included. Y o u r instructor may ask y o u to submit a report that includes additional items not covered on the Report Sheet. Such a report might include a statement of the procedures you used (especially if any of y o u r procedures differed from the instructions y o u were originally given) and a discussion of the l i m i t s placed on the accuracy of your results. A sample of such a report is presented in A p p e n d i x One (page 3 5 5 ) . This type of report does not have to be more than t w o or three pages long. In performing your laboratory experiments, supplying the " r i g h t " answer is sometimes less important than your ability to observe accurately and explain y o u r observations. If you obtain an unexpected result, try to explain w h y . Some of the experiments in this manual consist of identifying an " u n k n o w n , " and the reports for these experiments w i l l simply be a recording o f y o u r results. Y o u r mastery o f the material involved in such an experiment w i l l be reflected in y o u r ability to obtain the correct experimental results, and these results w i l l be o f prime importance in determining your grade for that experiment.
Safety in the Laboratory

One way in which a chemistry laboratory differs f r o m , say, a philosophy or a calculus course is that y o u must take certain precautions so that y o u w i l l not be
Introduction
physically injured. Because a laboratory accident cannot be predicted, y o u must constantly adhere to safety precautions while y o u are in the laboratory. The f o l l o w i n g list of procedures indicates areas where caution is essential. 1. Wear goggles or eyeglasses at all times. Even if y o u are careful not to splash chemicals i n t o y o u r eyes, someone close to y o u may accidentally do so. Goggles pushed up o n t o y o u r forehead (or left in y o u r desk) offer your eyes no p r o t e c t i o n . If y o u r laboratory is equipped w i t h an eye shower, learn where it is located and how to use it. 2. Wear suitable clothing and shoes. Shorts or bare feet leave large areas of skin exposed to potential chemical burns. Long, full sleeves may drag in y o u r chemicals or catch on y o u r equipment; b o t h the sleeves and the experiment could be ruined! Long hair should not be w o r n loose, especially when y o u are using a burner or centrifuge. 3. Take precautions to avoid c u t t i n g yourself. Discard cracked or chipped glassware. ( I n the next section, y o u w i l l be t o l d how to insert glass t u b i n g i n t o a stopper and how to fire-polish t u b i n g to smooth sharp ends.) 4. Work under a hood when so instructed. A few chemical experiments involve unpleasant or harmful substances. Their vapors w i l l be suctioned out o f the laboratory if y o u set up y o u r equipment under a hood. 5. Dispose of waste chemicals as directed. Do not return any substances to reagent bottles. Usually, y o u r instructor w i l l ask y o u to place waste chemicals in waste jars or to pour them d o w n a sink w i t h plenty of running water. When in doubt, ask! 6. Always pour concentrated acid into water (not water i n t o acid). Otherwise, some acid may spatter from the solution and burn y o u . 7. Report any i n j u r y - n o matter how m i n o r it may s e e m - t o y o u r instructor. 8. Never attempt an unauthorized experiment. The procedures in this manual have been designed w i t h y o u r safety in m i n d . D o n ' t risk injury to yourself or to others by m i x i n g chemicals r a n d o m l y or by setting up unauthorized reactions or equipment.
Some Laboratory Protocol

F o l l o w i n g a few general rules of procedure in the laboratory can make y o u r w o r k and the w o r k of the other students around y o u much more orderly and pleasant. 1. Clean up! Y o u are responsible for cleaning up any chemicals y o u spill in the reagent or balance area. Also, be sure to clean your o w n w o r k area before y o u leave the laboratory; plan y o u r w o r k so that y o u have adequate time to clean up.
L a b o r a t o r y E q u i p m e n t and T e c h n i q u e
2. Never take reagent bottles to your desk. A n o t h e r student's w o r k may be needlessly delayed by searching for a reagent. The proper way to obtain the reagents y o u need is to use a clean beaker or a test tube for liquids or a beaker for solids to obtain substances f r o m the reagent shelf. 3. D o n ' t waste chemicals. Large quantities of scarce energy resources are consumed to make and to purify the chemicals y o u use in the laboratory. Take whatever y o u need, but do not waste resources or unnecessarily increase y o u r school's expenses by taking more of a chemical than y o u need. Also, remember that any excess chemical y o u must throw away is a potential air or water pollutant. 4. D o n ' t return leftover chemicals to reagent bottles. Sometimes mistakes are made: chemicals are returned to the wrong bottles or contaminated chemicals are returned to reagent bottles. Y o u may have put the material i n t o a d i r t y beaker; water, d i r t , or some other chemical may have splashed i n t o a substance while it was sitting on your desk; y o u may have diluted a solution of a specific concentration by p u t t i n g it into a wet container. As a result, the entire contents of a reagent bottle could be contaminated. This whole problem can be avoided if y o u dispose of any excess material as y o u r instructor directs. 5. D o n ' t put a n y t h i n g into reagent bottles. The obvious reason for this precaution is to eliminate the possibility of c o n t a m i n a t i o n . Always pour a l i q u i d from a b o t t l e and do not place the bottle l i d or stopper on a desk or other laboratory surface. To pour a solid from a b o t t l e , t i p the bottle slightly while rotating i t ; do not use y o u r spatula.
Laboratory Equipment and Technique

Many operations are performed so often in the laboratory that a special section describing them is provided here rather than in i n d i v i d u a l experiments. Read this section now and then reread the relevant parts as y o u conduct the experiments.
EQUIPMENT
Several c o m m o n pieces of laboratory equipment are shown and discussed on the f o l l o w i n g pages.
LABORATORY BURNER
A m i x t u r e of natural gas and air is burned in the Bunsen-type burner to provide a source of heat. Figure i-1 shows burners. A Tirrill burner has a needle valve under the barrel to c o n t r o l gas How. A i r is a d m i t t e d by unscrewing the barrel of the burner or by changing the position of the slots around the lower p o r t i o n of the barrel. When the air intake is adjusted properly, the flame should l o o k like the one depicted in Figure i - 2 ; it w i l l have a bright blue inner cone and a darker blue outer cone. The
Introduction
Evaporating dish
Screw clamp
Pinchcock clamp
Universal clamp
F I G U R E i-1
Bunsen-type burners: {left) a Bunsen burner; (right) a T i r r i l l burner.
hottest part of the name is the t i p of the inner cone. If insufficient air is being mixed w i t h the gas, the flame w i l l be long and y e l l o w . I f this happens, adjust the air intake u n t i l y o u have the proper blue flame. T o o m u c h air w i l l cause the flame to "flash b a c k " ( t o burn inside the barrel, making it very h o t ) ; the flame may even shoot out of the b o t t o m of the barrel. If this happens, t u r n o f f the gas, adjust the air supply, and relight the burner.
CUTTING A N D BENDING GLASS
Soft glass rod or tubing can be cut easily if y o u place the tubing on the desk top and make a single scratch across it w i t h a triangular file or a glass scorer. Grasp the glass f i r m l y w i t h y o u r thumbs on the side of the glass away from the scratch; break the t u b i n g away from you, as shown in Figure i-3. Glass broken in this way w i l l have a sharp and perhaps rough edge on w h i c h y o u could cut yourself. Always take the
FIGURE i-2 Flame of a properly adjusted Bunsen burner.
10
Introduction
Breaking glass tubing.
extra few minutes required to fire-polish the cut ends of glass tubing. First, remove any jagged edges by rubbing the end of the tubing on wire gauze held over a waste can. Then, hold the end of the tubing in the tip of a burner flame (as shown in Figure i-4) and turn the tubing so that it is heated evenly. After the glass has become partially melted and smoothed, set the tubing d o w n on wire gauze or asbestos to cool. T o bend glass tubing, y o u w i l l need to heat a fairly long section o f the glass to softness. A flame spreader, often called a wing-tip, w i l l provide a wide flame. Rotate the tubing in this flame u n t i l it is soft. Then remove the tubing from the flame and hold it for a second or t w o to permit even heat d i s t r i b u t i o n . Bend the tubing to the desired shape and hold it u n t i l it hardens (see Figure i-5). Place the
12
Introduction
FIGURE i-6
Inserting glass tubing into a stopper.
glass on wire gauze or asbestos to c o o l . O n l y soft glass can be w o r k e d in this manner. Borosilicate glass, such as Pyrex, has too high a melting point to be softened by a Bunsen burner flame.
INSERTING G L A S S T U B I N G INTO A STOPPER
Some of the worst injuries possible in the first-year chemistry laboratory result from t r y i n g to force a thermometer, the stem of a glass funnel, or a piece of glass tubing i n t o a stopper. If the glass breaks, it may be shoved so forcefully i n t o y o u r hand that it causes a long, deep gash. The safest way to insert tubing is to wet it first w i t h soapy water or glycerin. Then grasp the tubing just above the area to be inserted into the stopper. Holding b o t h the tubing and the stopper w i t h a t o w e l , twist the stopper o n t o the tube (see Figure i-6). D o n ' t hesitate to use a lot of soap or glycerin; it can always be washed o f f w i t h water when y o u are finished.
13
POURING
CHEMICALS
Many l i q u i d reagents are contained in stoppered bottles. To pour from a stoppered b o t t l e , first remove the stopper and grasp the top of it between y o u r index and t h i r d fingers w i t h y o u r hand turned palm up. Then pick up the bottle w i t h the same hand (see Figure i-7). The t w o advantages to this pouring method are that the stopper is never placed where it can become contaminated and that your other hand is free to hold the container into which y o u are pouring the l i q u i d . A solid should be poured from a bottle by slightly tipping and then rotating the bottle (see Figure i-8). If y o u must put the lid d o w n while you pour the solid, be sure to place the top of the lid d o w n on your desk or w o r k i n g area.
FILTRATION
A solid can be separated from a supernatant l i q u i d by f i l t r a t i o n . One of t w o m e t h o d s - g r a v i t y f i l t r a t i o n or vacuum filtrationmay be used. B o t h methods leave the solid on a piece of filter paper and the l i q u i d (the filtrate) in a flask or a beaker underneath a funnel. In gravity filtration, gravitational force draws the l i q u i d through the funnel and the filter paper; in vacuum filtration, the liquid is sucked through the filter paper by an aspirator vacuum. Gravity f i l t r a t i o n is accomplished w i t h a conical funnel. The funnel stem touches the wall of the beaker to permit smooth l i q u i d How; the weight of the water column in the funnel stem speeds the f i l t r a t i o n . Fold a piece of filter paper in half; then fold one half over the other half, keeping an angle of about 10 between the edges.
F I G U R E i-8
Pouring a solid.
14
Introduction
FIGURE -9 Folding filter paper into a cone.
Tear a small wedge o f f the smaller p o r t i o n of the filter paper (see Figure i-9), open the paper i n t o a cone, and place it in the tunnel. Wet the paper and press it f i r m l y against the sides o f the funnel; having torn out the wedge w i l l enable y o u to form a seal at the fold of the filter cone to prevent air leakage behind the paper. The filter paper should be slightly below the rim of the funnel. Decant the supernatant l i q u i d from the solid into the funnel by pouring it d o w n a stirring rod (see Figure i-10). When y o u have filtered as much of the l i q u i d as y o u can using this method, transfer the solid using a stream of water from a wash bottle
FIGURE i-10 Gravity filtration.
15
and a stirring rod. A d d i n g the solid last will save y o u time in that most o f the solution will be filtered before the paper can become clogged by the solid. During the course of the f i l t r a t i o n , the funnel should never be more than about threequarters full. Suction f i l t r a t i o n requires a thick-walled flask w i t h a sidearm, a Blichner funnel, thick-wallcd rubber tubing, and a trap (all shown in Figure i-1 1). The filter flask must be clamped, so that it will not tip over, i f the heavy vacuum tubing Hops around. A f t e r clamping the flask, insert the Biichner funnel. Place a piece of filter paper in the b o t t o m of the funnel; use a size that lies flat in the b o t t o m of the funnel w i t h o u t extending up the sides of the funnel. Connect suction tubing between the flask and the trap and between the trap and an aspirator. The trap w i l l prevent water from the aspirator from backing up into the filter flask if the water pressure drops. Wet the filter paper w i t h a l i t t l e solvent and press it t i g h t l y against the b o t t o m of the funnel. T u r n on the aspirator and suck the solvent through the paper. Decant as much of the solution as y o u can i n t o the funnel and draw it through the paper before adding the solid. A f t e r y o u add the solid, suction it u n t i l it is as dry as possible. Always break the vacuum by disconnecting the tubing from the flask or from the trap; then turn o f f the aspirator. If y o u t u r n o f f the aspirator first, water may be drawn into the flask, where it w i l l dilute or contaminate the filtrate, and may even pass into the funnel.
CLEANING
GLASSWARE
For most laboratory purposes, it is sufficient to wash glassware w i t h detergent and tap water and to rinse w i t h tap water and then w i t h distilled water. If a more
16
Introduction
FIGURE -12 Clean and dirty glassware.
thorough cleaning is necessary, y o u r instructor w i l l give y o u directions. The glassware is completely clean when water Hows smoothly d o w n the sides of the vessel w i t h o u t collecting in droplets (see Figure i-12). If droplets collect, reclean the glass. High precision volumetric glassware (pipets, burets, volumetric flasks) should be thoroughly rinsed w i t h tap water and w i t h distilled water after each use and should always be clean when put away.
Scientific
Measurement
Scientists are interested not only in k n o w i n g what happens during experiments b u t also in making quantitative measurements of natural events. For example, scientists were interested to learn that moon rocks contain both silicon and oxygen, but they also wanted to measure how much of each of these elements is usually present in the rocks. Do m o o n rocks contain eqtial amounts of silicon and oxygen, or is there far more of one element than of the other? When this k i n d of quantitative i n f o r m a t i o n is available, comparisons between rocks on the moon and rocks on earth become possible. When copper and sulfur are heated together, it is obvious that they react to f o r m a black c o m p o u n d . However, the chemist wants to k n o w how many atoms of copper react w i t h how many atoms of sulfur; that is, does the c o m p o u n d produced have the formula C u S , or CuS, or some other composition? This i n f o r m a t i o n can be obtained by measuring the weights of copper and sulfur that combine to form the c o m p o u n d . A l m o s t all experiments in the chemistry laboratory include quantitative measurements (weights, volumes, lengths, and so o n ) , and this section w i l l show y o u how to deal w i t h these numerical measurements.
3 2
A C C U R A C Y AND PRECISION
Accuracy and precision are i m p o r t a n t terms in discussing measurement. Accuracy refers to h o w well a measured value agrees w i t h the true value. Precision
17
Scientific Measurement
refers to how well several determinations of one q u a n t i t y agree w i t h each other. Naturally, a scientist's goal is to make measurements that are both accurate and precise. However, it is possible to be quite precise w i t h o u t being at all accurate. For example, if the length of a table were measured several times, all of the values obtained might*ie almost identical (let's say 3.13, 3.1 I, and 3.12 m ) . But if the length of the measuring stick used was only 0.91 m ( 1 y d ) when it was thought to be 1.00 m, these precise values w o u l d not accurately represent the true length of the table. Several factors that lessen the accuracy of measurements are said to introduce systematic ox determinate errors (errors w i t h i n the system that can be determined and eliminated). One source of these errorsinaccurate equipmenthas already been mentioned; t w o other sources are impure chemicals and inexact chemical procedures. Pure chemicals and tested procedures are provided in this laboratory. When necessary, equipment is calibrated to compensate for possible inaccuracies and minimize systematic errors. Therefore, the measurements y o u obtain should be reasonably accurate. The precision of a measurement is affected by random or indeterminate errors (errors that are beyond the experimenter's c o n t r o l ) . Indeterminate errors include the effects of factors such as small temperature variations during the course of an experiment, the absorption of water by objects while they are being weighed, differences in j u d g m e n t about the color change of an indicator, and the loss of extremely small amounts of material in pouring, filtering, or other manipulations. Indeterminate errors may be just as apt to affect a measurement in a positive direction as in a negative d i r e c t i o n , so a particular measurement may be either slightly too large or slightly too small. Hence, t w o or more measurements are usually made and their average is used in the hope that positive and negative random errors will cancel one .another. But random errors can never be completely eliminated, and perfect precision or r e p r o d u c i b i l i t y is never expected. It must be noted here that, for the purposes of this discussion, we have assumed that y o u r laboratory technique is good enough that y o u will be able to w o r k carefully, w i t h o u t making such blunders as spilling half of a substance before y o u weigh it. In a first-year laboratory course, the process of developing a good experimental technique may make it more d i f f i c u l t for y o u to obtain accurate and precise data, but this d i f f i c u l t y can be overcome by care and practice. However, no matter how good y o u r laboratory technique is or how thoroughly systematic errors are eliminated, the existence o f random errors w i l l place limits on the accuracy o f your measurements. Y o u should record the limits placed on the accuracy of measurements whenever y o u report numbers.
Evaluation of Precision
As mentioned above, t w o or more measurements of a q u a n t i t y are usually made. The average value of these measurements is then taken as the best estimate of the quantity being measured, since small random errors w i l l tend to cancel one another. Random errors are likely to be small, so we can have much greater confidence in our results if successive determinations of the same q u a n t i t y deviate only slightly from the average. For example, three separate measurements of one side of a cubical box might be 10.32, 10.34, and 10.31 centimeters. The average of these three measurements is therefore
18
Introduction
10.32 10.34 10.31 3 )30.97 10.32 cm But three other people might measure the box and obtain lengths of 10.39, 10.29, and 10.35 c m . The average value in this case w o u l d be 10.34 cm -a value that is very close to the first result but that is less precise. A quantitative indication of the precision of a set of data is the average amount by which individual measurements deviate from the average value of the set of measurements; this is called the average deviation. The calculation of the average deviation (a.d.) for each of these t w o sets of data is illustrated below: Set I : 10.32 10.34 10.31 3 )30.97 10.32 cm a.d. 0.00 0.02 0.01 3 )0.03 0 . 0 1 = a.d. 10.39 10.29 10.35 3 ) 3 1.03 10.34 cm Set II: a.d. 0.05 0.05 0.01 3 ) 0.1 1 0.04 = a.d.
The more precise data set (Set I) w o u l d be considered more reliable; in other words, it is probably more accurate.
U n c e r t a i n t y and Significant Figures
Next, consider the actual process by w h i c h measurements are made, again using the example of measuring the length of a table w i t h a meter stick. The stick is divided into 100 major divisions (centimeters), each of w h i c h is subdivided i n t o 10 units (millimeters). If the stick is placed along the table edge, the corner may be positioned between the 96- and 97-cm marks (see Figure i-13). An even closer estimate of the table's length can be obtained by n o t i n g that the corner falls between 96.7 and 96.8 c m ; that is, the table is longer than 96.7 cm but is n o t as long as 96.8 c m . The length appears to be closer to 96.8 c m . A further refinement of the measurement can be made by mentally dividing the space between the 96.7- and 96.8-cm marks into 10 divisions and estimating where the corner falls. It falls about
Table
96
97
FIGURE i-13 Measuring the length of a table w i t h a meter stick.
19
0.7 of the way between the t w o marks, so 96.77 em is the best measurement we can make of the table's length. It is true that the last digit in the measurement 96.77 cm is somewhat uncertain. Someone else might estimate 6 rather than 7. Nevertheless, reporting this figure gives more i n f o r m a t i o n than simply saying that the length is 96.8 cm because the table's actual length is only close to (not exactly) 96.8 cm. We therefore report the table length as 96.77 c m . To be as honest as possible, the l i m i t on the accuracy of this measurement should be indicated in reporting this figure. The distance between 96.7 and 96.8 cm can probably be estimated to about 0 . 0 2 cm. This means that if the measurement were repeated under the same conditions, the last digit might be estimated to be 5, 6, 8, or 9 rather than 7. (This l i m i t a t i o n on r e p r o d u c i b i l i t y exists because it is simply not possible to estimate the measurement any more closely w i t h the unaided eye and a meter stick. If we wanted to measure the length any more accurately, we w o u l d have to use a caliper or a finer measuring instrument than a meter stick.) N o w we k n o w that the length of the table is 96.77 0.02 c m . We say that this measurement has four significant figures, four figures that tell tts how accurately the measurement was made; three of these figures are k n o w n exactly and the f o u r t h is slightly uncertain because it was estimated. Generally, in any measured result that is reported, the last figure can be assumed to be estimated. Just how uncertain the final digit is depends on the measuring process and instruments employed. The closest estimate possible for the last digit of the table's length was 2 . In the absence of i n f o r m a t i o n to the contrary, y o u can assume that the last digit is k n o w n to 1 in figures reported in y o u r text and in other scientific books and journals. Whenever you make any measurement in the laboratory (or anywhere else!), always try to place l i m i t s on y o u r o w n accuracy of estimation. Scientific n o t a t i o n . Let's extend our consideration of the measured table length of 96.77 c m . We might also express this measurement as 0.9677 meter, as 967.7 millimeters, or as 9,677,000,000 Angstroms. T w o of these numbers contain more than four digits, but all three numbers are simply different ways of expressing the i n f o r m a t i o n obtained from one measurementthe length of a t a b l e - a n d not all of the digits are necessarily significant. Each of these three numbers contains only the three significant figures that were obtained exactly and the f o u r t h significant figure that was estimated in the original measurement; the additional zeros are not significant. To w r i t e a number in a way that shows immediately how many figures are significant, we express the number in scientific notation; that is, we write it as a number between 1 and 10 m u l t i p l i e d by some power of 10, and we retain only the significant figures. Thus, 0.9677 m w o u l d be w r i t t e n 9.677 X 10"' m; 967.7 mm = 9.677 X 10 m m ; and 9,677,000,000 A = 9.677 X 10 A. Even though three different sets of units are used here, all three numbers are the result of the same measurement and contain only the original four significant figures.
2 9
N o w consider the number 0.000207. The zeros at the beginning of this number serve merely to locate the decimal p o i n t . The only three significant figures are 2, 0, and 7 ( 2 0 7 ) . When this number is w r i t t e n in scientific n o t a t i o n as 2.07 X 1 0 " , it is immediately obvious that it contains only three significant figures. Making the usual assumption that the uncertainty in the last digit is 1, this number has an accuracy of 1 part in 207.
4
20
Introduction
The number 1 200 g is a somewhat more confusing example. Does 1 200 g contain t w o , three, or four significant figures? The answer depends on the accuracy of the original measurement. Was the balance that was used accurate to l g ? If so, all four figures are significant: three digits are k n o w n exactly and the f o u r t h digit is an estimate. This number is w r i t t e n 1.200 X 10 g. But if the measurement is accurate to 10 g, then the number is 1.20 X 1 0 . A n d if the measurement is accurate to only 1 0 0 g, then the number is 1.2 X 1 0 . Scientific n o t a t i o n removes the ambiguity. Y o u should use it in all your w o r k to communicate i n f o r m a t i o n about the accuracy of y o u r measurements, just as all scientists do.
3 3 3
Calculations using significant figures. The results of many measurements are used in formulas to calculate other quantities. The use of significant figures is especially i m p o r t a n t in these calculated quantities, so that the proper degree of uncertainty in the result is shown. Suppose, for example, that a square table has a side s that is 96.77 cm long. Stated another way, the table length is k n o w n to 2 parts in 9677 or to roughly 1 part in 4 8 0 0 , if we assume 0.02 cm uncertainty in the measurement. If we wish to calculate the area of the table, we use the formula A = s = (96.77 c m ) = 9 3 6 4 . 4 3 2 9 c m . On closer examination, however, this result does not make sense. Using all of the figures obtained in the m u l t i p l i c a t i o n implies that we k n o w the area to an accuracy of 1 part in 93,644,329 (roughly, 1 part in 94,000,000). But our knowledge of the length of the side of the table was accurate to only 1 part in about 4 8 0 0 . It is clearly impossible for us to k n o w the calculated q u a n t i t y more accurately than we k n o w the measured quantities used in the calculation. Simply p e r f o r m i n g a m u l t i p l i c a t i o n cannot increase the accuracy of an original measurement. So we cannot determine the area of the table to an accuracy greater than 1 part in 4 8 0 0 , or 9366 2 c m . Reporting the area as 9366 c m indicates the approximate accuracy to which this number is k n o w n on the basis of the original measurement.
2 2 2 2 2
This example illustrates the fact that we cannot simply perform arithmetic operations b l i n d l y , w i t h o u t paying attention to the meaning of the numbers we use. In scientific calculations, we are not using mere abstract numbers but numbers that reflect our knowledge of a physical situation. Hence, in the above example, it was necessary to report the area using a specific number of significant figures ( f o u r ) , w h i c h made clear the accuracy to w h i c h we actually knew the measurement. Similar care must be exercised when any measurement is used to calculate other quantities. To maintain honesty about the uncertainty of calculated numbers, they must be reported to the proper number of significant figures that reflect the degree of accuracy of the original measurements. It is i m p o r t a n t to recognize that no calculated quantity can be known with more certainty than the least certain number used in the calculation. The f o l l o w i n g are guidelines for using significant figures in calculations. 1. For addition and subtraction: The term that is in error by the greatest p o r t i o n of a unit l i m i t s the accuracy of the answer. For example: 102.7 g 0.1 14 g 9.77 g 1 12.584 g= 1 12.6 g
21
2.
The first q u a n t i t y is k n o w n to only 0 . 1 g, so the sum of the three quantities can be k n o w n to only this degree of accuracy. For multiplication and division: When the units in w h i c h the answer is expressed and the units of the quantities used in the calculation are not the same, the number of significant figures in the answer is the same as the number of significant figures in the q u a n t i t y having the fewest significant figures. For example: ?= 18.13 m/sec = 18 m/sec 65 sec
: m
1 1 7
Counting. The kinds of measurements discussed thus far have all been of properties that can vary c o n t i n u o u s l y - p r o p e r t i e s that can have any value. Measurements of this k i n d are subject to uncertainty, but there are some numbers that can be k n o w n exactly. The c o u n t i n g of discrete objects is a k i n d of measurement that can be made w i t h complete accuracy and precision. Thus, in using such numbers in calculations, the uncertainty of the final result is determined by other measurements. For example, three people weigh 160.2, 175.0 and 180.9 lbs, respectively. What is their average weight? 160.2 lbs 175.0 lbs 1 80.9 lbs 3 ) 516.1 lbs \22-0 lbs = average weight The average weight has four significant figures and is accurate to 0.1 lb, as is each weight used in the calculation. The counted number 3 is exact and does not l i m i t the accuracy of the result.
P R A C T I C A L HINTS ABOUT L A B O R A T O R Y M E A S U R E M E N T
In making measurements in the laboratory, you will often have more than one instrument at y o u r disposal. For example, y o u could measure the volume of a solution using a buret or a graduated cylinder; the choice of w h i c h piece of equipment to use depends on the accuracy required of the measurement. A butcher doesn't weigh a steak to the nearest 0.0001 g on an analytical balance; steak is weighed to the nearest 0.01 l b , because-even at S2.99/lbthe l i t t l e bit of extra money the butcher might collect f r o m a more accurate weight w o u l d not justify the extra time required or the extra expense of a more accurate balance. Y o u should be just as economical of y o u r time and effort in the laboratory. Do not waste time making measurements w i t h instruments that are far more accurate than required. T w o i m p o r t a n t kinds of measurement are volume and weight. The f o l l o w i n g table indicates the degree of accuracy that it is possible to attain w i t h various instruments for measuring volume and weight.
22
Introduction
Measurement Volume
Available
Instruments
Instrumental
Precision
Weight
5-ml pipet Buret 10-ml graduated cylinder 100-ml graduated cylinder A n a l y t i c a l balance Triple-beam balance
0 . 0 1 ml 0 . 0 2 ml 0.1 ml 1 ml 0 . 0 0 1 , or better* 0.01 g
Depends on type of balance. In first-year chemistry laboratory w o r k , it is important to achieve the greatest possible accuracy in measuring y o u r results, but not every measurement in a particular experiment has to be made w i t h m a x i m u m accuracy. As an example, consider the reaction for the synthesis of zinc sulfide x Z n ( s ) + vS(s) A c o m m o n laboratory experiment is to determine the formula of this sulfide - t h a t is, to determine the numerical values of the subscripts x and yby reacting a weighed q u a n t i t y of zinc w i t h sulfur and determining how much zinc sulfide is produced. The experiment consists of heating an accurately weighed amount of zinc w i t h an excess of sulfur. No specific amount of sulfur must be used; the amount must simply be k n o w n to exceed the amount required for the reaction. Using more sulfur than is needed to react w i t h the zinc ensures that all o f the zinc w i l l react; the remaining sulfur will be converted to gaseous sulfur dioxide and will escape from the reaction vessel. The amount of sulfur in the resulting c o m p o u n d can be found as follows: 1.571 g (weight of zinc sulfide) - 1.052 g (weight of zinc) = 0.5 19 g (weight of sulfur). Thus, the amount of sulfur actually present in the c o m p o u n d can be accurately calculated. For this reason, it w o u l d be pointless to weigh the reactant sulfur to the nearest 0.001 g. Since we only need to be sure that an excesssay, 2 gof sulfur is present, weighing the reactant on a triple-beam balance to the nearest 0.1 g is the only measurement necessary. Before making any measurement, always ask yourself how accurate it must be to give the result of the required accuracy in the least amount of time using the least amount of effort. When in d o u b t , consult y o u r instructor.
VOLUME MEASUREMENTS
Y o u will often need to measure the volumes o f liquids in y o u r laboratory w o r k . Several vessels may be available, and their use will depend on the accuracy o f the measurement required.
Graduated Cylinders
Rough estimates of volume can be made using beakers w i t h graduation marks, but these measurements have a very low accuracy. If accuracy is i m p o r t a n t , a graduated cylinder should be used.
23
F I G U R E -14
Measuring volume w i t h a graduated cylinder.
A 10-ml graduated cylinder has graduation marks corresponding to one m i l l i l i t e r . Each large division of 1 ml is divided i n t o five smaller divisions of 0.2 ml each. The position of the b o t t o m of the l i q u i d meniscus gives the volume reading. In Figure i-14, the meniscus lies between 7.6 ml and 7.8 m l . Obviously, the volume is more than 7.6 ml but less than 7.8 m l . It is customary to divide the distance between the marks mentally i n t o smaller divisions and then to estimate where the meniscus lies along this scale. But because the 0.2-ml divisions on the 10-ml graduated cylinder are already so close together, y o u w i l l probably find i t possible only to divide the intervening distance i n t o halves rather than i n t o fifths or tenths; that is, y o u r eye will probably be able to distinguish a distance that corresponds to only half the length between each of the 0.2-ml divisions. A n y volume from about 7.65 ml to 7.75 ml w o u l d be indistinguishable to y o u r eyes, and the meniscus w o u l d look like it was about halfway between 7.6 ml and 7.8 m l . Y o u r reading w o u l d therefore be 7.7 m l ; the second digit is estimated. Since any " t r u e " volume from 7.65 ml to 7.75 ml w o u l d l o o k the same to y o u , there is ah uncertainty of 0 . 1 ml in the volume reading of 7.7 m l . It is customary to report the volume as 7.7 0.1 m l , or simply as 7.7 m l , w i t h the understanding that an uncertainty of 1 exists in the second digit. Thus, the volume of the l i q u i d is k n o w to 1 part in 77, or to about 1.3%. This measurement has t w o significant figures; one that is k n o w n exactly and one that is estimated. Perhaps this seems like a l o t of attention to devote to such a simple measurement, but the l i m i t a t i o n on y o u r a b i l i t y to estimate the second digit is a fundamentally i m p o r t a n t concept in making any laboratory measurement. This random error is impossible to eliminate even w i t h practice, because it arises from the l i m i t a t i o n s of y o u r eyes and the equipment.
V o l u m e t r i c Glassware
It is possible to make much more accurate volume measurements in the laboratory by using volumetric glasswarepipets, burets, and volumetric flasks. The construction of this type of glassware removes some of the limitations on accuracy that graduated cylinders present. V o l u m e t r i c vessels are more time-consuming to use
24
Introduction
and clean than graduated cylinders. As an example of the greater accuracy that is possible when y o u use v o l u m e t r i c glassware, a 5-ml pipet w i l l deliver 5.00 0.01 m l of l i q u i d . The volume is k n o w n to three significant figures. The uncertainty of 1 in the t h i r d figure means that the volume measurement is accurate to 1 part in 500, or to 0.2%a measurement that is almost 10 times more accurate than the same measurement made w i t h a graduated cylinder. Pipets and burets are used to measure the volumes of liquids that are transferred i n t o receiving vessels and are stamped " T D " ( " t o deliver"). V o l u m e t r i c flasks are used to prepare solutions of precisely k n o w n volumes and are stamped " T C " ( " t o c o n t a i n " ) . Pipets. A pipet (see Figure i-15) w i l l deliver a very accurately k n o w n q u a n t i t y of l i q u i d . L i q u i d is drawn i n t o the tube by suction u n t i l its level is above the marking around the stem. Y o u should use a bulb for suction. Then the l i q u i d is
Control liquid level with index
25
allowed to drain out of the pipet u n t i l the b o t t o m of the meniscus just touches the calibration line; the flow is controlled by placing y o u r index finger [not your t h u m b ) on the top of the pipet. When the meniscus level has been adjusted, the tip of the pipet is touched to the side of a waste beaker to remove any drop of clinging l i q u i d and then to the wall of the vessel into which the l i q u i d is to be transferred. Y o u r finger is then removed from the top of the pipet to permit the contents to flow out the t i p . Best results are achieved when the pipet is held vertically and the receiving vessel is tipped. When the l i q u i d has stopped f l o w i n g , wait another 30 seconds for any remaining liquid to drain d o w n the sides o f the pipet. Then roll the pipet against the side of the receiving vessel so that an additional drop flows out. Some liquid w i l l remain in the pipet. This is all right, because the pipet is calibrated to deliver the proper volume of l i q u i d when these few drops are retained. To be certain that the pipet delivers an accurate volume, the l i q u i d must flow smoothly and completely d o w n the walls of the pipet and not collect and adhere to the walls in droplets. Therefore, the pipet must be thoroughly cleaned. A f t e r the pipet has been cleaned and completely rinsed w i t h distilled water, it should be rinsed three times w i t h small portions of the solution to be transferred to make sure that no water remains in the pipet to dilute the solution. A f t e r y o u have finished using a pipet, rinse it several times w i t h distilled water so that it can be put away clean. Burets. Cleaning and filling the buret. Before using a buret, it should be thoroughly washed w i t h a buret brush and detergent, rinsed w i t h tap water, and then rinsed w i t h three portions (about 10 ml each) of distilled water. L i k e the pipet, the buret should be cleaned u n t i l l i q u i d drains smoothly d o w n its sides and does n o t collect in droplets on its walls. N e x t , grease the stopcock by placing a small ring of grease around it-on either side of the hole (make sure that no grease clogs the hole); burets w i t h T e f l o n stopcocks do not need to be greased. Then rinse the buret w i t h a small amount of the solution that is to be put i n t o it to remove any remaining water so that the solution w i l l not be d i l u t e d . Close the stopcock and pour about 5 ml of the solution i n t o the buret. Hold the buret horizontally and roll it so that the solution washes over the entire inside w a l l . Then drain the solution out of the stopcock, discard i t , and repeat this procedure t w o more times. Clamp the buret in place and fill it w i t h the s o l u t i o n . Open the stopcock and drain o u t solution u n t i l the t i p of the buret is filled and does not contain an air bubble. If necessary, add more solution so that the buret is filled to just below the 0.00 mark. Reading the buret. In any volume measurement, y o u should read the position of the l i q u i d meniscusnot the p o i n t at w h i c h the solution comes i n t o contact w i t h the glass. Each graduated mark on the buret corresponds to 0.1 m l . As usual, y o u are to estimate visually the fractional distance between t w o of these marks to obtain a reading that is accurate to 0 . 0 2 m l . The position of the meniscus in Figure i-16 is 18.36 m l ; four significant figures are obtained. It is i m p o r t a n t to eliminate the uncertainties in y o u r readings that result if y o u view the meniscus from various angles. Note that the meniscus seems to change position, depending on whether y o u l o o k at it from above or below (again, see Figure i-16). To make an accurate measurement, the eye must be level w i t h the meniscus. To ensure this, l o o k at the buret so that the back of the ml graduation
Introduction
27
mark nearest the meniscus is superimposed on the front of this same mark, and your eyes see o n l y a single line. Read the meniscus level from this position. Operating the buret. When y o u begin to use a buret, y o u may find it d i f f i c u l t or awkward to master the proper technique. However, it w i l l pay y o u t o exert the effort required to use a buret properly. To achieve the best results, operate the stopcock w i t h y o u r left hand (see Figure i-17). Grasp the tip l i g h t l y between y o u r third and f o u r t h fingers and c o n t r o l the flow of l i q u i d by turning the stopcock w i t h your t h u m b and index finger. The flask i n t o w h i c h the solution flows should be
F I G U R E i 18
Making up a standard solution using a volumetric flask.
28
Introduction
swirled w i t h y o u r right hand. If you are left-handed, you w i l l probably prefer to operate the stopcock w i t h y o u r right hand and to swirl the tlask w i t h y o u r left hand. Before beginning any t i t r a t i o n , touch the buret tip against the side of a waste beaker to remove the drop of l i q u i d that may be clinging to i t . A f t e r running solution o u t of a buret, wait a minute before making a volume reading, so that the l i q u i d remaining on the upper walls has time to drain d o w n . V o l u m e t r i c flasks. V o l u m e t r i c flasks (see Figure i-18) are used to prepare solutions of precisely k n o w n m o l a r i t y . F o r example, 0.100 mole of NaCl may be put i n t o a 1.00-liter volumetric flask and the flask filled w i t h water to the calibration mark giving 1.00 liter of solution so that the concentration is k n o w n to be 0.100/V/. The solid that is to be dissolved must be very carefully weighed, but it is not necessary to measure the a m o u n t of solvent that is used; instead, the final volume of the solution is k n o w n precisely. After y o u put the solid into the tlask, use a little of the solvent to wash o u t the container in w h i c h the solid was weighed and add the washings to the contents of the tlask (be sure that none of the carefully weighed solid is lost). A d d a l i t t l e more water and swirl the flask to dissolve as much of the solid as possible before the tlask is completely filled w i t h water. Then add more water u n t i l the meniscus just touches the calibration line ( i t is helpful to use a medicine dropper to add the last few m i l l i l i t e r s ) . Stopper the tlask and m i x the solution by repeatedly inverting and u p r i g h t i n g the flask (while holding y o u r hand t i g h t l y over the stopper!). Like pipets and burets, v o l u m e t r i c flasks must be scrupulously clean, especially in the area of the neck above the calibration line. If the neck of the tlask is d i r t y enough to allow water to collect in droplets, an u n k n o w n quantity o f water will remain on the neck when the solution is being prepared, and the volume of solution will not be the calibrated capacity o f the tlask. Consequently, the molarity o f the solution will not be accurately k n o w n . A l t h o u g h the tlask must be clean, it does not have to be dry if y o u are using water as the solvent; just remember to rinse the flask w i t h distilled water. When y o u are finished w i t h the tlask, pour out the solution and rinse the tlask w i t h tap water and then several times w i t h a l i t t l e distilled water. The tlask should be stored w i t h the stopper in place so that dirt cannot get i n t o i t ; the tlask does not have to be stored dry if there is only distilled water in it.
MAKING MASS M E A S U R E M E N T S
Y o u will need to make many weighings to determine the masses o f the materials y o u will use in laboratory w o r k . Because the instruments used for weight measurements require more instruction and more practice to master than the instruments used for volume measurement, the first experiment in this manual is devoted to weighing.
Experiment 1 The Use of Balances: Hydrated Compounds

Introduction
A c c o r d i n g to the Law of Constant C o m p o s i t i o n , any sample of a pure c o m p o u n d contains the same elements in the same proportions. F o r example, every sample of cobalt chloride ( C o C l ) , consists of 45.39% cobalt and 5 4 . 6 1 % chlorine on a weight basis. However, this c o m p o u n d , like many others, also exists in a form k n o w n as a hydrate; the crystalline form characteristic of the solid contains water as well as cobalt chloride. The amount of water in the crystal may vary for some hydrated compounds. Some solids absorb water when they are in contact w i t h moist air; in contrast, water may evaporate from some hydrated crystals when they are in contact w i t h dry air. However, many compounds contain a definite p r o p o r t i o n of water. For example, the composition of hydrated cobalt chloride is represented by the formula C o C L 6 H 0 , w h i c h means that the crystal contains six molecules of water for each C o C l u n i t . On a weight basis, the crystal consists of 24.77% cobalt, 29.80% chlorine and 45.43% water. The water can be removed from this hydrate (and from many others) by heating it to a temperature of 1 0 0 C or higher.
2 2 2
The c o m p o s i t i o n of a c o m p o u n d can be determined by carefully weighing each of the elements-that combine to form it or each of the substances i n t o w h i c h it can be decomposed. In this experiment, y o u will use a form o f the latter procedure to determine the percentage o f water in a hydrate. First y o u w i l l weigh the hydrated c o m p o u n d , and then y o u w i l l weigh the anhydrous c o m p o u n d that remains after the water has been removed from the solid by heating i t . Both a triple-beam balance and an analytical balance w i l l be used in this experiment. Each of these balances has its o w n advantages. Much more accurate measurements ( t o 0 . 0 0 0 1 g) can be made on the analytical balance. The smallest graduation on a triple-beam balance is 0.1 g or 0.01 g, and it is d i f f i c u l t to estimate weights any more closely than this. However, the analytical balance has a more l i m i t e d total c a p a c i t y - u s u a l l y 160 g in comparison to 610 g for most triple-beam balances. The triple beam balance is more convenient to use when y o u want to weigh out a particular amount of a substance. Y o u can weigh a container, adjust the weights for the proper total weight of the container and the substance, and then pour the substance i n t o the container u n t i l y o u have the desired total weight. A triple-beam balance is a rugged instrument. (Some are practically indestructable!) In contrast, an analytical balance can be easily damaged by misuse. If damage occurs, the top of the balance may have to be removed to enable y o u r instructor or a technician to make an adjustment; even if the damage is not extensive, this wastes valuable laboratory time. More serious damage to the balance can be quite expensive to repair and w i l l deprive other students o f the use o f the balance u n t i l it can be repaired. Even when damage is not immediately apparent, general misuse can 29
30
Experiment 1
gradually lessen the sensitivity of an analytical balance. Consequently* u n t i l y o u are completely proficient in the proper use of the analytical balance, it is advisable to make preliminary weighings on the triple-beam balance so that y o u will be less likely to misuse the analytical balance.
BRIEF BALANCE INSTRUCTIONS
Analytical Balance
Y o u r instructor w i l l provide detailed instructions for the particular type of balance that y o u are using. A few general comments are given here. 1. The balance must be level when it is in use. If the leveling bubble indicates that the balance is not level, ask y o u r instructor to make the necessary adjustment. Do not move or bump the balance. Do not lean on, bump, or move the table on which the balance is resting. 2. Always check and set the zero point of the balance each time you use it. This ensures that the balance records a weight of zero when there is no object on the balance pan. 3. Be sure tliat the balance is arrested, b o t h when y o u place the object on the pan and later when you remove the object from the pan. 4. The object to be weighed should be clean and dry, so that its weight w i l l not change as a result of loss of d i r t or moisture. This also protects the balance from damage that might be caused by moisture. If a solid chemical is to be weighed, it should be placed in a b o t t l e , a beaker, or a metal weighing pan, and not on a piece of paper. If a liquid is to be weighed, it should be in a closed container so that vapor cannot escape and possibly corrode parts of the balance. If a very accurate measurement of the weight of the object is required, handle the object w i t h tongs or a test-tube holder or by a piece of paper wrapped around i t . Otherwise, y o u r hands might deposit moisture, d i r t , o i l , salts from y o u r skin, and so on, on the object, changing its weight. 5. Be sure that the arrest-release control of the balance is in the proper position before you dial the weights. A f t e r recording y o u r weighing, arrest the balance, return all weight settings to zero, remove the object, and close the doors of the balance case.
Triple-Beam Balance (Figure 1-1)
Place the object on the balance pan. Be sure that all sliding weights are set at their zero marks. First, locate the beam that has 100-g graduations and move the weight alone this beam to the right one notch at a time u n t i l it causes the beam to
31
The Uses of Balances: Hydrated Compounds
FIGURE 1 1
Triple-beam balance.
d r o p . Then move the weight back to the left one n o t c h ; the beam w i l l rise. Second, move the weight along the beam that has 1 0 - g graduations u n t i l the beam drops; move the weight back to the left one n o t c h . F i n a l l y , move the weight along the beam that hasT-g graduations u n t i l the scale is in balance. The pointer should move just as far upward as it does d o w n w a r d from zero; y o u do not need to wait for the pointer to come to rest. Read the weight to the nearest 0.1 g. Return the weights to zero, remove the object, and clean up any material spilled on or around the balance. Y o u r first step in weighing an object on an analytical balance is to check and set the zero p o i n t . On a triple-beam balance, this procedure can be fairly tedious and is usually o m i t t e d unless y o u r weighing must be as accurate as possible. Y o u w i l l often weigh " b y difference" on the triple-beam balance; that is, a container is first weighed e m p t y , then it is weighed w i t h a chemical in i t , and the weight of the chemical is the difference between these t w o weights. As w i t h the analytical balance, the triple-beam balance must register a weight of zero when there is no object on the pan or the weighing w i l l be incorrect. However, each weighing w i l l be in error by the same amount, and the difference between the weights of an empty container and the container w i t h the chemical w i l l give the correct weight of the chemical. When y o u compare results obtained by weighing the same object on each type of balance, remember that the triple-beam balance may be in error by as much as several tenths of a gram if the zero p o i n t was not set.
EQUIPMENT
NEEDED
analytical balance asbestos square beaker tongs
Bunsen burner clay triangle porcelain crucibles and lids
32
Experiment 1
ring ring stand
triple-beam balance
CHEMICALS
NEEDED
u n k n o w n hydrated c o m p o u n d
PROCEDURE
Wash and dry t w o porcelain crucibles and their lids. Record the numbers that are on the crucibles and lids; identify one set for T r i a l 1 and the other for Trial 2 (see Report Sheet 1 on page 35). Support one of the crucibles and its lid on a clay triangle (see Figure 1-2), and heat them w i t h the full heat o f a Bunsen burner for at least 10 minutes to remove any absorbed volatile or combustible material. If a soot deposit forms, burn it o f f completely. A l l o w the crucible and the lid to cool for about one minute on the triangle. Then use tongs to transfer them to a clean piece of asbestos and allow them to cool to room temperature. Cooling should take about 15 minutes, but it w i l l be more rapid i f the l i d is removed from the crucible. Heat the second crucible and l i d while the first crucible and lid are cooling. Weigh the cooled crucible and lid on the triple-beam balance and then on the analytical balance. Remember to handle them w i t h tongs. If they appear to be changing in weight during the measurement on the analytical balance, they are still
33
The Uses of Balances: Hydrated Compounds
warmer than room temperature; immediately remove them from the balance and wait 5 additional minutes before repeating the measurement. Return to the triple-beam balance and weigh about 1-1.5 g of the hydrated c o m p o u n d i n t o the crucible. Then use the analytical balance to weigh the crucible, l i d , and hydrated c o m p o u n d as accurately as possible. Weight a similar sample of the hydrate into the second crucible (after it has been heated, cooled, and weighed). Be sure that y o u correctly identify each sample using the numbers on each crucible and lid. Support the first crucible on a clay triangle w i t h the l i d very slightly ajar to permit water vapor to escape. Heat the crucible using the lowest possible flame; h o l d the burner in y o u r hand so that you can remove it q u i c k l y if necessary. A puddle of water may form around the solid; gentle heating is required to ensure that the solid does not splash out of the crucible as this water boils away. Even if there is no apparent water loss, the hydrate may crackle and bounce around (like popcorn); again, gentle heating and a nearly closed lid are necessary to prevent escape of solid material from the crucible. Y o u may notice that the c o m p o u n d changes color or changes from a crystal to a powder; on the other hand, there may not be any obvious change in its physical properties. When there is no longer any splashing or spattering, place the burner on the desk top and continue to heat the crucible w i t h a low flame for a total of about 10 minutes. If the c o m p o u n d is heated too strongly, some decomposition other than just the loss of water may occur or the compound may react w i t h oxygen that is in the air. A l l o w the crucible to cool to room temperature and then weigh it on b o t h balances. During the cooling and weighing, the crucible must be covered to prevent the anhydrous c o m p o u n d from reabsorbing water from the air.-Repeat this procedure w i t h the second crucible.
R E S U L T S AND
DISCUSSION
Review the i n t r o d u c t o r y section on accuracy and precision in scientific measurement (page 16). The difference between the weight of the crucible, l i d , and hydrate and the weight of the crucible, l i d , and anhydrous c o m p o u n d is the weight of water that was lost during heating. Express this weight as a percentage of the total weight of the c o m p o u n d that was originally present. Record all these data on the Report Sheet for this experiment. Be sure to retain the proper number of significant figures in y o u r answer; express y o u r result in scientific notation if the degree of accuracy w o u l d be ambiguous w i t h o u t i t .
QUESTIONS
1. How many significant figures are there in the result y o u obtained for the percentage of water in the hydrate, using weights measured on the triple-beam balance? Using weights measured on the analytical balance? 2. Imagine that your sample of hydrated c o m p o u n d weighed 137.2306 g. F r o m the result y o u obtained using the analytical balance, calculate the weight of water in this sample. Be sure to retain the proper number of significant figures. If y o u
34
Experiment 1
3.
had measured the sample weight and water loss for this sample using the triplebeam balance, what w o u l d these weights have been What w o u l d y o u r calculated value be for the percentage of water in the hydrate, using these triple-beam balance weights? H o w w o u l d y o u r experimental result for the percentage of water in the hydrate compare to the true value if y o u made each of the f o l l o w i n g errors? (a) Some of the hydrated c o m p o u n d is spilled after it is weighed. ( b ) Solid spatters out of the crucible during the heating. (c) The anhydrous c o m p o u n d absorbs moisture from the air while it cools. (d) Some of the anhydrous c o m p o u n d is spilled before it is weighed.
9
REFERENCE
Yoder, C . H . , Suydam F . H . , and Snavely, F . A . Chemistry. New Y o r k : Harcourt Brace Jovanovich, Inc., 1975. Chapter 2.
REPORT
SHEET
EXPERIMENT 1
Name Section TBB* Note: A l l numbers must be reported w i t h proper units attached. Trial 1: Weight of crucible and l i d Weight of crucible, l i d , and hydrate Weight of hydrate Weight of crucible, l i d , and anhydrous c o m p o u n d Weight of anhydrous c o m p o u n d Weight of water lost Percentage of-water in the hydrate Trial 2: Weight of crucible and lid Weight of crucible, l i d , and hydrate Weight of hydrate Weight of crucible, l i d , and anhydrous c o m p o u n d Weight of anhydrous compound Weight of water lost Percentage of water in the hydrate Average of the t w o trials: Percentage of water in the hydrate
* T B B = triple-beam balance. * * A B = analytical balance.
Date
AB**
(Answer the questions from pages 33-34 on
the back of the Report Sheet.)
EXERCISES
1. How many significant figures are there in each of the f o l l o w i n g numbers? If the accuracy is ambiguous, state the m i n i m u m and the m a x i m u m number of significant figures that may be present. 152.36 127.210 2. 0.0032 62000 20.000 0.0870
Express each of the above numbers in scientific n o t a t i o n .
3.
Carry out each of the f o l l o w i n g calculations, retaining the proper number of significant figures. Assume that all numbers represent measured quantities. Express each answer in " n o r m a l " form and in scientific n o t a t i o n . (a) 628.2 + 0.761 + 2.05 (b) 215.07 - 19.7623 (c) (2.18 X . l ' 0 " ) + (7.41 X 1 0 " ) + (8.54 X 10~ )
s 6 4
(d) 2476 + 0.1207 + 0.0214 + 0.0081 (e) 417 X 2.1 (0 628.718-8.72
(g) 31 - 0.0671 (h) (5.16 X 1 0 ) X (2.1 X 10~ ) X (1.07 X 10~ )

4 2 3
(i) 4 . 0 ^ ( 6 . 0 2 3 X 1 0 )
2 3
(j) 0.5761 X 0.0821 X 373 * 0.976 * 0.2824 ( k ) 12.01 1 15 + (1.66 X 1 0 "

2 4
) - (6.023 X 1 0 )
2 3
( Use the back of this page for your calculations, if necessary.)

37
Experiment 2 Properties of Substances

Introduction
Chemists study chemical reactions; that is, they seek to learn about the nature of processes that convert one substance into another (for example, iron to rust, or lysergic acid to L S D ) . Several facets of chemical reactions can be investigated; how fast they occur; whether they evolve heat; whether they produce a large or a small amount of the desired p r o d u c t ; and so on. The first requirement for studying reactions is to recognize when one has occurred. Sometimes this is easy because the appearance of the product is different from the appearance of the reactants. For example: copper metal + (copper color) sulfur copper sulfide (black)
(yellow)
But there are many reactions, especially in organic chemistry, in which the reactants and the products have the same appearance (for example, they may all be white powders). The chemist is then faced w i t h the problem of h o w to tell whether m i x i n g the reactants has actually produced a new substance. In other words, the chemist must be able to identify pure substances. The physie-al properties of a substance are usually measured to identify i t . Some of the properties normally considered are; 1. Color. 2. Melting point: The temperature at w h i c h a substance changes from a solid to a liquid. 3. Boiling point: The temperature at w h i c h the vapor pressure equals atmospheric pressure. 4. Density: Mass per unit of volume. 5. Solubility: H o w much dissolves in a given q u a n t i t y of a particular l i q u i d . Several of these physical properties are measured to identify a substance. For example, suppose that a compound is a colorless solid w i t h a melting p o i n t of 9 5 C and a b o i l i n g p o i n t of 3 4 7 C . This i n f o r m a t i o n permits us to determine that the substance is benzil. Of course, many compounds are colorless crystals. Several of these colorless crystal compounds probably have melting points around 9 5 C , and more than one of these compounds may boil at 3 4 7 C . But it is quite u n l i k e l y that t w o compounds that are colorless crystals and that melt at 9 5 C and that boil at 3 4 7 C exist. The c o m b i n a t i o n of these three properties leaves no doubt that the compound is benzil. (Properties other than m e l t i n g and b o i l i n g points can be used to identify substances. Y o u w i l l learn about some o f these i n later experiments.) It is most meaningful to measure physical properties that have numerical values, because there can be no d o u b t about the result (assuming that the l i m i t s on the
39
40
Experiment 2
accuracy of the measurement are clearly stated). In contrast, the description of a property like color can be quite ambiguous; what one person describes as " ' p i n k , " another might call "rose," or " l i g h t r e d , " or even " c o r a l . " Nonetheless, such a qualitative and subjective description still has value; at least we k n o w that the " p i n k " substance has color and it is not black or green! Thus far, a very i m p o r t a n t aspect of the study of chemical reactions has been neglected: a reaction can produce several products; it does not always produce just one. When more than one product is produced, the chemist must separate these products from one another to identify t h e m . This is generally accomplished by subjecting the m i x t u r e to d i s t i l l a t i o n , crystallization, sublimation, or chromatography. A f t e r the components have been separated f r o m one another by one of these processes (some o f which y o u w i l l use in later experiments), the substances can be identified by their physical properties. In this experiment, yoti will measure some o f the physical properties o f pure substances and mixtures o f substances. Y o u w i l l then use these measured values to identify an u n k n o w n solid and an u n k n o w n l i q u i d . This experiment is designed to give y o u experience in (1) making accurate numerical measurements of the physical properties of substances and (2) i d e n t i f y i n g pure substances by their physical properties.
EQUIPMENT
NEEDED
beakers Bunsen burner capillary tubes copper wire cork
cork borer paring knife 5-ml pipet ring ring stand
rubber bands spatula test tube (25 X 200 m m ) thermometer wire gauze
CHEMICALS NEEDED
l-chloro-4-nitrobenzene methanol mineral oil
naphthalene u n k n o w n l i q u i d ( f r o m list on page 45) unknown solid ( f r o m list on page 45)
PROCEDURE
A.
L i q u i d Density
Density is defined as mass per unit of volume. Measurements of density can be quite simple to make. Y o u merely take an accurately k n o w n volume of a substance and determine its mass by weighing i t . A pipet or a buret is usually used to obtain accurate volume measurements of liquids. In this experiment, y o u w i l l use a pipet that delivers 5.00 ml of l i q u i d . (Before proceeding, review the discussion of volume and weight measurements on page 21 and the instructions for cleaning and using pipets on page 24.)
41
Properties of Substances
Cover a 50-ml beaker w i t h a watch glass and weigh it on the analytical balance. Return to y o u r desk w i t h the beaker, and use the pipet to transfer 5.00 ml of the u n k n o w n l i q u i d i n t o the beaker. Reweigh the filled beaker and watch glass. The weight of the l i q u i d is the difference between the weights of the filled beaker and the empty beaker w i t h watch glass. Dispose of the l i q u i d by pouring it i n t o a waste jar; dry the beaker and repeat this density d e t e r m i n a t i o n . The weight of the second sample should agree almost exactly w i t h the weight of the first. If it does n o t , y o u can conclude that y o u are pipeting or weighing i m p r o p e r l y , and y o u should ask y o u r instructor for advice.
B.
Boiling Point
Cautions: Work under the hood. The vapors of y o u r u n k n o w n l i q u i d may be toxic. Most of the unknowns are flammable; never pour them near a flame. Use the lowest flame possible to avoid the possibility of igniting the vapors as they leave the test tube. Do not leave your burner on after you have heated the hath. 1. K n o w n c o m p o u n d . The purpose of w o r k i n g w i t h a pure l i q u i d of k n o w n boiling p o i n t is to enable y o u to assure yourself that y o u r technique is correct. When you are confident that y o u can make this measurement accurately, proceed to Part 2 and collect data on y o u r u n k n o w n l i q u i d . Set up a ring and place a 250-ml beaker half-filled w i t h water on wire gauze so that y o u can heat it w i t h a burner. Clamp a test tube so that it extends i n t o the water bath. A d d about 5 ml of methanol ( C H O H ; b o i l i n g p o i n t 6 5 C ) to the test tube; be sure that the water level in the bath is above the l i q u i d level in the test tube. Using a cork borer, bore a hole in a no. 10 cork i n t o w h i c h y o u can fit a thermometer. Cut a wedge o u t of the cork w i t h a paring knife (see Figure 2-1). A t t a c h a capillary tube ( w i t h about half the length broken o f f ) to the thermometer, open end d o w n and closed end up. Place the vented cork containing the thermometer in the tube, so that the thermometer bulb is immersed in the l i q u i d . ( Y o u r apparatus should l o o k like that in Figure 2-2.) As y o u begin to heat the water bath, watch what happens in the capillary tube. It is i n i t i a l l y filled w i t h air at atmospheric pressure. As the bath is heated, the air (like any gas) expands and begins to escape from the open end of the tube as tiny bubbles. Vapor from the sample also rushes i n t o the tube, expelling even more air. When the l i q u i d starts to b o i l , the capillary tube provides a surface on w h i c h bubbles of vapor can f o r m ; it acts as a boiling chip.
3
fESK" '"'
v
FIGURE 2-1
Cork with vent.
HI
Experiment 2
Remember that the b o i l i n g p o i n t is defined as the temperature at which the pressure exerted by the vapor of the l i q u i d equals the atmospheric pressure on the surface of the l i q u i d . For the vapor bubbles to rise to the l i q u i d surfaceagainst the d o w n w a r d force of atmospheric pressure and the pressure exerted by the l i q u i d that is above the b u b b l e s - t h e y must exert a pressure that is slightly greater than atmospheric pressure. Consequently, the temperature at which the l i q u i d boils may be slightly higher than its defined b o i l i n g p o i n t . Since the vapor pressure of the l i q u i d when it starts to boil is somewhat higher than atmospheric pressure, the vapor present in the capillary tube will force liquid out o f the tube and the liquid level will be higher in the test tube than it is in the capillary. At this point, turn o f f the burner and stop heating the bath. The temperature will begin to fall approaching the boiling point o f the l i q u i d from above. When the liquid's b o i l i n g point is reached, the pressure due to the vapor in the capillary will be equal to the pressure o f the atmosphere; the liquid levels will be the same in the capillary and in the test tube. Record this temperature as the boiling point of the l i q u i d . F r o m the d e f i n i t i o n of b o i l i n g p o i n t , it can be seen that the temperature at which a l i q u i d boils depends on the pressure of the atmosphere. In tables, the b o i l i n g points of substances are given for a pressure of 760 torr; this is called the normal boiling point. If a b o i l i n g p o i n t (b.p.) is measured at some pressure other than 760 torr, the pressure at which the b o i l i n g p o i n t was determined is reported ( f o r example, b.p. l 0 2 C / 6 0 0 t o r r ) . Y o u are measuring boiling points at a pressure that is probably not exactly 760 t o r r ; read the correct atmospheric pressure from a barometer. 2. U n k n o w n c o m p o u n d . Use the procedure described in Part 1 to determine the boiling point of y o u r u n k n o w n l i q u i d . Repeat the procedure using a fresh capillary tube. This measurement combined w i t h y o u r density measurement should enable y o u to identify the u n k n o w n l i q u i d from the list on page 45. Be sure to record the identification number for the u n k n o w n .
C. Melting Point
I. Pure, k n o w n c o m p o u n d . First, y o u are to determine the melting p o i n t of a k n o w n c o m p o u n d to assure yourself that y o u r technique is accurate enough to reproduce a k n o w n result. As before, this should make you confident about the accuracy of your measurement on the u n k n o w n . Pour about 1 5 ml of mineral oil into a 25 X 200 mm test tube that is clean and dry. Clamp the tube so that y o u can heat it w i t h a burner. Make a ring stirrer from a long piece of copper wire. Loop one end and bend the wire so that the plane o f the loop is perpendicular to the rest o f the wire. Drill a small hole into y o u r vented no. 10 cork and insert the stirrer. Place a small sample of naphthalene ( C , H ; melting point 7 9 - 8 0 C ) on a piece of paper and crush it to a fine powder using a spatula. Heap the powder and scoop up some of it by plunging the open end of a capillary tube into the heap. H o l d the tube upright and tap it on the desk top u n t i l the powder is shaken to the b o t t o m of
0 S
43
a
I I i i^-^ Thermometer
5 i ^ r r:.,
s
a1__
I T!j -
\^ _s "Rubber band ci i j on
Inverted capillary tube
F I G U R E 2-2 Determining the boiling point of methanol.
the tube, where it should form a tightly packed layer. Repeat this process u n t i l the sample layer is about 5 mm deep. A t t a c h the capillary tube to a thermometer w i t h a rubber band (see Figure 2-3). Carefully position the capillary tube end alongside the thermometer bulb. Be sure that the rubber band is well above the l i q u i d level. Begin heating the mineral oil gently; for accurate results, the temperature should increase about 2 per minute. When y o u k n o w the expected melting point for a substance, y o u can heat it fairly rapidly to a temperature about 2 0 below the melting point and then reduce the heat. During the heating, continually stir the o i l bath w i t h the ring stirrer. Stir gently so that y o u do not bump the thermometer or the capillary tube. Y o u r sample should melt w i t h i n 2 of 7 9 - 8 0 . If it does not, repeat the determination and heat the bath more s l o w l y . Y o u should notice that a pure substance melts over a small temperature range of 0 . 5 - 1 . 0 C . The sharpness of its melting point (m.p.) is one way of telling that a substance is pure. 2. Mixtures. Crush well and thoroughly m i x some l-chloro-4-nitrobenzene ( C H N O , C I ; m.p. 8 3 - 8 4 C ) w i t h your naphthalene and determine a melting point for this m i x t u r e . Note that although the separate pure substances melt at very similar temperatures, the mixture melts at a lower temperature and over a much wider temperature range. The lowering and spreading of the melting point can also be used in c o m p o u n d i d e n t i f i c a t i o n . A material that is thought to be substance A can be mixed w i t h a . k n o w n sample of substance A. I f t h e melting point of the mixture is the same as the melting point of pure A, the u n k n o w n material is indeed substance A, for only pure A w o u l d have the correct, sharp melting point. If the u n k n o w n material is not substance A , the m i x t u r e will melt over a fairly wide temperature range and at a temperature different from that of pure A (usually lower, but occasionally higher). This proceudre is k n o w n as taking a mixture melting point.
6 4
3. U n k n o w n compound. Obtain an u n k n o w n solid from y o u r instructor. Determine its melting p o i n t and identify the c o m p o u n d from the list of substances on page 45. ( A d d i t i o n a l data of this type may be found in the Handbook of
44
Experiment 2
FIGURE 2-3
Determining the melting point of a solid.
Chemistry and Physics, published annually by the Chemical Rubber Company.) Samples of various solids are available in the laboratory, so that y o u can take m i x t u r e melting points to assist y o u in identifying unknowns. In general, y o u can expect y o u r melting point data to agree w i t h i n 2 C of the literature. Be sure to record the identification number of y o u r u n k n o w n . Dispose of mineral o i l by pouring it back i n t o the original container or i n t o the waste jar as y o u r instructor directs.
DATA AND
RESULTS
The density of a substance is defined as weight per unit of volume. Use the weights y o u measured for 5.00-ml volumes of y o u r u n k n o w n l i q u i d to calculate its density for each of the t w o trials. Be sure to report y o u r results to the correct number of significant figures. (First, review the discussion of the meaning and the use of significant figures in the i n t r o d u c t o r y section on scientific measurement on pages 16-2 1.) Use y o u r density and boiling point data to identify your l i q u i d u n k n o w n . Identify yotir u n k n o w n solid on the basis of its melting point and its m i x t u r e melting points. Record y o u r data and conclusions on the Report Sheet for this experiment.
45
Substance
in.p.(C)
b.p.CO 278 305 decomposes 250 254-255 196 57 77-78 242/761 t o r r 80.7 174 >300 sublimes 98 65 42 218 285 97 82
Density(g/ml)* 1.024 1.21 1.103 1.316 1.6 1.576 1.817 0.884 1.520 0.774 1.458
acenaphthene 95 acetanilide 114 acetoacetanilide 85 benzoic acid 122.4 biphenyl 69-72 /;-bromochlorobenzene 67 14>romo-2,2-difluoroethane - 7 4 . 5 b u t y l chloride -123 l-chloro-4-nitrobenzene 83-84 cyclohexane 6.5 /;-dichlorobenzene 53 dimethylterephthalate 140-142 N,N-diphenylacetamide 103 heptane -91 methanol -98 m e t h y l iodide -66 naphthalene 80 phthalic anhydride 131-132 1- propanol -127 2- propanol -89
0.684 0.792 2.279 1.145 1.527 0.807 0.785
* A t room temperature. Source: Data ate from N . A . Lange, Handbook of Chemistry (New Y o r k : McGrawHill, 1967.); and Handbook of Chemistry and Physics (Cleveland: Chemical Rubber Publishing Co., published annually).
QUESTIONS
1. Why is a pipet used instead of a graduated cylinder to make the volume measurement for the density determination? 2. Which measurement-weight or volumelimits the number of significant figures in y o u r calculated density? 3. Why must the cork be vented in the b o i l i n g p o i n t determination?
REFERENCE
Yoder, C . H . , Suydam, F . H . , and Snavely, F . A . Chemistry. New Y o r k : Harcourt Brace Jovanovich, Inc., 1975. Chapter 1.
REPORT
SHEET
EXPERIMENT 2
Name Section (Note: All numbers must be reported with proper units attached.) Trial 1
Date
A. L i q u i d density: Weight of beaker and watch glass Weight of beaker, watch glass, and liquid Weight of liquid Density o f u n k n o w n l i q u i d Average of the t w o trials B. Boiling p o i n t : Methanol Unknown liquid C. Melting p o i n t : Naphthalene M i x t u r e of naphthalene and l-chloro-4-nitrobenzene U n k n o w n solid M i x t u r e melting points: C o m p o u n d added to u n k n o w n C o m p o u n d added to u n k n o w n C o m p o u n d added to u n k n o w n Results: Number o f u n k n o w n l i q u i d Identity o f u n k n o w n l i q u i d Number of u n k n o w n solid I d e n t i t y of u n k n o w n solid (Answer the questions from page 45 on
Trial 2
m.p. m.p. m.p.
Experiment 3 Compound Stoichiometry

Introduction
It is of great importance to chemists to k n o w the formulas of compounds that form when elements react w i t h one another. Stated another way, the chemist must determine exactly how many atoms of one element combine w i t h how many atoms of another element. For example, we can allow magnesium to react w i t h oxygen by heating the magnesium in 0 to form magnesium oxide. One gram of magnesium w i l l produce 1.66 grams o f magnesium oxide. The weight o f the oxygen in the oxide can be found quite simply by subtraction:
:
1.66 g (weight of magnesium o x i d e ) - 1 . 0 0 g (weight of magnesium) 0.66 g (weight of oxygen) Thus, 0.66 g o f oxygen w i l l react w i t h 1.00 g o f magnesium to form an oxide. If.the gram-atomic weights of magnesium and oxygen are k n o w n , it is possible to calculate how many moles of each element reacted to f o r m the oxide and the relative numbers of atoms involved in this reaction. W i t h a table of atomic weights at our disposal, this is a straightforward process: moles M g = moles O 1 00 " L ^ ^ _ = 0.041 1 mole 24.3 g/mole = ?-^Li = 0.041 mole 16.0 g/mole
F r o m these calculations, we see that the simplest or the empirical formula of the c o m p o u n d is Mgo.4iOo.4i = MgO It is easy to appreciate the difficulties w h i c h arose in the early history of chemistry before the atomic weights for the elements were k n o w n . Even then, it was simple to determine by the weighing operation described above that 1.00 g of magnesium reacted w i t h 0.66 g of oxygen to f o r m magnesium oxide. But w i t h o u t k n o w i n g the relative weights of magnesium and oxygen atoms, it was impossible for early chemists to discover how many moles of each element were involved in the reaction. They could not have calculated the formula w i t h o u t k n o w i n g atomic weights. On the other hand, / / t h e formula had been k n o w n , the relative atomic weights of magnesium and oxygen could have been calculated. Since MgO is the formula for magnesium oxide, an equal number of atoms must be contained in 1.00 g of magnesium as in 0.66 g of oxygen. This must mean that the relative weights of Mg
49
50
Experiment 3
and 0 atoms arc 1.00/0.66 = 3/2. We now know that these atomic weights are 24 and 16, respectively; these weights are in a 24/16 or a 3/2 ratio. The problems of determining the formulas of compounds and the atomic weights of elements seemed inseparably linked: if either one were k n o w n , the other could be found. But neither piece of i n f o r m a t i o n was available to early chemists. Obviously, the development of an accurate table of atomic weights was a real necessity for the progress of chemistry. In this experiment y o u w i l l determine the formula o f the c o m p o u n d that forms when a metal reacts w i t h sulfur. An accurately weighed sample of the metal is heated w i t h an excess of sulfur to form a metal sulfide. Whatever sulfur is not needed to react w i t h the metal combines w i t h oxygen in the air to produce gaseous sulfur d i o x i d e . The weight of sulfur that reacts w i t h the metal can be determined as the weight of the oxygen was in the MgO example. Y o u can determine the empirical formula of the sulfide using the k n o w n atomic weights of the metal and the sulfur.
EQUIPMENT
NEEDED
Bunsen burner clay triangle crucibles and lids
crucible tongs ring wire gauze or asbestos square
CHEMICALS
NEEDED
copper wire or metal shavings powdered sulfur
PROCEDURE
Set up a clean crucible and lid as shown in Figure 1-2 (page 32). A p p l y full heat to the crucible and the lid for about 10 minutes to burn o f f any possible contaminants or volatile material. Then use crucible tongs to place the crucible and the lid on a piece of asbestos to cool. When they are at room temperature (after 15-20 minutes), weigh them on the analytical balance. Handle the crucible and lid w i t h tongs after the heating. While the crucible is cooling, obtain a piece of copper wire or metal shavings weighing about 1 g. If y o u use copper wire, coil it around a pencil and compress the coil so that it will fit in the b o t t o m o f the crucible. A f t e r y o u have weighed the crucible and l i d , place the wire or the metal shavings in the crucible and weigh the crucible, l i d , and metal. N o w add about 1.3 g of sulfur to the crucible; since an excess of sulfur is used, it need not be weighed any more accurately than to the nearest 0.1 g (see page 32 and Experiment 1). Cover the crucible, place it on the triangle, and heat it gently w i t h a low tlame u n t i l the sulfur ceases to burn at the edge o f the crucible l i d . Caution: This heating must be done in the hood. Sulfur vapor and sulfur dioxide are extremely i r r i t a t i n g and can be toxic.
51
Compound Stoichiometry
When y o u no longer see the blue flame of burning sulfur, increase the flame and heat the crucible u n t i l the b o t t o m is dull red. Then continue to heat the crucible for an additional five minutes. {Be sure (he crucible remains covered during this heating, so that the metal or the metal sulfide cannot react with oxygen in the air.) Remove the covered crucible from the triangle, cool it to r o o m temperature, and weigh the covered crucible and the metal sulfide that it contains. (Remember to handle the crucible w i t h tongs.) Since some o f the excess sulfur may still remain in the crucible at this p o i n t , y o u should return the covered crucible to the triangle and heat it strongly for about five more minutes. Then cool and weigh the crucible again. This weighing should agree w i t h the first weighing to 0 . 0 0 2 g. If it does not, add another 0.2 g of sulfur to the crucible and repeat the heating, cooling, and weighing procedures u n t i l y o u obtain two successive weighings that e x h i b i t this desired precision. Use the last weight you obtain in your calculations. A second weight determination should be made using 2.0 g o f sulfur. This will allow y o u to determine whether or not the amount of sulfur used in the reaction affects the formula of the compound that forms. While the first crucible is cooling, heat the second crucible. Then heat the reaction m i x t u r e of metal and sulfur in the first crucible, while the second crucible is cooling. By dovetailing y o u r operations for the t w o crucibles, y o u will not waste time. One crucible can be heating while you are cooling and weighing the other crucible.
NOTEBOOK
In y o u r notebook, prepare a data table like the one on the Report Sheet for this experiment and record y o u r data there as y o u collect them. Also include any pertinent observations y o u make in the course of the experiment. For example, y o u will want to record the color and the appearance o f reactants and products. Be sure to record any difficulties y o u have or any mistakes y o u make that might affect y o u r results.
RESULTS
Use the atomic weights of the metal and of sulfur to calculate (to the correct number of significant figures) how many moles of each element reacted in each of the t w o trials. Calculate (to the correct number of significant figures) a value for the ratio of moles of metal to moles of sulfur present in the metal sulfide for each of the t w o trials. Change the ratio of moles of metal to moles of sulfur to the simplest whole number ratio. Write the empirical formula for the metal sulfide.
QUESTIONS
1.
What evidence is there that a reaction actually occurred between the metal and sulfur'.'
52
Experiment 3
2. 3.
4.
Write an equation for the reaction that occurred between the metal and sulfur. The uncertainty in each weighing y o u performed is probably about 1 in the last digit. This means that the figure farthest to the right of the decimal p o i n t in each weighing could have been estimated 1 higher or 1 lower than the figure y o u chose. Calculate the largest possible value that the weight of metal taken in T r i a l I could possibly have (assuming that y o u made an error in the last figure of each weighing). N o w calculate the smallest possible value of the weight of the metal in T r i a l 1 for each weighing. Also calculate the extreme possible weights of metal sulfide produced in T r i a l 1. Use these largest and smallest possible weights of metal and metal sulfide to calculate the m i n i m u m and the m a x i m u m values of the number of moles of metal for each 1.00 mole of sulfur in the metal sulfide. What effect, if any, w o u l d these weighing uncertainties have on the formula that y o u determined? What difference, if any. did y o u observe between T r i a l 1 and T r i a l 2, in w h i c h different amounts of sulfur were used'' What is the reason for this behavior?
REFERENCE
Yoder, C M . , Suydam, F . H . , and Suavely, F . A . Chemistry. New Y o r k : Harcourt Brace Jovanovich, Inc., 1975. Chapter 3.
REPORT
SHEET
EXPERIMENT 3
Name Section
Date
(Note: Data:
All numbers
must
be reported
with
proper
units attached.) Trial 1 Trial 2
Weight of metal sulfide, crucible, and lid Weight of metal, crucible, and lid Weight of crucible and lid Weight of metal sulfide formed Weight of metal reacted I d e n t i t y of metal Weight of sulfur in product
Calculation of formula: Moles of metal reacted Sample calculation:
Moles of sulfur reacted . . .. moles metal Actual ratio moles S Simplest whole number ratio Empirical formula of the metal sulfide
(Answer the questions from pages 51-52 on
the
back of the Report Sheet.)
Experiment 4 Stoichiometry of a Reaction

Introduction
The net result of a chemical reaction is described by a chemical equation. For example: H + C l "+ 2HC1 states that the reaction of 1 molecule of hydrogen w i t h 1 molecule of chlorine produces 2 molecules of hydrogen chloride. Of course,/V (Avogadro's number) hydrogen molecules w i l l require /V chlorine molecules to produce 2/V molecules of hydrogen chloride.
2 2
Cl
2HC1 2 molecules 2 moles
1 molecule 1 mole
+ I molecule + 1 mole
In order to write a chemical equation, a chemist must first determine experimentally what the reactants are, in what ratio they react (the stoichiometry of the reaction), and what quantities and types of products result from the reaction. This experiment is designed to determine the stoichiometry of the reaction between sodium h y p o c h l o r i t e (NaOCl) and sodium thiosulfate ( N a S 0 ) , or potassium iodide ( K I ) , or-sodium sulfite ( N a S 0 ) , or potassium thiocyanate ( K S C N ) .
2 2 3 2 3
When t w o or more substances are m i x e d , it is possible to determine if a reaction has taken place by noting whether or not the properties of the m i x t u r e differ from the properties of the original components of the m i x t u r e . Further, by n o t i n g how an observed p r o p e r t y varies w i t h the proportions in w h i c h the reactants are m i x e d , the s t o i c h i o m e t r y of the reaction may be determined. Consider the f o l l o w i n g example in w h i c h solutions of A and B are m i x e d to form a precipitate P. In a series of different experiments, solutions of A and B are m i x e d so that the sum of the moles of A and B remains constant and the amount of precipitate P that forms is determined. If A is in excess of the amount required to react w i t h B, then an increase in the a m o u n t o f B w i l l result in the f o r m a t i o n o f more precipitate and vice versa. The m a x i m u m amount of precipitate w o u l d be formed if A and B were mixed in the correct stoichiometric amounts. This stoichiometric point can be determined by p l o t t i n g the amounts of precipitate that form against the amounts of A used in various reactions (see Figure 4-1). In this example, the m a x i m u m precipitate occurs at a ratio of 1 A : 1 B. The f o r m a t i o n of a precipitate is only one of many properties that can be used to determine the stoichiometry o f a reaction. In this experiment, y o u w i l l base y o u r decision about the proper ratio between reactants on the amount of heat that is evolved d u r i n g the reaction. For example, w i t h sodium thiosulfate ( N a S 0 )
2 2 3
x Na S 0
2 2
+ y NaOCl -* products + Q
55
JU
txperiment 4
A + B = fixed value = .10 mole
FIGURE 4-1
Quantity of precipitate as a function of relative amounts of reactants.
where Q represents the heat that is evolved. This heat causes the temperature of the m i x t u r e to rise by an amount
AT (7final
înitial)
As the amount of heat that is released in the reaction increases, AT increases. Consequently, y o u can use the temperature change AT to m o n i t o r the a m o u n t of heat that is released in the reaction. H o w does the q u a n t i t y of heat released relate to the stoichiometry of a reaction? Suppose we k n o w the values of x and y in the preceding equation. If we m i x exactly x moles of N a S 0 w i t h y moles of NaOCl, a certain number of calories of heat Q w i l l be produced. On the other hand, i f we m i x fewer than .v moles o f N a S 0 w i t h more than y moles o f NaOCl, n o t enough N a S 0 w i l l be present to react w i t h all o f the NaOCl. Thus, a smaller amount o f heat w i l l be evolved because fewer units o f N a S 0 w i l l be present to react, resulting in a smaller AT. This argument can also be applied when N a S 0 is in excess.
2 2 3 2 2 3 2 2 3 2 2 3 2 2 3
It is i m p o r t a n t to note that the total number of moles (moles N a S 0 + moles NaOCl) remains constant in any of these reactions. If the number of moles of N a S 0 is increased, then a corresponding number of moles of NaOCl must be decreased and vice versa. We therefore conclude that the m a x i m u m amount of heat is released resulting in a m a x i m u m AT when the reagents are mixed in the correct stoichiometric ratio. I n this experiment, y o u w i l l be asked to apply the above reasoning as y o u m i x reagents in various ratios and observe the temperature increases. Y o u can conclude that the ratio that produces the largest AT is the correct stoichiometric ratio.
2 2 3 2 2 3
I n carrying o u t this experiment, y o u w i l l use a basic solution o f 0.50A/ N a S 0 , or 0.50/Vf K I , or 0.50/W N a S 0 , or 0.50A/ K S C N , as y o u r instructor directs. The expression 0.50A/ means that the solution contains 0.50 mole of the solute in 1.0 liter of s o l u t i o n . Using solutions of k n o w n concentrations allows y o u
2 2 3 2 3
57
Stoichiometry of a Reaction
to obtain a certain number of moles of a reactant simply by measuring a specific volume o f s o l u t i o n . For instance, i f y o u measure 1 . 0 liter o f a 0 . 5 0 Y W solution o f NaOCl. y o u k n o w that this solution contains 0 . 5 0 mole o f N a O C l ; 5 0 0 m l o f this solution contains 0 . 2 5 mole of NaOCl; and so o n .
EQUIPMENT NEEDED
1 0 0 - m l graduated cylinder Styrofoam cup thermometer graduated i n 0 . 1 intervals N O T F : Bring a piece of graph paper and a ruler w i t h y o u to the laboratory, so that y o u can plot the AT vs. moles of NaOCl data.
CHEMICALS NEEDED
0.50/W
NaOCl
0.50A/
solution o f N a S 0 , or K I , or
2 2 3
Na S0
2
or KSCN (in 0AM N a O H )
PROCEDURE
Measure the temperature o f 5 0 ml o f 0 . 5 0 / V / NaOCl in a Styrofoam cup. Measure the temperature.of 5 0 m l o f 0 . 5 0 ; W N a S 0 (or other 0 . 5 0 J W reactant, as directed by y o u r i n s t r u c t o r ) in a graduated cylinder. I n i t i a l l y , these temperatures should be identical. M i x the reagents thoroughly in a Styrofoam cup and record the m a x i m u m temperature. The m i x t u r e w i l l warm up at first and then gradually cool u n t i l i t returns to r o o m temperature. The Styrofoam acts as an insulator, so the m i x t u r e w i l l cool slowly and y o u should have no trouble observing the m a x i m u m temperature. N o w repeat the above procedure, using different amounts of each reagent and a total volume of 1 0 0 m l . Y o u should use the f o l l o w i n g five volume combinations and any other combinations y o u feel w o u l d b e desirable: 5 0 : 5 0 ; 4 0 : 6 0 ; 6 0 : 4 0 ; 2 0 : 8 0 ; and 8 0 : 2 0 . After y o u have measured and recorded the temperature changes for at least these five different mixtures of the t w o reactants, construct a graph of the temperature change, AT. vs. the moles of NaOCl used. (Refer to A p p e n d i x I I , page 3 5 7 , for i n f o r m a t i o n o n graphing.) F r o m this p l o t , determine the stoichiometry o f the reactants by applying the method used in the precipitation experiment described in the I n t r o d u c t i o n . If y o u cannot draw a definitive conclusion from y o u r graph, continue to w o r k w i t h different mixtures of the reactants and to p l o t additional points u n t i l y o u can interpret y o u r data conclusively.
2 2 3
RESULTS
Plot AT vs. moles of NaOCl on an 82" X 11 i n . piece of graph paper. Then use this plot to determine the stoichiometry of the reaction. Write the equation for the
58
Experiment 4
reaction x X + v NaOCl -* products + Q, using the correct coefficients x and y determined from y o u r data p l o t . (X refers to the material w i t h which y o u allowed the NaOCl to react. Y o u are not expected to k n o w the i d e n t i t y of the products.) Explain how y o u obtained the values for.v and y from y o u r p l o t of AT vs. moles of NaOCl.
QUESTIONS
1. Why must the total volume of the reacting solutions remain the same when y o u w o r k w i t h different mixtures of the reactants to determine their stoichiometric ratio? 2. Imagine that a reaction occurs so that the absorption of heat causes the temperature of the m i x t u r e to drop as the reaction progresses. Sketch a graph that shows AT vs. number of moles of a reactant for a reaction of this type. Is AT a negative or a positive q u a n t i t y ?
REFERENCES
1. Bigelow, M.J. Journal of Chemical Education 46, 378 ( 1 9 6 9 ) . 2. Yoder, C.H., Suydam, F . H . , and Snavely, F.A. Chemistry. New Y o r k : Harcourt Brace Jovanovich, Inc., 1974. Chapter 3.
REPORT SHEET EXPERIMENT 4
Name Section (Note: Data: 0.50yW NaOCl (ml) 0.50/v/ reactant X (ml) 7WU, All numbers must be reported with proper units attached.)
Date
7Vinai
A7
A t t a c h y o u r graph of AT vs. number of moles of NaOCl. Explain how y o u determined the coefficients, and w r i t e the equation for the reaction.
(Answer
the questions from page
58 on
the
back of the Report Sheet.)
Experiment 5 Synthesis of
Introduction
Co(NH ) CI
3 6
One activity that occupies chemists is the synthesis or prepration of chemical compounds. A goal of synthetic chemistry is to make substances that have never been previously prepared. Some chemists w o r k in the laboratory to prepare compounds that are k n o w n to occur in nature; other chemists strive to make t o t a l l y new, u n k n o w n compounds. In order to perfect the techniques involved in making compounds, chemists must spend a good deal of time duplicating syntheses of k n o w n compounds in the course of their academic training. The purpose of this experiment is to gain experience in using the laboratory techniques involved in synthetic chemistry. The c o m p o u n d to be prepared is called a coordination compound. In C o ( N H ) C l , the cation has six molecules of ammonia bonded to C o ( I I I ) in a regular geometric fashion (see Figure 5-1); the CP ions balance the charge o f this cation. The c o m p o u n d w i l l be prepared by the reaction o f cobalt chloride, ammonia, and hydrogen peroxide, as in Equation (5-1):
3 6 3
2CoCl -6H 0 + 2 N H C l + 10NH + H 0

2 2 4 3 2
2Co(NH ) Cl + 14H 0
3 6 3 2
(5-1)
Many synthetic reactions are carried out in solution by dissolving the reactants and a l l o w i n g them to f o r m the desired product. A f t e r a c o m p o u n d forms in s o l u t i o n , the experimenter must isolate it (get it out of s o l u t i o n ) and purify it ( r i d it of all traces of the unused reactants and any side products, reaction products other than the one of interest). Since the solubility of most compounds decreases w i t h temperature, a c o m m o n technique for isolating a product is to cool the solution u n t i l the amount of c o m p o u n d dissolved exceeds its s o l u b i l i t y at that temperature. The excess then crystallizes o u t of the s o l u t i o n . U n f o r t u n a t e l y , as the temperature drops, com-
H N
3
FIGURE 5 1
Hexaamniinecobalt(lII) ion.
i
i
61
62
Experiment 5
pounds other than the desired one, such as unreacted starting material or other reaction products, often crystallize also. These contaminants can be removed by recrystallization; that is, by dissolving the impure product in a m i n i m u m amount of hot solvent, filtering the s o l u t i o n to remove insoluble impurities, and then cooling the solution to crystallize the desired c o m p o u n d while unwanted materials ( h o p e f u l l y ) remain in s o l u t i o n . Sometimes the recrystallization procedure must be repeated many times to achieve p u r i t y . In this experiment, however, y o u can stop after only one recrystallization, since C o ( N H ) C l can be purified fairly easily by this m e t h o d .
3 6 3
It is necessary to plan y o u r w o r k carefully in order to use y o u r laboratory time most efficiently. Bring w i t h y o u to the laboratory an outline of how y o u intend to proceed w i t h the experiment.
EQUIPMENT
NEEDED
beakers B c h n e r funnel Bimsen burner 125-ml Erlenmeyer flask 125-ml filter flask filter paper 100-ml graduated cylinder medicine dropper
pneumatic trough ring stand spatula stirring rods test tube w i t h cork thermometer vacuum tubing wire gauze
CHEMICALS NEEDED
CoCl -6H 0 cone. HCl 0.5A/ HCl 30% H 0 cone. N H

2 2 2 2 3
NH C1 acetone activated charcoal ice

4
BRIEF OUTLINE OF SYNTHETIC PROCEDURE
NH C1 in H 0 ; I A. boil. Dissolve C o C l - 6 H 0 .
4 2 2 2
i
Add i Add I Add i to flask containing charcoal; cool under running water. cone. N H ; cool in ice bath. H 0 dropwise; A, destroy excess H 0 .
3 2 2 2 2
63
Synthesis of C o ( N H ) C I
3 6
Cool u n t i l product containing charcoal crystallizes.
i
Collect product and charcoal by f i l t r a t i o n . I Recrystallize to remove charcoal. Caution: All work must be performed under the hood!
PROCEDURE
A. Making the C o m p o u n d
Weigh out 9 . 0 0.1 g of C o C l 6 H 0 . Record the weight y o u actually take. This weight must be k n o w n to this degree of accuracy; the exact weights of other materials used in the synthesis are less i m p o r t a n t .
2 2
Weigh about 1 g of activated charcoal i n t o a clean 125-ml Erlenmeyer flask. This charcoal is not a reactant in the synthesis; it simply acts as a catalyst, causing the reaction to occur rapidly. Weigh about 6 g of N H C 1 ( a m m o n i u m chloride) i n t o a clean 100-ml beaker. A d d 15 ml of distilled water to the N H C 1 . Place the beaker on wire gauze on a ring over y o u r burner. Use a l o w flame to bring the solution to a b o i l ; stir it during this heating.
4 4
When the solution is b o i l i n g , add the C o C l ' 6 H 0 to it gradually. Continue stirring during-this a d d i t i o n ; be sure to stir gently so that drops o f h o t l i q u i d w i l l not spatter out of the beaker. A f t e r all the C o C l - 6 H 0 has dissolved, t u r n o f f the burner. Use beaker tongs or a towel to pick up the hot beaker and pour the hot solution i n t o the Erlenmeyer flask containing the charcoal. Cool the flask under running water. T o this cooled m i x t u r e , add 2 3 m l o f concentrated N H solution ( a m m o n i u m h y d r o x i d e ) . C o o l the flask in a pneumatic trough full of ice u n t i l the temperature of the m i x t u r e is 10C or lower. ( T w o students should share a trough of ice.)
2 2 2 2 3
While the m i x t u r e is cooling, use a graduated cylinder to measure 13 ml of 30% H 0 (hydrogen peroxide) and pour it i n t o a small beaker. Caution: Hydrogen peroxide can cause severe burns. If y o u splash even a drop of it onto y o u r skin, wash it off immediately w i t h lots of r u n n i n g water. If y o u spill any of it onto the desk t o p , wipe it up w i t h a sponge and then wash o u t the sponge repeatedly under running water. Hydrogen peroxide can also damage y o u r clothing. When the temperature of the reaction m i x t u r e in the flask is 10C or lower, add the H 0 to the m i x t u r e a l i t t l e at a time; use a medicine dropper so that y o u can add only a few drops at a time. During this a d d i t i o n , leave the flask in the ice bath; swirl the flask gently to m i x the H 0 w i t h the other reactants.
2 2 2 2 2 2
A f t e r the H 0 has been added, return the flask to the wire gauze and heat the mixture gently to 5 0 - 6 0 C . A n y temperature w i t h i n this range is satisfactory, but the temperature must not be lower than 5 0 C or higher than 6 0 C . S w i r l the flask occasionally to keep the contents m i x e d . Continue heating and swirling for about 20 minutes, or u n t i l the original pink color characteristic of C o C l * 6 H 0 turns to a
2 2 2 2
64
Experiment 5
golden yellow. A good way to test the color o f the solution (which w i l l l o o k black because of the charcoal) is to dip a stirring rod into the flask and transfer a d r o p of solution from the t i p o f the rod o n t o a piece o f white filter paper. The s o l u t i o n w i l l spread out enabling y o u to see its color. After the proper color change has occurred, the flask and its contents may be stored in y o u r desk u n t i l the next period if y o u must i n t e r r u p t y o u r w o r k . Otherwise, cool the s o l u t i o n in an ice bath. The product w i l l precipitate. Continue the cooling u n t i l no more crystals seem to be forming. Filter the solution using a B c h n e r funnel containing t w o pieces of filter paper (see page 15 for instructions on the use o f suction f i l t r a t i o n ) . It does not matter i f a little charcoal passes i n t o the filtrate, but be sure y o u d o n ' t lose any of the crystals of the product. Wash the precipitate in the funnel w i t h t w o 5-ml portions of ice water. To perform the washing operation, disconnect the suction, add the wash solvent, allow the m i x t u r e to stand about 10 seconds, and then suck the solvent through the filter paper. If y o u must i n t e r r u p t the synthesis, place the filter paper and product in an evaporating dish and store it in y o u r desk u n t i l the next laboratory period.
B. R e c r y s t a l l i z a t i o n of the I m p u r e P r o d u c t
In a 250-ml beaker, bring 75 ml of 0.5A/ HCl to a b o i l . Transfer the impure product (filter paper and all) to this beaker. Stir the m i x t u r e and continue heating it u n t i l nothing else seems to be dissolving. Filter the hot solution through a B c h n e r funnel to remove the charcoal. In this f i l t r a t i o n , y o u should be sure that the filtrate is free of charcoal. If any charcoal passes i n t o the filtrate, y o u must pour the m i x t u r e back i n t o the beaker, reheat i t , and refilter it to remove the remaining charcoal. Pour the golden y e l l o w , charcoal-free solution i n t o a clean 125-ml flask; if any crystals form in the filter flask, scrape them all out. A d d 21 ml of concentrated HCl to the solution. C o o l the s o l u t i o n in an ice bath to precipitate the product. When no more crystals seem to be f o r m i n g , filter the m i x t u r e through a B c h n e r funnel containing t w o pieces of filter paper. Wash the crystals in the funnel w i t h t w o 5-ml portions of ice water to remove any HCl that may be on the crystals. Then wash them w i t h 10 ml of acetone to wash away the water; acetone is much more volatile than water, so the crystals w i l l dry faster than they would i f they were wet w i t h water. Dry the precipitate as thoroughly as possible by suction. T h e n scrape the crystals o n t o a large piece of dry filter paper and spread them out so that any solvent that is s t i l l on them can evaporate. Weigh the d r y c o m p o u n d by difference i n t o a clean, dry test tube and stopper the tube. Label the tube w i t h y o u r name and w i t h the i d e n t i t y and weight of the c o m p o u n d . T u r n i t i n t o y o u r instructor.
RESULTS
The equation for the preparation of C o ( N H ) C l is given as Equation (5-1) in this experiment. Perform the f o l l o w i n g calculations involving this preparation.
3 6 3
C5
Synthesis of C o ( N H ) C I
3 6
1. Calculate the number of moles of C o C l - 6 H 0 that y o u used in the synthesis. 2. Using Equation (5-1), calculate the number of moles of C o ( N H ) C l that y o u r synthesis could have produced. 3. Use the expected number of moles of C o ( N H ) C l to calculate the expected number of grams of product. This is the theoretical yield of the p r o d u c t . 4. Use the theoretical yield and y o u r actual yield to calculate y o u r percentage yield.
2 2 3 6 3 3 6 3
QUESTIONS
1. 2.
If the product had n o t been recrystallized, w o u l d y o u r percentage yield have been larger or smaller? E x p l a i n . Calculate the approximate number of moles of N H C 1 that y o u used in the synthesis. W o u l d all of this react? Explain.
4
REFERENCES
1. Yoder, C.H., Suydam, F . H . , and Snavely, F . A . Chemistry. New Y o r k : Harcourt Brace Jovanovieh, Inc., 1975. Chapter 3. 2. Femelius, W.C. (ed.). Inorganic Synthesis, Volume I I . New Y o r k : M c G r a w - H i l l , 1946, p. 217.
REPORT
SHEET
EXPERIMENT 5
Name Section Data:
Date
Weight of C o C l - 6 H 0 used
2 2
Weight o f C o ( N H ) C l isolated
3 6 3
Results: Moles C o C l 6 H 0 used

2 2
Show
calculation:
Moles C o ( N H ) C l possible
3 6 3
Weight o f C o ( N H ) C l possible
3 6 3
Show
calculation:
Percentage yield o f C o ( N H ) C l
3 6
Show
calculation:
(Answer the questions from page
65 on
T u r n in y o u r product in a labeled test tube.
Experiment 6 Line Spectra of Elements

Introduction
Early experimental results on the combining weights of the elements could be accounted for by Dalton's atomic theory. An element was believed to consist of a collection of identical atoms, each having the same weight. The observation that t w o elements always combine in the same weight ratio to f o r m a particular c o m p o u n d was simply a reflection of the fact that a certain number of atoms of each k i n d , each one having a characteristic weight, combined. As long as these were the o n l y kinds of experimental results to be accounted for, atoms could be thought of as small billiard balls; if one were cut open, it w o u l d look the same t h r o u g h o u t , just as a potato does. In the nineteenth century, some experiments showed that the structure of atoms must be far more complicated than had been previously believed. These experiments investigated the behavior of atoms excited (that is, provided w i t h excess energy) in an electric discharge. Experimenters found that light of characteristic colors was emitted by these excited atoms. This emitted light is called the atomic spectrum ( p l u r a l , spectra). Passing the e m i t t e d light through a prism separates it i n t o beams, each of a single wavelength and color. Prisms separate light by refracting i t ; when light of different wavelengths passes through a prism, it is bent through different angles (see Figure 6-1). The fact that excited atoms emit light of o n l y certain discrete wavelengths is evidence that their internal structure must be more complex than a potato-like structure; otherwise, there w o u l d be no reason w h y light of every wavelength is not e m i t t e d . I n this experiment, y o u w i l l study the light emitted by excited atoms and draw some conclusions about their inner structure. The apparatus y o u w i l l use to observe spectra is a Bunsen spectroscope (shown schematically in Figure 6-2). The function of the spectroscope prism is to disperse ( t o separate according to wavelength) the light from the element by refraction. At the same t i m e , the prism superimposes a scale on this refracted l i g h t by reflecting an image f r o m the scale arm. The sharpness o f the spectral lines y o u see through the viewing arm w i l l depend on the w i d t h o f the slit opening: the narrower the slit, the sharper the lines. However, a very narrow
Prism
59
70
Experiment 6
FIGURE 6-2
Schematic drawing of a Bunsen spectroscope.
slit w i d t h w i l l result i n a d i m image, because very little light w i l l enter the spectroscope. The best slit w i d t h w i l l obviously be a compromise between the sharpest lines possible and sufficient light intensity to see the lines easily. It should be apparent from Figure 6-2 that the alignment of the prism is c r i t i c a l . Y o u r spectroscope prism w i l l be adjusted properly by y o u r instructor before y o u begin; any further prism adjustments should be made o n l y by y o u r instructor. The purposes of this experiment are: 1. To observe qualitatively the light emitted by excited atoms of hydrogen, h e l i u m , neon, and argon, and to resolve this light i n t o lines of particular wavelengths w i t h the spectroscope (this is called observing the line spectrum of an element). 2. To make quantitative conclusions about the relationship of the line spectrum of the simplest a t o m , H, to the internal (electronic) structure of the a t o m . In order to accomplish the second objective, y o u w i l l have to (1) calibrate the spectroscope and then ( 2 ) take quantitative measurements of the lines that appear in the hydrogen spectrum. A l t e r n a t i v e l y , y o u r instructor may project a slide of a camera's view through the slit of a Bunsen spectroscope so that y o u can obtain data.
A. Calibration of the S p e c t r o s c o p e
Many scientific instruments are equipped w i t h a numerical scale of some k i n d . In order to make quantitative measurements, some correlation must obviously exist
71
between the scale reading and the property being measured. A c o m m o n way to establish such a correlation is to observe some property whose numerical value is already k n o w n and then to see what scale reading it produces. By making several such observations, a correlation can be established between the scale readings and values of the property. This correlation can then be used to measure the values of the same property on other u n k n o w n materials. This procedure is called calibrating the instrument. The Bunsen spectroscope has a numerical scale across the top of the viewing field; these numbers are not wavelengths. Y o u must relate the numbers on the scale to actually k n o w n wavelengths. This is done by viewing the line spectrum of helium (the wavelengths of helium are given on the Report Sheet for this experiment) and n o t i n g the scale reading for each line. A plot is then made of wavelength versus scale reading; this p l o t , called the calibration curve, w i l l enable y o u to read the wavelength of any line in a spectrum if y o u k n o w the scale reading for that line. It is i m p o r t a n t to note that, because of the way the spectroscope prism is adjusted, different spectroscopes w i l l give different scale readings for the same line in a spectrum. Once a calibration curve is determined, the prism must not be moved; the hydrogen and helium data must be taken on the same spectroscope.
B. Energy Levels and the Hydrogen Line S p e c t r u m
Light behaves according to the laws of wave mechanics; it is characterized by frequency and wavelength. The velocity of any traveling wave is equal to the product of its frequency and wavelength. For light waves, the equation describing this relationship- is c = Xt> where c = speed of light X = wavelength v = frequency
(6-1)
Light can be viewed as consisting of small bundles of energy called photons. The energy of a p h o t o n of light E is directly p r o p o r t i o n a l to its frequency
E = hv
(6-2)
The h in Equation (6-2) is a p r o p o r t i o n a l i t y constant called Planck's constant; its value is 6.62 X 1CT erg-sec. Solving Equation (6-1) for v and substituting the result i n t o Equation (6-2) gives
27
= X
(6-3)
Equation (6-3) relates the p h o t o n energy to the wavelength of light. The emission of light of only certain discrete wavelengths by excited atoms corresponds to the emission of certain discrete amounts of energy. (See Figure 6-3.) A c c o r d i n g to the Bohr theory of the hydrogen a t o m , the single electron in the hydrogen atom can possess only certain energies. If this electron is in an excited (high) energy level E and drops to a lower energy level E\, then the atom w i l l emit a p h o t o n of light of an energy E that is exactly equal to the difference in energy
n
72
Experiment 6
between these levels: E = E, Ex he (6-4)
Long before the Bohr theory of the hydrogen atom was developed, Johannes Robert Rydberg, a nineteenth-century Swedish physicist, discovered that the experimentally measured wavelengths in the hydrogen spectrum could be reproduced by Equation (6-5) 1 (6-5)
where R is a constant having the value 109,737 c m , and n and n are integers. This was a completely empirical result; that is, it reproduced the experimental results for hydrogen, but no one understood why it did so. Later, Niels Bohr postulated that o n l y certain energy levels characterized by integral q u a n t u m numbers were possible for the electron in a hydrogen a t o m . Bohr also showed that the energy of each level was p r o p o r t i o n a l to - 1/n , where n is the
- 1 { 2
73
Liny Spectra of Elements
principal q u a n t u m number. If Bohr's postulates are valid, then the difference between the energy levels characterized by quantum numbers n and n is
t n
E -E =R (-i--LA
u l H
\ " i
(6-6)
"117
where R is the p r o p o r t i o n a l i t y constant. If this q u a n t i t y of energy is emitted in the form of a light p h o t o n as the electron loses energy from level to level n then
H n l t
E=E
- E = R
l
l - L - - ^ = i
(6-7)
D i v i d i n g Equation (6-7) by he gives
hc\ni~
flu*/
H
Equation (6-8) is the same as Equation (6-5) if R - R /he. Or, stated another way, R is simply the Rydberg constant expressed in ergs. The p o i n t of this argument is that assuming the Bohr postulates to be true, we w o u l d expect to see a line-emission spectrum w i t h wavelengths given by Equation (6-8) rather than a continuous spectrum. Moreover, the f o r m of Equation (6-8) is the f o r m of the empirically obtained Equation (6-5). This result lent c r e d i b i l i t y to the Bohr postulates and pointed out the physical significance of n and n as quantum numbers in E q u a t i o n (6-5).
H t I (
As an example of the use of Equations (6-7) and (6-8), consider an electron having n = 5 falling to the level n = 1. The energy of light emitted in this process is
n x
E =
R (-^j = R
H
( \ - ) = R (0.960) =
H
(6-9)
The wavelength w i l l be
X = ^ ( _ L ) = i ( 1 . 0 4 ) = 9.48 X 10~
R \0.96J
H
cm
(6-10)
EQUIPMENT
NEEDED
aluminum foil Bunsen spectroscopes flashlights gas discharge tubes graph paper power supplies (high-voltage transformers) ring stands and clamps
74
Experiment 6
PROCEDURE
Y o u should w o r k in pairs for this experiment. Measurements arc made using equipment that has already been set up in the laboratory. Y o u r instructor w i l l show y o u how to connect the gas discharge tubes to the power supply. When the tubes are connected, observe and record the characteristic color of the emission of each gas that you use. In your laboratory n o t e b o o k , prepare a data table similar to the data section on the Report Sheet for this experiment, so that y o u can record data in an orderly fashion throughout the experiment.
A. Calibration of the S p e c t r o s c o p e
The gas discharge source must be properly aligned w i t h the spectroscope slit, and the slit must be adjusted to its narrowest w i d t h so that y o u can view the sharpest spectrum. Y o u r instructor w i l l show you how to do this. The spectrum of h e l i u m is used to calibrate the scale. The Report Sheet gives the positions of the lines in the helium spectrum and their relative intensities on a comparison scale that assigns a value of 1000 to the most intense (brightest) line.* Y o u will probably n o t be able to see the lines that have an intensity 20 or less; be sure to correlate the more intense, visible lines w i t h the proper wavelength. Position the helium discharge tube, and wrap the tube and the slit area in a l u m i n u m foil to block o u t the laboratory light (overhead fluorescent lights emit a very strong green line). Clamp the flashlight at the end of the scale arm, so that the scale is visible in the eyepiece when the flashlight is turned on. One student observes the spectrum (being careful not to introduce parallax error by moving the head while taking the readings) and calls out the colors and the scale values for the helium lines ( t o at least three significant figures) to the other student, who records the data.
B. Position of H Lines
Remove the helium tube from the spectroscope slit and replace it w i t h the hydrogen tube. Record the scale reading for each line in the hydrogen spectrum as y o u did for the helium spectrum. There are four visible lines in the hydrogen spectrum. The line farthest i n t o the violet region of the spectrum is sometimes d i f f i c u l t - e v e n i m p o s s i b l e - t o see, because the human eye is not highly sensitive in this region. The t w o students should then reverse roles to see if they agree on the assignments. The readings obtained w i l l probably not be exactly the same; each student's data w i l l be internally consistent, however
C. Spectra of Neon and Argon
Replace the hydrogen tube w i t h a neon tube and observe the line spectrum. Describe qualitatively what y o u observe (you do not need to record the scale
T h e s e data are from the Handbook of Chemistry and Physics (Cleveland: Chemical Rubber Publishing Co., published annually).
75
readings of the lines). Note the colors of prominent lines; describe bundles of lines of a particular color; and so on. Y o u r description should be clear and detailed enough that others can read it and k n o w what they w o u l d see if they looked at the spectrum themselves. Repeat this procedure for argon.
RESULTS
Using y o u r data for the helium spectrum, plot a calibration curve of wavelength vs. scale reading on graph paper. Remember to spread the graph over as much of the page as possible. A smooth curve should be drawn through the points. If y o u r points do n o t lie along a smooth curve, y o u have probably incorrectly assigned one or more of the helium lines. For example, y o u may have assigned the red line at 7065 A to the scale reading that should be correlated w i t h the red line at 6678 A. T r y different assignments of lines u n t i l your calibration curve is fairly smooth. F r o m the calibration curve and y o u r scale readings for the hydrogen spectrum, determine the wavelength for each hydrogen line. Indicate on the calibration curve how y o u did this. Transitions occurring between energy levels give rise to the hydrogen spectrum. We have n o t yet identified these energy levels, but it is possible to assign values to n and n for the transition corresponding to each line in a simple way, by using Equation (6-5):
n
( 2 - - ^ )
yii
ii /
109,737 cm"
\ " i
(6-5)
1 1 /
This equation contains only one term that y o u do not k n o w for each line, the term in parentheses containing the principal q u a n t u m numbers n. By using the k n o w n value of the Rydberg constant and by t r y i n g various combinations of ti\ and n , y o u can find a c o m b i n a t i o n for these numbers that reproduces y o u r experimental 1/X values. In deciding w h i c h n values to t r y , keep in m i n d the f o l l o w i n g considerations:
u
1. A l l the n values w i l l be fairly small. Since the H energy levels are proportional to \/n , they w i l l be closer together as n becomes larger. Very large values o f n w i l l produce lines o f very great X ( i f b o t h n and n are large) or of very short X ( i f only n is large). The lines produced by these transitions are of greater or shorter wavelength than we can perceive as visible l i g h t ; hence, they cannot be a part of the spectrum that y o u see.
2 t n u
2.
The i and n values o f lines toward the red end o f the spectrum w i l l differ less than those toward the violet end of the spectrum. 3. Begin w i t h the simplest combinations: n = 1 and n = 1\ri\ = 1 and n = 3 ; n = 1 and n - 4. If these values do not reproduce a value of 1/X that corresponds to the value y o u calculated from y o u r experimentally determined wavelength, t r y values of rt\ - 2 and n\\ - 3 ; / i i = 2 and tin 4; and so on.
u x u n x n =
Use the determined values of wavelengths of light for the lines in the hydrogen spectrum to calculate the energy of each transition. Construct an energy level
76
Experiment 6
diagram for the H a t o m . Use graph paper so that y o u will have an accurate scale for the energy levels. As the base line for the diagram, use the lowest energy level involved in the transitions that produced lines in the spectrum. A l o n g the energy scale, show the amount by w h i c h the energy of each higher level is greater than the energy of the lowest level. Label each level w i t h the proper q u a n t u m number. Draw arrows indicating the transitions between the energy levels that produce lines in the spectrum. Label each arrow w i t h the wavelength of the light that is produced by the transition.
QUESTIONS
1. Show that a transition between t w o energy levels w i t h large n values results in the emission of light of very long wavelength. (Hint: Choose similar values of 20 or higher for n and n to calculate the wavelength of the e m i t t e d light.) 2. Show that a transition between energy levels of very large n and very small n emits light of very short wavelength.
{ u u {
REFERENCES
1. Yoder. C.H., Suydam, F . H . , and Snavely, F . A . Chemistry. New Y o r k : Harcourt Brace Jovanovich, Inc., 1975. Chapter 5. 2. Handbook of Chemistry unci Physics. Cleveland: Chemical Rubber Publishing Co., published annually. t
Experiment 7 A Simple Covalent Compound: Synthesis and Proper ties

Introduction
Many compounds can be synthesized by the interaction of elements w i t h one another. This is especially true of binary compoundscompounds that contain only t w o elements. The formula of the compound that results and the type of bonding w i t h i n the compound depend on the natures of the atoms that comprise the elements. A fairly great difference in the electronegativities of the atoms results in a transfer of electrons from one atom to the other so that ions are formed. A t o m s of similar electronegativities share electrons; this covalent bonding produces a molecule. In this experiment, y o u w i l l allow t i n and iodine to react w i t h one another. The electronegativities of 1.8 for t i n and 2.5 for iodine correctly suggest that the bonding should be covalent. The iodine a t o m , w i t h seven electrons in its valence level, attains a noble gas configuration by the f o r m a t i o n of one covalent bond. The tin a t o m , w i t h o n l y four electrons in its valence level, can form four covalent bonds. Consequently, the formula of the resulting c o m p o u n d is S n l ( t i n tetraiodide or stannic iodide).
4
Ionic and covalent compounds can often be distinguished by their physical properties. The.attractive forces between molecules that h o l d them together in the solid or the l i q u i d state are generally much weaker than the strong attractive forces between the oppositely charged ions of an ionic c o m p o u n d . Consequently, compounds composed of molecules have much lower melting points and b o i l i n g points than ionic compounds. They are also much more volatile. A n o t h e r significant difference is in the solubilities of ionic and molecular compounds. Ionic compounds are more likely to be soluble in water than in other liquids; however, some ionic compounds are n o t soluble even in water. Molecular compounds are soluble in many liquids that are composed of polar or nonpolar molecules, but are less likely to be soluble in water. I n this experiment, y o u w i l l compare these properties for some selected molecular and ionic compounds.
EQUIPMENT
NEEDED
beaker Bunsen burner 125-ml Erlenmeyer flask graduated cylinder rubber stopper
spatula 4-ml test tubes triple-beam balance watch glass
CHEMICALS NEEDED
benzene
calcium sulfate
79
80
Experiment 7
carbon tetrachloride dichlorome thane granular tin
iodine naphthalene sodium chloride
PROCEDURE
A . Synthesis o f S n l
I n t o a clean and dry 125-ml Erlenmeyer flask, weigh 1.0 0.1 g of granular t i n using the triple-beam balance; record the weight as accurately as possible. To this t i n , add 30 ml of C H C 1 (dichloromethane); stopper the flask loosely. Because C H C 1 is quite volatile and is poisonous if large amounts are inhaled, y o u should uncover it only when necessary and then for as brief a time as possible. When y o u pour C H C 1 , place the m o u t h of the bottle as close as y o u can to the graduated cylinder to minimize vaporization. Weigh 3.0 0 . 1 g of iodine i n t o a beaker and record the weight that y o u actually take. If aluminum weighing dishes are available, do not use one here; the a l u m i n u m and iodine may react on contact. Cover the beaker w i t h a watch glass, so that iodine vapor will not pass i n t o the air in the laboratory. A d d a few crystals of iodine to the mixture of tin and C I I C 1 ; i m m e d i ately restopper the flask. Note the color that appears as the iodine dissolves in the C H C 1 . Gently swirl the flask u n t i l the solution has the red-brown color that is characteristic of S n l instead of the purple-red color of a m i x t u r e of iodine and S n l . Be patient; it w i l l take at least five minutes and may take 15 minutes or more for this color change to occur. A f t e r the color of the solution changes, add a few more crystals of iodine to the flask. Continue to swirl the flask and to add a few crystals of iodine at a t i m e ; after each a d d i t i o n , wait for the proper color change to occur before adding more iodine. Remember to keep the watch glass over the beaker as much of the time as y o u can and to keep the flask stoppered except when y o u are actually adding iodine to the s o l u t i o n . Have a beaker of cold water nearby as y o u add the iodine; if b u b b l i n g occurs that shows the C H C 1 is starting to b o i l , immediately cool the flask in the water. A f t e r all the iodine has been added continue to m i x the contents of the flask for at least ten minutes after the color suggests that all the iodine has reacted. A l l o w a m i n i m u m of one hour for the total reaction time from the first addition of iodine.
2 2 2 2 2 2 2 2 2 2 4 4 2 2
In the hood, decant the C H C 1 solution of S n l into a 50-ml beaker leaving the unreacted tin in the flask. Use a few ml of C H C 1 to wash out the flask. Y o u will now evaporate the C H C 1 to obtain the solid crystalline product. Several ways to do this are described here. Y o u r instructor w i l l tell y o u which method to use.
2 2 4 2 2 ; 2
Method I: L o w e r the h o o d w i n d o w so that just enough space remains to place the beaker under the w i n d o w . Position the beaker so that about half of it extends in front of the w i n d o w and half of it extends behind the w i n d o w . As air is drawn i n t o the hood, it w i l l pass over the solution and speed the evaporation of the C H C 1 . This is the simplest and most convenient method to use if a hood that draws well is available.
2 2
31
A Simple Covalent Compound: Synthesis and Properties
Method 2: If compressed air is available, direct a stream of it across the surface of the solution (as shown in Figure 7-1). This must be done in the hood. Method 3: Use a water aspirator to pull a stream of air across the surface of the solution (see Figure 7-2). This also should be done in the hood. Method 4: Instead of decanting the C H C 1 solution i n t o a beaker, decant it i n t o a f i l t e r flask. Stopper the flask and connect it to a trap bottle that is connected to a water aspirator. T u r n on the aspirator. The suction of the aspirator will cause the C H C I to boil away. Again, this should be done in the hood.
2 2 2 2
When the S n l is d r y , scrape it out of the beaker o n t o a piece of filter paper. Break up large pieces of the solid to allow C H C 1 trapped inside to evaporate. Do not continue y o u r investigation of the properties of S n l u n t i l y o u are sure that it is completely d r y . ( S n i f f it cautiously; if you can detect the odor of C H C 1 , the compound is not yet d r y . ) Weigh the S n l so that y o u can calculate y o u r percentage yield.
4 2 2 4 2 2 4
FIGURE 7-1
Using compressed air to evaporate solvent.
82
Experiment 7
B. S o l u b i l i t y of Covalent and Ionic C o m p o u n d s
Place about 0.1 g of S n l in each of three 4-ml test tubes. To one tube, add about 2 ml of water; to another tube, add about 2 ml of benzene ( C H ) ; and to the t h i r d tube, add about 2 ml of CC1 (carbon tetrachloride). In each case, record whether or not the S n l is soluble. The c o m p o u n d does not have to dissolve completely to be classified as soluble; simply l o o k for the characteristic S n l color in the solvent. If the S n l does not seem to dissolve, allow the m i x t u r e to stand and observe it again after five minutes and again after half an hour. Has there been any change in the appearance of the S n l to suggest that it has reacted w i t h the solvent? It will react w i t h one o f these solvents. Repeat this procedure w i t h samples o f iodine, C H (naphthalene), NaCl (sodium chloride), and C a S 0 (calcium sulfate). Categorize each of these compounds as soluble or insoluble in water, in benzene, in C H C 1 , and C C 1 . Dispose of the solutions as y o u r instructor directs.
4 6 6 4 4 4 4 4 1 0 8 4 2 2 4
C. T h e Melting Point and V o l a t i l i t y of Covalent and Ionic C o m p o u n d s
This p o r t i o n of the experiment must be done in the hood. Be sure that no one is evaporating C H C 1 in the same h o o d . Y o u r instructor may designate specific hoods for each procedure. Hold one end of a spatula (preferably a broad, white porcelain one) in the flame
2 2
33
A Simple Covalent Compound: Synthesis and Properties
of a Bunsen burner for about one minute. Remove the spatula from the flame and immediately place a very small amount of S n l on i t . Observe the behavior of the S n l . Does it melt? Does it vaporize? If so, what is the color of the l i q u i d or of the vapor? Repeat this procedure w i t h samples of iodine, naphthalene, sodium chloride, and calcium sulfate.
4 4
R E S U L T S AND DISCUSSION
On the Report Sheet for this experiment, briefly explain the reason for each step in the synthesis. Include answers to the f o l l o w i n g questions: Why was C H C 1 chosen as the solvent in which to carry out the reaction? Why is excess t i n used instead of excess iodine? Why is the iodine added in small amounts instead of all at once? Provide the i n f o r m a t i o n about yield and properties requested on the Report Sheet.
2 2
QUESTIONS
1. When the five materials were heated as described in the experiment, what compounds behaved similarly? A c c o u n t for these similarities in terms of the type of particle of w h i c h each c o m p o u n d is composed. A c c o u n t for differences in behavior. 2. Draw Lewis electron d o t formulas for S n l , naphthalene, benzene, and C H C 1 . Is each of these molecules polar or nonpolar? 3. What similarities in solubilities did y o u observe for the five materials? A c c o u n t for these similarities. A c c o u n t for differences in behavior.
4 2 2
REFERENCES
1. Brauer, G. Handbook of Preparative Inorganic Chemistry. New Y o r k : Academic Press, 1963, p. 735. 2. Yoder, C . H . , Suydam, F . H . , and Snavely, F . A . Chemistry. New Y o r k : Harcourt Brace Jovanovich, Inc., 1975. Chapters 6, 7, and 9.
3.
Describe the physical appearance of S n l .

4
Solubilities: Substance Snl I

4
In water
In benzene
In C H C 1
2
In CC1
NaCl CaS0
4.
Describe the change in appearance of S n l in any solvent w i t h w h i c h it seemed to react.

4
Behavior Snl I: Ci H
0 8 4
when
heated:
NaCl (Answer the questions from page 83 on a separate sheet of paper and attach it to the Report Sheet.)
Experiment 8 Salt Identification Using Visible and Infrared Spectra

Introduction
Experiment 6, " L i n e Spectra of Elements," showed y o u (among other things) that gaseous atoms excited in an electric discharge e m i t light of characteristic color ( f o r example, red for Ne). By using the Bunsen spectroscope, this colored light can be resolved i n t o lines of a single wavelength. The behavior of excited atoms reveals interesting facts about the arrangement of electrons in atoms. Characteristic light colors can also be put to a simpler, more practical use: they can be used to determine the presence of particular elements. Given the elements w h i c h may possibly be present in an u n k n o w n m i x t u r e , y o u could observe the light emission from each one separately and compare it w i t h the light emission from the u n k n o w n . For example, if Ne and Ar are present in a m i x t u r e , then the emission spectrum w i l l show lines from b o t h elements; i f only Ne is present, then only lines from Ne w i l l be observed. D u r i n g the nineteenth century, the Bunsen spectroscope was used extensively to make determinations of this k i n d . Even before the reasons for the existence of line emission spectra were k n o w n , chemists relied on observations of the wavelengths of e m i t t e d light as evidence for the presence or absence of particular elements. If the light e m i t t e d is in the visible region of the electromagnetic spectrum, an observation of its color is often sufficient to identify the e m i t t i n g element. The color is, of course, determined by the wavelengths of emission. Determining w h i c h elements are present in a sample is called qualitative analysis. The usual method for testing the presence or absence of elements is to observe a property that is unique to the element being tested for. Some ions when excited by the heat of a flame emit characteristic colors of light in the visible region (4000 7000 A) of the electromagnetic spectrum as their electrons d r o p back i n t o lower energy levels. A m o n g the ions w h i c h can be identified by the characteristic colors of their electronic emission spectra are N a , K , C a , S r , and B a .
+ + 2 + 2+ 2 +
F o r the most part, the electronic spectra of simple anions do not e x h i b i t emission or absorption bands in the visible region. Many p o l y a t o m i c anions do e x h i b i t vibrational spectra resulting from the absorption of electromagnetic radiation in the 1-100 p. (1 ju = 1 micron = 10,000 A) region as they stretch and bend. The exact number and intensity of such absorptions depend on the number of atoms in the p o l y a t o m i c species and h o w they are arranged w i t h respect to one another. As an example, the N 0 ~ i o n has a bent planar structure and may undergo t w o kinds of stretches ( k n o w n as the t w o stretching modes); the stretching modes and also a binding mode of this ion are depicted in Figure 8-1.
2
In the symmetric mode in Figure 8 - l ( a ) ; ' b o t h NO bonds stretch and compress

37
88
Experiment 8
in unison; energy absorbed in the 1 3 2 5 - 1 3 8 0 c m " region (~7.5 y ) w i l l cause the ion to vibrate in this fashion. In the antisymmetric mode in Figure 8-1(b), one bond stretches as the other compresses; this vibration is excited by energy in the 1 2 3 0 - 1 2 7 5 c m region ( ~ 8 . 0 u ) . In a d d i t i o n , a bending m o t i o n in w h i c h the O - N O angle changes is depicted in Figure 8-1 (c); this v i b r a t i o n is excited by energy i n the 810850 c m region ( ~ 1 2 y ) . The infrared spectrum o f N a N 0 (Figure 8-2) shows h o w strongly the salt absorbs infrared radiation at each wavelength. Y o u can see that there is a strong absorption at 830 c m corresponding to the ONO bend. The stretching absorptions are quite close energetically, so that o n l y one rather broad band i n c l u d i n g b o t h stretching absorptions appears in the spectrum o f N a N 0 . Y o u are not expected to k n o w exactly h o w many absorptions any particular anion should have. The purpose of this discussion is simply to acquaint y o u w i t h the analysis of one particular spectrum. ( N o t e that it is more convenient to measure and discuss absorptions than emissions in the infrared region.)
1 - 1 - 1 2 - 1 2
Wavelength (microns) 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8 9 10 11 12 14
4000
3000
2000
1800
- 1
1600
1400
1200
1000
800
Frequency ( C M )
FIGURE 8-2 Infrared spectrum of N a N 0 in K B r pellet. (Recorded on Perkin-Elmer 700.)

2
89
Salt I d e n t i f i c a t i o n U s i n g V i s i b l e and I n f r a r e d S p e c t r a
Table 8-1 Salts Used as U n k n o w n s
Dromates: K B r 0 , N a B r 0 Carbonates: ( N H ) C 0 , B a C 0 , L i C 0 , K C 0 , N a C 0 , S r C 0 Nitrates: N H N 0 , B a ( N 0 ) , L i N 0 , K N 0 , N a N 0 , S r ( N 0 ) Nitrites: K N 0 NaN0 Phosphates: ( N H ) H P 0 , K H P 0 - 3 H 0 Sulfates: ( N H ) S 0 , B a S 0 , K S 0 , N a S 0 , S r S 0 Sulfites: B a S 0 , K S 0 2 H 0 , ~Na S0 , S r S 0 Thiocyanates: N H N C S , B a ( N C S ) - 2 H 0 , K N C S , NaNCS
3 3 4 2 3 3 2 3 2 3 2 3 4 3 3 2 3 3 3 3 2 2 ) 2 4 2 4 2 4 2 4 2 4 4 2 4 4 4 3 2 3 2 2 3 3 4 2 2
Even when an experimenter does not k n o w the particular atomic motions causing each absorption band, the infrared spectrum of a polyatomic anion serves as a property by w h i c h the anion can be identified. Several spectra of inorganic salts are depicted at the end of this experiment. Y o u may notice that the appearance of some spectra depends n o t only on the anion b u t also on the cationat least to some extent. This arises because the solid state packing of anions and cations introduces some complications that we will not pursue here. Nevertheless, it should be obvious that infrared spectra are characteristic properties by w h i c h a particular salt can be identified. Y o u r i n s t r u c t o r , w i l l provide y o u w i t h an u n k n o w n inorganic salt from the group whose infrared-spectra are given following page 9 1 . (These salts are listed in Table 8-1). Y o u w i l l then identify the cation and the anion present, using flame tests (for the cation) and infrared spectroscopy (for the anion).
CHEMICALS NEEDED
BaCl CaCl cone. HC1 K B r (solid) KG LiCl NaCl

2 2
NH C1 SrCl acetone u n k n o w n salt (from group whose infrared spectra are provided), dried overnight at 7 0 C
4 2
EQUIPMENT NEEDED
attenuator burner cobalt glass cork hexagonal wrenches ( 2 )
infrared spectrophotometer mortar and pestle pellet press platinum or nichrome wire watch glass
90
Experiment 8
PROCEDURE A. F l a m e Tests
Obtain a piece of p l a t i n u m or nichrome wire and make a small loop in one end by wrapping the wire around a pen or a pencil. Insert the other end of the wire i n t o a small cork, which w i l l serve as a handle. This wire w i l l be used to introduce samples i n t o the burner flame. Obviously y o u w i l l want to be sure that the wire itself is free of any material that could color the flame. Y o u can clean the wire by dipping the loop i n t o some concentrated HC1 in a small test tube and then holding it in the hottest part of the burner flame. Repeat this process u n t i l the wire no longer gives a color to the flame. It will be necessary to clean the wire each time y o u change salts. (Why?) The HC1 w i l l convert any compounds on the wire to their chlorides, which can then be easily volatilized. The HC1 will eventually become contaminated and should be changed before w o r k i n g w i t h y o u r u n k n o w n salt. Obtain a small sample of a k n o w n salt of each cation ( L i C l , NaCl, K G , N H C 1 , B a C l , S r C l ) . For each sample, dip the wet loop of the clean wire into the solid and thrust it i n t o the (lame. Observe the characteristic flame color of each sample and note any pertinent features of the color (Does the color appear immediately when the sample is inserted i n t o the flame? Does it last for a long time or a short time?) Record these observations in y o u r n o t e b o o k . Y o u should observe each flame test several times. Then identify y o u r u n k n o w n cation by its flame behavior.
4 2 2
The yellow color produced by N a emission w i l l appear in all flame tests. This is because N a impurities are impossible to remove (they are introduced from glass storage bottles). T o determine whether an u n k n o w n is a sodium salt, y o u w i l l have to compare the intensity of the observed y e l l o w color w i t h a k n o w n sodium salt. In some cases, the yellow color from N a impurities masks emissions from other cations that are present. This is particularly true for K . So it is advisable to view the flame test for any u n k n o w n suspected of containing K through a double thickness of blue cobalt glass. This glass will filter out the y e l l o w light from N a .
+ + + + + +
B. Infrared Spectra
A convenient way to record the infrared spectrum of a solid is to use a solid solution in K B r . (Water absorbs strongly in the infrared region and therefore cannot be used as a solvent.) Potassium bromide does not absorb in the infrared region above 650 c m " . This solid solution is pressed i n t o a translucent pellet. To make a pellet, y o u should take only y o u r solid sample and a spatula to the spectrophotometer area. A small mortar and pestle w i l l be provided there. Remove the KBr from the desiccator, where it is kept to exclude water. Place about 70 mg of K B r on the mortar and return the K B r to the desiccator. With your spatula, add 3 or 4 mg of y o u r u n k n o w n solid. G r i n d the m i x t u r e to a very fine powder w i t h the pestle. This grinding w i l l take about two or three minutes. Y o u should stop occasionally to scrape the powder i n t o a pile in the mortar and then begin grinding again. When the sample is a fine powder, obtain the pellet press, which consists of a metal block w i t h a threaded hole and t w o polished end bolts (see Figure 8-3(a)).
1
91
Salt Identification Using Visible and Infrared Spectra
<a)
(b)
FIGURE
8-3
(a) Pellet press block and bolt. (b) Making a KBr pellet.
Screw one of these bolts about halfway i n t o the block. W i t h y o u r spatula, sprinkle a t h i n coating o f the powder over the b o l t surface u n t i l i t is evenly covered. This w i l l probably not require all the powder y o u prepared. N o w insert the other bolt and tighten it as much as y o u can w i t h y o u r fingers. F i t the t w o hexagonal wrenches around the bolts, and tighten b o t h bolts against each other as much as y o u can to create pressure on the powder inside (see Figure 8-3(b)). Maintain the pressure for a few seconds, and then let the block sit for about three minutes. At the end of this time, loosen b o t h ' b o l t s . Y o u should have a translucent pellet inside the threaded cavity of the block. If the pellet broke or is not translucent, repeat the procedure. The block is placed in the sample beam of the infrared spectrophotometer. (See A p p e n d i x I I I concerning the construction of a spectrophotometer.) Record the spectrum, f o l l o w i n g the instructions supplied by y o u r instructor. If y o u r sample has absorbed water from the air, y o u w i l l see additional bands around 2.9 and 6.25 n. Wash the mortar, pestle, block, and bolts w i t h distilled water; f o l l o w w i t h an acetone rinse.
RESULTS
On the Report Sheet for this experiment, record your observations regarding the flame tests y o u conducted. Identify y o u r u n k n o w n salt from the flame test and the infrared results.
REFERENCES
1. Yoder, C . H . , Suydam, F . H . , and Snaveley, F . A . Chemistry. New Y o r k : Harcourt Brace Jovanovich, Inc., 1975. Chapter 8. 2. A c k e r m a n n , M . N . Journal of Chemical Education 47, 69 ( 1 9 7 0 ) .
F I G U R E 8-4
2.5
Infrared spectra of unknown salts in KBr pellets. (Recorded on Perkin-EImer 700.)

Wavelength (microns) 4 -T
* /
4.5
5.5
4-
6.5
7.5
10
I L
I,
II 1
12
14 1
u i
\
/ / /
/
f
a. KBr0
400(1
3000
2000
1800
1600
1400
1200
1000
800
Frequency ( C M " ' ) Wavelength (microns) 3.5 4.5 5 5.5 6 6. 10 11 12
4000
3000
2000
1800
1
1600
1400
1200
1000
800
Frequency ( C M ' )
H ) 0 0
92
3000
2000
1800
1
1600
1400
1200
1000
800
Frequency ( C M " )
Experiment 9 Synthesis of Coordination Compounds and Their Identification Using Spectrophotometry

Introduction
Several features of synthetic chemistry have already been discussed in the i n t r o d u c t i o n to Experiment 5. Y o u should review this material in conjunction w i t h Experiment 9 . Here, y o u w i l l gain experience in synthetic techniques by preparing a synthetic intermediate, isolating i t , and using it as starting material to synthesize another complex. This intermediate is related to the cobalt complex of Experiment 5; the difference is that one of the neutral N H molecules coordinated to C o has been replaced by the dinegative carbonate ion C 0 ~ (see Figure 9-1). This decreases the charge on the complex ion to + 1 , so that only one nitrate is needed to balance the charge. The formula for this c o m p o u n d is often w r i t t e n [ C o ( N H ) ( C 0 ) ] ( N 0 ) to show that the molecules and ions w i t h the square brackets are attached to C o . The name of this compound is pentaamminecarbonatocobalt(III) nitrate.
3 + 3 2 3 3 s 3 3 3 +
The method o f preparation is given in Equation ( 9 - 1 ) : 4 C o ( N 0 ) - 6 H 0 + 4 ( N H ) C 0 + 1 6 N H + 2 0 ->

3 2 2 4 2 3 3 2
4[Co(NH ) (C0 )](N0 ) + 4NH N0 + 26H 0

3 5 3 3 4 3 2
(9-1)
3 +
The purpose of the oxygen is to oxidize the C o
2 +
in the starting material to C o .
105
106
Experiment 9
This avoids using H 0

2
as in Experiment 5, w h i c h must be disposed of by heating: 2H 0

2
>~ \ o
b0
3 s 3
+ 2H 0
2
(9-2)
After y o u have prepared [ C o ( N H ) ( C 0 ) l ( N 0 ) , your instructor w i l l give y o u an u n k n o w n substance to react w i t h i t . This is to replace the carbonate ion w i t h some group X to produce the complex ion [ C o ( N H ) X ] " . The value o f n will depend on the charge ( i f any) on the group X. If X has no charge, then n - 3; the complex ion charge is determined o n l y by the +3 charge on the Co, since all the groups bonded to Co are uncharged. The [ C o ( N H ) X ] ion w i l l pick up some o f the N 0 " ions in solution to form solid [ C o ( N H ) X | ( N 0 ) . If the group X has one negative charge, it w i l l neutralize one o f the postive charges on the cobalt to produce a [ C o ( N H ) X | c a t i o n . In this case, the cation can utilize either N 0 ~ or X " anions t o neutralize its charge, and [ C o ( N H ) X ] ( N 0 ) o r [ C o ( N H ) X ] X (whichever is less soluble) precipitates.
3 + 3 5 3 + 3 5 3 3 5 3 3 2 + 3 5 3 3 5 3 2 3 5 2
The reaction in which An X group replaces carbonate is carried out in H N 0 solution which destroys the C 0 ~ i o n and causes C 0 gas to bubble o f f :
2 3 2
C 0 ~ + 2 H ^ H C 0 -> H 0 + C 0 ( g )
2 + 3 2 3 2 2 +
(9-3)
Once y o u have isolated a solid containing the [ C o ( N H ) A ' ] " cation, y o u w i l l identify i t . Since these cations are b r i g h t l y colored, they can be identified by their characteristic colors. Y o u may remember that in Experiment 2 the property color was not used as a possible means of identification because there was no precise .numerical way to measure i t . Y o u will now learn to measure the color o f a c o m p o u n d quantitatively so that y o u can identify the complex y o u prepared. The technique, called s p e c t r o p h o t o m e t r y , makes use of the fact that substances are colored because they absorb visible light of certain colors and transmit the remaining colors. As y o u probably remember from high school science courses, ordinary white light is composed of light of all colors visible to the naked eye. The color of light depends on its wavelength X. Figure 9-2 indicates the approximate wavelength ranges for various colors. Ordinary visible white light is a m i x t u r e of light having all wavelengths between 40007000 A. Light having wavelengths shorter than 4000 A is called ultraviolet light and cannot be seen by the human eye. Infrared light, which has wavelengths longer than 7000 A, is also invisible to the human eye.
3 5
107
Synthesis of Coordination Compounds and Their Identification Using Spectrophotometry
FIGURE 9-3 Light passing through a cell.
Solutions of various compounds are co'ored, then, because they absorb light of some wavelengths and transmit light of ov wavelengths. The color y o u see corresponds to the color of the transmitted l i g h t . For example, a solution of plant food appears green because it absorbs the light in the red, orange, y e l l o w , blue, and violet wavelength regions and transmits green light. L i g h t in the visible and ultraviolet regions of the spectrum causes electrons to j u m p to higher energy levels when it is absorbed. Figure 9-3 diagrams a quantitative way of measuring light absorption by a solution. Some of the sample is placed in a small vessel called a cell or cuvette. Light of a single wavelength X having an intensity I is shined into the cell. The solution may absorb some light of this wavelength and transmit the rest w i t h reduced intensity /. The q u a n t i t y ( 7 / / ) is obviously related to h o w strongly the solution absorbs the light. I f most o f the light is absorbed, / w i l l be quite small and ( / / / ) w i l l be quite small. Conversely, if most of the light is transmitted, / w i l l be large and ( / / / ) w i l l also be large. The q u a n t i t y ( / / / ) X 100 is called the percent transmittance T:
0 0 0 0 0
The d e f i n i t i o n of A indicates that, at any wavelength where the sample absorbs strongly (where I / I is large),/! w i l l also be large. When little light is absorbed,/! w i l l be small. A plot of the absorbance of a solution at various wavelengths, called an absorption spectrum, shows what colors are strongly absorbed and what colors are transmitted. The spectrum o f [ C o ( N H ) ( C 0 ) ] ( N 0 ) i s depicted i n Figure 9-4. The strong absorption of light in the orange, y e l l o w , green, blue, and violet regions of the spectrum gives the complex the red color of the transmitted light. The color of the solution is complementary to the colors that are absorbed.
0 3 5 3 3 2
108
Experiment 9
Tire spectrum of a c o m p o u n d is a characteristic property and may be used to identify the c o m p o u n d . Rather than reproducing the entire spectrum, it is customary to report the wavelengths of m a x i m u m absorbance. These are indicated on the spectrum of [ C o ( N I l ) ( C 0 ) ] ( N 0 ) in Figure 9-4. Y o u can identify y o u r compound by measuring its absorption spectrum and comparing it to the spectra of the possible products given at the end of this experiment. Note that this type of color comparison is similar to the flame tests for color that y o u made in Experiment 8. However, the more precise technique used here allows y o u to distinguish easily between different shades o f red, for example, because they w i l l have slightly different wavelengths of m a x i m u m absorption.
3 5 3 3 2
Locating the exact position of the m a x i m u m absorption X can be d i f f i c u l t , since the absorption curves are somewhat flat. A good technique is shown in Figure 9-5. Lines are drawn tangent to both sides of the curve and extrapolated to the point where they intersect. This p o i n t is taken as the point of m a x i m u m absorption.
m a x
The measured value of the absorbance A is related to several experimental factors by the B e e r - L a m b e r t Law A = eel
(9-6)
where e is the e x t i n c t i o n coefficient, c the concentration in moles/liter, and / the thickness of the cell. This law simply states that the absorbance A at any wavelength X depends on ( 1 ) how many absorbing molecules a light beam encounters in passing through the cell (this number w i l l obviously increase as the cell thickness / and the concentration c increase), and ( 2 ) an intrinsic property of the molecules for absorbing at wavelength X (e). A p p e n d i x I I I describes how measurements of absorbance at various wavelengths are made experimentally.
109
EQUIPMENT NEEDED
50-ml beakers Buchner funnel burner 125-ml and 250-ml Erlenmeyer flasks filter flask filter paper graduated cylinder medicine dropper pneumatic trough
ring ring stand spectrophotometer thermometer universal clamp vacuum tubing volumetric flask wire gauze
CHEMICALS
NEEDED
CH3OH (methanol)
20 g of C o ( N 0 ) - 6 H 0 ice cone. N H
3 2 2 3
30 g o f ( N H ) C 0 u n k n o w n solution (provided by instructor)

4 2 3
PROCEDURE
A. S y n t h e s i s of P e n t a a m m i n e c a r b o n a t o c o b a l t ( l l l ) n i t r a t e
[Co(NH ) (C0j)]
3 s
(NO3K H 0
2
Weigh a clean, empty 50-ml beaker and record its weight. N o w add about 20 g of C o ( N 0 ) * 6 H 0 and record the weight of the beaker and salt. The weight of C o ( N 0 ) * 6 H 0 is the one on which your yield calculation w i l l be based, and it is the only weight that must be k n o w n accurately. To a 250-ml Erlenmeyer flask, add about 30 g of ( N H ) C 0 ( a m m o n i u m carbonate) and dissolve this in about 30 ml of distilled water. A d d about 50 ml of
3 2 2 3 2 2 4 2 3
110
Experiment 9
concentrated N H s o l u t i o n . Dissolve the C o ( N O _ ) 6 H , 0 in 10 ml of water and pour this solution i n t o the Erlenmeyer flask; be careful to rinse the beaker to remove all of the cobalt salt. Continue to swirl the flask gently u n t i l the contents of the flask are t h o r o u g h l y m i x e d .
, 3 1 2
The solution is now o x i d i z e d by bubbling air into the flask. The most convenient method for doing this is to attach a piece of rubber tubing to the air jet and to place a medicine dropper in the other end of the tubing. The medicine dropper is placed in the flask, and the air jet turned on to provide gentle bubbling. The bubbling should be continued overnight or for at least 10 hours. Y o u may need to add a l i t t l e distilled water to replace some of the water lost by evaporation during the o x i d a t i o n step. T r y to be sure that all the material is still in solution at the end of the oxidat i o n . However, do not heat the s o l u t i o n to dissolve any precipitate. Let the flask stand while y o u obtain a pneumatic t r o u g h full of ice. (This ice bath can be shared by t w o students.) Set the flask in the ice bath to c o o l , and when the temperature is near 0 , crystals should begin to f o r m . Crystallization occurs slowly and may require scratching the beaker w i t h a stirring r o d . Do not expect all the product to precipitate i m m e d i a t e l y . Isolation of a crystalline product requires considerable patience. C o o l the flask in the ice bath u n t i l no more crystals of the red product seem to be forming. If y o u have trouble crystallizing the product, y o u may add some methanol to the s o l u t i o n . (The solution absolutely cannot be allowed to sit in y o u r drawer u n t i l the next laboratory period and then cooled.) A f t e r this cooling, collect the crude product by f i l t r a t i o n on a Buclmer funnel; wash the product w i t h a l i t t l e ice water and then w i t h cold methanol. Place the c o m p o u n d in an evaporating dish in your desk; allow air to dry the product for several days. Then weigh the dry product.
B. Synthesis of [ C o ( N H ) X ] ( N 0 )
3 s 3
Y o u r instructor w i l l provide y o u w i t h enough o f a c o m p o u n d that is a source o f an X group to react w i t h 3.0 g of f C o ( N H ) ( C 0 ) ] ( N 0 ) . Depending on the nature o f y o u r u n k n o w n s o l u t i o n , y o u r instructor will direct y o u to follow Procedure A or Procedure B below in synthesizing your final product.
3 s 3 3
Procedure A. Place 3.0 g of [ C o ( N H ) ( C 0 ) ] ( N 0 ) in a 250-mI Erlenmeyer flask A d d about 15 ml of distilled water. T h e n , working under a hood, add the u n k n o w n solution provided by y o u r instructor. C A U T I O N : This solution contains concentrated H N 0 ! A f t e r stirring occasionally for about 30 minutes, add 150 ml of methanol to precipitate y o u r product. Collect the product by suction f i l t r a t i o n on a Biichner funnel (see I n t r o d u c t i o n , page 15). Wash the c o m p o u n d w i t h cold water and then w i t h methanol. A i r dry the solid and then weigh i t .
3 5 3 3 3
Procedure B. Place 3.0 g of [ C o ( N H ) ( C 0 ) ] ( N 0 ) in a 125-ml Erlenmeyer flask. A d d about 15 ml of distilled water. Then, working under a hood, add the u n k n o w n solution provided by y o u r instructor. C A U T I O N : This solution contains concentrated H N 0 ! Place the flask on a ring stand w i t h wire gauze and heat the flask flask w i t h a burner. The s o l u t i o n should be heated at a temperature range of 6 5 - 7 5 C for one hour, either using a burner or a steam bath. Cool the solution in an
3 s 3 3 3
111
ice bath and collect the precipitate by Filtration on a Buchner funnel (see I n t r o d u c t i o n , page 15). Wash the precipitate w i t h cold water and then w i t h methanol. A i r dry the solid and then weigh i t .
C. P r o d u c t Identification
Y o u will identify the product y o u have prepared by measuring its absorption spectrum. As precisely as possible, weight out 0.5 g of y o u r dry u n k n o w n c o m p o u n d . Transfer the compound quantitatively to a clean, 250-ml volumetric tlask. A f t e r completely dissolving the c o m p o u n d in a few ml of distilled water, dilute the solution so that the b o t t o m of the meniscus matches the mark on the neck of the tlask. Then invert the tlask several times to ensure complete m i x i n g . Place some of the solution in the cuvette of the spectrophotometer and read the percent of transmittan.ee at intervals of 250 A over the visible range. Y o u r instructor will provide directions for using the spectrophotometer. (A c o m m o n type o f visible-UV spectrophotometer is discussed in A p p e n d i x 111.) ( I f the 0.5 g q u a n t i t y of your product w i l l not dissolve completely in 250 ml of distilled water, discard the solution and rinse the volumetric tlask w i t h distilled water. T h e n , as precisely as y o u can, weigh out about 0.2 g of y o u r dry u n k n o w n and proceed as before.)
113
Synthesis o Coordination Compounds and Their Identification Using Spectrophotometry

:
RESULTS
1. Using the weight of C o ( N 0 ) - 6 H 0 w i t h which y o u began the experiment, the weight of y o u r product, and Equation (9-1), calculate the percentage yield of (Co(NH )' (C0 )](N0 ). 2. Plot absorbance vs. wavelength on a piece of graph paper. Draw a smooth curve through y o u r experimental points to obtain the spectrum of y o u r u n k n o w n c o m p o u n d in the visible region. 3. Locate the positions of m a x i m u m absorbance. 4. Compare y o u r spectrum w i t h the spectra for k n o w n cobalt complexes, and identify the final product y o u prepared. (Consult Figures 9-6 through 9-10.) 5. (a) K n o w i n g the i d e n t i t y of y o u r product, compute its formula weight by using a table of atomic weights. (b) F r o m the formula weight and the amount of the product that was weighed . o u t , calculate the concentration c of the solution y o u prepared. (c) F r o m your plot, read the absorbance values at the points of m a x i m u m absorbance. Use this i n f o r m a t i o n and the solution concentration to compute the e x t i n c t i o n coefficient e at each m a x i m u m from Equation (9-6).
3 2 2 3 5 3 3
6.
7.
K n o w i n g the i d e n t i t y of the final product y o u synthesized, write an equation for its p r o d u c t i o n from [ C o ( N H ) ( C 0 ) ] ( N 0 ) . Assume that anions are provided as their sodium salt or come from H N 0 . Compute the percentage yield of this compound. T u r n in y o u r products in test tubes labeled w i t h your name, section number, and instructor's name.
3 5 3 3 3
QUESTION
What are possible sources of random or systematic error in the values of e y o u calculated?
REFERENCES
1. Yoder, C.H., Suydam, F . H . , and Suavely, F . A . Chemistry. New Y o r k : Harcourt Brace Jovanovich, Inc., 1975. Chapter 8. 2. Basolo, F., and M u r m a n , R.K. Inorganic Syntheses 4, 1 7 1 ( 1 9 4 8 ) . 3. Olson, G . L . Journal of Chemical Education 46, 508 ( 1 9 6 9 ) .
)
Name Section
REPORT
SHEET
EXPERIMENT9
Date
6.
Equation for product synthesis:
Percentage y i e l d of product Show calculation:
(Answer the question from page 113 in the space remaining below; use the back of the Report Sheet, if necessary.)
I I I I
I I
I
I
I I I
Experiment 10 Vaporization of a Liquid: Vapor Pressure and Heat of Vaporization

Introduction
A n y l i q u i d contained in a closed vessel evaporates to at least a small extent. In other words, some molecules leave the surface of the l i q u i d and become vapor. As these molecules in the vapor phase move about r a n d o m l y , some may strike the surface of the l i q u i d and again become part of the l i q u i d phase; that is, they may condense. Eventually, a state o f equilibrium will be reached in which molecules vaporize and condense at exactly the same rate and there is no change in the number of molecules in either the l i q u i d or the vapor phase. This vapor, like any gas, exerts pressure. When the l i q u i d and vapor phases of a substance are in e q u i l i b r i u m , this pressure is called the vapor pressure of the l i q u i d . The vapor pressure is the m a x i m u m pressure that can be exerted by the vapor phase of a substance at a particular temperature. It is possible to tell when this e q u i l i b r i u m between phases has been reached, because at this p o i n t the volume of l i q u i d ( w h i c h can be measured) no longer decreases and the pressure exerted by the vapor ( w h i c h can be measured) no longer increases. I n this experiment, y o u w i l l determine when e q u i l i b r i u m has been established between the l i q u i d and vapor phases of a substance by measuring the pressure exerted by the vapor. The size of a liquid's vapor pressure is a measure of the number of molecules in the vapor phase at e q u i l i b r i u m . It therefore reflects the tendency of molecules to escape from the surface of the l i q u i d . In the l i q u i d phase, molecules exert attractive forces on one another. A certain amount of energy is required for a particle to overcome these forcesto leave the l i q u i d and to become part of the gas phase. Since temperature is a measure of average molecular kinetic energy, it is reasonable to expect that as the temperature increases, the p r o b a b i l i t y increases that the molecules w i l l possess the energy necessary for escape. Consequently, vapor pressure should increase as temperature increases. In part o f this experiment, y o u w i l l measure the vapor pressure o f one liquid at several temperatures; y o u w i l l see that these t w o measurable properties of the l i q u i d do indeed decrease or increase together. Y o u w i l l take measurements that show that the vapor pressure o f a liquid is related to temperature and then use these measurements to calculate the energy^ needed to overcome intermolecular attractions in the l i q u i d . The q u a n t i t y y o u w i l l calculate is called the molar heat of vaporization AH . This is the heat necessary to convert one mole of l i q u i d i n t o one mole of vapor at a constant temperature. F o r example, CC1 (1) + AII -* C C l ( g ) . The mathematical relationship between vapor pressure and the molar heat of vaporization is given by the Clausius-Clapeyron equation:
V 4 V 4
119
120
Experiment 10
log P = v
2.303
(-) + C R\TJ
(10-1)
This equation was derived in the branch of chemistry and physics k n o w n as thermodynamics; y o u must use this equation here, but y o u do not need to be concerned w i t h its derivation. Equation (10-1) is in the form of the equation for a straight line y - mx + b. H e r e , ^ = log P and x - \/T. If the logarithm (to the base 10) of the vapor pressure is p l o t t e d against the reciprocal of the Kelvin temperature, a straight line is obtained. The y intercept b corresponds to the constant C in the ClausiusClapeyron equation; y o u w i l l not be concerned w i t h this constant. The slope of the line equals -AH /2.303 R, where R is the gas constant 1.987 c a l / K mole. A f t e r determining the slope of the line from your p l o t , a value for AH in cal/mole can easily be calculated. This determination of the heat of vaporization is a good example of how scientists measure a q u a n t i t y which is not easily accessible ( A / / ) by using measurements that are easy to make (P and T) and by applying an equation (the ClausiusClapeyron equation) that relates these quantities.
v v V v
EQUIPMENT
NEEDED
W;!-*^^-^
400-ml beaker ring stand - v ^ v f * capillary tubes rubber band - kr A*clamp serum cap copper wire stirrer syringe cork ( w i t h vent) test tube 1 2 5 - m l filter flask thermometer manometer T y g o n tubing ring wire gauze
^ â**.*^
CHEMICALS NEEDED
ice organic liquids
M E A S U R I N G P R E S S U R E WITH A M A N O M E T E R
The pressure of a confined gas sample can be measured w i t h a manometer. This simple instrument consists of a U-shaped glass tube partially tilled w i t h mercury. When b o t h arms of the U are open to the atmosphere, the pressure on the mercury in the t w o arms is the same; thus, the mercury levels w i l l be the same in b o t h arms. A t t a c h one arm of the manometer to a closed flask containing air at atmospheric pressure; the mercury levels w i l l remain the same in b o t h arms, since the pressure on the mercury in the t w o arms is still the same (atmospheric pressure). Then a l i q u i d w i l l be put i n t o the flask. As the l i q u i d vaporizes, the pressure inside the flask w i l l rise above atmospheric pressure and the mercury w i l l be pushed d o w n in the arm that is connected to the flask (see Figure 10-1). The difference in the mercury levels
121
Vaporization of a L i q u i d : Vapor Pressure and Heat of Vaporization
FIGURE 10-1
Using a manometer to measure vapor pressure.
Ah is the amount by which the pressure in the flask exceeds atmospheric pressure: Pfiask ^ . t m + A/; (10-2)
The total pressure in the flask after the l i q u i d vaporizes is the air pressure in the flask plus the vapor pressure of the l i q u i d : . v / fl.k^.ir+/ ,
> > a atm atm v
(10-3)
Since P = P , the total pressure is the same as P + P , and the difference Ah is simply the vapor pressure of the l i q u i d . Y o u can measure Ah in either mm or cm of mercury; just be sure that y o u k n o w which unit y o u are reading and that y o u record the proper unit. If the vapor pressure of the l i q u i d were extremely high, the mercury might be pushed d o w n past the bend of the U, so that the height of the mercury c o l u m n could not be measured; mercury might even be pushed out of the open arm. To measure the pressure of such a l i q u i d , the flask should be partially evacuated before the l i q u i d is put i n t o the flask. To do this, the needle from a syringe is inserted through the cap closing the flask u n t i l the needle extends i n t o the flask. V a c u u m tubing is then used to attach the needle to a water aspirator. The aspirator is turned on and air is drawn out of the flask u n t i l the mercury in the arm connected to the flask is w i t h i n about a centimeter of the bend (see Figure 10-2). The air pressure in the flask is now less than atmospheric pressure by the amount Ah': fair^tm-AV (10-4)
After the liquid is put i n t o the flask and has vaporized, the mercury w i l l be pushed d o w n in the arm connected to the flask, as First shown in Figure 10-1. Once again, the difference Ah is the amount by w h i c h the pressure in the flask exceeds atmospheric pressure (see Equation 10-2). As before, the t o t a l pressure inside the flask is the sum of the air pressure and the vapor pressure (see Equation 10-3).
However, now the air pressure does not equal the atmospheric pressure. Y o u must use Equation (10-4) to calculate the air pressure, Equation (10-2) to calculate the total pressure inside the tlask, and, finally, Equation (10-3) to calculate the vapor pressure. Obviously, this procedure and the accompanying calculations here are more troublesome than they were in the first example._If y o u r attempt to measure vapor pressure at room temperature indicates that the second procedure is necessary, consult y o u r instructor before y o u begin i t .
PROCEDURE
The filter tlask must be clean and d r y . Stopper it w i t h a serum cap. The center p o r t i o n of the cap should be placed inside the neck of the tlask and the p o r t i o n that extends upward should be pulled d o w n around the neck on the outside of the tlask; pull the outside portion of the cap d o w n as low as you can so that it fits as t i g h t l y as possible. Clamp the flask to a ring stand. Use a short piece of T y g o n t u b i n g to attach the flask to the manometer; do this after y o u have positioned the serum cap. When you put the tubing o n t o the manometer, grasp the glass tubing as close to the end as possible; push the T y g o n t u b i n g on only far enough to be sure that it cannot fall off. The mercury levels should be the same in b o t h arms of the manometer; if they are not, remove and reconnect the tubing. Draw about 1 ml of y o u r l i q u i d i n t o a syringe. T u r n the syringe upside d o w n and push the plunger far enough to expel any air bubbles. Then plunge the needle through the center of the serum cap and inject the l i q u i d i n t o the tlask. As y o u do this, keep a firm grip on the plunger of the syringe so that it cannot be pushed upward by pressure f r o m the vaporizing l i q u i d . Remove the needle f r o m the cap. As y o u do this, be sure that the needle and the syringe do not separate f r o m one another; if they do, air and vapor can escape through the needle. A f t e r a p p r o x i mately three minutes, read the mercury levels in the t w o arms of the manometer. Repeat this reading at one-minute intervals u n t i l the levels longer change. When
123
Vaporization of a L i q u i d : Vapor Pressure and heat of Vaporization
the levels have stabilized, the difference All is the vapor pressure of the l i q u i d . If y o u find that the difference Ah is decreasing after several minutes, there is a leak in the system w h i c h must be found and eliminated; y o u may need your instructor's assistance. A f t e r completing this measurement, disconnect the t u b i n g from the flask, pour the l i q u i d in the flask i n t o a waste container, and t h o r o u g h l y dry the flask (preferably w i t h a strong stream of compressed air). It is absolutely essential to dry the flask. I f vapor remains in the flask, it w i l l l i m i t the amount o f additional liquid that can vaporize; this will cause y o u r measurements to be l o w . Next, measure the liquid's vapor pressure at 0 C . Immerse the stoppered flask as deeply as possible in a beaker of water and ice; let it stand for at least 10 minutes. Be sure to use enough ice to maintain a temperature of 0 C d o w n to the b o t t o m of the flask. T h e n attach the flask to the manometer. Wait five minutes; if the mercury levels remain the same in b o t h amis, inject the l i q u i d and measure its vapor pressure. If the levels have changed during this time, the air in the flask has not yet cooled to 0 C and its pressure is still dropping as it cools further; disconnect the flask and reattach it before injecting the l i q u i d . After y o u are finished, pour out the l i q u i d and dry the flask. N o w measure the vapor pressure of y o u r l i q u i d at a temperature of about 1015C. Immerse the stoppered flask in a beaker of cold tap water or in water that has been cooled by the addition of ice. A d d ice or cold water as needed to maintain a constant temperature. Be sure to record the actual temperature of this bath. A f t e r y o u are sure that the flask and the air have cooled sufficiently, add the l i q u i d and measure its vapor pressure. A f o u r t h set of temperature/vapor pressure data can be obtained by recalling the definition of boiling p o i n t : the temperature at w h i c h the vapor pressure of a l i q u i d equals the pressure of the atmosphere above the l i q u i d . Use the technique y o u learned in Experiment 2 to measure the boiling p o i n t . Read the barometer to determine the atmospheric pressure; that is, the vapor pressure of the l i q u i d at the measured b o i l i n g point.
R E S U L T S AND
DISCUSSION
Review A p p e n d i x II (page 357) on graphing experimental data. Prepare a graph p l o t t i n g the vapor pressure of y o u r l i q u i d on the ordinate and the temperature on the abscissa. On the back of the graph, compile a data table showing the values of P and of T that y o u used. The line through the experimental points should be a continuous one; discuss what the general shape of this plot tells y o u about the relationship between vapor pressure and temperature.
v
N o w prepare a graph p l o t t i n g log P along the ordinate and 1 / T ( i n K ) on the abscissa. Y o u must convert each \/T to a decimal; do not use fractions. Draw the best straight line through the points. On the back of the graph, compile a data table showing P , log P , T, and 1/7 for each measurement.
v v v
Determine the slope of the straight line for this second graph. F r o m the slope and the Clausius-Clapeyron equation, calculate the value of AH for y o u r l i q u i d . Be sure to include the proper units.
V
124
Experiment 10
QUESTIONS
1.
2.
How w i l l each o f the f o l l o w i n g affect the measured vapor pressure in comparison to the true vapor pressure for your liquid? (a) A long length of slightly porous rubber tubing is used instead of a short length o f T y g o n tubing. (b) The flask is immersed only halfway in the 0 C bath. (c) A large air bubble is injected i n t o the flask along w i t h the l i q u i d . (d) A 250-ml flask is used instead of a 125-ml flask. L i q u i d A has a vapor pressure of 10.2 cm of Hg at room temperature and l i q u i d B has a vapor pressure of 26.8 cm of Hg at the same temperature. In w h i c h l i q u i d are there stronger intermolecular attractions? Which l i q u i d w o u l d be expected to have the higher normal boiling point? A higher heat of vaporization?
REFERENCE
Yoder, C . H . , Suydam, F . H . , and Snavely, F . A . Chemistry. New Y o r k : Harcourt Brace Jovanovich, Inc., 1975. Chapters 9 and 10.
Experiment 11 Molar Weight by Vapor Density

Introduction
The ideal gas law describes the quantitative relationship among the pressure exerted on or by a gas sample, the volume that the gas occupies, its temperature, and the number of moles of gas n in the sample: PV=nRT (11-1)
An i m p o r t a n t aspect of this relationship is that it applies to all gases: it does not depend on the size, shape, mass, or composition of the particles of the gas. Consequently, it is possible to use measured pressure, volume, and temperature data to " c o u n t " the number of moles (or number of molecules) of gas in any gas sample w i t h o u t k n o w i n g the i d e n t i t y of the gas. If one more piece of data is k n o w n , it is also possible to learn one i m p o r t a n t physical property of the specific gas in the sample: if the mass of the gas sample is k n o w n , the weight of one mole of the gas can be calculated. The number of moles of a substance in any weighed sample can be calculated by dividing the mass of the sample by the weight of one mole of the substance: ' i grams moles = - grams/mole or g /; = M
Ml
(11-2)
This expression for n can be put i n t o the ideal gas law: PV=(l-)RT (11-3)
The equation now contains the four measurable variables of a gas samplepressure, volume, temperature, and massthat can be used to calculate the molar weight of the gas. Rearranging the terms in Equation (11-3) to solve for molar weight gives M =
g R T
PV
(11-4)
In this experiment, y o u w i l l w o r k w i t h a compound that is a liquid at room temperature but that has a boiling point below the boiling point o f water. Y o u w i l l measure the mass of gas that occupies a particular volume at 1 0 0 C and at atmospheric pressure. Then, y o u w i l l use y o u r measured values for these properties to calculate the molar weight of the c o m p o u n d . Remember that the equation y o u are using to calculate molar weight is called the ideal gas law. It is an exact description of the behavior of a gas only if the gas is ideal; that is, if there are no attractive forces between the particles of the gas and if the particles of the gas are volumeless points. Of course, neither of these characteris127
128
Experiment 11
tics is true for a real gas. However, the behavior of a real gas is nearly described by the ideal gas law if the t o t a l volume occupied by the gas is much greater than the volume that is actually taken up by the gas particles and if the temperature is high enough that the gas particles have enough energy to resist intermolecular attractions. Because the compounds that y o u w i l l use do not behave ideally, your calculated molar weight might not be exactly correct even if y o u could eliminate all random errors. However, y o u should be able to obtain a molar weight that is w i t h i n 3-10% of the true value. A f t e r y o u have calculated an approximate molar weight for your u n k n o w n , y o u r instructor w i l l give y o u the elemental percentage composition o f the c o m p o u n d . F r o m these data, y o u can calculate the empirical formula of the c o m p o u n d . Use y o u r approximate molar weight and the empirical formula to determine the molecular formula of the c o m p o u n d and then to determine its true molar weight. Chemists actually use this procedure to determine the i d e n t i t y of new, u n k n o w n substances. The main difference between y o u r w o r k here and the w o r k of a chemist i d e n t i f y i n g u n k n o w n substances is in the sophistication of the equipment that is u s e d - n o t in the procedure itself. The equation PV = nRT applies to ideal gases. It has been modified to describe real gases that behave nonideally. This m o d i f i c a t i o n is called the van der Waals equation:
T w o terms here account for the ways in w h i c h real gases differ from ideal gases. The van der Waals constant a is a measure of the attractive forces between particles of the gas; the greater the attractive forces are, the greater the numerical value of this constant is for the gas. These attractions cause the measured pressure P to be lower than predicted by the ideal gas law for a particular volume of gas. The measured pressure plus the correction factor containing a equals the ideal pressure. The van der Waals constant b is the volume occupied by the molecules themselves in one mole of a gas (liters/mole); the compressible volume (that is, the free space that is available and i n t o which the particles can be pushed) is reduced by this amount. In Equation (11-5), V is the measured volume (including the actual molecular volume) and (V- nb) is the compressible or ideal volume. A f t e r y o u have calculated the approximate molar weight o f y o u r u n k n o w n , y o u r instructor w i l l also give y o u the density of the l i q u i d (in g / m l ) . In a l i q u i d , particles are about as close together as they can possibly be, so the l i q u i d density can be used to calculate a good a p p r o x i mation of b (the volume taken up by the molecules). Then, y o u w i l l use this calculated value of b, the correct molar weight for the u n k n o w n , and y o u r measured values of pressure, volume, temperature, and mass to calculate a numerical value for a (the measure of intermolecular attractions w i t h i n the gas).
EQUIPMENT N E E D E D
analytical balance barometer 50-ml beaker
800-ml beaker Bunsen burner 250-ml Florence flask
129
' lolar Weight by Vapor Density
ring
ring stand thermometer #4 one-hole Neoprene stopper w i t h glass t u b i n g
triple-beam balance universal clamp wire gauze
CHEMICALS WEEDED
U n k n o w n l i q u i d w i t h boiling point below 9 0 C (elemental analysis and density at room temperature to be provided by your i n s t r u c t o r ) .
TECHNIQUE
A small amount of the l i q u i d is poured i n t o a previously weighed tlask. The flask is closed w i t h a Neoprene stopper. A short piece of glass t u b i n g extends through the stopper to allow vapor to escape from the tlask. The tlask, w i t h the stopper in place, is heated in a water bath to about 1 0 0 C . As the l i q u i d boils, its vapor and air rush out o f the flask. Vapor w i l l escape from the flask u n t i l only enough remains to exert a pressure that exactly balances the pressure being exerted on the vapor by the atmosphere. The flask is then cooled to condense the vapor to a l i q u i d . As the flask cools and the vapor condenses, the pressure inside the flask drops; air rushes back into the flask, u n t i l the pressure inside the flask again equals atmospheric pressure. During this cooling, the stopper is replaced by a beaker that is inverted over the neck of the flask and rest's on the l i p of the flask. Of course, the beaker is. not an airtight seal and air cari easily return to the flask, but the beaker does decrease the possibility of the loss of a small amount of vapor by diffusion i n t o the atmosphere. The flask containing the l i q u i d is then weighed (on the analytical balance) to determine the mass of the compound that was present as a vapor when the flask was in the water bath. The volume of the flask is determined by weighing the flask when it is empty and then weighing the flask filled w i t h water. Since the density of water is 1.00 g / m l , the measured mass of water equals the volume of water, w h i c h , in t u r n , equals the volume of the flask. A triple-beam balance can be used for this measurement to obtain a volume w i t h four significant figures. Since the mass o f the vapor will contain only four figures (or three, depending on the type o f balance used), this w i l l not noticeably lessen the accuracy of the calculated molar weight.
PROCEDURE
Weigh the clean, dry flask ( w i t h the beaker over its neck) on the analytical balance. Put 3 ml of the u n k n o w n l i q u i d i n t o the flask. Insert the stopper very loosely; it should f i t snugly enough that it w i l l not fall o u t but loosely enough that it can be removed easily and q u i c k l y . Caution! Y o u r u n k n o w n is probably flammable. Do n o t pour it near a flame and do not use more of the u n k n o w n than instructed. If a fire does start, immediately turn o f f y o u r burner and use a t o w e l to smother the flames.
130
Experiment 11
FIGURE 11-1 Flask during heating.
C a u t i o n ! A v o i d inhaling the vapor from y o u r u n k n o w n . Do not stand over the flask while the sample vaporizes. Immerse the flask as completely as possible in a water bath clamping it in place as shown in Figure 1 1-1. Heat the water to boiling, and then lower the burner flame to maintain a gentle b o i l . Y o u w i l l probably be able to see the liquid boil and to see a stream of vapor (and perhaps droplets of l i q u i d ) rush from the flask. A f t e r the water is boiling and after y o u can no longer tell that there is l i q u i d in the flask or that vapor is being emitted from the flask, leave the flask in the bath for at least another five minutes to ensure that all the vapor is at the same temperature. Note that y o u are to leave the flask in the bath for five minutes after both of these conditions exist. Measure the temperature of the bath. N o w remove the flask from the bath. I t will probably be easiest to remove the clamp, still holding the hot flask, from the ring stand. Cool the flask under cool tap water or in a beaker of cool water; be sure that no water enters the flask t h r o u g h the glass tubing in the stopper. Remove the clamp when the tlask is cool enough that y o u can handle it easily. Dry the outside of the flask. If water has splashed i n t o the lip of the flask, absorb it w i t h a tissue. Remove the stopper and immediately replace it w i t h an inverted 50-ml beaker, so that the b o t t o m of the beaker rests against the lip of the flask, as shown in Figure 1 1-2. A l l o w the flask to continue to cool u n t i l it is at room temperature (at least five minutes, but probably not more than ten minutes). Weigh the cooled flask and the beaker on the analytical balance. A d d another 2 ml of y o u r u n k n o w n to the flask and repeat the experiment. It is not necessary to remove the remainder of the first sample of the l i q u i d ; no matter how much liquid is present originally, vaporization w i l l occur until only enough vapor remains to exert a pressure that is equal to atmospheric pressure. Carry o u t a t h i r d determination.
131
Mol?r Weight by Vapor Density
F I G U R E 11-2
Flask during cooling.
After you have completed three determinations of the mass of vapor in the flask, measure the volume of this vapor. Pour the remaining liquid out of the flask ( i n t o the appropriate waste container, not down the drain). Dry the flask and weigh it on the triple-beam balance. Then fill the flask w i t h water and insert the stopper loosely in the flask to push out a little water. The volume of water remaining in the flask w i l l equal the volume occupied by the vapor when the stopper was in place. Remove the stopper, dry the outside of the flask, and weigh the water-filled flask. Then pour out the water and fill and weigh the flask again. As usual, use an average o f y o u r results. Read the laboratory barometer to determine the atmospheric pressure.
Calculate the molar weight of y o u r u n k n o w n l i q u i d . Use Equation (1 1-4), inserting your measured values of volume, mass, temperature, and the atmospheric pressure. Report the average of the three trials. Briefly describe any difficulties y o u encountered while performing the experiment that might affect this result. List what y o u t h i n k your main sources of error were and how they affected y o u r results. Determine the empirical formula of y o u r u n k n o w n from the elemental analysis provided by y o u r instructor. Then use this formula in c o m b i n a t i o n w i t h y o u r calculated value for the molar weight of y o u r u n k n o w n to determine the molecular formula and the true molar weight of your u n k n o w n c o m p o u n d . Use the l i q u i d density of y o u r u n k n o w n (given to y o u in g / m l ) and its true molar weight to calculate an approximate value for the van der Waals constant /; in liters/mole. N e x t , consider Equation (1 1-5), the van der Waals equation for real gases. Y o u have a numerical value for each variable in this equation. Y o u have just calculated a value for the constant Y o u can now calculate a value for the constant a for y o u r u n k n o w n . Y o u can rearrange the equation to solve for a, or y o u can insert y o u r numerical values in the equation and then complete the arithmetic to obtain a value for a. The latter procedure w i l l probably be easier. Use y o u r experimental measurements of volume, temperature, and atmospheric pressure. The number of moles of
132
Experiment 11
gas should be based on an a.erage of the measured weights of y o u r gas and the true molar weight of your gas. As y o u w o r k through this problem, retain and pay close attention to all units.
QUESTIONS
1.
2.
3.
4.
In this experiment, there are many avoidable sources of error. Explain how the calculated molar weight of y o u r u n k n o w n compound w o u l d compare to its true molar weight as a result of each of the f o l l o w i n g errors: (a) The tlask is not completely submerged in the boiling water bath. ( b ) The flask is removed from the bath before all the vapor is at the boiling point of water. (c) Vapor is still being e m i t t e d from the flask when it is removed from the bath (d) The temperature of the vapor is still well above room temperature when the flask and the vapor are weighed. (e) The flask is open to the atmosphere for several minutes, w i t h neither the stopper nor the inverted beaker in place. (f) Several air bubbles are trapped in the tlask when y o u fill it w i t h water to determine the volume of the flask. The most i m p o r t a n t unavoidable source of error in this experiment is the nonideality of the vapor, especially the existence of intermolecular attractive forces. Will this nonideality make the calculated molar weight of y o u r u n k n o w r compound higher or lower than its true molar weight? Explain y o u r answer. Consider y o u r answers to Questions 1 and 2 and other possible sources of error in this experiment. Does it seem more likely that your calculated molar weight w i l l be higher or lower than the true value? Does the direction in which y o u r calculated molar weight is in error agree w i t h your answer to this question? If it does not, try to account for the difference. What does a large value for the van der Waals constant a tell y o u about a substance? What w o u l d a value of zero for this constant mean?
REFERENCE
Yoder, C.H., Suydam, F . H . , and Suavely, F . A . Chemistry. New Y o r k : Harcourt Brace Jovanovich, Inc., 1975. Chapter 10.
Experiment 12 Molecular Interactions in Solution

Introduction
There are several kinds of solutions: solidsolid, s o l i d - l i q u i d , liquidliquid, gasliquid, and gasgas. In first-year chemistry, y o u w i l l work mostly w i t h solutions of solids and liquids. This experiment, however, is concerned w i t h how the properties of l i q u i d - l i q u i d solutions are reflected by their vapor pressures. The properties of two-component solutions are related to the properties of the solvent, the component that is present in greater amount. In fact, for solutions in l i q u i d solvents, several properties (vapor pressure, freezing point, boiling p o i n t , and osmotic pressure) depend only on the relative numbers of molecules of each component. H o w the presence of a solute affects the vapor pressure of the solvent depends on the interactions that occur in the solution. First, consider the simplest solution of t w o l i q u i d components A and B. In this case, the interactions between A molecules and B molecules in the solution are no different f r o m the interactions between A molecules in component A's pure state and between B molecules in component B's pure state. A n o t h e r way of t h i n k i n g about this is to realize that the potential energy of an A molecule or a B molecule in the solution is the same as the potential energy of the molecule in the liquid's pure state. Because the energy state of each molecule is the same in s o l u t i o n and in the pure l i q u i d , no energy in the form of heat must be given out or absorbed when A and B are m i x e d . F o r this s o l u t i o n , the enthalpy change A / / i is zero. A solution for which A / / | = 0 is called an ideal solution.
s o u t i o n S O u t i o n
N o w consider the vapor pressure of such a s o l u t i o n . Y o u should remember from Experiment 10 that the vapor pressure of a l i q u i d reflects the tendency of molecules to escape from the surface of a l i q u i d into the vapor phase. As long as there are no differences between A - A and A - B interactions in solution (that is, as long as the solution is ideal), the only factor affecting the escape tendency of A molecules in solution w i l l be the fact that there are fewer o f them per unit o f surface area, since some space is occupied by B molecules (see Figure 12-1). Statistically, there are fewer chances per second for an A molecule to leave the surface of the s o l u t i o n . Obviously, the o p p o r t u n i t y for vaporization of A in solution is related to the fraction of the molecules that are A. This behavior is formulated mathematically as Raoult's Law:
PA=PAXA
The law states that the vapor pressure due to A in solution is the vapor pressure of pure A ( / 7 ) m u l t i p l i e d by the mole fraction o f A . As long as B is volatile (as long as B has an appreciable vapor pressure), the same argument can be made for B:
A
1>U=PB X =p {\ ~X,0
a B
(12-2)
135
136
Experiment 12
The second equality follows f r o m the fact that the sum of the mole fractions of all (here, onl> t w o ) components of the solution must be 1. The total vapor pressure above the s o l u t i o n is simply the sum of the individual vapor pressures of the components of the solution (Dalton's L a w ) :
Ptotal = PA PB= PA *A + PB (1 " * A )
+
(12-3)
A p l o t of the t o t a l vapor pressure and the partial pressures of A and B as a function of the composition of the solution is shown in Figure 12-2. It is obvious that a simple c r i t e r i o n can be used to determine whether liquids form an ideal solution. Solutions of various compositions can be prepared and their vapor pressures measured. I f the solutions are ideal, a plot o f P i vs. c o m p o s i t i o n w i l l be a straight line, as in Figure 12-2. Y o u can readily imagine one factor on a molecular level that tends to produce interactions in solution that are similar to interactions in pure components: a similarity in the shape and the p o l a r i t y of component molecules.
tot:i
137
Molecular Interactions in Solution
Ideal solutions that obey Raoult's Law are a particularly simple case. A d d i t i o n a l complications leading to deviations from Raoult's Law can occur when the molecular interactions in a solution are different f r o m those in a pure l i q u i d . Suppose, for example, that two liquids C and D are m i x e d and that D molecules attract C molecules more strongly than C molecules attract one another. This k i n d of interaction is called solvation. Such a solution w o u l d have the structure represented in Figure 12-3. The additional attraction that C and D molecules have for one another means that they are in a more stable c o n d i t i o n (they have lower energy) in solution than in their pure states. Consequently, energy in the form o f heat w i l l be given out during thedissolving process, or A / / < 0. This solvation can result when C and D are polar molecules of suitable shape and dipole m o m e n t to be attracted toward one another.
s u k l t j o n
In a solution displaying solvation effects, the vapor pressure of C is influenced not only by the statistical factors present in ideal solutions but also by the fact that solvation by D molecules keeps C molecules from escaping i n t o the vapor phase. A similar argument can be made for the vapor pressure of D. Figure 12-4 shows the vapor pressure curve for a two-component solution as a function of c o m p o s i t i o n
138
Experiment 1 2
when solvation is i m p o r t a n t . The dotted lines indicate what the vapor pressures w o u l d be if" the solution were ideal. The real solution shows negative deviation from Raoult's L a w ; that is, the vapor pressures are lower than they are for an ideal s o l u t i o n . Notice that very dilute solutions (X 0.0 or = 1.0) obey Raoult's Law fairly closely. The final possible solution behavior is that molecules of each of the t w o components w i l l have stronger attractions for their own kind o f molecule than for a different k i n d of molecule. In this case, the solution structure (shown in Figure 1 2-5) w o u l d consist of regions of like molecules. The vapor pressures of the components w o u l d be enhanced in comparison to the pure l i q u i d , because each k i n d of molecule w o u l d tend to "squeeze out'" the other type of molecule from the solution in order to interact w i t h its own type. Figure 12-6 is a plot of vapor pressure vs. composition for a solution displaying interactions of this type, k n o w n as association. Again, the dotted lines show the expected behavior if the solution were ideal. Dilute solutions behave approximately according to Raoult's Law. More
c
139
Molecular Interactions in Solution
concentrated solutions show positive deviations; that is, their vapor pressures are higher than Raoult's Law w o u l d predict. A solution e x h i b i t i n g association w i l l be in a higher energy state than its pure components, so heat energy will be absorbed when the components are m i x e d . I n this case, AH> 0. Y o u should be able to determine whether a solution exhibits ideal behavior, solvation, or association by preparing solutions of" several different compositions, measuring their vapor pressures, and constructing plots o f p vs. mole fraction. Of course, y o u can use the procedure given here to measure only the total vapor pressure of the solution and not the individual pressure of each component. A f t e r obtaining these results, y o u will be asked to account for the observed solution behavior on the bases of molecular shapes and p o l a r i t y . Y o u or y o u r instructor should select one of the pairs of liquids listed below for investigation:
v a p o r
acetone-hexane acetoneethanol acetone-isopropylamine acetone-propionic acid ethanol-isopropylamine hexane-heptane
buret clamp 125-ml filter flask manometer
serum cap syringe thermometer T y g o n tubing
CHEMICALS NEEDED
Liquids from the list above.
PROCEDURE
Prepare nine different solutions: 9 ml of one l i q u i d and 1 ml of the other, 8 ml of one and 2 ml of the other, and so on. The volumes should be measured to 0 . 0 2 ml w i t h a buret (see I n t r o d u c t i o n , page 25). Y o u need not measure exactly 9.00 m l ; just be sure to record the volume y o u actually take. M i x each solution t h o r o u g h l y . Measure the vapor pressure of each solution and the vapor pressure of each pure component l i q u i d , using the technique o u t l i n e d in Experiment 10. For some solutions, the vapor pressure will be so great that i t w i l l be necessary to partially evacuate the flask before the measurement can be made. Consult y o u r instructor before y o u do this. Use only 1 ml of solution for each measurement. Be sure that
140
Experiment 12
the flask is dried thoroughly between each t r i a l . Waste liquids should be poured i n t o the proper waste container; they should not be poured into the sink. Y o u may w o r k in pairs; each student should make half of the measurements.
DATA AND R E S U L T S
Obtain the density of each l i q u i d from the Handbook of Chemistry and Physics. Use the volumes measured for each l i q u i d to compute the number of moles of each l i q u i d and the mole fraction of the l i q u i d y o u designate as A for each solution. Calculate the vapor pressure of each s o l u t i o n , as y o u did in Experiment 10. Plot vapor pressure for each s o l u t i o n , vs. mole fraction of A on 8r X 1 1 in. graph paper. Draw the best possible smooth curve through your data points.
QUESTIONS
1. Explain why the mole fraction of acetone in a solution of 9.00 ml of acetone and 1.00 ml of c h l o r o f o r m is different from the mole fraction of acetone in a solution of 9.00 ml of acetone and 1.00 ml of carbon disulfide. 2. H o w w o u l d the plot that y o u prepared have differed if you had graphed P | vs. X instead of P otai vs. /V ? 3. The instructions in Experiment 10 tell y o u to inject about 1 ml of liquid i n t o the flask for each vapor pressure measurement. Why is it important for y o u to use only a small volume of the solution instead of the entire 10 ml of solution that you prepared'.'
t o t a B t A
REFERENCE
Yoder, C . H . , Suydam, F . H . , and Suavely. F.A. Chemistry. New Y o r k : Harcourt Brace Jovanovich, Inc., 1975. Chapter I 1.
Vapor pressure measurements:

After Solution Pure A 1 2 j> 4 5 6 7 8 9 Pure B
*A partial evacuation should be performed only if necessary and only w i t h your instructor's approval. If a partial evacuation is not necessary, leave these data columns blank.
evacuation * Open arm
A fter Flask arm
injection Open arm

"vapor
Flask arm
Results: A t t a c h y o u r plot of .P otai - %A - D your solutions obey Raoult's Law or do they show positive or negative deviation from Raoidt's Law? Do the solutions behave ideally or does solvation or association occur? Draw electron d o t structures for the component molecules. Discuss the predominant type of intermolecular interactions in the system you studied. Suggest how molecular shape, dipole moments, and other characteristics might be related to the vapor pressure behavior y o u observed.
v s t
(Answer the above questions and the questions from page paper and attach it to the Report Slicet.)
140 on a separate sheet of
Experiment 13 Freezing Point Lowering

Introduction
In this experiment, y o u w i l l study the nature o f solutions by making use o f one of their colligative propertiesfreezing point lowering. Y o u have already been briefly exposed to this phenomenon in Experiment 2. There y o u observed that a m i x t u r e of comparable amounts of t w o solids has a melting p o i n t lower than the melting point of either pure solid. Since melting and freezing points are really the same phenomenon considered from opposite directions, y o u already dealt w i t h freezing point lowering when y o u took a m i x t u r e melting p o i n t . The subject of this experiment is also related to Experiment 12, except that one of the t w o solution components here is a solid and has a negligible vapor pressure. The / ^ v a p o r o f the solution is determined by the properties o f the solvent, which is more volatile than the solute. The reason for the lowering of the freezing point of a solvent by the addition of a nonvolatile solute is discernible from Figure 13-1. The solid curves represent vapor pressure vs. temperature plots for b o t h the pure solid (frozen) solvent and the pure l i q u i d solvent. At point A, the curves for the solid and the liquid intersect; that is, b o t h the solid and the l i q u i d have the same vapor pressure at point A This means that any l i q u i d which vaporizes at this temperature and pressure could just as likely recondense as a solid, and viee versa. This is just another way of.saying that solid, l i q u i d , and vapor are in e q u i l i b r i u m at p o i n t A The temperature at p o i n t / I is the freezing temperature of the pure solvent in the presence of air. N o w consider the dashed curve in Figure 13-1, which represents the vapor pressure of a solution of given composition made by dissolving some nonvolatile solute in the solvent. The vapor pressure of this solution is always lower than the
143
144
E x p e r i m e n t 13
vapor pressure of the pure solvent. The situation is related to the case of solvation discussed in Experiment 1 2. w i t h the qualification that the solid component has a negligible vapor pressure. This means that the point of intersection of the dashed curve w i t h the vapor pressure curve o f the solid solvent will occur at a lower temperature than before and therefore that the solid, solution, and vapor w i l l be in e q u i l i b r i u m at a lower temperature (see p o i n t B in Figure 13-1). This temperature is what we call the freezing point of the s o l u t i o n . When the temperature of the solution is lowered to r , the solution will be in equilibrium w i t h the pure solid solvent; crystals o f solvent will appear. As the solvent begins to crystallize, the composition o f the solution will change becoming more concentrated in the solute. O f course, this w i l l change the position o f the solution vapor pressure curve and w i l l necessitate further cooling to cause more freezing. For our purposes, this complication can be ignored by defining the freezing point of the solution as the temperature at which the first crystals of solvent appear. The lowering of the freezing point of any solvent by a solute in moderately dilute solutions depends on t w o factors, as shown in Equation (13-1):
s
At =t -t = K m
f p s f
(13-1)
fhe t w o factors are the identity of the solvent (through the value of Kf) and the concentration of solute particles (as measured by the m o l a l i t y m). Table 13-1 lists the freezing points and the molal freezing point constants Kf for four c o m m o n solvents. By c o m b i n i n g the i n f o r m a t i o n in Table 13-1 and Equation (13-1), y o u can see that dissolving a solute which supplies a mole o f particles in a kg o f water w i l l result in a freezing point of - 1.86 for the s o l u t i o n , compared to 0 C for pure water. Freezing point lowering data can be used to find the molecular weight of a dissolved solid. From Equation ( 13-1), you can see that once a particular solvent is chosen, K is fixed and the freezing point lowering Atf depends only on the m o l a l i t y of the solution. By measuring the Atf, y o u can easily evaluate the m o l a l i t y of the solution: in = Atf/Kf. Using weighed quantities of an u n k n o w n solute and of the solvent benzene ( C ' I I ) , y o u can set up and solve an expression for the m o l a l i t y of the solution, having the molecular weight of the solute as the u n k n o w n . The solvent benzene can be measured w i t h a buret and the volume can be converted to weight by k n o w i n g that the density is 0.874 g / m l .
f 6
T A B L E 13-1
-\
Solvent Acetic acid Benzene Naphthalene Water
Freezing Point . CO 16.6 5.5 so.: 0.0
Kf ' ( C kg/mole) 3.90 5.12 6.80 1.86
145
Freezing Point Lowering
800-ml beaker clock w i t h second hand freezing p o i n t apparatus graph paper thermometer ( f r o m y o u r desk) thermometer w i t h 0.1 graduations ( f r o m s t o c k r o o m )
CHEMICALS NEEDED
benzene (reagent grade) ice u n k n o w n solids
TECHNIQUE
Freezing points can be measured using the apparatus shown in Figure 13-2. The 800-ml beaker contains an ice-water m i x t u r e for cooling the solution and a stirrer. It is covered w i t h a metal or an asbestos l i d , through w h i c h a test tube is inserted. The test tube contains another tube, w h i c h , in t u r n , contains the solution whose freezing point is to be determined. An air jacket between the tubes permits slow and u n i f o r m
146
Experiment 13
cooling in the inner tube. The inner tube is equipped w i t h a stirrer; the solution should be continually stirred d u r i n g the cooling. Stirring should be gentle to avoid disturbing'the thermometer or breaking the b o t t o m ot" the tube. A thermometer that is graduated to 0 . 1 C w i l l be provided to measure the temperature o f the solution as it is cooled.
PROCEDURE
Obtain a freezing point apparatus and a thermometer (graduated to 0 . 1 C ) from the s t o c k r o o m . Also obtain some ice, and prepare an ice and water bath in the 800-ml beaker. T h r o u g h o u t the experiment, this bath must always contain several pieces of ice to keep the temperature as close to 0 C as possible. Put the large stirrer, the l i d , and the outer test tube in place. Place y o u r own thermometer {not the special thermometer from the s t o c k r o o m ) in the bath to determine its temperature.
A. Determining the Freezing Point of Benzene
F r o m a buret, measure about 20 ml of benzene i n t o the clean, dry inner test tube. Y o u do not have to take exactly 20 m l ; just be sure to record to the nearest 0.02 ml the volume that y o u actually take. Place this inner tube inside the test tube in the freezing point apparatus; stopper it w i t h the cork fitted w i t h a stirrer and the thermometer graduated to 0 . 1 . Be sure that the thermometer bulb extends i n t o the liquid. Record the temperature of the benzene every 20 seconds. ( Y o u can estimate the temperature to the nearest 0 . 0 5 C . ) Tap the thermometer l i g h t l y w i t h y o u r finger before you take each reading to ensure that the mercury in the thermometer does not stick to the walls. It is possible that the mercury column may separate; examine the mercury very closely before y o u begin to use the thermometer and again after y o u conduct each part of the experiment to see if this has happened. If the mercury does separate, ask y o u r i n s t r u c t o r for advice or assistance; y o u cannot make accurate temperature readings when the thermometer is in this c o n d i t i o n . The benzene may supercool; that is, it may drop to a temperature below its freezing point before it starts t o freeze. I f this happens, the temperature w i l l rise to the freezing point t as freezing occurs because of the release of the heat of fusion. For this reason, you should keep recording the temperature u n t i l it remains the same for at least four successive readings as the l i q u i d is converted i n t o crystals. To determine t , the freezing p o i n t of pure benzene, plot the temperature vs. time. Take the horizontal part of the curve, corresponding to a constant temperature, as the freezing p o i n t . Y o u r plot should look like the one in Figure 13-3.
p p
Remove the tube containing the benzene from the apparatus and melt the benzene by warming the tube in y o u r hand. Then repeat the determination of the freezing point in the same manner that y o u conducted the first t r i a l . The t w o trials should agree w i t h i n 0 . 1 . If they do not, determine the value a t h i r d time and use the average of the three trials as t . If y o u compare y o u r results w i t h those of other students, y o u may find that y o u r values for the freezing p o i n t of pure benzene differ by a degree or more. Do not let this upset y o u . The thermometer that y o u are using
p
147
Freezing Point Lowering
FIGURE 13-3 Cooling curve of a pure l i q u i d .
may not be perfectly accurate. However, since you are concerned in this experiment w i t h the difference between t w o temperatures-the temperature of a pure l i q u i d and the temperature of a solution in which the l i q u i d is solventboth of y o u r measurements w i l l contain the same error and you can accurately determine a difference despite this error. Y o u should recognize that, because of this possible inaccuracy in your thermometer, it is extremely i m p o r t a n t that y o u use the same thermometer to take measurements for benzene and for the s o l u t i o n .
B. Molecular Weight of an U n k n o w n Solid
Obtain an u n k n o w n solid from y o u r instructor. The molecular weight w i l l be roughly between 100 and 200. On the analytical balance, weigh a 0.8-g sample of the u n k n o w n ; record the weight y o u actually use. A d d the u n k n o w n to the benzene in the sample tube. Be sure that all of the solid dissolves. N o w measure the freezing point of the solution t , as y o u d i d for pure benzene A plot o f temperature vs. time for the solution will look somewhat different from y o u r plot for benzene. In Figure 13-4, y o u can see that the solution temperature
s
148
Experiment 13
continues to fall as crystallization occurs, because o f the changing solution concentration as the solvent crystallizes. The rate of this decline is slower than the temperature drop was before the solvent began to freeze; the freezing point t can be located at the break in the curve. Y o u may find it easier to locate the freezing point of the solution as y o u warm it and watch the crystals of the solvent disappear. Begin by placing the solution in the freezing point apparatus (in the ice bath) and stir it u n t i l nearly all the solution has frozen. Remove the outer tube and the inner tube from the apparatus, but keep the inner tube inside the outer tube. The air jacket will permit slow and uniform warming of the inner tube. If you held the inner tube in y o u r hand to warm i t , some spots w o u l d probably be warmed more than other spots and the temperature w o u l d not be u n i f o r m . A l l o w the solution to warm up as y o u stir it gently. Determine the temperature at w h i c h the last solvent crystals just disappear. This is the freezing point of the s o l u t i o n . Repeat this freeze-thaw cycle u n t i l y o u are satisfied that y o u have a reproducible figure for the freezing p o i n t . Then discard the benzene solution into the designated waste container; do not pour the solution down the drain.
s
Use the volume of the benzene that y o u took and its density to calculate the weight of benzene. Set up an expression for calculating m in terms of the weights of solvent and solute and the molecular weight of the u n k n o w n . Equate this expression for m to the value of m that y o u found from the freezing point lowering. Solve the equation to determine a numerical value for the molecular weight of the u n k n o w n solute.
QUESTION
H o w w o u l d the molecular weight of the u n k n o w n solute that y o u calculated be affected by each of the f o l l o w i n g blunders? (a) Some benzene is accidently spilled before the u n k n o w n solid is added. (b) Some of the solution is spilled. (c) N o t all of the solid is dissolved in the benzene.
REFERENCE
Yoder, C . H . , Suydam, F . H . , and Snavely, F . A . Chemistry. New Y o r k ; Harcourt Brace Jovanovich, Inc., 1975. Chapter 1 1.
Experiment 14 Chemical Kinetics: Oxidation of Ethanol by Chromium(VI)

Introduction
Chemical kinetics is the study of the rates of chemical reactions and of the mechanisms by which they occur. The rate of a reaction is affected by (1) what the reactants are, (2) the temperature at which the reaction occurs, and (3) the concentrations of the reactants. The rate of a particular reaction at a constant temperature w i l l depend only on reactant concentrations. For a general reaction aA + bB cC + d D
this dependence can be expressed mathematically by a rate law of the form rate = k[A\
m
[B]
The exponents m and n are usually the integers 0, 1,2, or possibly 3; these exponents may occasionally be fractions or negative numbers. The sum (m + n) is k n o w n as the overall reaction order. The A: is a constant called the rate constant; its value is characteristic of a particular reaction at a particular temperature. The reaction y o u w i l l study in this experiment is the o x i d a t i o n of ethanol or e t h y l alcohol ( C H C H O H , o r C H 0 ) t o acetic acid ( C H C 0 H , o r C H 0 ) . The oxidizing agent is prepared by dissolving potassium dichromate ( K C r 0 ) in hydrochloric acid; d u r i n g this dissolution, the acid and the dichromate ion react to form C r 0 C l ~ :
3 2 2 6 3 2 2 4 2 2 2 7 3
C r 0 " + 2 H 0 + 2CF
2 + 2 7 3
2Cr0 CF + 3 H 0
3 2 3
(14-1)
As the alcohol is oxidized to acetic acid, the c h r o m i u m atom in C r 0 C l ~ i s reduced from C r ( V I ) to the ion C r :
3 +
12H CT + 3 C H 0 + 4 C r 0 C F
3 2 6 3
3C H 0 + 4Cr
2 4 2
J +
+ 4CF + 21 H 0
2
(14-2)
To emphasize the i m p o r t a n t feature of the o x i d i z i n g a g e n t - t h e fact that it contains a c h r o m i u m atom that is reduced from the o x i d a t i o n state + V I to the o x i d a t i o n state + I I I i t w i l l be referred to in the following discussion as simply C r ( V I ) . The rate law for Equation (14-2) might be expected to have the form rate = / t [ H 0 1 [ C H 0 ] [ C r ( V I ) ]
+ x v 3 2 6 2
(14-3)
However, if the concentrations of hydrochloric acid and of alcohol are far greater than the concentration o f C r ( V I ) , they w i l l undergo only a slight relative change
151
152
Experiment 14
during the reaction. When these t w o reactant concentrations remain nearly constant, the rate law reduces to rate = i f c ' [ C r ( V I ) ]
+ x v z
(14-4)
where k' = k[H 0 ] [ C H 0 ] - . This means that if the concentrations of acid and alcohol are relatively constant, it is possible to determine the effect that a change in the concentration of C r ( V I ) has on the rate of the reaction w i t h o u t being concerned w i t h the simultaneous effects of changes in the concentrations of all three reactants. The rate of a chemical reaction can be measured in either of t w o general ways: (1) by observing the rate of appearance of the products, or (2) by observing the rate of disappearance of the reactants. In this experiment, one could determine how rapidly C r or acetic acid is produced, or one could determine how rapidly alcohol or C r ( V I ) is consumed. Since a fairly convenient way of determining [ C r ( V I ) ] exists, y o u w i l l use the latter method to f o l l o w the reaction in this experiment. The rate law states that the rate of a reaction depends on the concentrations of the reactants, each raised to some power. Of course this means that the reaction rate w i l l be constantly changing as the reaction progresses, because the reactant concentrations keep changing as the reactants are consumed. If the concentration of C r ( V I ) is measured at t w o different times after the reaction begins, the average rate of reaction over the time interval can easily be calculated. For example:
3 2 6 3 +
At r, = 24 sec, [ C r ( V I ) ] = 0 . 0 0 5 4 5 M At t = 35 sec, [ C r ( V I ) ] = 0.00500A/

2
rate
= ~
At
' = - ( [Cr(VI)] , - [Cr(VI)] \ t -t

f 2 {
\ )
_ - ( 5 . 0 0 X 1 0 " - 5.45 X 1 0 " ) M _ 0.45 X 10" A/

3 3 3
(35 - 24) sec = 4.4 X 10" /v//sec

5
11 sec
The rate calculation above gives an average rate over the time interval At = t ~ t,. In reality, there is a different rate for every instant of time, since the rate of disappearance of C r ( V I ) changes continuously as this reactant is consumed. The instantaneous rate can be found by making At smaller and smaller. The rate at any instant t is defined as
2
v
r a t e = :
lim
Ar-*0
-A[Cr(,VI)l -rf[Cr(VI)]
=
5 )
At
dt
where the times 1 and t are taken as an arbitrarily small interval on either side of t. This l i m i t as At -> 0 is the derivative of concentration w i t h respect to timea f o r m that may be familiar to y o u from calculus. However, y o u w i l l not need to use calculus here. In this experiment, y o u w i l l be asked to determine values for z, the reaction order w i t h respect to C r ( V I ) , and for k , the rate constant in Equation (14-4). To do
1 2 1
153
Chemical Kinetics: Oxidation of Ethanol by Chromium ( V I )
this, y o n w i l l measure the concentration o f C r ( V l ) that has not reacted w i t h the alcohol at /arious time intervals and then determine z and k' graphically. To determine the rate of the reaction at various times, a graph is prepared p l o t t i n g [ C r ( V I ) ] (on the y axis) as a function of time (on the x axis). This plot w i l l be a curve showing how [ C r ( V I ) ] decreases as time passes. The average rate over any time interval can easily be determined from the graph by p i c k i n g t w o points on the curve and dividing the change in ( C r ( V I ) ] by the change in time, as described above. The rate at a particular instant t is not as easy to determine. The instantaneous rate is lim - A [ C r ( V I ) ] -o " A/
st
This l i m i t is equal to the slope of a straight line that is tangent to the curve at the point (t, [ C r ( V I ) ] ) . Thus, to determine the reaction rate at various times, y o u must draw tangents to the curve at various points, as shown in Figure 14-1. The slope of the tangent describes the instantaneous rate of change of [ C r ( V I ) ] ; this is a negative q u a n t i t y , since ( C r ( V I ) ) decreases as the reaction progresses. The reaction rate, expressed as a positive q u a n t i t y , is equal to this slope m u l t i p l i e d by - 1 . At t\, for example, when [ C r ( V I ) ] = c , the reaction rate is equal to -1 times the slope of tangent A. At t , when [ C r ( V I ) ] = c , the reaction rate is equal to -1 times the slope of tangent B. Note that the slope of tangent B is less than the slope of tangent A, showing that the reaction rate is lower for a lower [ C r ( V I ) ] .
{ 2 2
After determining the reaction rate at several points on the curve, y o u are to determine the order of the reaction w i t h respect to [ C r ( V l ) ] . First, suppose that z = 0. Then rate = / c ' [ C r ( V I ) ] = k'
0
(14-6)
This equation states that the rate of the reaction is constant; the reaction rate does not change as [ C r ( V I ) ] changes. If the rate at which the reaction occurs does not depend on the concentration o f this particular reactant, the rate w i l l be the same at every [ C r ( V I ) ] ; all the tangents w o u l d have the same value, and the graph o f
154
Experiment 14
[Cr(VT)] vs. t w o u l d be a straight line. However, for the reaction y o u are investigating in this experiment, the order is not zero; y o u w i l l find that the reaction rate does depend o n [ C r ( V l ) ] . Suppose the reaction is first order w i t h respect to [ C r ( V I ) ] ; that is rate = fc'[Cr(VI)] (14-7)
According to this equation, the reaction rate is directly p r o p o r t i o n a l to [ C r ( V I ) | . When this is the case, a graph of rate vs. [ C r ( V I ) ] is a straight line w i t h a slope equal to k'. N o w suppose that the reaction is second order; that is rate = A ' [ C r ( V I ) |
2
(14-8)
2
Here, the reaction rate is directly proportional to [ C r ( V I ) J , and a graph of rate vs. [ C r ( V I ) ] is a straight line w i t h a slope equal to k'. To determine the order of the reaction w i t h respect to [ C r ( V I ) ] , y o u must prepare the graphs described here: rate vs. [ C r ( V I ) ] and rate vs. [ C r ( V I ) ] . Once you decide w h i c h graph is linear, y o u w i l l k n o w the reaction order. Then use the linear plot to determine the value of k'.
2 2
TECHNIQUE
First, a solution is prepared containing C r ( V I ) by dissolving potassium dichromate in h y d r o c h l o r i c acid. To a p o r t i o n of this solution, ethanol is added at time t = 0. The redox reaction'. Equation (14-2), then begins to occur. At various time intervals, the concentration of C r ( V I ) remaining unreacted in solution will be determined. This is done by w i t h d r a w i n g an accurately measured volume of the reaction m i x t u r e and adding it to some potassium iodide solution. The potassium iodide immediately reacts w i t h all the remaining C r ( V I ) : 2Cr0 Cl"+6I"+12H 0
3 3 +
3I
+ 2 C r + 1 8 H 0 + 2CI"
J + 2
(14-9]
(orange)
(brown)
(green)
3 +
The fairly intense iodine color w i l l mask the pale green color o f C r . The addition of a starch solution to this m i x t u r e causes an even more intensely colored starchiodine complex to f o r m . Sodium thiosulfate is used to reduce the iodine back to colorless iodide: ' L + 2S 0 "
2 2 3
>2r+S 0
4
2 6
31
(14-10)
When all the iodine is reduced, the pale green color o f Cr " w i l l be apparent. F r o m the amount of sodium thiosulfate required for the reaction of Equation (14-10), it is possible to calculate the a m o u n t of iodine present in the solution. This iodine is formed by the reaction to Equation (14-9); consequently, it is possible to calculate the amount of C r ( V I ) that was still present in the solution and that reacted w i t h iodide to form this iodine.
155
Chemical Kinetics: Oxidation of Ethanol by Chromium (VI)
Before y o u use the sodium thiosulfate solution as described above, y o u must determine its concentration. It is d i f f i c u l t to prepare a solution of k n o w n concentration of this salt, because it exists as a hydrate in which the amount of water may vary. Also, the thiosulfate ion slowly decomposes in solution so that its concentration gradually decreases. Consequently, the only way to be sure of its concentration is to measure it shortly before y o u use the solution. To do this, y o u w i l l add sodium thiosulfate to a p o r t i o n o f y o u r C r ( V l ) solution that has been treated in the same way as the solution y o u w i l l use for the kinetics experiment, except that no alcohol has been added. Y o u k n o w the concentration of C r ( V I ) in this solution. Y o u w i l l add potassium iodide solution to i t , so that all of the C r ( V I ) reacts as shown in Equation (14-9). The iodine that forms is titrated w i t h the sodium thiosulfate solution to the pale green end p o i n t , Equation (14-10). This determ i n a t i o n also gives y o u the o p p o r t u n i t y to practice titrations for the kinetics experiment. Remember that when y o u begin the kinetics experiment, each t i t r a t i o n is unique: it measures [ C r ( V I ) ] at a specific time. T h a t time cannot be recaptured; the t i t r a t i o n cannot be repeated if y o u do it sloppily.
analytical balance burets (2) clock w i t h minute markings and a second hand Erlenmeyer flasks
glass stirring rod 10-ml graduated cylinders (2) 100-ml graduated cylinder 2-ml pipet 250-ml volumetric flask
CHEMICALS NEEDED
ethanol 12/V/HC1 K Cr 0
2 2 7
3% KI solution N a S 0 solution 0.2% starch solution

2 2 3
PROCEDURE
A. Preparation of Cr(VI) Solution
Before y o u begin this experiment, review the procedure for cleaning and using volumetric glassware in the I n t r o d u c t i o n (pages 2 3 - 2 8 ) . Prepare 300 ml of 3.6/W HC1 from concentrated (11.6/V/) HC1. Make the necessary calculations before y o u come to the laboratory. Prepare a 0.0035-0.0040/W solution of potassium dichromate in a 250-ml volumetric flask using y o u r 3.6A/ HC1 as the solvent; any concentration in this range w i l l be satisfactory. (Again, y o u should make the necessary calculations before y o u come to the laboratory.) Weigh the potassium dichromate on the analytical balance for the greatest possible accuracy. Use Equation (14-1) to calculate the concentra-
156
Experiment 14
tion o f C r 0 C l (referred to simply as C r ( V l ) here) that will form in this s o l u t i o n . Rinse and fill one buret w i t h this solution.
3
B. Standardization of N a S 0
: 2
Solution
Rinse and fill a second buret w i t h sodium thiosulfate solution provided by y o u r instructor. Y o u will now determine the concentation o f the sodium thiosulfate s o l u t i o n . F r o m the buret, measure about 10 ml of C r ( V I ) solution into a clean Erlenmeyer flask; record the volume to the nearest 0.02 m l . To this solution add 4 ml of 3% potassium iodide solution; the color of the solution w i l l immediately change from orange to b r o w n as iodide is o x i d i e d to iodine by C r ( V l ) ; see Equation (14-9). T o this m i x t u r e add 2 m l o f starch s o l u t i o n ; a dark brownish-black color w i l l result from the starch-iodine complex that forms. Titrate this solution w i t h sodium thiosulfate solution to a pale green endpoint; the color will gradually change from dark b r o w n to dark blue and then to light blue just before the endpoint. Repeat this procedure u n t i l you have t w o results that agree w i t h i n 2% for the concentration of the sodium thiosulfate solution.
C. Reaction of Ethanol and Cr(VI)
Use a graduated cylinder to measure 1 50 ml of the C r ( V I ) solution into a clean, dry 250-ml Erlenmeyer flask. Be sure to rinse the cylinder w i t h this solution first to remove any distilled water w h i c h w o u l d lower the C r ( V l ) concentration. Use a pipet to add 2.00 ml of ethanol to this C r ( V l ) s o l u t i o n ; then use a glass rod to mix the solution w e l l . Note the exact time (to the nearest second) that this addition is made; it w i l l be "zero t i m e " for the remainder o f the experiment. Drain the buret containing the C r ( V l ) solution. Rinse and fill the buret w i t h the a l c o h o l - C r ( V l ) m i x t u r e . Into a clean Erlenmeyer tlask, measure about 10 ml of this solution to the nearest 0.01 m l . Five to ten minutes after "zero t i m e , " add 4 ml of 3% potassium iodide solution to this p o r t i o n of the alcoholC'r(VI) m i x t u r e ; record the exact time of this a d d i t i o n . A l l of the C r ( V I ) that has not yet reacted w i t h the alcohol w i l l react immediately w i t h iodide, converting it to iodine. A d d 2 m l o f starch solution and titrate the solution w i t h sodium thiosulfate to the pale green endpoint. Repeat this procedure w i t h a fresh 10-ml sample of the a l c o h o l - C r ( V I ) m i x t u r e every five to ten minutes. Make a total of eight to ten titrations spread over a 5070 minute time period. The flask i n t o which y o u put the a l c o h o l - C r ( V T ) mixture should e clean and as dry as possible. If a few drops of distilled water remain, do not allow the solution to stand in the tlask for more than a few seconds before adding the potassium iodide; extra water w i l l dilute the solution and lower the reaction rate.
RESULTS
AND
CALCULATIONS
To determine the sodium thiosulfate concentration, use the volume of C r ( V I ) solution required in a t i t r a t i o n and the m o l a r i t y of the C r ( V I ) solution to calculate the number of moles of C r ( V I ) used in the t i t r a t i o n . Use Equation (14-9) to calcu-
157
Chemical Kinetics: Oxidation of Ethanol by Chromium (VI)
late the number of moles of iodine that formed when potassium iodide reacted w i t h this C r ( V I ) solution. Use Equation (14-10) to calculate the number of moles of S 0 ~ . t h a t w o u l d react w i t h this amount of iodine. T h e n use this calculated number o f moles o f S 0 and y o u r measured volume o f sodium thiosulfate solution to calculate the m o l a r i t y of the sodium thiosulfate solution. Record the average value for y o u r best trials.
2 2 3 2 2 3
f o r the kinetics experiment, use the m o l a r i t y and the volume of the sodium thiosulfate solution to calculate the number of moles of S 0 ~ required for each t i t r a t i o n . Use Equation (14-10) to calculate the number of moles of iodine that reacted w i t h S 0 ~ \ Use this amount of iodine to calculate the number of moles of C r ( V l ) that reacted according to Equation (14-9). Use this number of moles of C r ( V I ) and y o u r measured volume of C r ( V I ) solution to calculate [ C r ( V I ) ] in the solution at each time.
2 2 3 2 2 3
Prepare a graph p l o t t i n g [Cr(VT)] on the y axis vs. time on the x axis. Include a point for t = 0 at w h i c h [ C r ( V l ) ] is the value y o u calculate on the basis of the weight of the potassium dichromate used to prepare the solution. Be sure to spread your graph over as much of the page as possible. Use a sharp pencil to draw a fine line through the points to produce a smooth curve. The [ C r ( V I ) ] changes continuously w i t h t i m e ; therefore, any deviation from a smooth curve w i l l be the result of experimental error. T h e n , using a ruler and sharp pencil, draw tangents to the curve at a m i n i m u m of four points spread about evenly over the total t i m e ; the curve should bend away from a tanget line by an equal amount on each side of the point of tangency. Determine the slope of each tangent. M u l t i p l y the value of each slope by -1 to determine the reaction rate at each point of tangency. N o w , on one graph, plot reaction rate on the y axis vs. [ C r ( V I ) ] on the x axis and also vs. [ C r ( V I ) ] on the x axis. Y o u w i l l need t w o different scales for the t w o quantities plotted on the x axis. Position one across the top of the graph and the other across the b o t t o m of the graph; be sure that each axis is clearly labeled and that each plot is properly identified. In addition to the points for reaction rate that y o u determined experimentally, each plotted line should also include the p o i n t (0,0), since the reaction rate w i l l be zero i f no C r ( V I ) is present to react. Use the plot that is a straight line to determine the order of the reaction w i t h respect to [ C r ( V I ) ] . Use this straight-line plot to determine the value of the rate constant k' in equation (14-4) to t w o significant figures.
2
QUESTIONS
1. If the concentration of alcohol is far greater than the concentration of C r ( V I ) , the alcohol concentration will undergo a very small relative change during the reaction and w i l l not affect the rate at which the reaction occurs. Calculate the molar concentration of alcohol in the alcoholCr(VI) solution to show that it is far greater than the concentration of C r ( V I ) . The density of e t h y l alcohol is 0.789 g / m l . 2. How w i l l the calculated [ C r ( V I ) ] compare to the true [ C r ( V I ) ] for a particular time, if: (a) The a l c o h o l - C r ( V I ) buret is accidentally filled w i t h the original C r ( V I ) solution that did not have alcohol added to it? ( b ) A measured p o r t i o n of the alcoholCr(VI) solution is allowed to stand w i t h
158
Experiment 14
3.
several ml of distilled water for several minutes before the potassium iodide is added? (c) Some of the a l c o h o l - C r ( V I ) solution is spilled during the titration? (d) Four ml rather than 2 ml of starch solution is added? Use your value of the rate constant to calculate the reaction rate when [ C r ( V I ) ] = 0.002CW and when [ C r ( V I ) ] = 0.001 OA/.
REFERENCES
1. Yoder, C . H . , Suydam, F . H . , and Suavely, F . A . Chemistry. New Y o r k : Harcourt Brace Jovanovich, Inc., 1975. Chapter 12. 2. Finlayson, M . E . , and Lee, D . G . Journal of Chemical Education 48, 473 ( 1 9 7 1 ) .
Experiment 15 A Complete Rate Law

Introduction
The rate at which any chemical reaction proceeds depends on several factors. The most obvious factor is what the reacting species are. Other factors are the temperature, the concentrations of the reactants, and whether or not a catalyst is present. In this experiment, y o u will study in some quantitative detail how reactant concentrations influence a reaction rate. Instead of m o n i t o r i n g reaction speed by f o l l o w i n g the concentration of one reactant over time (as y o u d i d in Experiment 14), y o u will use a simpler technique here a measurement o f how long it takes for a particular amount of reaction to be completed. Obviously, the longer the time required for c o m p l e t i o n , the slower the reaction and the smaller the rate. Similarly, y o u w o u l d conclude that a track runner who t o o k 14 seconds to complete the 100-yard dash traveled at a slower rate than a runner who took 10 seconds. Mathematically, the relationship is an inverse one: rate a
1
completion time
(15-1)
The reaction to be studied here has been selected because it can be visually m o n i tored by a color Change. The reaction y o u w i l l investigate i s the o x i d a t i o n o f I " t o I ~ b y H 0 (hydrogen peroxide):
3 2 2
II 0
2
+ 31"+ 2 H 0 - > I
+ 3
" + 41I 0
2
(15-2)
The rate law for this reaction can be w r i t t e n rate = /c 1 H 0 1 [ I " V [H 0 \

x 2 2 3 + z
(15-3)
Y o u r task w i l l be to determine the exponents x, y, and z. In other words, y o u w i l l be asked to find the order of the reaction in H 0 , I " , and H 0 , respectively. An obvious way to begin w o u l d be to vary the [ H 0 ] in several trials, while keeping [ I ~ ] and [ H 0 ] the same, and to measure the relative rates. For example, if the [ I I 0 ] is twice as large in one trial as it is in another and the reaction rate is four times as large (all other concentrations being equal for the t w o trials), then we could conclude that x = 2 (that is, that the rate depends on [ H 0 ] ) . A similar procedure could be used to determine y and z. The rate of the reaction in Equation (15-2) can be measured easily by visual means. Y o u can determine how long it takes for the same [ I ~ ] to be produced under varying sets of concentration conditions. A small concentration of N a S 0 and some starch indicator are added to each t r i a l . I ~ reacts very rapidly w i t h thiosulfate:
+ 2 2 3 2 2 + 3 2 2 2 2 2 3 2 3 3
I
163
" + 2S 0
2
2 3
~^ S 0
4
2 6
' + 31"
(15-4)
164
Experiment 1 5
Thiosulfate converts I back to iodide and prevents any change in [ 1 ~ | as long as it is present. When the small amount o f [ S 0 ~ ] is used up in the reaction. I ~ w i l l no longer be able to react w i t h a n y t h i n g and w i l l begin to accumulate in s o l u t i o n . The I ~ w i l l form a deep blue complex with the starch indicator, and the solution w i l l suddenly change color. Thus, the length of time that it takes for the blue color to appear is a measure of h o w long it takes the reaction in Equation (15-2) to produce enough I ~ t o consume a given concentration o f S 0 ~ . Obviously, this time interval is related to the reaction rate.
_ 3 2 2 3 3 3 2 3 2 3
For this method of f o l l o w i n g the reaction rate to w o r k , the concentrations of the reactants should not change very much during the time interval required for the blue color to appear. If this condition is f u l f i l l e d , the concentrations of all starting reactants w i l l be effectively constant over the measurement time. As pointed out above, this w i l l definitely be true for I " ; [ H 0 ] w i l l also remain the same, because buffer solutions designed to keep a constant [ H 0 | are used. The concentration of S 0 ~ in all solutions w i l l be about .003/V/. As long as a sufficiently large [ H 0 1 is chosen, the a m o u n t that reacts to produce the necessary 1 ~ to consume the S 0 ~ w i l l be negligible compared to the original a m o u n t o f H 0 present in the reaction m i x t u r e .
+ 3 + 3 2 2 3 2 2 3 2 2 3 2 2
EQUIPMENT NEEDED
100-ml and 400-ml beakers 50-ml burets (3) burner 125-ml Erlenmeyer flasks 10-ml and 100-ml graduated cylinders 10-ml pipet pneumatic trough
ring ring stand stirring rods watch w i t h second hand or stopwatch (to be provided by student) wire gauze
CHEMICALS NEEDED
Buffer D: [ H 0 * ] = 1.0 X 10~ .V/ (contains 2 g/liter starch indicator) Buffer E: [ H 0 ] = 2.0 X 10~ A/ (contains 2 g/liter starch indicator) 0.1 OA/ H 0 0.10MKI 0.03A/ N a S 0 ice
S 3 + S 3 2 2 2 2 3
PROCEDURE
Y o u w i l l need to measure out volumes o f the stock solutions o f reactants in such a way that: (1) the [ S 0 ~ ] is the same in every solution, and (2) the concentrations of the other reagents are varied systematically. One simple way of doing this is to m i x reagents in proportions that always yield the same total volume and to add the same volume of sodium thiosulfate solution to each m i x t u r e .
2 2 3
155
A C o m p l e t e Rate L a w
Solution I Na S 0 H 0 Buffer D Buffer E KI

2 2 3 2 2
Volume 11 10 20 45
(ml) IV 10 10
111 10 10 30
V 10 20 20
10 15 50
25
25
50
55 25
50
Each o f the five sample solution volumes suggested in the table above w i l l yield a total final volume of 100 m l . The decomposition of H 0 is catalyzed by many substances; therefore y o u must be sure that all y o u r glassware is completely clean. Use a pipet to measure N a S 0 . Be certain to use a pipet bulb. Measure H 0 , buffers D and E, and KI w i t h a buret. M i x all solutions except KI in the same Erlenmeyer flask. Measure the KI i n t o a separate flask. When y o u are ready to begin your t r i a l , pour the KI solution i n t o the other flask as y o u start t i m i n g . Pour the contents back and f o r t h between the t w o flasks a couple of times to m i x the solut i o n completely. Set the flask on a piece of white paper and stop t i m i n g when the first faint but definitely blue color appears. Record this as the c o m p l e t i o n time. If y o u have enough laboratory time, make t w o trials for each s o l u t i o n .
2 2 2 2 3 2 2
C A L C U L A T I O N S AND
RESULTS
1. Prepare a table showing the concentration of each reactant in each of the five sample solutions. The [ H 0 ] w i l l be the same as the H 0 concentration in buffer D or E, because buffer solutions do not change pH on d i l u t i o n . 2. Record the c o m p l e t i o n times y o u measured and their average for each solution. 3. Recalling the relationship between reaction rate and c o m p l e t i o n time shown in Equation (15-1), determine the dependence of the rate on each reagent. Use average c o m p l e t i o n times in y o u r calculations. Note that sometimes more than one reactant concentration is varied.
+ + 3 3
4.
Write the rate law for the reaction y o u studied.
SUGGESTIONS FOR F U R T H E R W 0 R K
Y o u may also study the influence of temperature on the reaction rate by cooling ( i n an ice bath) or heating (in a water bath) all reactants to the same temperature before the final m i x i n g . Note that varying T changes the rate by changing k in Equation (15-3).
REFERENCE
Yoder, C.H., Suydam, F . H . , and Snavely, F . A . Chemistry. New Y o r k : Harcourt Brace Jovanovich, Inc., 1975. Chapter 12.
I [Na S 0 ] [H 0 ] [H 0 1 [KI] Time (trial 1) Time (trial 2) Time (trial 3) Average time
2 2 3 2 2 + 3
11
III
IV
1.0
10~
1.0
10"
1.0
10^
2.0
10
- 5
1.0
10"
Show sample calculations for determining the dependence of rate on [ H 0 ] ,

2 2
[ H 0 ] , and [ I ] .
+ 3
Rate law:
Experiment 16 Chemical Equilibrium

Introduction
Reactants are not completely converted i n t o products in every chemical reaction. In fact, it is more c o m m o n for a reaction to reach a state such that b o t h reactants and products are present in a reaction m i x t u r e and their concentrations do not change. For example, consider the reaction of nitrogen w i t h oxygen to produce nitric oxide: N (g) + 0 (g)
2 2
>2NO(g)
(16-1)
It is obvious that these t w o gaseous elements do not react extensively in this manner at what we consider normal temperatures, because our atmosphere is primarily a m i x t u r e of nitrogen and oxygen. F r o m a commercial p o i n t of view, it w o u l d often be advantageous if reactions did reach c o m p l e t i o n . A m m o n i a is an i m p o r t a n t industrial chemical and is also used as a fertilizer. A m m o n i a is produced commercially by the reaction of nitrogen and hydrogen: N (g) + 3H (g)
2 2
-2NH (g)
3
(16-2)
At a temperature high enough for a convenient reaction rate and at a pressure of 1000 atm, o n l y 57% of the nitrogen is converted to ammonia. B o t h reactions (16-1) and (16-2) are examples of chemical systems that reach e q u i l i b r i u m . When the reaction appears to " s t o p , " b o t h reactants and products are present; the rate at w h i c h products are forming equals the rate at w h i c h products are being reconverted to reactants, so there is no net change in the amount of reactants or products. The equations for such reactions are often w r i t t e n w i t h t w o arrows to indicate that b o t h the forward and the reverse directions of the reaction can occur. N ( g ) + 0 ( g ) ^ 2NO(g) N (g) + 3H (g) * 2NH (g)
2 2 2 2 3
The relative amounts of reactants and products present at e q u i l i b r i u m can be expressed quantitatively by an e q u i l i b r i u m constant K. This constant states the ratio of product to reactant concentrations, w i t h each concentration raised to a power that is the coefficient from the balanced equation. For reaction (16-1) = [NO' .iQ-40 [N ] [0 ]
2 2 :
(16-3)
For reaction (16-2) () K=

| N H
3 J ~
2
[N ] [ H ]
2
= Q.Q8 at 5 0 0 C
3
(16-4)
169
170
Experiment 16
The value of A" is characteristic of the particular reaction at a particular temperature. For both of these reactions, K < 1. This must mean that the numerator is smaller than the denominator in the concentration ratio. For both reactions, the amount o f products present at e q u i l i b r i u m w i l l be small compared to the amount o f reactants that is still present. For these reactions, the position o f equilibrium is said to lie to the left, meaning that when chemical e q u i l i b r i u m is established, the materials on the left side of the equation (the reactants) predominate in the reaction mixture. For many reactions, however, K > 1. One example is the reaction of hydrogen and chlorine to produce hydrogen chloride: Kt (g) + C I ( g ) * 2HCl(g)
2 2
(16-5)
'mjlkr "
,0
M25 c
- -
(l6 6)
This large value of K shows that when the reaction "stops," nearly all the hydrogen and chlorine has been converted to hydrogen chloride. The position of e q u i l i b r i u m lies far to the right. Changing the conditions o f a chemical system in equilibrium will generally result in a change in the amounts of substances present. The change that occurs can be predicted using Le Chatelier's principle: If a stress is applied to a system in equilibrium, the system will adjust in such a way as to relieve the stress and establish a new equilibrium state. Possible ways of disturbing a system in e q u i l i b r i u m include changing reactant or product concentrations by adding or removing some substance, changing the temperature, and changing the pressure (in reactions involving gases). In this experiment, y o u w i l l work w i t h reversible reactions, studying the extent of reaction and the shifting of equilibria and investigating some of the changes that disturb systems in e q u i l i b r i u m . The differing colors of the reactants and the products that y o u will work w i t h in this experiment w i l l allow y o u to determine whether the position of e q u i l i b r i u m lies to the left or to the right for a particular reaction.
beakers burner 10-ml graduated cylinder medicine droppers ring
ring stand test-tube holder test-tube rack 20-ml test tubes wire gauze
CHEMICALS NEEDED
2M A g N 0 . 0.5A/Co(NO ), 0.5A/Cr(NO ) 0.5M C u ( N 0 )

3 3 3 3 3 2
K Cr0 6M HC1 12M HC1 6/V/HN0

2 4
171
Chemical Equilibrium
K Cr 0, KNCS 6M KNCS
2 2
6 M NaOH ice
T E C H N I Q U E AND P R O C E D U R E
A. A Reversible Reaction
A solution that is prepared by dissolving a salt containing the chromate ion C r 0 ~ or by dissolving a salt containing the dichromate ion C r 0 can actually have both of these ions present. If the solution is basic, C r 0 predominates; if the solution is acidic, C r 0 ~ predominates. Because the characteristic colors of these t w o ions are different, it is possible to tell which ion is present in a solution, or at least to tell w h i c h ion is present in a greater amount when b o t h ions may be present. Reactions for the reversible conversion of one ion i n t o the other are
2 2 _ 4 2 7 2 4 2 2 7
Cr 0
2
2 7
- + OH" ^ HCrCV + CrCV

2 4 2
(16-7) (16-8)
HCrCV + OH" ^ Cr0 ~ + H 0
These reactions can be summarized in one equation that overlooks the presence of HCr0 ":
4
Cr 0 ~ + 20H- ^ 2Cr0 ' + H 0

2 2 2 7 4 2
(16-9)
This simplification will be used in this experiment. Equation (16-9) makes it clear that C r 0 ~ in solution can be converted to C r 0 ~ by the addition o f hydroxide ions (that is, by adding a base). Y o u w i l l use NaOH (sodium h y d r o x i d e ) and watch for a color change indicating that the forward reaction given in Equation (16-9) is occurring. It is not as obvious from Equation (16-9) how C r 0 ~ in solution can be converted to C r 0 " . Keep in m i n d that a solution prepared from one o f the ions w i l l also contain at least a trace of the other ion because of the interconversion. If a solution is prepared from C r 0 ~ , the extent to w h i c h the reverse reaction of Equation (16-9) occurs w i l l be increased i f hydroxide ions are removed from the s o l u t i o n ; this is the same as saying that the position o f e q u i l i b r i u m w i l l be farther to the left. The easiest way to remove h y d r o x i d e ions is to add an acid (a source of h y d r o n i u m ions, H 0 ) to the s o l u t i o n , so that the f o l l o w i n g reaction w i l l occur:
2 2 7 2 4 2 4 2 2 7 2 4 + 3
H 0* + OH3
2H 0
2
(16-10)
As O H " ions are removed, the extent to w h i c h the reverse reaction given in Equation (16-9) occurs w i l l increase, and the accompanying color change w i l l be y o u r visual evidence o f the f o r m a t i o n o f C r 0 ~ . Dissolve 0.3 g of K C r 0 (potassium dichromate) in 20 ml of water. Dissolve 0.4 g of K C r 0 (potassium chromate) in 20 ml of water. Record the color of each
2 2 7 2 2 7 2 4
172
Experiment 16
solid and of each solution. The t w o solutions contain different weights of materials and different concentrations of c h r o m i u m - c o n t a i n i n g ions, but each solution has the same concentration of c h r o m i u m atoms. 1. Pour about one-fourth of the K C r 0 solution into a 20-ml test tube. Save the rest of the K C r 0 as a standard for color comparisons. To the s o l u t i o n in the test tube, add 6M NaOH dropwise; after each drop shake the tube to m i x the contents t h o r o u g h l y . A d d NaOH u n t i l a definite color change occurs. Record the amount of base required. A c c o u n t for the color changes in terms of the preceding equations. N o w add 6M H N 0 ( n i t r i c acid) dropwise to this basic s o l u t i o n ; as before, mix the solution after y o u add each d r o p . A d d the acid u n t i l a definite color change occurs, and explain this color change in terms of the appropriate equations. Again, add base to the s o l u t i o n , and explain any color change. Remember that d i l u t i o n will make the colors slightly lighter than they were in the original solutions.
2 2 7 2 2 7 3
2. Pour about one-fourth of the K C r 0 solution into a 20-ml test tube. To this solution, add bM nitric acid dropwise; m i x the solution u n t i l a definite color change occurs. N o w , add NaOH u n t i l a further color change occurs. Then add n i t r i c acid, as before. A c c o u n t for y o u r observations in terms of the appropriate equations.
2 4
B. Relative " P o s i t i o n " of E q u i l i b r i u m
Transition metal ions exist in aqueous solution as complex ions in w h i c h water molecules are bound by coordinate covalent bonds to the metal. For c o b a l t ( I I ) , c h r o m i u m ( H I ) , and c o p p e r ( I I ) , these complex ions are believed to have the formulas C o ( H 0 ) , C r ( H 0 ) , and C u ( H 0 ) , respectively. The water molecules can be replaced by other ions or molecules to form different complex ions. If t w o complex ions of a particular metal differ in color, then it is easy to tell w h i c h ion is present in a solution. In this experiment, y o u w i l l attempt to convert the aquo complex ions listed above to chloro complex ions, using concentrated HCI as a source of chloride ions. For C o , for example, the reaction is
2 + 3 + 2 + 2 6 2 6 2 6 2 +
Co(H 0)
2
2 + 6
+ 4CP - CoCl " + 6 H 0

2 4 2
(16-11)
A general equation for various metal ions w o u l d be M ( I f O ) " + yCI" - M C 1 } " " y > + xH O
+ + 2 x 2
(16-12)
In w o r k i n g w i t h the three metal ions chosen for this experiment, y o u w i l l be asked to decide whether or not there is any visual evidence of the f o r m a t i o n of a complex ion w i t h i n a short period o f time. Y o u will then be asked to list the ions on the basis of how extensive the reaction of Equation (16-12) is for a particular a m o u n t of chloride i o n . In other words, y o u will be asked to order the ions on the basis o f the size of the e q u i l i b r i u m constant for the reaction of Equation (16-12). A f t e r comparing the chloro complex ions of the three metal ions in this experiment, y o u w i l l then be asked to compare different complex ions o f one metal i o n .
173
You will investigate the reactions in Equations (16-1 1) and (16-13) Co(H 0)
2 2 + 6
+ 4C1" * C o C l " + 6 H 0
2 4 2 2 4 2
(16-11) (16-13)
Co(H 0)
2
2 + 6
+ 4NCS" ^ C o ( N C S ) " + 6 H 0
to determine which reaction is more extensive for a particular amount of a complexing agent (Cl~ or N C S ) ; that is, which reaction has a larger e q u i l i b r i u m constant.
-
1. Pour 5 ml of 0.5M C o ( N 0 ) (cobalt nitrate) into each of t w o 20-ml test tubes. Pour 5 ml of 0.5/W C r ( N 0 ) ( c h r o m i u m nitrate) i n t o each of a second set of t w o 20-ml test tubes. Pour 5 ml of 0.5A/ C u ( N 0 ) (copper nitrate) i n t o each of a t h i r d set of 20-ml test tubes. Record the color of each solution. These solutions contain the aquo ions for w h i c h the formulas are given above. Set aside one test tube of each solution to use as a standard for color comparisons. To each of the three remaining test tubes, add 1 2M HC1. A d d the HC1 w i t h a medicine dropper from a 10-ml graduated cylinder containing 10 ml of the acid. Record, to the nearest 0.5 m l , the volume of HC1 that is required to produce a definite color change in each solution. A f t e r y o u t h i n k that a color change has occurred, add another drop or t w o of acid to each solution to decide if y o u are seeing a distinct color rather than a m i x t u r e of t w o colors. For example, if a solution changes color from red to orange, the orange may be the color of the product or it may be a mixture of the redcolored reactant and a yellow-colored p r o d u c t . Do not add more than 10 ml of acid to each s o l u t i o n . If y o u are n o t sure whether the solution has changed color, add to the color comparison tube a volume of water equal to the volume of acid that y o u used; a slight color change may occur just from the d i l u t i o n . A c c o u n t for the differences among the three solutions on the basis of the position of e q u i l i b r i u m for the reaction of Equation (16-12). In other words, for which of the three metal ions does the position of e q u i l i b r i u m appear to be farthest to the right for a particular amount of chloride? For w h i c h of the three metal ions does the position of e q u i l i b r i u m appear to be farthest to the left for a particular amount of chloride?
3 2 3 3 3 2
2. M i x 3 ml of 0 . 5 M C o ( N 0 ) and 3 ml of 0 . 5 M C u ( N 0 ) in a 20-ml test tube. A d d 12A/ HC1 to this m i x t u r e dropwise u n t i l a definite color change occurs. Record the volume of acid that y o u use. Does the chloro complex of cobalt or the chloro complex of copper form first? Does this agree w i t h y o u r previous conclusions about the positions of e q u i l i b r i u m for the reactions of these two metal ions w i t h chloride ions? The colors that y o u see in this m i x t u r e w i l l not be exactly like the colors y o u observed for the solutions containing only one metal i o n . However, the colors of C o C l " and C u C l ~ are sufficiently intense and different enough from one another that y o u should be able to recognize either one despite the presence of another colored species.
3 2 3 2 2 2 4 4
3. Pour 5 ml of 0.5yV/ C o ( N 0 ) i n t o each of t w o 20-ml test tubes. To one test tube, add 6 M KNCS (potassium thiocyanate) dropwise from a graduated cylinder u n t i l a definite color change occurs. To the second test tube, add 6M HCI dropwise, u n t i l a definite change occurs. Do not add more than 10 ml of either solution to the C o ( N 0 ) ; record the volume of solution that is required in each case. The
3 2 3 2
174
Experiment 16
colors o f the t w o complex ions C o C l a n d C o ( N C S ) ~ w i l l appear to be the same. A c c o u n t for any difference in the amounts of c o m p l e x i n g agent required in terms of the relative positions of e q u i l i b r i u m for the reactions of Equations (!(>-! I) and (16-13). Y o u should also be able to account for the difference in your results here and y o u r results when y o u added 12M HC1 to C o ( N 0 ) .
2 2 4 4 3 2
C. " S h i f t i n g the P o s i t i o n " of E q u i l i b r i u m
The colors of C o ( H 0 ) and C o ( N C S ) " are quite distinct, so y o u can easily tell w h i c h of these complex ions is present in the greater amount in a solution. If comparable amounts o f these two ions are present, the solution will have an intermediate color that can be described as reddish-purple. If anything is added to this solution that causes the forward reaction in Equation (16-13) to occur to a greater extent (that is, that shifts the position of e q u i l i b r i u m to the r i g h t ) , the color should become more blue. If a change in conditions causes the reverse reaction of Equation (16-13) to occur to a greater extent (that is, shifts the position of equilibrium to the left), the color should become more pink. Y o u w i l l investigate how the position of e q u i l i b r i u m for this reaction is affected (1) by adding each of t w o materials involved in the reaction, (2) by removing one of the materials, and ( 3 ) by varying the temperature.
2 + 2 2 6 4
In a small beaker, add 7 ml of 6M KNCS to 3 ml of 0.5M C o ( N 0 ) . The solution should have the intense blue color characteristic of Co(NCS) ~. Dilute this solution w i t h no more than 15 ml of distilled water (perhaps a little less), u n t i l it has a purplish color intermediate between the colors of C o ( H 0 ) and Co(NCS) ~ This intermediate color indicates that a moderate amount of each complex ion is present. Divide this solution as evenly as possible among seven test tubes. Set tube 1 aside to use as a standard for color comparisons.
3 2 2 4 2 + 2 6 2 4
1. Effect of concentration of a reactant. To tube 2, add 1 ml of distilled water. Record any color change, and account for this change in terms of the forward or the reverse direction of the reaction of Equation (16-13); that is, in terms of a shift in the position of e q u i l i b r i u m when the material that is involved in the reaction is added to the reaction m i x t u r e . To tube 3, add 5 ml of distilled water. Compare the colors-of the solutions in tube 2 and tube 3; account for y o u r observations. To tube 4, add about 0.5 g of solid KNCS. A c c o u n t for your observations in terms of the position of e q u i l i b r i u m for the reaction of Equation (16-13). To tube 5, add 1 ml of 2M A g N 0 . The white precipitate that forms is insoluble AgSCN; the addition of A g causes the removal of NCS" from the s o l u t i o n . A f t e r the precipitate settles, compare the color of the solution in tube 5 to the color of the standard solution in tube 1. Has the position of e q u i l i b r i u m shifted? In which direction? Why? Compare the color of the solution in tube 5 to the solution in tube 2, to which 1 ml of distilled water was added. Is the color change that y o u observe in tube 5 simply the change that y o u w o u l d expect after adding the water in the A g N 0 solution, or has a greater change occurred? Explain y o u r answer.
3 + 3
175
2. Effect of temperature. Heat a beaker of water to b o i l i n g . Use a test-tube holder to place tube 6 in this boiling water. A f t e r several minutes, compare the color of the solution in tube 6 to the standard solution in tube 1. Explain what has happened. Place tube 7 in a beaker of ice and water. A f t e r several minutes, compare the color of the solution in tube 7 to the color of the standard solution in tube 1, w h i c h remained at room temperature, and to the color of the solution in tube 6, which was heated. Determine whether the t w o color changes in tubes 6 and 7 are reversible. What can y o u conclude about the effect of temperature changes on the position of e q u i l i b r i u m for the reaction of Equation (16-13)'.' Is the forward or the reverse reaction favored by an increased temperature? Is the forward or the reverse reaction favored by a decreased temperature? Which direction of the reaction is endothermic? Which direction of the reaction is exothermic?
RESULTS
Letters and numbers match those in the Procedure and on the Report Sheet.
A. A Reversible Reaction
On the Report Sheet for this experiment, provide the requested i n f o r m a t i o n about the colors of the original materials and about the color changes that provide visual evidence of the reaction that is occurring. A c c o u n t for each color change in terms of the forward or the reverse direction of the reaction in Equation (16-9).
B. Relative "Position" of Equilibrium
1. Provide the requested i n f o r m a t i o n about colors that is the basis for comparing the extent of the reaction in Equation (16-12) for the three metal ions. In addition, calculate the concentration of chloride ion that has been added to each solution (that is, the total concentration of C I " that w o u l d be present if none reacted w i t h a metal ion) when the color indicates that the aquo complex has been converted to the chloro complex. If no color change occurred, calculate the chloride ion concentration that is present after the addition of the entire 10 ml of concentrated HC1. As an example of such a calculation, assume that a color change occurs when 2.5 ml of \2M HC1 is added to 5.0 ml of the original s o l u t i o n ; the total volume is now 7.5 m l . In the total solution _ (12 moles CI"/1 liter HC1) X (0.0025 liter HC1) 0.0075 liter of s o l u t i o n [ C P ] = 4.0M (16-14)
2. Because it is d i f f i c u l t to assign specific terms to the descriptions of colors, especially when they are mixtures, not all students w i l l have the same answers here. However, y o u r conclusions about positions of e q u i l i b r i u m should be the same, regardless of how y o u describe the colors of your solutions.
176
3. In a d d i t i o n to describing your observations and explaining them in terms of the relative positions of e q u i l i b r i u m for the reactions in Equations (16-1 1 ) and (16-13), calculate the concentrations of chloride and thiocyanate ions that y o u put into the solutions.
C. "Shifting the Position" of Equilibrium
Describe the appearance of the solution in each tube. Account for each observation in terms of the effect that each change has on the position of e q u i l i b r i u m for the reaction of Equation (16-13). Write an equation for the reaction of Equation (16-13) p u t t i n g the w o r d "heat" on the proper side to indicate its effect on the reaction.
QUESTION
Is it possible to reach any definite conclusion about whether or not C r reacts w i t h C I " in aqueous solution to form a chloro complex ion? (a) If the reaction is extensive but slow, how w o u l d y o u show that this is the case'' (b) If the reaction is extensive at some temperature other than r o o m temperature, how wotdd y o u show that this is the case? (c) If the reaction is extensive at r o o m temperature but forms a chloro complex that is nearly the same color as the aquo complex, how w o u l d y o u show that this is the case'.' {Hint: Refer to Experiment 9.)
3 +
REFERENCE
Yoder, C . H . , Suydam, F . H . , and Suavely, F . A . Chemistry. New Y o r k : Marcourt Brace Jovanovich, Inc., 1975. Chapter 13.
B. Relative " p o s i t i o n " of e q u i l i b r i u m : M(H 0)

2 + 6
" +>C1" ^ M C l / * " ^ + 6 H 0

2
(16-12)
1. Color of aquo complex Color of chloro complex ml of 1 2M HC1 to form complex [ C P ] to form complex
Co
: +
Cr
3 +
Cu
2 +
Show calculation of [ C P ] added to C o ( H 0 )

2
2 + 6
w h e n C o C l ~ color appears:
2 4
Most extensive reaction w i t h Least extensive reaction w i t h Reaction w i t h largest e q u i l i b r i u m constant Reaction w i t h smallest e q u i l i b r i u m constant
2 . M i x t u r e containing C o ( H 0 )
2
2 + 6
and C u ( H 0 )
2
2 + 6
Original color of solution Color after addition of ml of \2M HC1 *
Ion for which the chloro complex is present
Conclusion about relative positions of e q u i l i b r i u m for chloro complexes o f C o and C u :

2 + 2 +
Does this agree w i t h y o u r conclusions in Part 1?
Experiment 17 Spectrophotometric Determination of an Equilibrium Constant

Introduction
The extent to w h i c h a chemical reaction occurs can be expressed in terms of the e q u i l i b r i u m constant for the reaction. This number is characteristic of the reaction at a particular temperature and states the ratio of product concentrations to reactant concentrations (each raised to a power that is the coefficient from the balanced equation for the reaction) in the reaction m i x t u r e when chemical e q u i l i b r i u m is attained (that is, when these concentrations no longer change). For example, for a general reaction aA + bB ^ cC + dD j g ^ c i M D i ; [A] [B]
a
(17-1) .
( 1 7 b
2 )
The greater the numerical value o f K, the more extensive the reaction will be and the greater the tendency for the reaction to occur w i l l be. A n o t h e r indicator of the tendency and the extent of a reaction is the free energy change AC that accompanies that reaction. This property takes i n t o account the enthalpy change AH and the entropy change AS that occur during any chemical or physical process: AG = AH - 7 A S (17-3)
A process is most l i k e l y to occur if AH is negative (energy is evolved) and AS is positive (disorder increases). This combination causes AG to be negative. Consequently, a negative value o f A G for a chemical change shows that this change w i l l occur spontaneously. The more negative the value of A G , the greater the tendency o f the reaction to occur, that is, the more extensive the reaction will be before chemical e q u i l i b r i u m is established. The relationship between A G (the standard free energy change) and K is A G = -RT(2.3 log A.') (17-4)
Calculations involving AG and K are easy when one of these variables is k n o w n . Y o u have also performed calculations involving K and concentrations of reactants and products in a reaction m i x t u r e . Of course, this type of calculation requires that y o u k n o w the value for an e q u i l i b r i u m constant in the first place. The purpose of this experiment is to acquaint y o u w i t h one m e t h o d that can be used to determine the numerical value of an e q u i l i b r i u m constant. In problems in your chemistry t e x t ,
181
182
Experiment 1 7
you have calculated e q u i l i b r i u m constants from data stating the number of moles of each reactant and product in a reaction m i x t u r e . However, for many reactions it is d i f f i c u l t , or even impossible, to measure these concentrations directly. In this experiment, y o u w i l l be asked to use an indirect method that makes it unnecessary to measure the concentration of each component of an e q u i l i b r i u m m i x t u r e . The reaction that y o u w i l l investigate is the formation of a complex ion in aqueous solution from reactants in aqueous s o l u t i o n : F e ( a q ) + NCS(aq)"^ FeNCS(aq)
3 + 2+
(17-5)
The concentration ratio that y o u w i l l determine is ^JFeNCS**] [Fe | [NCS ]

3 + -
Y o u w i l l need to k n o w the total concentration o f F e and the total concentration o f NCS" put i n t o the solution. However, y o u will not need to k n o w how much o f either of these materials is in the f o r m of the complex ion or how much remains uncomplexed. A n d y o u w i l l never need to k n o w the actual concentration o f F e N C S i n the s o l u t i o n . Instead, the only piece of experimental data that y o u must determine is the absorbance A due to F e N C S i n a solution prepared from k n o w n amounts of F e and NCS". Y o u should recall from Experiment 9 that absorbance is a measure of the amount of light absorbed by a colored material. Its numerical value is directly related to the concentration of the absorbing product in solution c, to the depth or thickness of the sample through which light passes /, and to an intrinsic physical property of the absorbing product called its molar e x t i n c t i o n coefficient e:
3 + 2 + 2 + 3 +
A=ecl
(17-7)
In this experiment, y o u w i l l not need to k n o w the values o f any o f these terms except A; however, the symbols e, c, and / w i l l be used in the following discussion.
beakers cuvettes or test tubes 1-ml pipet
10-ml pipet spectrophotometer 100-ml volumetric flask
CHEMICALS NEEDED
0AM F e ( N 0 ) in 0.5M I I N 0 0.5M H N 0 0 . 0 0 2 M KNCS in 0.5M H N 0

3 3 3 3
133
Spectrophotometry Determination of an Equilibrium Constant
TECHNIQUE
Y o u w i l l begin w i t h an accurately k n o w n volume o f a solution that contains an accurately k n o w n concentration of KNCS (potassium thiocyanate). To this solution, you will add an accurately measured volume o f a solution that contains an accurately k n o w n concentration o f F e ( N 0 ) (ferric nitrate). Then y o u will measure the absorbance of the solution, using a wavelength of visible light at which F e N C S absorbs strongly. A f t e r adding more ferric nitrate solution, y o u w i l l measure the absorbance again. The increased amount o f F e in the solution w i l l cause the position of e q u i l i b r i u m for the reaction of Equation (17-5) to shift to the right; because more F e N C S i s present in the second solution, the absorbance characteristic o f this species w i l l increase. This process is repeated for increasing amounts o f F e . Before conducting this experiment, read A p p e n d i x IV for a discussion of spectrophotometers. Before y o u begin w o r k , y o u r instructor w i l l provide directions for the specific spectrophotometer that y o u w i l l be using.
3 3 2+ 3 + 2+ 3+
T R E A T M E N T O F T H E DATA
Y o u are t r y i n g to determine a value for the ratio

[F
K-
[Fe ] [NCS-]
3 +
CS2+l
(17-6)
A way must be found to relate these three u n k n o w n concentrations to k n o w n quantities. The concentration of F e N C S can be related to your one experimental measurement, absorbance A:
2+
A = eel = e / [ F e N C S ]
2+
(17-8)
Rearranging this equation gives [ F e N C S ] =A/el

2+ n
(17-9)
Y o u w i l l k n o w T , the total concentration of N C S " p u t i n t o the solution, but y o u will not k n o w how this concentration is divided between complexed and uncomplexed (free) NCS": T = [NCS-]
n f r e e
+ [FeNCS ]
2+
(17-10)
Rearranging this equation gives [NCS-]

f r e e
=r-[FeNCS
2 +
(17-11)
Substituting Equation (17-9) into Equation (17-1 1) [NCS-]

f r e e
= T-A/el
(17-12)
184
Experiment 1 7
On the basis of the d i l u t i o n that occurs, you can calculate 7)-, the total concentration of F e , put i n t o the s o l u t i o n , w i t h o u t k n o w i n g how much of this concentration is complexed or uncomplexed F e :
3+ 3 +
7>= [ F e Rearranging this equation gives [Fe

3 +
3 +
f r e e
+ [FeNCS ]
2+
(17-13)
f r e e
= 7 > - [FeNCS ]
2+
(17-14)
Substituting Equation (17-9) i n t o Equation (17-14) [Fe

3 +
f r e e
= T -Alel
f
(17-15)
When Equations (17-9), (17-11), and (17-15) are substituted i n t o Equation (17-6), the new expression for the concentration ratio becomes K = (17-16)
(T
A/el)
(T -A/el)
n
M u l t i p l y i n g by the denominator gives KT T - KT A/el - KT A/el + K(A/el)

f n n f 2
= AI el
(17-17)
These terms can be rearranged and combined i n t o the more familiar form K(A/el) - (KT
2 n
+ KT + 1) (A/el) + KT T
f f
=0
(17-18)
which y o u should recognize as a quadratic equation of the general form ax +bx +c = 0

2
(17-19)
In this case, the term A/el is the x in Equation (17-19). Quadratic equations w i t h numerical coefficients are simple although sometimes tedious to solve. Here, the c o m p l e x i t y of the coefficients makes the equation quite d i f f i c u l t to solve. An approximate solution is A/el =
T +T
f
Tfln
H
(17-20)
UK
A stepwise rearrangement o f this equation puts it i n t o the form that y o u w i l l use: T + T

f n
+ \/K_ T T
f
el T +T
f n +
A \/K_ T T
f n
(17-21)
el T +T
f
el 1 elK
A . TfT A
(17-22)
el
(17-23)
185
Spectrophotometric Determination of an Equilibrium Constant
The final form of this equation is 1112. = (1 /e/)( 7> + T ) + (1 lelK) A This equation is now in the f o r m of a general equation for a straight line y = mx + b (17-25)
T T
(17-24)
If (TfT lA) is p l o t t e d along the y axis and ( 7 } + 7" ) is p l o t t e d along the x axis, a straight line results. Its slope is (1 /el), and its y intercept is ( \ / e l K ) . To o b t a i n a value of K, the numerical value of the slope is divided by the numerical value of the intercept
n
slope _Uel_ intercept \/e!K

= =K
Thus, the value of K has been determined by using t w o pieces of easily calculated data and one simple experimental measurement, w i t h o u t ever k n o w i n g the equil i b r i u m concentrations of the components of the m i x t u r e .
PROCEDURE
Prepare a 2 X 10~ A/ solution of KNCS (potassium thiocyanate) in 0.5M H N 0 ( n i t r i c acid) in the f o l l o w i n g manner: Clean and rinse a 100-ml v o l u m e t r i c flask; then rinse the flask w i t h three 5-ml portions of 0 . 5 M H N 0 . Clean and rinse a 10-ml pipet giving it a final rinse w i t h the 2 X 1 0 A / KNCS solution that is provided. Pipet 10 ml of 2 X 1 0 A / KNCS i n t o the volumetric tlask, and then add Q.5M H N 0 to the 100-ml calibration mark on the neck of the tlask. Invert the stoppered flask several times to ensure homogeneity. Be sure to record the exact m o l a r i t y of the KNCS solution that is provided. In a small clean beaker obtain about 20 ml of the 0. \M solution of F e ( N 0 ) (ferric nitrate) in 0.5A/ H N 0 that is provided. If y o u r beaker is not completely d r y , rinse it several times w i t h a few ml of the F e s o l u t i o n , so that the 20 ml of F e solution w i l l not be diluted by any water remaining in the beaker. Clean and rinse a 1-ml pipet, and then rinse it several times w i t h the F e ( N 0 ) s o l u t i o n . Pour the KNCS solution that y o u prepared i n t o a clean, dry, 4 0 0 - m l beaker. Assume that the volume of solution transferred is 0.100 liter. I n t o this s o l u t i o n , pipet 1.00 ml of 0.1A/ F e ( N 0 ) . Gently swirl the beaker to ensure thorough m i x i n g . T h r o u g h o u t the experiment, it is essential not to lose any of the s o l u t i o n , because each measurement and calculation in a series of ten is based on the assumption that all of the original solution has been retained. Adjust the wavelength c o n t r o l o f the spectrophotometer t o 447 n m ( 4 4 7 0 A ) . I f the wavelengths on y o u r instrument are marked every 5 n m , rather than every 1 n m , set the wavelength c o n t r o l at 445 to be sure of a reproducible setting; if wavelengths are marked only every 10 n m , set the c o n t r o l at 4 5 0 . Adjust the zero c o n t r o l . Rinse a clean sample cuvette or test tube several times w i t h 0.5A/ H N 0 , and then fill i t
4 3 3 _ 3 _ 3 3 3 3 3 3 + 3 + 3 3 3 3 3
186
Experiment 17
w i t h 0 . 5 M H N 0 . Place this tube in the sample holder and adjust the light c o n t r o l to " 0 " absorbance to ensure that the absorbance y o u measure is due o n l y to reaction components. It is assumed that y o u w i l l share a spectrophotometer w i t h other students. Before y o u use the instrument each time, check the wavelength setting and the zero setting; then use the tube of 0.5M H N 0 to check the light c o n t r o l . The settings may d r i f t slightly while the instrument is in use, or y o u or another student may accidentally b u m p the knobs and change the settings. I n t o a clean and dry matching sample tube, pour some of the K N C S - F e ( N 0 ) solution, and then measure its absorbance. Pour this solution back i n t o the beaker and retain the sample tube. Pipet another 1.00 ml of 0. \M F e ( N 0 ) i n t o the s o l u t i o n ; m i x t h o r o u g h l y by swirling the beaker gently. Pour about 2 ml of this solution i n t o the sample tube, and then pour it back i n t o the beaker. Repeat this process three more times washing the s o l u t i o n over the entire inside wall of the tube to ensure that no solution is lost and that all o f the s o l u t i o n has the same concentration o f components. F i l l the tube and measure the absorbance. Pour the solution back i n t o the beaker and retain the tube. Repeat this procedure, adding 1.00 ml of F e ( N 0 ) at a time u n t i l a t o t a l of 10 ml has been added. It is i m p o r t a n t not to lose any solution. If any s o l u t i o n ever drips d o w n the side of the tube during pouring, rinse only the outside of the tube w i t h distilled water and dry it so that no solid residue can remain to affect the absorbance. Do not add the distilled water to the solution. Record the temperature in the laboratory.
3 3 3 3 3 3 3 3
CALCULATIONS
For each of the ten mixtures, calculate the total concentation of NCS~ on the basis of the d i l u t i o n that has occurred _ (M of N C S " in stock s o l u t i o n ) x (V of stock s o l u t i o n ) V of total s o l u t i o n For each m i x t u r e , calculate the total concentration of F e tion T - CM of F e If
3 + 3 +
(17 2 7 )
added to the solu-
in stock s o l u t i o n ) X ( V of stock s o l u t i o n ) V of total solution
r\n~>Q\ ( l I-la)
In each calculation of concentration, be sure to retain the proper number of significant figures given on the stock solutions of KNCS and F e ( N 0 ) . F o r each m i x t u r e , calculate the terms TfT /A and ( 7 } + T) that are to be graphed. Be careful in placing y o u r decimal points! Plot TfT /A ( o n the y axis) vs. (7} + T) (on the x axis). Use scales that enable you to p l o t data to three or four significant figures. Draw the best possible straight line through y o u r p l o t t e d points. Determine the slope and the y intercept of the line. Calculate K to three significant figures (K = slope/intercept).
3 3 n n
137
Spectrophotometric Determination of an Equilibrium Constant
QUESTIONS
1.
2. 3. 4.
5.
6.
Use your value of the concentration ratio to calculate the concentration of each component in the tenth mixture. Use a calculator, and retain as many figures as possible t h r o u g h o u t the calculation; then round o f f each answer to the appropriate number of significant figures. According to y o u r answers to Question 1, what proportion of the total NCS"is in the complex ion? What proportion of the F e is in the complex ion? Use y o u r experimentally determined value of A' to calculate the standard free energy change for the reaction between F e a n d N C S ' t o form FeNCS . What experimental conditions are used to define the standard free energy change? How do the conditions under w h i c h y o u prepared the first m i x t u r e differ from standard conditions'.' It is assumed that the reaction between F e a n d N C S ' i s quite rapid, so that e q u i l i b r i u m has been attained by the time y o u measure absorbance. If this is true, what is the free energy change at the time y o u measure absorbance? Does it seem more reasonable to expect the e n t r o p y change for the reaction y o u arc investigating to be positive or negative? E x p l a i n your answer.
3 + 3 + 2+ 3 +
REFERENCES
1. Yoder, C.H., Suydam, F . H . , and Suavely, F . A . Chemistry. New Y o r k : Harcourt Brace Jovanovich, Inc., 1975. Chapter 13. 2. Ramette, R.W. Journal of Chemical Education 4 0 , 7 1 ( 1 9 6 3 ) . 3. Frank, H.S.,.and Oswalt, R.L. Journal of the American Chemical Society 69, 1321 ( 1 9 4 7 ) .
REPORT SHEET E X P E R I M E N T 17
Name
Date
Section
Data and calculated quantities for the ten mixtures:
Molarity of stock KNCS Molarity o f stock F e ( N 0 )

3 3
7} 1. 2. 3. 4. 5. 6. 7. 8. 9. 10. .
TT
f
T/TJA
7} + T
Show the calculation of Tf for m i x t u r e 10: Show the calculation of T for m i x t u r e 10:
A t t a c h the graph of TfT /A vs. (7} + T) to the Report Sheet. Show the calculation
n
of the slope of the straight-line p l o t : KShow calculation of K: 187 on the back of the Report Sheet; attach extra
(Answer the questions from page sheets of paper, if necessary. )
Experiment 18 Enthalpy of Reaction

Introduction
Every chemical reaction is accompanied by an energy change in w h i c h energy is absorbed or evolved, usually in the form of heat. Energy must be supplied to break the chemical bonds in the reactants and energy is released when bonds f o r m in the products. Whether the net result of these t w o steps requires energy to be supplied or released depends on the relative sizes of the energies associated w i t h bond breaking and bond f o r m a t i o n . The amount of heat associated w i t h a reaction depends not only on what the reaction is but also on the temperature at w h i c h the reaction occurs, and on whether the reaction occurs under conditions of constant pressure or constant volume. In the laboratory, reactions are conveniently carried out at the constant pressure of the atmosphere in beakers or flasks that are open to the air. The amount of heat absorbed or released under these conditions is called the enthalpy change AH for the reaction AH //products ^reactants
Enthalpy H can be thought of as the "heat c o n t e n t " of a substance; this heat is stored as potential energy in the f o r m of bond energies, energy of solvation, and other energies. When atoms rearrange in the course of a reaction, the heat content of the products is usually different from the heat content of the reactants, because the bond energies and other energies in the products are not the same as in the reactants. The difference in heat content appears as heat absorbed or released and is generally expressed in calories per mole (cal/mole) of a particular material. For example, in this experiment y o u w i l l study an acid-base neutralization in aqueous solution //*(aq) + O H - ( a q ) H 0
2
(18-1)
The enthalpy change that y o u w i l l be asked to determine could be given in cal/mole o f I T , o r i n cal/mole o f O H , o r i n cal/mole o f H 0 . Note that the enthalpy change AH = H -H is defined as positive if heat is absorbed ( i f # >// ) ; such a reaction is called endothermic. Release of heat is associated w i t h a negative enthalpy change (// ducts *> Reactants); this k i n d of reaction is called exothermic. The enthalpy change for a reaction helps to determine whether the reaction w i l l be spontaneous. Consider an exothermic process. Because heat is released in the course of an exothermic reaction, the system is changing from a high energy state to a low energy state. The formation of new bonds between atoms causes the system to be in a state of greater stability, and the "excess" energy is released as heat. I n t u i tively, it seems plausible that reactions w o u l d have a natural tendency to proceed spontaneously to a state o f m i n i m u m energy, as a ball rolling d o w n a h i l l . Indeed, this is part of what causes some reactions to occur spontaneously.
2 p r o i i u c t s n e t C t a n t s p r o d u c t s r e a c t a n t s pr0
191
192
EXPERIMENT 18
Whether a reaction w i l l be spontaneous depends not only on AH but also on the entropy change AS that accompanies the reaction. A n y process in w h i c h a system becomes more disordered (AS > 0) is more likely to occur than a process in w h i c h a system becomes more ordered (AS < 0 ) . D u r i n g a chemical reaction, an entropy increase may result f r o m an increase of material in a less ordered physical state (gas rather than l i q u i d or solid; l i q u i d rather than solid), from an increase in number of particles, or from a chemical m i x i n g of one material w i t h another (as in the conversion o f H and C l t o H C l ) . The Gibbs free energy change AG considers changes in b o t h enthalpy and entropy
2 2
AG = AH -TAS
(18-2)
If b o t h factors are conducive to spontaneity (AH < 0 and AS> 0), then AG is negative; AG < 0 can be used as a criterion for spontaneity. If b o t h factors oppose spontaneity (AH > 0 and AS < 0 ) , then AG > 0; such a reaction is not spontaneous. Or one factor may oppose spontaneity and the other factor may favor i t ; in such cases, the temperature and the relative magnitudes of AS and AH determine whether the reaction w i l l occur spontaneously.
EQUIPMENT
NEEDED
asbestos square clamp ring clock w i t h a sweep second hand cork glass stirrer
100-ml graduated cylinder stand 8-oz S t y r o f o a m cups (2) 0. l thermometer
CHEMICALS
NEEDED
0.503/ C u S 0 2.0A/ H C l
2.OA/ N a O H 6A/ N H
3
MEASURING
AH:
CAL0RIMETRY
Measuring the heat change for a reaction at constant pressure is easier if the reaction is exothermic than if it is endothermic. The heat that is produced in the reaction is trapped and allowed to cause some measurable physical change. This change is then compared w i t h the size of the change produced by adding some k n o w n amount of heat to the heat trap. The device used to measure heat changes is called a calorimeter. In this experiment, y o u r calorimeter w i l l be constructed using t w o nested Styrofoam cups and a square o f asbestos for a l i d ; a thermometer and stirrer w i l l be inserted through the lid i n t o the cups, as shown in Figure 18-1. A perfect calorimeter should trap all the heat f r o m the reaction, allowing none to escape. The trapped heat causes the temperature inside the calorimeter to rise, and the amount of trapped heat can be
133
Enthalpy of Reaction
where C i is the heat capacity of the entire system, or the number of calories required to raise the temperature o f the system 1 . The reactions y o u will study in this experiment w i l l occur in aqueous solutions in the Styrofoam cups. The t o t a l heat capacity is the sum of the heat capacities of the individual parts of the system:
t o t a
^total "^solution
^calorimeter
(18-4)
Heat capacity data for various kinds of solutions can often be found in chemical tables. However, because every type o f calorimeter is different, C | j t e r must be determined experimentally. This procedure w i l l be described later in the experiment. Basically, it consists of i n t r o d u c i n g a k n o w n amount of heat i n t o the calorimeter and measuring the temperature change that occurs; this w i l l enable y o u to calculate the heat capacity in c a l / C . It might seem quite simple to measure AT. Ideally, if no heat escaped f r o m the calorimeter, we w o u l d only need to measure r i , m i x the reactants, and then measure r . U n f o r t u n a t e l y , some heat leakage that must be compensated for does occur when using any type of calorimeter. A graphical procedure is generally used to o b t a i n AT. A typical plot of temperature 7 vs. t i m e t for an exothermic reaction is shown in Figure 18-2. A reaction was begun by m i x i n g the reactants at time t - 0. A large increase in temperature is followed by a steady drop in T, caused by heat leakage from the calorimeter. The i n i t i a l points p l o t t e d on the graph may
c a 0 r m e i n i t i a f i n a l
194
Experiment 18
fluctuate w i t h o u t revealing any real trend if the m i x t u r e was not thoroughly stirred immediately. Then the temperature drop becomes fairly linear w i t h time. A straight line is drawn (perhaps o m i t t i n g the first p o i n t or t w o before temperature equil i b r i u m was established) and extrapolated to time t = 0. The value of T at t = 0 in terms of y o u r measurements is 7Y,nai the reaction that occurs as rapidly as the reactant solutions can be stirred together. This is the temperature that the calorimeter and its contents w o u l d have reached if e q u i l i b r i u m had been established instantaneously and if no heat leakage had occurred.
l o r
PROCEDURE
A. Determination of Calorimeter Heat Capacity
Heat about 75 ml of distilled water to 6 0 - 7 0 C . If the thermometer (graduated in 0 . 1 ) y o u are using does not register this high a temperature, heat the water to about 5 above the highest temperature that y o u r thermometer can record. Use a graduated cylinder to measure 50.0 ml of distilled water, and then pour the water i n t o the calorimeter. Measure its temperature T w i t h the 0.1 thermometer. N o w use the graduated cylinder to measure 50.0 ml of the heated water. A l l o w the water to stand in the cylinder for about 30 seconds. Then stir the water gently and briefly and record its temperature T . Reinsert the 0.1 thermometer in the calorimeter l i d . Pour the hot water i n t o the calorimeter; make the transfer as rapid and as completely as possible. Note the time of the a d d i t i o n ; this is t = 0 for y o u r temperature measurements. Q u i c k l y put the calorimeter l i d , thermometer, and stirrer in place. Stir the water gently w i t h an up and d o w n m o t i o n for a few seconds;
c h
195
be careful not to b u m p the thermometer. Wait 30 seconds after the hot water is added and then record the temperature; continue to record the temperature at 30-second intervals for three minutes. Dry the calorimeter thoroughly w i t h a clean towel. Repeat the determination. Dry the calorimeter again when y o u finish the second determination.
B. Heat of Neutralization
Y o u are to combine 50.0 ml of 2.OA/ HC1 and 50.0 ml of 2.OA/ N a O H . Measure one of these solutions and pour it i n t o the calorimeter. Measure the temperatures of both solutions. Be sure to rinse and dry the thermometer when transferring it from one solution to the other. If the temperatures of the t w o solutions are different, allow them to stand u n t i l their temperatures are the same, or record the average of the temperatures of the t w o solutions as the initial temperature. Pour the second solution into the calorimeter containing the first s o l u t i o n ; note the time. Q u i c k l y put the l i d , thermometer, and stirrer in place, and.stir the m i x t u r e gently for a few seconds. Record the temperature at 30-second intervals for three minutes. Rinse the calorimeter w i t h distilled water and dry it t h o r o u g h l y . Repeat the determination. When y o u finish the second determination, rinse and dry the calorimeter again.
C. Heat of Formation of C u ( N H )
3
2+ 4
The reaction is C u ( a q ) + 4 N H ( a q ) - C u ( N H )
2+ 3 3 2 + 4
(18-5)
A n excess o f ammonia is used to ensure that the position o f e q u i l i b r i u m w i l l be far enough to the right that v i r t u a l l y all of the C u reacts as shown. Measure 50.6 ml of 0.5A/ C u S 0 and 50.0 ml of 6M N H . Pour one of these solutions i n t o the clean, dry calorimeter. Record the i n i t i a l temperature of each solution or an average of the temperatures of b o t h solutions. Note the time when you add the second solution to the calorimeter. Position the l i d , thermometer, and stirrer, stir the m i x t u r e gently and briefly, and record the temperature at 30-secorid intervals for three minutes. Thoroughly rinse and dry the calorimeter, and repeat the determination. Clean and dry the calorimeter again before y o u return it to the s t o c k r o o m .
2 + 4 3
R E S U L T S AND C A L C U L A T I O N S
A. Determination of Calorimeter Heat Capacity
Ideally, the final temperature after m i x i n g the cold and hot water should be exactly halfway between T and T ; the heat lost by the hot water should exactly
c h
196
Experiment 18
equal the heat gained by the cold water. I n reality, the final temperature w i l l be lower than this, because the h o t water w i l l lose more heat than the cold water w i l l gain. The difference between these t w o heat terms is the heat absorbed by the calorimeter. Plot T vs. t on a piece of graph paper. Draw the best possible straight line through y o u r data points and extrapolate this line to t = 0 to determine 77 in terms of the heat transfer process w i t h i n the calorimeter. Calculate the heat gained by the cold water Q :
final c
Q = V X 1.00 g/ml X 1.00 cal/g C X ( 7

c c
r i m i l
- T)
c h
(18-6)
In a similar fashion, calculate the heat lost by the hot water Q . The difference between Q and Q was absorbed by the calorimeter. Divide this heat term {Q - Q ) by the temperature change that occurred w i t h i n the calorimeter (Tfinai ~ T ) when the hot and cold water were mixed. Y o u r result is the heat capacity of the calorimeter in c a l / C .
h c h c c
B. Heat of Neutralization
Plot T vs. t on a piece of graph paper. Extrapolate the straight line to t = 0 to determine Tf \ for the reaction. The heat released d u r i n g the reaction is absorbed by the solution and by the calorimeter, raising the temperatures of b o t h :
tna
A / / = (^calorimeter
Cisolution
( ' 8-7)
Each of these terms must be calculated separately using the heat capacity of the particular part of the system being considered and the temperature change that it undergoes. For the calorimeter
Gcalorimeter
=
C i i
c a o r
m e t e r
X. AT
(18-8)
After the neutralization, a solution of NaCl is present. Because heat capacities arc defined for one gram of a material, the volume must be converted to mass to calculate the heat absorbed by the solution: Solution = V X density X C
s o l u t i o n
X AT
(18-9)
The density of a sodium chloride solution of the concentration y o u are using here is 1.06 g / m l . The heat capacity of this solution is 0.931 cal/g C . A f t e r calculating the heat of the reaction for the amounts of the reactants used here, convert this heat term to cal/mole of a reaetant.
C. Heat of F o r m a t i o n of C u ( N H )
3
2 +
F o l l o w the procedure described in Part B for dealing w i t h the data. Here, y o u will also need to k n o w that the resulting C u ( N H ) S 0 solution has a density o f 1.06 g/ml and a heat capacity of 1.00 cal/g C . Express AH as cal/mole of C u .
3 4 4 2 +
197
QUESTIONS
1. Assume that after determining the heat capacity of y o u r calorimeter, y o u study an endothermic reaction for w h i c h 7 7 | equals 2 5 C . (a) Draw a small sketch, showing what a graph of T vs. t w o u l d look like for such a reaction. On the T scale, mark 2 5 C to make it obvious how r f i n a | w o u l d compare to 7 " i. (b) What w o u l d the direction of the heat "leakage" be? 2. B o t h of the reactions that y o u studied in this experiment are spontaneous; this means that AG is negative. For each reaction, explain whether it seems more likely that AS is positive or negative. In each case, does the entropy change act w i t h or against the enthalpy change to determine spontaneity?
initia initia
REFERENCE
REPORT
SHEET
E X P E R I M E N T 18
Name Section
Date
A. Determination of calorimeter heat capacity: Trial 1 Trial 2
T
T
^filial
AT for cold water AT for hot water
Qn
^calorimeter
^calorimeter
Average
c a l o r i m e t
er
Show the calculation of Q for one t r i a l :

c
Show the calculation of Q
for one t r i a l :
Show the calculation o f
for one trial:
(Attach your two graphs ofT vs. t. On the back of each graph, construct a table showing the time and the temperature data that you used to prepare the graph.)
B. Heat of neutralization: Trial 1

* initial
Trial 2
^filial
AT calorimeter solution AH A/7/molc o f I P Average A / / / m o l e o f H

+
On a separate sheet of paper, show calculation of calorimeter. solution. A / / , and A/Y/inole: C. Heat of f o r m a t i o n of C u ( N H )
3 2 + 4
: Trial 1 Trial 2
înitial ^t'inai AT
calorimeter
Oso, ution AH A///mole of C u

2 +
Average A H / m o l e o f C u
2 +
On a separate sheet of paper, show calculation of calorimeter. solution. AH, and A///'mole: (Attach your graphs ofT vs. t with data. Answer the questions from page 197 on a separate sheet of paper and attach it to the Report Sheet.)
Experiment 19 Solubility of an Electrolyte

Introduction
Different substances have considerably different solubilities in water. Calcium carbonate ( C a C 0 ) , which occurs naturally as the mineral limestone, is practically insoluble; it dissolves to the extent of only about 1CT mole in 1 liter of water at 2 5 C . On the other hand, sodium chloride (NaCI), or c o m m o n table salt, is fairly soluble; at 2 5 C , 1 liter o f water w i l l dissolve about 1.1 moles o f NaCI. Solubility depends not only on the identity of the substance but also on the temperature and the solvent. Thus, the solubilities of C a C 0 and NaCI in water w o u l d be different at a different temperature and might be very different in some other solvent.
3 4 3
In this experiment, y o u w i l l study the solubility o f C u ( I 0 strong electrolyte, in water at r o o m temperature. The purpose electrolyte system as a model for more complex systems, such solutions that contain several electrolytes and nonelectrolytes Water is often the best solvent for dissolving electrolytes such C u ( I 0 ) ( s ) ^ C u ( a q ) + 210 "(aq)
2+ 3 2 3
) is as in as
2
(copper iodate), a to study a simple physiological aqueous solution. copper iodate (19-1)
for t w o reasons. First, water is a l i q u i d of high dielectric constant. This means that the electrostatic attraction between cations and anions is considerably reduced by the intervening water molecules compared to the c a t i o n - a n i o n attraction in the crystalline state. In other words, the water molecules help to break d o w n the crystal lattice. Second, water molecules, w h i c h are polar, can surround ions to produce i o n - d i p o l e attractive interactions (see Figure 19-1). This further lowers the energy of ions in solution compared to ions in a crystal. Copper iodate is practically insoluble in water; the e q u i l i b r i u m in Equation (19-1) can be described by the value of A , the solubility product constant for this salt. In this experiment, y o u w i l l be asked to determine the value o f A at r o o m temperature, using the technique described below. If no substances are present in the solution except water and C u ( I 0 ) each ion will be in an environment like the one pictured schematically in Figure 19-1: each ion w i l l be completely separated from all other ions by the surrounding water molecules. Because C u ( I 0 ) is not very soluble, there w i l l be many more water molecules than ions and each ion w i l l "see" only water molecules in solution. However, if a reasonable concentration ( ~ 1 0 A / ) of other ions, such as K and N O J , is present in the solution, then the C u a n d l O j i o n s have some probability of encountering and interacting w i t h these ions as well as w i t h the water molecules. In effect, the presence of other ions changes the nature of the m e d i u m in w h i c h the copper iodate is being dissolved. In the second part o f this experiment y o u w i l l investigate the effect of the added, chemically inert electrolyte K N 0 (potassium nitrate) on the solubility of copper iodate.
s p s p 3 2 ) 3 2 _ 1 + 2 + 3
201
202
Experiment 19
beakers B c h n e r funnel buret burner Erlenmeyer flasks filter flask filter paper long-stemmed funnel
10-ml pipet ring ring stand rubber stoppers stirring rods vacuum tubing wire gauze
CHEMICALS NEEDED
C u S < V 5 H 0 , or C a ( N 0 ) - 4 H 0 , or C d ( N 0 ) - 4 H 0 KI0 O.lAf, 0 . 2 M , 0 . 3 M , and 0 A M K N 0 0.0S7W N a S 0 acetic acid 0.2% starch solution
2 3 2 2 3 2 2 3 3 2 2 3
TECHNIQUE
The experimental procedure to be followed in this experiment is straightforward. A sample o f copper iodate w i l l be prepared and then this sample will be used to prepare saturated solutions of the salt in distilled water and in K N 0 solutions. ( A l t e r natively, these solutions may be supplied by the instructor.) Carefully measured 10-ml portions o f these solutions w i l l be taken, and the amounts o f C u and I 0 " ions that each solution contains w i l l be determined. Using this i n f o r m a t i o n , the s o l u b i l i t y of the salt in moles/liter and the solubility product can be calculated.
3 2 + 3
203
S o l u b i l i t y of an E l e c t r o l y t e
An indirect procedure is employed in calculating the amounts of C u and I 0 ~ ions in each 10-ml p o r t i o n of saturated s o l u t i o n . Some solid KI (potassium iodide) is added to the solution causing the f o l l o w i n g reactions to occur:
2 + 3
Cu
3
2 +
+ 2I"
+ 3
->CuI(s) + f [, 3I + 9H 0
2 2
(19-2) (19-3)
I 0 - + 51" + 6 H 0
3 2
For each mole of C u ( I 0 ) that dissolves, 6.5 moles of F are produced: 0.5 mole from the reaction of one mole of C u ions and 6.0 moles from the reaction of the t w o moles o f I 0 ~ ions. By determining the amount o f I produced, it will be easy to calculate the q u a n t i t y of copper iodate originally present in the s o l u t i o n . The amount of iodine produced in the reactions of Equations (19-2) and (19-3) can be determined by t i t r a t i o n w i t h a standardized N a S 0 (sodium thiosulfate) s o l u t i o n , using a starch indicator. Iodine forms a deep-blue complex w i t h starch; the color w i l l disappear when all the I has been reconverted to colorless iodide ions by its reaction w i t h the thiosulfate ion
2 + 3 2 2 2 3 2
2S 0 - + I
2 2 3
S 0 " + 2r
2 4 6 2
(19-4)
Equation (19-4) states that for every mole o f I i n the s o l u t i o n , t w o moles o f S 0 w i l l be needed for t i t r a t i o n . Since each mole o f C u ( I 0 ) produces 6.5 moles o f I , each mole o f C u ( I 0 ) originally present in the solution w i l l require 13 moles of S 0 " . K n o w i n g the m o l a r i t y and the volume of the S 0 " solution used in the t i t r a t i o n permits the calculation of the number of moles of S 0 ~ used and consequently of the number of moles of C u ( I 0 ) originally present in the s o l u t i o n . I t w i l l be necessary to determine the exact m o l a r i t y o f the N a S 0 s o l u t i o n ; this is called standardizing the solution. The solution that w i l l be supplied is ~0.08/V/, but its molarity must be measured to a greater number of significant figures. Weighed samples of K I 0 (potassium iodate) can be dissolved in distilled water and then treated w i t h I " t o produce I via the reaction shown i n Equation (19-3). The I can then b e titrated w i t h N a S 0 s o l u t i o n . Since the number o f moles o f K I 0 i s k n o w n from weighing, the number o f moles o f N a S 0 required for the t i t r a t i o n can be calculated from Equations (19-3) and (19-4). Because this number of moles must be contained in whatever volume of N a S 0 solution was used in the t i t r a t i o n , the molarity can then be calculated.
2 2 3 3 2 2 3 2 2 2 2 3 2 3 2 2 3 3 2 2 2 3 3 2 2 2 2 3 3 2 2 3 2 2 3
Each t i t r a t i o n analysis should be made three times and the average of the results should be used. Before coming to class, reread the section on the use of a buret in the I n t r o d u c t i o n (see page 25).
PROCEDURE
The class should be divided i n t o teams of four students. Each student should prepare C u ( I 0 ) and determine its K in water and in one of the four K N 0 solutions. Data on the solubility in K N 0 solutions w i l l then be shared among team members.
3 2 ip 3 3
204
Experiment 19
Preparation o f C u ( I O , )
Y o u may be directed to o m i t this part of the experiment if the copper iodate is to be supplied by y o u r instructor. Use the triple-beam balance to weigh out about 2 g of C u S 0 ' 5 1 1 2 0 and 3.5 g of K 1 0 separately. In a 250-ml beaker, dissolve the K I 0 in about 50 ml of distilled water. In another beaker, dissolve the C u S 0 in about I 0 ml of distilled water. Pour the C u S 0 solution i n t o the K I 0 s o l u t i o n ; stir constantly. Use a Buchner funnel and a filter flask to collect the precipitated C u ( I 0 ) . Y o u are not interested in saving the s o l u t i o n , so y o u may discard the contents of the filter flask. Wash the precipitate w i t h three 5-ml portions of distilled water.
4 3 3 4 4 3 3 2
Preparation o f Saturated C u ( I O , )
Solution
Y o u may be directed to o m i t this part of the experiment if saturated solutions are to be supplied by y o u r instructor. Place about 1 g of C u ( I 0 ) in a 125-ml Erlenmeyer flask and add about 100 ml of distilled water. Swirl the flask repeatedly as y o u warm the m i x t u r e to 5060C w i t h a burner. Then cool the tlask and its contents to r o o m temperature. ( I f time permits, it is simplest to stopper the tlask and let it cool in y o u r desk u n t i l the next laboratory period.)
3 2
A. Standardization of N a S 0 j Solution
2 2
Y o u r instructor w i l l provide a sodium thiosulfate solution o f about 0.0SW concentration. Y o u must determine this concentration to as many significant figures as possible. Record y o u r results in y o u r notebook. (Prepare a data table similar to the one on the Report Sheet for this experiment.) Weigh 0.1 0 - 0 . 1 2 g of K I 0 as acctirately as possible on the analytical balance. Place this sample in an Erlenmeyer tlask and dissolve it in 2 5 - 3 0 ml of distilled water. A d d about 2 g of solid KI to this solution and swirl the tlask u n t i l all of it dissolves. Obtain about 400 ml of N a S 0 solution. This is all of this solution that y o u will use for the entire experiment. A f t e r the standardization, save the remaining N a S 0 solution in a stoppered container. Clean a 50-ml buret and rinse it w i t h three 5-ml portions o f the N a S 0 s o l u t i o n ; then fill the buret w i t h this s o l u t i o n . Be sure to record the i n i t i a l buret reading. N o w add 2 ml of acetic acid to the m i x t u r e in the Erlenmeyer tlask and begin to titrate this m i x t u r e w i t h the N a S 0 solution. The mixture in the tlask w i l l originally be y e l l o w - b r o w n in color because I is formed in the reaction of I0 "~ and I " . As S 0 converts I to colorless I ~ , the y e l l o w - b r o w n color will begin to fade. When the solution is a very pale y e l l o w , add 2 ml of starch solution. The remaining I w i l l form a deep-blue complex w i t h the starch. Titrate until the deep-blue color just disappears signaling that all of the 1 has reacted. Record the final buret reading to the nearest 0.02 m l .
3 2 2 3 2 2 3 2 2 3 2 2 3 2 3 2 _ 2 3 2 2 2
205
Make t w o more determinations, using t w o new portions o f K I 0 . Obviously, you w i l l not need to rinse the buret before each t i t r a t i o n , but y o u w i l l undoubtedly need to refill i t . Place the rest of the N a S 0 solution in a clean, dry, stoppered vessel. If necessary, y o u r w o r k may be interrupted here and continued during the next laboratory period.
3 2 2 3
B. Determination of C u ( I O . , )
Concentrations
First, remove any undissolved solid from the saturated C u ( I 0 ) solution by f i l t r a t i o n . Before y o u begin, reread the technique for gravity f i l t r a t i o n , described on p. 13 in the I n t r o d u c t i o n . Be sure the funnel and all glassware that y o u use in this f i l t r a t i o n are clean and dry; because y o u want to k n o w the concentration of C u ( I 0 ) in a saturated s o l u t i o n , it is essential that y o u do not dilute the solution. When all the solution has been filtered, check to see whether the filtrate seems cloudy. If it does, repeat the f i l t r a t i o n .
3 2 3 2
Pipet 10.00 ml of the clear filtrate [the saturated C u ( I 0 ) s o l u t i o n ] i n t o an Erlenmeyer flask. A d d about 1 5 ml of distilled water and then about 2 g of K I . Titrate this solution w i t h your standardized N a S 0 f o l l o w i n g the same procedure y o u used in the standardization. Be sure to add 2 ml acetic acid just before beginning the t i t r a t i o n and to add starch as the y e l l o w - b r o w n color fades. Remember to record the initial and the final buret volumes to the nearest 0.02 m l . Make this determination a total of three times.
3 2 2 2 3
C . Solubility o f C u ( l 0 )
3
i n K I M 0 , Solutions
To test the effect of an electrolyte on the solubility of C u ( I 0 ) , y o u should prepare a saturated solution of C u ( I 0 ) in one of the f o l l o w i n g solutions: 0 . 1 , 0.2, 0.3, or 0.4/V/ K N 0 . A l l o f these K N 0 solutions w i l l be provided. F o l l o w the technique for preparing a saturated solution given earlier, but substitute one of the K N 0 solutions for the distilled water. ( A l t e r n a t i v e l y , saturated solutions of C u ( I 0 ) i n K N 0 may b e provided b y your instructor.) This saturated solution is then filtered, just as y o u filtered the aqueous solutions, and three different 10-ml portions of the saturated solution are titrated w i t h standardized N a S 0 .
3 2 3 2 3 3 3 3 2 3 2 2 3
D . Solubility o f C a ( l 0 )
3
or C d ( l 0 , )
Calcium iodate or cadmium iodate can be prepared by substituting 4.9 g of C d ( N 0 ) - 4 H 0 or 4 g of C a ( N 0 ) - 4 H 0 for the C u S 0 in the first procedure ("Preparation o f C u ( I 0 ) " ) i n this experiment. The solubilities of these salts in distilled water and in K N 0 solutions can be determined using the technique described for C u ( I 0 ) . However, there is one i m p o r t a n t difference in the way that the calculations for these t w o electrolytes are
3 2 2 3 2 2 4 3 2 3 3 2
206
Experiment 19
made. The C a and C d ions do not react w i t h I" as C u does. Consequently, the only source o f the 1 that i s t i t r a t e d w i t h S 0 ~ i s the reaction o f the I 0 ~ w i t h I " [see Equation (19-3)] . This means that for each mole of the electrolyte that dissolves, 6.0 moles o f 1 w i l l be produced, instead o f the 6.5 moles o f iodine produced from C u ( I 0 ) .
2 + 2 + 2 + 2 2 2 3 3 2 3 2
C A L C U L A T I O N S AND
RESULTS
A. Standardization of N a S 0 j Solution
2 2
Calculate the number of moles of K 1 0 in each sample that y o u weighed. Equation (19-4) shows that 2 moles of S 0 a r e required to titrate each mole of I , while Equation (19-3) indicates that 3 moles o f I are produced b y each mole o f I 0 ~ i n y o u r weighed sample o f K I 0 . Thus, the number o f moles o f S 0 ~ used i n a t i t r a t i o n must be six times the number of moles of K I 0 y o u weighed out in the original samples. This is the number of moles contained in the number of liters of N a S 0 solution used in the t i t r a t i o n . The m o l a r i t y can be calculated from the definition
3 2 _ 2 3 2 2 2 3 3 2 3 3 2 2 3
,, M =
moles S 0 ~ 6 X moles KICK = liters o f solution liters o f N a S 0 solution

2 2 3 2 2 3 2 2 3
, . , , (lz-5)
n
Average y o u r three trials, and use this value as the m o l a r i t y M of the N a S 0 solution in the remaining calculations.
B. Determination of C u ( l 0 )
3
Concentrations
F r o m the volume of N a S 0 solution required to titrate the 10-ml portions of saturated solution and from the m o l a r i t y of the N a S 0 s o l u t i o n , calculate the number of moles of S 0 ~ used:
2 2 3 2 2 3 2 2 3
moles S 0 ~ = M X liters S 0 ~ solution used

2 2 2 3 2 3
(19-6)
From the i n t r o d u c t i o n to this experiment
molesCu(I0 ) =
3 2
m o l t f S
Ôa "
2
( 1 9
7 )
However, this is the number of moles contained in 10.00 ml of s o l u t i o n . F r o m this i n f o r m a t i o n , calculate the concentration of C u ( I 0 ) in the saturated solution in moles/liter. This is the s o l u b i l i t y s of C u ( I 0 ) .
3 2 3 2
Write the expression for / v for C u ( T 0 ) in terms of [ C u ] and [ I 0 ~ ] and then in terms of s. F o r each of the three trials y o u performed on the saturated s o l u t i o n , evaluate A ' using the value of s that y o u just determined. Take the average of these three trial values as the value of A " .
2 + s p 3 2 3 sp sn
207
QUESTIONS
1. F r o m y o u r team members, obtain the data for the three K N 0 solutions that y o t i did not study. What trend ( i f any) do y o u see in the s o l u b i l i t y of this typical strong electrolyte as a function of the concentration of the chemically inert electrolyte K N 0 ? Can y o u account for this trend w i t h a physical model? How? 2. Why is the saturated solution filtered to remove undissolved solid? Explain how y o u r calculated values of solubility ,y and of A ' w o u l d be affected if the undissolved solid were not removed. 3. Why is it important to filter the saturated solution into a dry vessel? Explain how your calculated values of 5 and A ' wotdd be affected if the saturated solution were collected in a wet vessel.
3 3 sp sp
REFERENCE
Yoder, C.H., Suydam, F . H . , and Suavely, E.A. Chemistry. New Y o r k : Harcourt Brace Jovanovich, Inc., 1975. Chapter 14.
Name Section Date
A . Standardization o f N a S 0 s o l u t i o n :
2 2 3
Trial 1 Weight o f K I 0 Moles K I 0

2 3 3
Trial 2
Trial 3
Moles S 0 ~ needed
2
V o l u m e S 0 " used
2 2 3
Molarity o f N a S 0
2 2
Average m o l a r i t y Show a sample calculation of the molarity of the N a S 0 s o l u t i o n . Be sure to include all units-and to retain the proper number of significant figures.
2 2 3
B . Determination o f C u ( I 0 )
3 3 2
concentrations:
1. S o l u b i l i t y of C u ( 1 0 ) in water Trial 1 V o l u m e S 0 ~ used

2 2 3
Trial 2
Trial 3
Moles S 0 ~ used
2 2 3
Moles C u ( I 0 )
3
present
3 2
Solubility o f C u ( I 0 ) in moles/liter
Ks
Average A '
sp
Show a sample calculation of moles S 0

2
2 _ 3
used:
Show a sample calculation of moles C u ( I 0 )

3
present:
Show a sample calculation of solubility of C u ( I 0 ) in moles/liter:

3 2
Show a sample calculation of K :

sp
Name Section
2 . Solubility o f C u ( I 0 ) i n
3 2
M KN0 Trial 1
Trial 2
Trial 3
V o l u m e S 0 ~ used
2 2 3
Moles S 0 " used

2 2 3
Moles C u ( I 0 )
3
present
3 2
Solubility o t " C u ( I 0 ) in moles/liter Average solubility Solubility o f C u ( I 0 ) i n

3 2
M KN0 :
3
(data from _ ^
Solubility o f C u ( I 0 )
3
in
M KN0 :
3
(data from
Solubility o f C u ( I 0 ) i n
3 2
M KN0 :
3
(data from
(Answer the questions from page 207 below and on
Experiment 20 Gravimetric Determination

Introduction
of Iron
Chemistry severed its connections w i t h the mystical practices of alchemy and became a modern science when the importance of precise quantitative methods of investigation was recognized. Perhaps the most fundamental quantitative measurement in chemistry is the measurement of the amounts of materials involved in chemical reactions. The nature of many chemical reactions and the composition of many compounds could not be understood u n t i l accurate mass (or weight) determinations became possible. We still base much o f our knowledge about the composit i o n of substances on measurements of the weights of their components. In this experiment, y o u w i l l deal w i t h gravimetric analysisanalysis by measuring weights an historical but still an i m p o r t a n t method of quantitative chemical analysis. Step by step, the general procedure for the gravimetric determination of a particular ion is as follows: 1. Dissolve a k n o w n weight of the sample containing the ion of interest. 2. A d d to the solution a substance that w i l l form an " i n s o l u b l e " c o m p o u n d w i t h the i o n of interest. The s o l u b i l i t y of this c o m p o u n d must be low enough that .the weight of the ion remaining in solution is too l o w to be measured w i t h the laboratory instruments available. 3. Collect the compound by f i l t r a t i o n . 4. Wash the c o m p o u n d to remove soluble contaminants. 5. Dry the compound and weigh i t . If the c o m p o u n d has been collected in filter paper, the paper must be burned o f f so that only the pure, dry c o m p o u n d remains. 6. Calculate the weight of the ion of interest contained in the precipitate. 7. Calculate the percentage by weight of the i o n of interest in the original sample. For an analysis of this type, y o u must learn three new skills that have long been a part of the chemist's repertoire: quantitative p r e c i p i t a t i o n , quantitative f i l t r a t i o n , and the i g n i t i o n of a precipitate to free it of f i l t e r paper and water. In this experiment, y o u w i l l be asked to p e r f o r m a gravimetric analysis for i r o n . This procedure can be used to determine the p u r i t y of iron salts, to measure the amount of i r o n that is present in alloys such as brass or bronze, and to determine the amount of i r o n in some ores. A precipitate forms when aqueous ammonia is added to a solution containing F e . F r o m the simplest point of view, the equation for this reaction is
3+
Fe
3 +
+ 30fP
Fe(OH) (s)
3
(20-1)
A c t u a l l y , the precipitate is hydrated w i t h an u n k n o w n , variable amount of water. Removal of water by drying above 8 0 0 C converts the precipitate to F e 0 (ferric
2 3
213
214
Experiment 20
oxide), one of the c o m m o n forms in which i r o n occurs in nature. K n o w i n g the weight of F e 0 , the weight and the percentage of iron in the original sample can be calculated.
2 3
EQUIPMENT NEEDED
ashless filter paper 100-ml beaker 400-ml beakers (2) 800-ml beaker Bunsen burner clay triangle desiccator ring funnels (2) glass stirring rods (2)
10-ml graduated cylinder 100-ml graduated cylinder medicine dropper Meeker (or other high-temperature) burner porcelain crucibles w i t h lids (2) ring stand small test tubes wash b o t t l e
CHEMICALS NEEDED
0.1 A/ A g N 0 6M HC1 cone. H N 0 cone. N H NH N0 unknown

3 3 4 3
TECHNIQUES
A. Preparing the Samples
The sample is a pure or an impure salt that contains i r o n as F e or F e . The sample is dissolved in an acidic solution, because many iron salts are insoluble at pH = 4 or greater. The analysis is based on the presence of F e ; consequently, F e must be oxidized to this state. N i t r i c acid is used to accomplish this. The reaction is
2 + 3 + 3+ 2 +
3Fe
2 +
+ NOJ + 4 H 0
3
3Fe
3 +
+ NO(g) + 6 H 0
2
(20-2)
The solution may darken, depending on what other ions are present in s o l u t i o n . It is boiled to hasten the o x i d a t i o n reaction and then to remove the N O . A clear, y e l l o w color characteristic of F e should be present.
3 +
B. Precipitation
The precipitate is not crystalline and does not even appear to be composed of particles. Instead, it has a gelatinous appearance because its particles are very small,
215
Gravimetric Determination of Iron
below the l i m i t s of ordinary microscopic v i s i b i l i t y . The smaller the particles are that comprise a precipitate, the more d i f f i c u l t it is to collect the precipitate by filtration; extremely small particles may clog the pores o f the filter paper or may simply pass through the paper. However, when the precipitate of hydrated F e ( O H ) forms at a high temperature, its particles are somewhat larger (although s t i l l invisible) thaji when it forms at r o o m temperature; consequently, the solution is maintained at a near b o i l d u r i n g the p r e c i p i t a t i o n . A f t e r the p r e c i p i t a t i o n is complete, boiling is continued for one minute to allow the particles to coagulate and to settle o u t of suspension as a gelatinous mass. Longer heating must he avoided, for it produces the opposite effect: aggregates break up and the precipitate becomes slimy and more d i f f i c u l t to collect by f i l t r a t i o n .
3
C. Collecting and Washing the Precipitate
Reread the technique for gravity f i l t r a t i o n described on page 13 in the Introduct i o n . Folding the filter paper properly, filtration by decantation, and the complete transfer of the precipitate to the filter paper are very i m p o r t a n t techniques here. The supernatant l i q u i d is decanted through the filter paper keeping as much of the precipitate as possible in the beaker; a large amount of solid in the funnel w o u l d slow the f i l t r a t i o n . A stirring rod is used to direct the s o l u t i o n , to prevent splashing, and to prevent d r i p p i n g from the beaker spout. The precipitate w i l l be contaminated w i t h other ions that were in the solution: C I " from the h y d r o c h l o r i c acid used to dissolve the salt, the anion that was originally combined w i t h the i r o n , and any other i m p u r i t y that was present in the sample. To ensure that only..ferric oxide remains after the i g n i t i o n , these adsorbed ions must be removed. The ions are simply washed away. Pure water could be used, but the aggregated precipitate has a tendency to disperse unless it is in contact w i t h an electrolyte s o l u t i o n . Therefore, a dilute solution of a m m o n i u m nitrate is used to wash away the unwanted ions. A n y a m m o n i u m nitrate that is retained by the precipitate w i l l volatilize during ignition. A l t h o u g h not all of the contaminating ions that might be present are k n o w n , chloride is k n o w n to be among them. A test for this i o n w i l l determine whether the precipitate has been washed sufficiently. A few drops of the filtrate are collected in a small test tube containing a silver nitrate s o l u t i o n . If Cl~ is still present, a white precipitate o f AgCl w i l l form. I f this happens, the test s o l u t i o n should be discarded and the precipitate should be washed u n t i l the filtrate shows no precipitate or only a very faint t u r b i d i t y in silver nitrate solution. A f t e r the precipitate in the beaker has been washed, it is transferred i n t o the funnel w i t h the aid of a stream of water from a wash b o t t l e and allowed to drain as thoroughly as possible.
D. Ignition of the Precipitate
The crucible is placed in a slanted position on a clay triangle on a ring; the lid is slightly ajar. Gentle heat is applied first to dry the filter paper. Strong heat could cause spattering and some precipitate could be lost.
216
Experiment 20
When the filter paper is d r y , it is charred at as low a temperature as possible. The crucible must be partially uncovered to allow contact w i t h air. In the absence of air, F e 0 could be reduced to F e 0 . The filter paper must not be allowed to burst i n t o flame, because gas currents might carry particles of the precipitate out of the crucible. If flames or even sparks appear, the crucible should be covered immediately to smother t h e m .
2 3 3 4
When the filter paper is entirely charred, the heat is increased to complete the c o m b u s t i o n of the carbon that remains and to drive all water out of the precipitate. When the i g n i t i o n is complete, the crucible is cooled in a desiccator to keep it clean and to prevent the crucible and the precipitate from absorbing moisture.
PROCEDURE
In an 8 0 0 - m l beaker, prepare 600 ml of a 1% (by weight) solution of N H N 0 , which y o u w i l l use to wash the precipitate. Begin heating this solution while y o u prepare the samples. Use the analytical balance to weigh o u t , by difference f r o m the sample b o t t l e , t w o 0 . 7 - 0 . 9 g samples of y o u r u n k n o w n i n t o t w o clean 4 0 0 - m l beakers. Be sure to mark the beakers, so that y o u w i l l k n o w w h i c h beaker contains which sample. A d d 50 ml of distilled water and 10 ml of 6M HC1 to each beaker. Heat one of the solutions to a near b o i l and add 2 ml (40 drops from a medicine dropper) of concentrated H N 0 to the solution dropwise. B o i l the solution gently u n t i l it has a clear, y e l l o w color (this takes at least 3-5 minutes). In a small beaker, add 10 ml of concentrated N H to 10 ml of distilled water. Stir constantly w i t h a glass r o d as y o u add about 15 ml of this solution in a slow stream to the F e s o l u t i o n . A l l o w the precipitate to settle slightly and then run a few drops of the N H s o l u t i o n d o w n the inside wall of the beaker; watch closely to see if any more precipitate forms. If it does, add N H dropwise u n t i l there is no evidence of precipitate f o r m a t i o n ; then add about a 2 ml excess of N H . If precipitat i o n appears to be complete, simply add the excess 2 m l o f N H . There w i l l be a noticeable o d o r of N H in the steam above the m i x t u r e after an excess of N H has been added. N o w gently b o i l the m i x t u r e for one minute. Then remove the burner and allow the precipitate to settle. Decant as m u c h of the supernatant l i q u i d as y o u can through filter paper in a funnel: transfer as l i t t l e as possible of the precipitate. Then add about 30 ml of h o t N H N 0 solution to the precipitate in the beaker. Stir the m i x t u r e t h o r o u g h l y and allow the precipitate to settle. Decant as much of the l i q u i d as y o u can i n t o the funnel. Repeat this washing t w o more times. Test a few drops of the filtrate for C P ; if CP is present, repeat the washing and the test for CP as often as necessary. When washing is complete, transfer the precipitate to the funnel. Use a stream of distilled water from a wash b o t t l e to remove particles from the beaker wall and stirring rod. D u r i n g the f i l t r a t i o n of the first sample, carry out the o x i d a t i o n and precipitat i o n of the second sample. Be careful not to interchange the t w o samples after y o u begin filtering the second sample. Once y o u start a f i l t r a t i o n , y o u must complete i t . If the precipitate is allowed to d r y , its surface w i l l crack and form channels through which the wash solution w i l l run w i t h o u t effectively washing the precipitate.
4 3 3 3 3 + 3 3 3 3 3 3 4 3
217
Gravimetric Determination of Iron
After washing, drain each precipitate as thoroughly as possible in the funnel. If y o t i r schedule permits, allow the precipitates and filter paper to dry in y o u r desk (where d i r t cannot fall i n t o them) u n t i l the next laboratory period. Wash a crucible and l i d ; support them on a clay triangle on a ring, and apply the full heat of a Meeker (or other high-temperature) burner to them for at least 15 minutes. A l l o w the crucible and l i d to cool on the triangle for a minute and then to cool to room temperature in a desiccator (this should take about 1 5 - 2 0 minutes). While the first crucible is cooling, wash and heat a second crucible and l i d . Weigh each crucible ( w i t h l i d ) on the analytical balance. When y o u record the weights, also record the i d e n t i f y i n g numbers and letters that are on each crucible and l i d , so that y o u w i l l k n o w which sample y o u put i n t o w h i c h crucible. Heat, cool, and weigh the crucibles as many times as y o u need to u n t i l y o u obtain t w o consecutive weighings that differ by no more than 0.0006 g. Use the final weight in y o u r calculations. Fold the open edge of the filter paper over to enclose the precipitate, and place the paper, open-end d o w n , in a crucible that has been heated to constant weight. Heat the nearly covered crucible slowly to dry the paper; hold the burner in y o u r hand, so that y o u can remove the heat immediately if the paper begins to flame or spark. Char the paper w i t h o u t i n f l a m i n g , and then burn o f f the carbon w i t h free access to the air. Be sure that the l i d , as well as the crucible, is freed of carbon. Then continue heating the open crucible at the highest possible temperature for at least 10 minutes to remove the last traces of water from the oxide. Be careful to keep the gases of the flame from entering the i n t e r i o r of the crucible, for they could react w i t h the F e 0 . Cool the crucible for a minute on the triangle; then cover the crucible and cool it to r o o m temperature in a desiccator. Repeat this process w i t h the second crucible. Weigh each crucible, l i d , and contents on the analytical balance. Repeat the h i g h t e m p e r a t u r e heating, cooling, and weighing u n t i l t w o consecutive weighings differ by no more than 0.0006 g. This w i l l indicate that all volatile and combustible materials (water, N H N 0 from the wash s o l u t i o n , and filter paper) have been removed, leaving pure F e 0 . Use the final weight in y o u r calculations.
2 3 4 3 2 3
CALCULATIONS
For each sample, determine the weight of F e 0 , the weight of i r o n in the oxide, and the percentage of the original sample weight that was i r o n . Report an average for the t w o samples. Be sure to retain the proper number of significant figures. Describe any departures that y o u made from the procedure given here and any problems y o u encountered or any blunders y o u made that could affect the accuracy of y o u r results for either t r i a l .
2 3
QUESTIONS
1.
What effect ( t o o high, t o o l o w , no change) w o u l d each of the f o l l o w i n g have on y o u r calculated percentage of i r o n in comparison to the correct percentage of i r o n for y o u r u n k n o w n ? (a) Some u n k n o w n sample is lost after it is weighed. ( b ) The F e is n o t completely precipitated.
3 +
218
Experiment 20
2.
3.
(c) The precipitate is n o t t h o r o u g h l y washed. (d) The filter paper is n o t completely burned off. (e) Some F e 0 is reduced to F e 0 . (f) The original sample contained a m i x t u r e of F e and F e . Using the procedure described in this experiment, a 0.8014 g sample of wet, hydrated F e ( N 0 ) yields a residue of F e 0 that weighs 0.1483 g after ignit i o n . Calculate the percentages of Fe, F e ( N 0 ) , and H 0 in the sample. If y o u use the quantities of reagents described in this experiment, the concentrat i o n of O H " remaining in the solution should be n o t less than \0~ M. (a) What concentration of F e can remain in solution w i t h this concentration of O H " , rather than be precipitated as F e ( O H ) ? (b) What weight of F e w o u l d remain in the volume of solution that y o u had in this experiment? (c) What weight o f F e 0 w o u l d contain the weight o f F e remaining i n solution? If this F e were precipitated entirely, could y o u detect the presence of the additional F e 0 ? E x p l a i n y o u r answer. Can this be considered an essentially complete p r e c i p i t a t i o n of F e ?
2 3 3 4 2+ 3 + 3 3 2 3 3 3 2 S 3 + 3 3 + 3 + 2 3 3 + 2 3 3+
REFERENCES
1. Yoder, C . H . , Suydam, F . H . , and Snavely, F . A . Chemistry. New Y o r k : Harcourt Brace Jovanovich, 1975. Chapter 14. 2. Vogel, A . I . Quantitative Inorganic Analysis, Second E d i t i o n . New Y o r k : John Wiley & Sons, Inc., 1 9 6 1 . Chapter V.
REPORT
SHEET
EXPERIMENT 20
Name Section
Date
Data: Trial 1 Weight of u n k n o w n sample Weight of crucible and l i d A f t e r first heating A f t e r second heating A f t e r t h i r d heating A f t e r f o u r t h heating Weight o f crucible, l i d , and F e 0
2
Trial 2
A f t e r first heating A f t e r second heating A f t e r t h i r d heating A f t e r f o u r t h heating Weight o f F e 0

2 3
Weight of Fe in sample Percentage Fe in sample Average percentage Fe Average deviation On the back of the Report Sheet, show the calculation of weight and percentage of Fe in the u n k n o w n for one trial. f Answer the questions from pages 217-218 on the back of the Report Sheet.)
Experiment 21 Acid-Base Titration

Introduction
Much of chemistry and biology is concerned w i t h the behavior of acids and bases. Many chemical reactions can be enhanced ( i f they are desirable) or can be retarded ( i f they are undesirable) by adjusting the acidity of the reaction m i x t u r e . For example, the concentration of acid in the stomach must be quite high (in comparison to the rest of the b o d y ) to break d o w n proteins in the digestive process. This experiment is designed to serve as an i n t r o d u c t i o n to a quantitative determination of the amount of acid or base in an aqueous s o l u t i o n . Acid-base t i t r a t i o n is a c o m m o n laboratory procedure of substantial chemical importance and it has many applications in biochemical and medical laboratory w o r k as w e l l . The procedure y o u w i l l use in this experiment is based on the most fundamental property o f acids and bases: their neutralization reaction H A + BOH > H 0 + BA
2
or
acid + base water + salt
The f o l l o w i n g discussion w i l l show that from a quantitative p o i n t of view, if the amount of base (or acid) in one solution is accurately k n o w n , then the amount of acid (or base) in a second solution can be determined by measuring how much of it w i l l exactly neutralize the base (or acid) in the first s o l u t i o n . Concentrations of acid and base solutions are often given in terms of n o r m a l i t y N: ..^ number of equivalent weights N = normality = - solution volume (in liters) The equivalent weight of an acid or a base is defined as equiv. w t . = molecular weight ; number of reactive H or OH / t o r m u l a unit
The equivalent weight of an acid or a base is therefore the number of grams that contains one mole of reactive H or O H " . The d e f i n i t i o n of equivalent weight makes it possible to state a simple relationship between acids and bases: one equivalent weight of an acid will react with exactly one equivalent weight of a base (for example, 0.04 equivalent weight o f acid will react w i t h 0.04 equivalent weight o f base). An equivalent weight is often referred to as an equivalent. Thus, in an acidbase neutralization reaction, a sample of acid (or base) of unknown equivalent weight w i l l be neutralized when it has combined w i t h the same
+
221
222
Experiment 21
number of equivalent weights of the titrant base (or acid) of known concentration; at neutralization no. e q u i v
s a m p l e
= no. e q u i v ,
itrant
(2 l - l )
In this experiment, y o u w i l l be asked to determine the equivalent weight o f an u n k n o w n acid by t i t r a t i n g an accurately weighed sample o f the acid w i t h a base solution of known n o r m a l i t y A ^ N a O H ) - Y o u w i l l use Equation (2 l - l ) and the definitions of the equivalent weight and the normality of a solution to accomplish this d e t e r m i n a t i o n . The t i t r a n t is the sodium h y d r o x i d e solution; the sample is an u n k n o w n solid acid: g acid 1 = no. e q u i v equiv wtacjd
=
acid
= no. e q u i v
H)
N a O H
^(NaOH) X K
(21-2)
By neutralizing a carefully weighed sample of an acid of known equivalent weight w i t h a base solution y o u prepare, y o u can calculate the n o r m a l i t y o f the base solution by using the relationship
AW>H)=
equiv w t
p arid
a c i d
V T / X K
(21-3)
( N a O H )
A f t e r the base has been standardized (that is, after its n o r m a l i t y has been determined), y o u can use it to titrate a carefully weighed sample of unknown acid, and thus find the equivalent weight of the u n k n o w n acid: equiv w t = g acid *L
*
a c i U
.
' (NaOH)
,~ , (21-4)
'V(NaOH)
This experiment consists of three parts: Using the stock solution o f 6 A N a O H , you will prepare a solution o f ~0.1/V N a O H by d i l u t i o n w i t h distilled water that has been boiled ( t o expel C 0 , w h i c h dissolves in water to form carbonic acid) and cooled. 2. Y o u w i l l standardize y o u r N a O H solution by titrating it w i t h an acid o f k n o w n equivalent weight. 3. Y o u w i l l then use y o u r standardized NaOH to determine the equivalent weight of an u n k n o w n solid acid. This experiment emphasizes how necessary it is to w o r k accurately in the laboratory at all times. If y o u r standardization is not carefully done, y o u r determination o f the equivalent weight o f the acid w i l l probably be inaccurate. Before c o m i n g to class, reread the section concerning the use of burets in the I n t r o d u c t i o n (pages 2 5 - 2 8 ) .
/ 2
1.
EQUIPMENT NEEDED
beakers 50-ml buret
clamps Erlenmeyer flasks
223
Acid-Base Titration
flat-bottomed flask graduated cylinder
rubber
stopper
CHEMICALS
NEEDED
K H C H 0 (potassium hydrogen phthalate) 6N NaOH phenolphthalein indicator u n k n o w n solid acid

8 4 4
PROCEDURE
A. Preparation of N a O H S o l u t i o n
Boil about 350 ml of distilled water in a 400-ml beaker for a few minutes to expel the dissolved C 0 . Pour about 295 ml of this water i n t o y o u r flat-bottomed flask; cool the flask under tap water. N o w , add about 5 ml of the 6N N a O H to the water. S w i r l the flask to m i x the contents t h o r o u g h l y . Y o u can prepare the N a O H solution the week preceding the titrations and store the solution in y o u r desk if it is well stoppered. Be careful not to permit the solution to come in contact w i t h the stopper. The flask should be stoppered as much as possible t h r o u g h o u t the remainder of the experiment.
2
B. S t a n d a r d i z a t i o n of N a O H Solution
The N a O H solution is standardized by measuring the volume needed to titrate an accurately k n o w n weight o f K H C H 0 (potassium hydrogen phthalate), w h i c h has an equivalent weight of 204.2 g. One advantage of using a solid for a standardization is that y o u do not have to rely on the accuracy of anyone else in preparing solutions you w i l l use. The only sources o f experimental error i n the amount o f acid are y o u r o w n weighings, and the errors in these should be m i n i m a l . Clean and fill a 50-ml buret w i t h the ~0.1yV NaOH solution that y o u prepared. D o n ' t forget to rinse the buret w i t h the solution first. Before filling the buret, swirl the flask to be sure that the solution is homogeneous. On the analytical balance, weigh about 0.6 g of K H C H 0 i n t o an Erlenmeyer flask. This weight must be k n o w n to the m a x i m u m precision of the balance. If small bottles of this standard acid are provided, it is advisable to weigh the b o t t l e , take a sample of the appropriate size, reweigh the bottle and determine the weight of the sample by difference. If y o u determine the sample weight by weighing the flask and then weighing the flask and the sample, y o u must be sure that the flask is dry; otherwise, evaporation w i l l occur during the weighing and y o u r sample weight w i l l be inaccurate. Dissolve the sample in about 30 ml of distilled water. A d d no more than 2 or 3 drops of phenolphthalein indicator, and titrate to the endpointthe palest possible p i n k color. Carefully note the volume of base that y o u used; estimate each reading to the nearest 0.02 m l .
8 4 4 8 4 4
224
Experiment 21
Make a total of three standardizations using samples of K H C H 0 of about 0.6 g each time. If t w o of y o u r calculated values for the concentration of y o u r NaOH s o l u t i o n do not agree w i t h i n 2%, repeat the standardization procedure one more time.
s 4 4
C. T i t r a t i o n of an U n k n o w n A c i d
Obtain a sample of an u n k n o w n solid acid from your instructor. Y o u must determine its equivalent weight by t i t r a t i n g accurately weighed samples of this acid w i t h the standardized base and noting the exact volume o f base used for each t i t r a t i o n . First y o u must decide h o w large a sample of the acid to weigh out for a t i t r a t i o n . Y o u do not want to take so much acid that more than 50 m l o f base w i l l be required to neutralize i t . If this were to happen, you w o u l d have to refill the buret in the course of one t i t r a t i o n ; not only w o u l d this be inconvenient, but it w o u l d also force y o u to make four (instead of t w o ) volume readings to determine the volume of the base that y o u used. Because each reading is subject to an uncertainty of 0 . 0 2 m l , y o u r t o t a l uncertainty could be 0 . 0 8 m l , or twice as great as when only t w o volume readings are required. On the other hand, it is advantageous to use as large a volume o f base as possible (as long as y o u do not have to refill the buret and y o u do not deplete y o u r supply of base s o l u t i o n ) . For any volume determ i n a t i o n , y o u must make an i n i t i a l and a final reading for a total uncertainty of 0 . 0 4 m l . This amount o f uncertainty w i l l make less percentage difference in a volume of, say, 40 m l than it w i l l i n a volume of, say, 10 m l . T o obtain the greatest accuracy, y o u must choose an amount o f acid that w i l l consume as large a volume o f base as possible w i t h o u t exceeding 50 m l . The u n k n o w n acids for this experiment have equivalent weights ranging from ~ 5 0 g to ~ 2 0 0 g. Since y o u do not k n o w the exact equivalent weight of y o u r acid, y o u should make a rough t i t r a t i o n to determine its approximate equivalent weight. Weigh out about 0.2 g of the u n k n o w n acid and titrate i t . The results of this titrat i o n w i l l help y o u choose an appropriate sample weight for the next t w o trials. Weigh out t w o more samples o f the u n k n o w n in amounts that will require about 3 0 - 4 0 m l o f base. Keep in m i n d that i f y o u run out o f base, y o u w i l l have to prepare and standardize a new s o l u t i o n . Therefore, y o u will probably want to take small enough samples that some base solution remains for a fourth t i t r a t i o n , in case t w o of y o u r three trials do not agree w i t h i n 2%. T i t r a t e these t w o samples of the u n k n o w n .
Calculate the n o r m a l i t y of the base [ E q u a t i o n (2 1-3)] for each of your three standardization trials. Report the average of these three trials or of y o u r best t w o trials as the n o r m a l i t y of the base. Using the n o r m a l i t y y o u just calculated for the NaOH s o l u t i o n , determine the average equivalent weight of the u n k n o w n acid from Equation (21-4). Note that y o u could calculate the molecular weight of this acid only when y o u k n o w h o w many acid hydrogens it has. T u r n in y o u r calculations and your identification code of the acid. Indicate the uncertainties in y o u r results on the Report Sheet.
225
Acid-Base Titration
QUESTIONS
1. H o w w o u l d y o u r calculated n o r m a l i t y of the sodium h y d r o x i d e solution be affected ( t o o high, too l o w , no change) by each of the f o l l o w i n g errors? (a) The buret is not rinsed w i t h the solution before it is filled. (b) Some K H C H 0 is spilled out of the flask after it is weighed. (c) Some solution splashes out of the flask during the t i t r a t i o n . (d) Y o u go past the endpoint in the t i t r a t i o n . 2. How w o u l d your calculated value for the equivalent weight of the acid be affected ( t o o high, too low, no change) by each of the f o l l o w i n g errors? (a) Some acid is spilled out of the flask after it is weighed. (b) Some solution splashes out of the flask during the t i t r a t i o n . (c) Y o u go past the endpoint in the t i t r a t i o n .
8 4 4
REFERENCE
Yoder, C.H., Suydam, F . H . , and Snavely, F.A. Chemistry. New Y o r k : Harcourt Brace Jovanovich, Inc., 1975. Chapter 15.
Experiment 22 Antacids
Introduction
An antacid is a substance that prevents or neutralizes acidity. We most comm o n l y use the term to refer to a medication (almost always nonprescriptive) used to neutralize acid in the stomach. Part of the digestion process takes place in the stomstomach, where food is acted on by gastric juices that contain digestive enzymes and hydrochloric acid. Pure gastric juice is quite acidic, w i t h a pH of ~1 ( [ H 0 ] = l C T ' A f but stomach contents consisting of a m i x t u r e of gastric juice and food are less acidic, w i t h a pH of ~3 ( [ H 0 ] = \0~ M). Hence, an "acid s t o m a c h " is perfectly normal, because the acidity is necessary for proper digestion to occur. However, under some circumstances such as e m o t i o n a l stress, a person may have an unusually large q u a n t i t y of acid in the stomach. Highly acidic or spicy foods may also cause a feeling of abnormal acidity. The terms "excess stomach a c i d , " "acid indigestion," " h y p e r a c i d i t y , " "sour stomach," and " h e a r t b u r n " are all used to describe these conditions. Antacids contain basic compounds that neutralize acid; these compounds either contain h y d r o x i d e ions or react w i t h water to produce h y d r o x i d e ions. Usually these are compounds that have a l o w solubility in water; they dissolve more readily in acid and neutralize the acid as they dissolve in i t . Antacids may be purchased either as tablets consisting of acid-neutralizing compounds, nonreactive " f i l l e r s , " and perhaps flavoring agents pressed together or as a water suspension of the ingredients. Common active ingredients are M g ( O H ) (magnesium h y d r o x i d e ) ; A l ( O H ) ( a l u m i n u m h y d r o x i d e ) ; C a C 0 (calcium carbonate); M g C 0 (magnesium carbonate); M g S i 0 (magnesium trisilicatc); and N H C H C 0 H (glycine). Just one or several of these ingredients may be present in a particular antacid.
+ 3 + 3 3 2 3 3 3 2 3 8 2 2 2
50-ml burets (2) clamps
Erlenmeyer flasks ring stand
CHEMICALS NEEDED
\2M HC1, or standardized \M HC1 K H C H 0 (potassium hydrogen phthalate) 6M N a O H , or standardized 0.5A/ N a O H antacids m e t h y l orange-xylene cyanole indicator phenolphthalein indicator
8 4 4
229
230
Experiment 22
TECHNIQUE
In this experiment, the antacids w i l l be in tablet f o r m . A l l o f these antacids are commercial products that can be purchased at almost any drugstore w i t h o u t a prescription. The brand name o f the antacid w i l l not be k n o w n (unless it has recognizable marks on i t ) , and the acid-neutralizing c o m p o u n d or compounds contained in the tablet w i l l not be identified. First, the weight o f h y d r o x i d e that is present in or that can be produced by a particular tablet w i l l be determined. A l l the antacids used for this experiment contain compounds that are only slightly soluble in water; these compounds are combined w i t h fillers that are insoluble in b o t h water and in dilute acid solutions. Because the stomach p H is normally ~ 3 , it w i l l be necessary to find how much acid a tablet w i l l neutralize while maintaining a pH of ~ 3 . To accomplish this, a tablet will be treated w i t h more than enough HC1 ( h y d r o c h l o r i c acid) to dissolve the tablet and to react w i t h the acid-neutralizing compounds it contains. Then the remaining acid w i l l be titrated w i t h a standardized N a O H (sodium h y d r o x i d e ) solution. The acid-base indicator to be used is a m i x t u r e of m e t h y l orange and xylene cyanole. Its color change f r o m violet through neutral gray occurs at pH = ~ 3 . 6 . By k n o w i n g the number of moles of h y d r o x i d e used in the t i t r a t i o n and the number of moles of h y d r o n i u m ion in HC1, the number of moles of h y d r o x i d e ion provided by the antacid can be determined.
PROCEDURE
Standardized solutions of HCI and N a O H may be provided or y o u may be instructed to prepare and standardize one or b o t h of these solutions. The standardization of sodium h y d r o x i d e is described in detail in Experiment 2 1 . Prepare 0.5M NaOH by d i l u t i n g about 25 ml of 6M N a O H to 300 ml of solution w i t h distilled water that has been boiled and cooled. This standardization w i l l require three samples of K H C H 0 , each weighing about 2 g. Be sure to make the weighings on the analytical balance. A f t e r y o u k n o w the concentration of the N a O H s o l u t i o n , y o u can use this solution to standardize the HCI s o l u t i o n . A 1/V/ HCI solution can be made by d i l u t i n g about 17 ml o f \2JVI HCI to 200 m l o f solution. Three 10-ml portions o f this solution (each measured to the nearest 0.02 ml from a second buret) can be titrated to the phenolphthalein endpoint w i t h the N a O H solution. Y o u will use three one-tablet samples to determine the h y d r o x i d e content o f the antacid. Weigh a tablet on the analytical balance (preferably by difference from the bottle containing the tablets), and put it i n t o an F.rlenmeyer flask. Weigh all three tablets before y o u begin the experiment instead of completing the analysis of one tablet before y o u weigh another. Immediately put a few milliters of distilled water into the flask; the tablet w i l l begin to crumble in the water and w i l l dissolve more readily later. Be sure to mark each flask clearly, so that y o u k n o w the weight of each tablet. Use a buret to measure about 15 ml of HCI into the flask. Remember to take the initial buret reading, but do not take a final buret reading yet. Swirl the flask to speed the dissolving. It may help to crush the tablet w i t h a glass rod (do not use a
8 4 4
231
Antacids
metal utensil, because it might react w i t h the acid); be sure to rinse all solution and solid particles o f f the rod and i n t o the flask when y o u remove the r o d . Ten to fifteen minutes may be required for complete dissolution of the active c o m p o u n d . However, at this p o i n t , undissolved solid w i l l still be present; the inert filler w i l l remain as a powder. Be certain that no obvious chunks or chips of the tablet remain; just a u n i f o r m l y fine powder should be present in the flask. It is essential to dissolve the antacid c o m p o u n d completely, because any hydroxide-producing c o m p o u n d that does not dissolve cannot be detected in the analysis. This may be the most time-consuming part of the experiment. I f the tablets y o u are analyzing contain carbonate ions, they w i l l react w i t h HCI t o produce C 0
2
2H 0 + C0 + 2 3 3
< H C 0
2
C0 (g) + 3 I I 0
2 2
(22-1 )
2
As a tablet dissolves, it w i l l effervesce. After the effervescence subsides, the C 0 in solution must be removed before y o u begin the t i t r a t i o n ; i f any C 0 remains, it will react w i t h N a O l l . To remove the C 0 from the solution, heat the m i x t u r e to a near b o i l ; be careful not to let any solution spatter out of the flask. Continue to heat the flask gently for about five minutes; then cool the flask to room temperature under cold water. When y o u are sure that dissolution is as complete as possible, add 4 drops of m e t h y l orange-xylene cyanole indicator to the m i x t u r e . From a buret, rapidly add a stream of N a O H solution u n t i l the solution is definitely basic (that is, u n t i l y o u i n t e n t i o n a l l y go past the e n d p o i n t ) . Then rapidly add HCI dropwise, u n t i l y o u are sure the solution is acidic. N o w , carefully titrate the solution w i t h N a O H to the endpoint, w h i c h is reached when a neutral gray or brown-gray color persists in the t u r b i d solution. If you t h i n k y o u have passed the endpoint, add another drop or t w o of HCI and titrate the solution again w i t h N a O H u n t i l y o u reach the endpoint. This kind of t i t r a t i o n is often faster than the titrations y o u have performed in earlier experiments; it can also be more accurate. Remember to record the final readings for both burets. If the antacid and the acid produced C 0 that was not completely removed from the solution, the endpoint color of the solution may fade to gray when the endpoint is reached; if this happens, be more thorough in removing C 0 from the next mixtures. In t i t r a t i n g the remaining samples, you should use a greater amount of HCI if the amount of base solution that y o u used for the first sample was less than 10 m l .
2 2 2 2
CALCULATIONS
1. Use the volume of the N a O H solution and the molecular weight of K H C H 0 to calculate the concentration of the base solution for each of y o u r trials. For the rest of the experiment, use the average value from y o u r three trials. 2. Use the concentration of the base solution and the volumes of the acid and base solutions to calculate the concentration of the HCI solution for each of the three trials. For the rest of the experiment, use the average of these three values. 3. For each t i t r a t i o n performed on an antacid tablet: (a) Use the concentration and the volume of the acid solution to calculate the number o f moles o f H 0 used.
8 4 4 + 3
232
Experiment 22
4.
(b) Use the concentration and the volume of the base solution to calculate the number of moles of O H " used. (c) How many moles of H 0 were neutralized by the N a O H solution? (d) The remainder of the H 0 was neutralized by the antacid. Calculate the number o f moles o f O H provided b y the antacid. (e) Convert moles o f O H " t o weight o f O H " . (f) Determine the percentage by weight of the antacid tablet that is O H " Report an average percentage of O H " for the three tablets.
+ 3 + 3 -
QUESTION
H o w w i l l the calculated percentage o f h y d r o x i d e be affected (too high, too l o w , or not at all) by each of the f o l l o w i n g factors? (a) Some of the acid-neutralizing c o m p o u n d remains undissolved. f ( b ) The C 0 produced by the reaction of acid w i t h a carbonate c o m p o u n d is not fully removed. (c) Three acid-neutralizing compounds (rather than just one) are present in the antacid. (d) Y o u go past the e n d p o i n t in the t i t r a t i o n w i t h the antacid. (e) Y o u incorrectly record y o u r initial buret reading for the acid in the t i t r a t i o n of an antacid tablet as 0.03 ml rather than 0.30 m l .
2
FOLLOW-UP
A f t e r the Report Sheets have been submitted for this experiment, y o u r instructor may compile y o u r results and then issue a report i d e n t i f y i n g the tablets and giving the percentage by weight of O H " for each antacid. The costs of the tablets might also be compared.
REFERENCE
(Attach
a separate sheet of paper with the
answers to the question on page 232.)
Experiment 23 Acidic and Basic Salts

Introduction
Water makes up about t w o thirds of the weight of a human b o d y . Other animals contain comparable proportions of water, and some plants are almost 95% water. Water covers much of the earth's surface; it is in the soil, and it is present as vapor in the atmosphere. Consequently, reactions w h i c h occur in aqueous solutions and reactions in which water participates are i m p o r t a n t to us; many are essential to the life and g r o w t h of all organisms. Many of these reactions affect the pH of water by producing h y d r o n i u m or h y d r o x i d e ions. It is obvious from their formulas that some compounds w i l l produce H 0 or O H " in aqueous solution. A l l Arrhenius acids contain hydrogen, w h i c h is usually w r i t t e n first in the formula to emphasize its a b i l i t y to react w i t h water. Ionic A r rhenius bases contain h y d r o x i d e ions that become separated f r o m the positive ions when these compounds dissolve in water. Salts such as N a S 0 are ionic compounds that contain a cation from a base (in this case, Na , which is present in the ionic Arrhenius base N a O H ) and an anion from an acid (here, S 0 ~ , w h i c h is present in the Arrhenius acid H S 0 ) . A l t h o u g h not all of these compounds contain H or O H , many of them do react w i t h water to alter its p H . Such a reaction is called the hydrolysis of a saltthe reaction of an ion of a dissolved salt w i t h water that produces H 0 or O H " . The hydrolysis of a negative ion produces the negative ion of water. This react i o n occurs if the anion is the conjugate base of a weak acid. For example, H C N is a weak acid; K = 4.9 X 1 0 " :
+ 3 2 4 + 2 4 2 4 + 3 1 0 a
HCN + H 0
2
H 0 * + CN"
3
(23-1)
The acid molecule H C N has little tendency to donate protons; the conjugate base C N " accepts protons readily. Consequently, when a salt containing C N " , such as N a C N , is dissolved in water, a Br0nstedLowry acid-base reaction occurs between H 0 (acid) and C N " (base); that is, a p r o t o n is transferred from H 0 to C N " :
2 2
H 0 + C N " =^ H C N + O H "
2
(23-2)
The resulting solution is basic, because h y d r o x i d e ions in excess of those produced by the autoionization of water are present. The hydrolysis of a positive ion produces the positive ion of water. This reaction occurs if the cation is the conjugate acid of a weak base. Molecular bases such as N H are weak bases:
3
NH
b
+ H 0
2 5
NH
+ 4
+ OH"
(23-3)
F o r this reaction, K = \ .8 X 1 0 " . The forward reaction shows the proton-accepting behavior of the base N H . The reverse reaction indicates the proton-donating a b i l i t y
3
235
236
Experiment 23
of N H V , the conjugate acid of the base. The a m m o n i u m ion can donate H to any substance that is capable of acting as a base. Consequently, when a salt containing N H is put into water, N H and H 0 react in a B r c m s t e d - L o w r y acid-base fashion:
+ + + 4 4 2
NH
+ 4
+ H 0 - NH + H 0
2 3 3
(23-4)
Some hydrated metal ions also h y d r o l y z e to produce acidic solutions. The strong attraction between a small, perhaps highly charged metal ion and the oxygen atom of a watei" molecule weakens an oxygenhydrogen bond in the water molecule. As a result, the hydrate acts as a p r o t o n donor: [M(H 0)J " + H 0 ^ [M(H 0) ,^
+ 2 2 2 (
(OH)]*"
- 1
+ H 0
3
(23-5)
Reactions of this type often are responsible for the acidity of s o i l s . ^ The extent to which a hydrolysis reaction occurs is related inversely to the extent to w h i c h the parent acid or base reacts w i t h water; that is, the weaker the acid or base, the stronger the conjugate base or acid. The constant describing the e q u i l i b r i u m concentration ratio is called the hydrolysis constant K . For the h y d r o lysis of an anion A
h -
[HA] [A"] where K

w
[ O H - ] ^
Ka
is the water ionization constant. For the hydrolysis of a cation BH* [H Q-|
3
[ B l
/ ^
K
b
[ BH ]
A buffer solution can neutralize an acid or a base; the solution utilizes the a b i l i t y of an ion from a salt to behave as an acid or as a base. A buffer solution may consist o f a weak base and a salt o f the base, such as a m i x t u r e o f N H and N H C I . The N H is a base and can neutralize added acid by the reaction
3 4 3
NH The N H
4 +
+ H 0 - NH
+ 3
+ 4
+ H 0
2
(23-8)
is a p r o t o n donor and can neutralize added base by the reaction NH

+ 4
+ Oil" - NH + H 0
3 2
(23-9)
Or, a buffer solution may consist of a weak acid and a salt of the acid, such as a m i x t u r e of acetic and sodium acetate: H C H 0 neutralizes added base, and C H 0 ~ neutralizes added acid.
2 3 2 2 3 2
In the t h i r d part o f this experiment, y o u will rely on the acidic nature o f a cation to determine the molecular weight o f a salt in which it is present. Y o u w i l l dissolve a 1:1 electrolyte containing N H in a carefully measured volume of standardized N a O H (sodium h y d r o x i d e ) . The reaction in Equation (23-9) w i l l occur, and the ammonia that forms can be boiled out of the solution. The remaining O H " w i l l
4 +
237
Acidic and Basic Salts
be titrated w i t h a h y d r o c h l o r i c solution. Y o u w i l l k n o w the number o f moles o f O H " put i n t o the solution from NaOH and the number of moles of O H " that remained to react w i t h HC1 after the reaction in Equation (23-9) occurred. The difference between these t w o quantities is the number of moles of O H " that reacted w i t h N H according to Equation (23-9); it equals the number of moles of N H in the salt sample. K n o w i n g both the weight of the salt sample and the number of moles that it contains, y o u can calculate the molecular weight of the salt.
+ 4 + 4
beaker Bunsen burner buret Erlenmeyer flasks p l l meter or pH paper 20-ml pipet
ring ring stand stirring rod test tubes watch glass wire gauze
CHEMICALS NEEDED
b r o m o t h y m o l blue 1A F e ( N 0 ) \M H C H 0 standardized 0,57V/ HC1 I/V/HNO3 "' lANaC H 0 \M N a C 0 \M N a H P 0 \M N a H P 0

3 3 2 3 2 2 3 2 2 3 2 4 2 4
standardized 0.5A/ N a O H IM NaOH \M N a N 0 lAf N H 1/V/NH C H 0

3 3
LMNH4CI
t h y m o l blue u n k n o w n a m m o n i u m salts \M solutions of u n k n o w n hydrolyzable salts
PROCEDURE
A. Hydrolysis and pH
1. K n o w n acids, bases, and salts. Use pH paper or a pH meter to measure the p H o f \ M solutions o f H C H 0 (acetic acid), N H ( a m m o n i a ) , N H C H 0 ( a m m o n i u m acetate), N H C 1 ( a m m o n i u m chloride), F e ( N 0 ) (ferric nitrate), H N 0 ( n i t r i c acid), N a C H 0 (sodium acetate), N a C 0 (sodium carbonate), N a H P 0 (disodium hydrogen phosphate), N a H P 0 (sodium dihydrogen phosphate), N a O H (sodium h y d r o x i d e ) , and N a N 0 (sodium nitrate). Also measure the pH of distilled water; do not assume that it is exactly 7.0. If the pH of the water is not 7.0, then the pH of a solution may be different from 7.0, even if no acidbase reactions occur between water and the solute. If y o u use pH paper, put a small amount of a solution i n t o a small test tube. Place a piece of wide-range pH paper on a clean watch glass, d i p a clean glass stirring
2 3 2 3 4 2 3 2 4 3 3 3 2 3 2 2 3 2 4 2 4 3
238
Experiment 23
rod i n t o the s o l u t i o n , and transfer a drop of the solution o n t o the paper. A f t e r d e t e r m i n i n g the pH of the solution w i t h i n one or two units, select the proper narrow-range pH paper and determine the pH of the solution w i t h i n a few tenths of one pH u n i t . Use an educated imagination about color to make approximations when necessary between the colors on the comparison charts. I f y o u use a p H meter, y o u r instructor w i l l provide the necessary instructions. Report the pH of each solution to the nearest 0.1 pi I u n i t . 2. An u n k n o w n salt. Measure the pi I of a 1.1/ solution of an u n k n o w n salt in which one o f the ions hydrolyzes. The salt w i l l contain only one hydrolyzable ion per formula unit; that is, the formula w i l l be of the type B X,. if B hydrolyzes and o f the type X A i f A * hydrolyzes. The salt does not contain any hydrolyzable i o n that y o u w o r k e d w i t h in the first part of this section of the experknent.
x+ ( V 1
B. A Buffer S o l u t i o n
T h y m o l blue is an acid-base indicator that changes from red to y e l l o w over the p l l range 1.2-2.8 and from yellow to blue over the p l l range 8.09.6. Y o u may be instructed to use either this indicator or a p l l meter for this section of the experiment. To see the colors characteristic of each f o r m of t h y m o l blue indicator, p u t 5 ml of distilled water i n t o each of three 20-ml test tubes and add 2 drops of t h y m o l blue to each test tube. Then to one tube, add \M I I N 0 dropwise u n t i l the color of the solution is the light red characteristic of pi I < 1.2. To a second tube, add 1/17 N a O H dropwise, u n t i l the blue color characteristic of pH > 9.6 appears. Save these three tubes to make color comparisons later in the experiment.
3
In a small beaker, m i x 10-ml of 1/V/ H C H 0 and 10-ml of \M N a C H 0 . This produces a buffer solution that contains 0.5/W of the acid and 0.5/1/ of the salt. Divide this mixture eveidy among four 20-ml test tubes.
2 3 2 2 3 2
To each 5-ml sample of the buffer s o l u t i o n , add 2 drops of t h y m o l blue. The color of the solution should be y e l l o w , showing that the pH of the buffer solution is between 2.8 and 8.0. Calculate the p l l of this solution before you come to the laboratory. To one 5-ml sample of the buffer s o l u t i o n , add 1A7 N a O H dropwise u n t i l the color indicates that the solution has become strongly basic; count the drops as y o u add t h e m . If you are using a pH meter, add N a O H u n t i l the solution is neutral ( p H - 7.0). To a second 5-ml sample of the buffer s o l u t i o n , add IM H N 0 dropwise u n t i l the color indicates that the solution has become strongly acidic. If y o u are using a p l l meter, add H N 0 u n t i l the solution is neutral (pH = 7.0). Does it seem surprising that an acidic solution can have an acid-neutralizing capacity comparable to its base-neutralizing capacity? f l o w does the amount of \M H N 0 required to change the buffer's pH (already well below 7) to about 1 compare to the amount of 1/V/ H N 0 required to change water's pH to about 1? Does it surprise y o u that a solut i o n that is already acidic has a greater resistance than water to being made more acidic? Combine 5 ml of \M H C H 0 and 5 ml of distilled water to produce 0.5.1/ H C H 0 . Divide this solution evenly between t w o test tubes and add 2 drops of t h y m o l blue to each test tube. Calculate the pH of this solution before you come to
3 3 3 3 2 3 2 2 3 2
239
Acidic and Basic Salts
the laboratory; note the color of the indicator in this solution and account for this color in terms of the p H . To show that the base-neutralizing capacity of the buffer is comparable to the base-neutralizing capacity of a solution containing only the same concentration of acid, add IM NaOH dropwise to 5 ml of 0.5M H C H 0 u n t i l the color of the solution turns blue. To show that the acid-neutralizing capacity of the buffer results from the presence of C H 0 ~ , a substance that can act as a p r o t o n acceptor, prepare 10 ml of 0.5M N a C H 0 , divide this solution evenly between t w o test tubes, and add 2 drops of t h y m o l blue to each test tube. Calculate the pH of this solution before you come to the laboratory; note the color of the indicator in this solution and account for this color in terms of the p H . Then add IM H N 0 dropwise to one test tube u n t i l the color of the solution changes to light red; count the drops as y o u add them. Are the acid-neutralizing capacities of the buffer and of the salt comparable?
2 3 2 2 3 2 2 3 2 3
To a third test tube containing 0.5,1/ 11C 11 0 and 0.5.1/ N a C H 0 , add \M H N 0 u n t i l the solution is strongly acidic. Then, add a few crystals of solid N a C H 0 . What happens'.' Why''
2 3 2 2 3 2 3 2 3 2
C. Molecular Weight of an A m m o n i u m Salt
On the analytical balance, weigh out three 0.1-0.3 g samples of the u n k n o w n a m m o n i u m salt i n t o Erlenmeyer flasks. Into each flask, pipet 20.00 ml of standardized 0.54/ N a O H . Heat the solutions to b o i l i n g and maintain a gentle b o i l (so that no solution spatters out of the flask) for at least 10 minutes to remove the ammonia that forms according to the reaction of Equation (23-9). To determine whether ammonia is still present after the boiling, hold a piece of moist litmus paper over the neck of the llask. When the vapors no longer test basic, y o u may discontinue the heating. Cool each flask under cold water. To each flask, add 4 drops of b r o m o t h y m o l blue. This acid-base indicator changes from y e l l o w to blue over the pH range 6 . 0 - 7 . 6 ; it is more convenient to use b r o m o t h y m o l blue indicator than to try to determine the p o i n t at which the more c o m m o n indicator phenolphthalein changes from pink to colorless as y o u titrate base with acid. Titrate each solution w i t h standardized 0.5.17 HC1 to the yellow endpoint.
RESULTS
A. H y d r o l y s i s and pH
1. K n o w n acids, bases, and salts. List the solutions from most acidic to most basic; give the pH of each s o l u t i o n . State whether each substance is an acid, a base, or a salt. For each s o l u t i o n , write an equation for any reaction that occurs and affects p H . For a particular salt, more than one proton-transfer reaction may occur. If this is the case for any of the salts, show all possible reactions and state w h i c h reaction is more extensive as indicated by the p H . (Space is n o t provided on the Report Sheet for this experiment; attach a separate sheet of paper w i t h these results and equations.)
240
Experiment 23
2. An u n k n o w n salt. Use the pH of the \M solution to calculate the [ H 0 | or the [ O H ] of the solution as a result of hydrolysis. Calculate K,, for the h y d r o l y z able ion.
+ 3 -
B. A Buffer Solution
Describe the color of the indicator in each solution: buffer s o l u t i o n , acid solut i o n , and salt s o l u t i o n . A c c o u n t for the color of each solution in terms of its pH and the pi I at which the indicator changes color. F o r each s o l u t i o n , state the q u a n t i t y of acid or base that is required to produce the requested change in p H . Compare the acid- and the base-neutralizing capacities of the solutions.
C. Molecular Weight of an Ammonium Salt
Calculate the number of moles of HC1 used in the t i t r a t i o n and the number of moles of NaOH that the HCI neutralized. Calculate the number of moles of NaOH that y o u pipetted into the tlask. The difference between these t w o quantities is the number of moles of N a O H that reacted w i t h N H according to Equation (23-9); it equals the number of moles of N H in the salt sample. Use the weight of the salt sample and the number of moles of N H that it contains to determine the molecular weight of the salt N H X . Report an average of y o u r results for the three trials. Round the figure o f f to three significant figures, even if y o u are entitled to four.
+ 4 + 4 + 4 4
QUESTIONS
1. Some compounds that are used as fertilizers are N H , N U N 0 , and ( N H ) P 0 . What effect w o u l d each of these compounds have on the pH of ground water?
3 4 3 4 3 4
2.
3. 4. 5.
Some compounds that are tised for the specific purpose of altering the soil's pH are C a C 0 , F e S 0 , and A 1 ( S 0 ) . What effect w o u l d each of these compounds have on soil pH? Equimolar amounts of NaOH and H C H 0 are combined in aqueous solution. Will the resulting solution be neutral? Explain yotir answer. Describe a way of preparing an acetic acid/sodium acetate buffer solution that has an acid-neutralizing capacity twice as great as its base-neutralizing capacity. Describe a way of preparing an acetic acid/sodium acetate buffer solution that has a base-neutralizing capacity three times as great as its acid-neutralizing capacity.
3 4 2 4 2 3 2
REFERENCE
Yoder, C.H., Suydam, F . H . , and Suavely, F . A . Chemistry. New Y o r k : Harcourt Brace .lovanovich. Inc.. 1975. Chapter 15.
C.
Molecular weight of an a m m o n i u m salt: Trial 1 Weight of salt M o l a r i t y o f NaOH V o l u m e N a O H used Moles N a O H M o l a r i t y of HCI V o l u m e HCI used Moles HCI Moles N a O H neutralized by HCI Moles NaOH neutralized b y N H Moles N H
+ 4 + 4
Trial 2
Trial 3
Moles N H X
4
Molecular weight o f N H X
4
___
Average molecular weight (Answer the questions from page 240 below; if necessary, paper to the Report Sheet.) attach a separate sheet of
Experiment 24 Electrochemistry: Voltaic Cells

Introduction
This experiment deals w i t h cells in which spontaneous o x i d a t i o n - r e d u c t i o n reactions can be used to produce electricity. The reactants in the o x i d a t i o n reduction reaction are separated physically, so there cannot be a direct electron transfer from one reactant to the other as there w o u l d be if the reactants were in physical contact. Instead, the two reactants are joined by a wire through which electrons travel from one reactant to the other. This How of electrons through a wire constitutes an electric current. Y o u should recognize one important difference between voltaic and electrolytic cells: in the voltaic cell, electrons flow unassisted from one reactant to the other, because the reaction is thermodynamically spontaneous; in an electrolytic cell, a nonspontaneous reaction is forced to occur by the application of an outside power supply (an external battery) that " p u m p s " electrons through the electrolytic cell. Figure 24-1 shows a voltaic cell in which C u cell reaction Zn + C u
2 + 2 +
ions are reduced by zinc by the
Cu + Z n
2 +
(24-1)
244
Experiment 24
The voltaic cell consists of: 1. A Zn strip immersed in a 0.54/ Z n S 0 solution. 2. A Cu strip immersed in a 0.54/ C u S 0 solution. 3. A salt bridge that is constructed by f i l l i n g a U-shaped tube w i t h 0.5M K S 0 , plugging the ends of the tube w i t h c o t t o n , inverting the tube, and immersing one arm of the tube in each beaker. 4. A conducting wire through w h i c h electrons flow from the Zn electrode to the Cu electrode.
4 4 2 4
A voltmeter is inserted in the c i r c u i t in Figure 24-1 to measure the cell voltage. The value of the voltage, or the electromotive force (emf), can be regVrded as a quantitative measure of the tendency of electrons to How in the cell, that is, the tendency of electrons to be transferred from one rcactant to the other. The overall reaction in a voltaic cell (or in an electrolytic cell) can be divided i n t o t w o half-cell reactions, an o x i d a t i o n half and a reduction half, each occurring at one electrode: Oxidation: Zn Reduction: C u
2 +
Zn + 2e~
2 +
2 +
+ 2e (at the anode) Cu (at the cathode)
(24-2) (24-3) (24-1)
Overall reaction: C u
+ Zn
Cu + Z n
2 +
Separating the total reaction i n t o t w o half reactions, each occurring in a half cell, implies that we can construct several different voltaic cells simply by replacing one of the half cells, say, Z n / Z n , w i t h different half cells. The concept that voltaic cells consist of t w o half cells also suggests that the measured cell voltage is the sum of the contributions from both half cells. In mathematical language
2 +
A total
^-oxidation
A reduction
(24-4)
In this experiment, y o u are to construct several voltaic cells, measure their voltages, and then investigate the effect of solution concentrations on cell voltage.
MEASURING
CELL VOLTAGE
The instrument that measures e m f is called a voltmeter. It consists of a scale w i t h a deflecting needle m o u n t e d in a case; t w o lead wires attached to the voltmeter are connected to the electrodes of the cell (see Figure 24-2). When the lead wires are connected to the proper electrodes, the needle will move from zero and the voltage generated by the cell can then be read. If the lead wires are connected in reverse, the needle w i l l not move. Before y o u begin the experiment, you must first determine how to connect the voltmeter to a cell. In the reaction between C u and Z n , y o u k n o w that the Zn electrode is the anode and that the Cu electrode is the cathode. Determine and record w h i c h lead wire on the voltmeter y o u must connect to w h i c h electrode before a voltage will register. For the remaining cells, use this i n f o r m a t i o n
2 +
245
Electrochemistry: Voltaic Cells
to determine w h i c h electrode is the anode and which electrode is the cathode, and, consequently, in w h i c h direction the electrons How through the external cell circuit.
alligator clips 250-ml beaker porous cup
sandpaper voltmeter (1000 f i / v o l t resistance)
CHEMICALS NEEDED
Cu strip - ' Fe strip M g strip Pb strip Sn strip Zn strip 0.5M C u S 0

4
0.5M 0.5yV/ cone. 0.5M 0.5A/ 0.5A-/
FeS0 MgS0 N H solution Pb(N0 ) SnCl ZnS0

4 4 3 3 2 2 4
PROCEDURE
To avoid'the time-consuming process of making U-tube salt bridges, y o u can construct a cell as illustrated in Figure 24-3. The porous cup allows ions to flow back and f o r t h through its walls to equalize the electrical charges in the t w o halves of the cell. The cup performs the same function as a salt bridge but is easier to handle.
Cell Voltages
First, pour about 150 ml of 0.5M C u S 0 i n t o a 250-ml beaker. Bend a sandpapered Cu strip and hang it over the side of the beaker so that it is partly immersed
4
246
Experiment 24
in the solution. Place the porous cup in the beaker and hang a cleaned strip of Zn over the side. A d d 0.5A/ Z n S 0 to the porous cup u n t i l the l i q u i d level is the same as it is in the beaker. Use alligator clips to connect the metal electrodes to the terminals of the voltmeter. Record the i n i t i a l voltage of the cell. N o w disconnect the voltmeter and remove the porous cup from the beaker. Discard the Z n S 0 solution and clean and dry the cup. Repeat this procedure, replacing Zn and 0.5/1/ Z n S 0 w i t h the f o l l o w i n g metal strips and solutions of their salts:
4 4 4
he and 0.5.4/ F e S 0 Mg and 0.5/1/ M g S 0 Pb and 0.5.1/ P b ( N 0 ) Sn and 0.5/1/ S n C l

4 4 3 2
Identify the anode and the cathode for each cell.
C o n c e n t r a t i o n Effects on Cell Voltage
A l l the solutions that y o u are using in this experiment are 0.5A/. Next y o u w i l l design experiments that determine (at least qualitatively) what effect changing the concentration of a salt solution has on cell voltage. As y o u design y o u r experiments, keep the f o l l o w i n g points in m i n d : 1. Use a Z n - C u cell, so that the results of different students can be easily compared. 2. If your time is l i m i t e d , the effect may be investigated for oidy the cathode compartment solution instead of for both solutions. 3. Vary the concentration of the solution slightly from O.SM to see what effect this has. Then try larger variations, such as 0.05A7, 0.005A7, and so on. 4. T r y to determine if the cell voltage varies in some regular way w i t h concen-
247
Electrochemistry: Voltaic Cells
t r a t i o n . For example, is the variation linear That is, does a tenfold decrease in concentration lower the voltage to one tenth of its former value? and so on.
0
Complexation Effects on Cell Voltage
The blue color of the 0.5,1/ C u S 0 solution is actually due to the presence of a complex ion o f copper C u ( I I 0 ) . Design and carry out an experiment that will show what effect ( i f any) is produced by the presence of copper in the form of the ammonia complex C u ( N H ) instead of in the form of the hydrated i o n . The hydrated ion can be converted to the ammoniated ion by adding concentrated N H solution to a C u S 0 solution u n t i l an intense deep-blue color results. For both of the above experiments that y o u design for yourself, y o t i r report should (1) describe the experimental procedures yoti use, (2) include the data y o u collect, and (3) discuss the conclusions y o u can draw from y o u r data.
4 2 + 2 6 2 + 3 4 4
R E S U L T S AND C A L C U L A T I O N S
1. For each cell for w h i c h y o u measured voltage, write the anode half reaction and the cathode half reaction. In each case, this involves determining w h i c h electrode is the anode and w h i c h electrode is the cathode. 2. F o r each cell, add the t w o half reactions to obtain the overall spontaneous cell reaction. 3. The e m f of each cell is the sum of the contributions from each half cell. The t w o half-cell contributions are d i f f i c u l t to separate; however, if we define that the C u / C u couple has E - 0.000 volts, we can assign the entire measured cell potential e m f to the other couple. The potential e m f will then represent in quantitative fashion the tendency of each couple to reduce C u to Cu. Write each half-cell reaction as a reduction. Then assign a standard cell potential to each reduction, as described above, attaching the correct algebraic sign. 4. Arrange the list of metals in order of their decreasing a b i l i t y to donate electrons to C u ; that is, list the metal w i t h the greatest tendency to donate electrons first. 5. F r o m your t e x t b o o k or from some other data source, obtain the accepted values of standard half-cell potentials for the couples used in this experiment. Next to the appropriate half reaction w r i t t e n as a reduction, record this value of E. For each half reaction, record the difference between this value and the value of E that y o u assigned in this experiment. 6. What do the differences between the tabulated standard potentials and the values y o u assigned f r o m y o u r measurements tell y o u about the E of the C u / C u couple? Explain y o u r answer. 7. Discuss y o u r data concerning cell voltage and its concentration dependence. 8 . What effect does the c o m p l e x a t i o n o f C u b y N H t o produce C u ( N H ) have on the half-cell potential of C u / C u ? Which species is the better o x i d i z i n g agent, C u ( H 0 ) or C u ( N H ) >
2+ 2 + 2 + 2 + 2 + 2 + 3 3 4 2+ 2 + 2 + , 2 6 3 4
248
Experiment 24
QUESTIONS
1. In this experiment, y o u assigned zero c o n t r i b u t i o n to cell potentials from C u / C u ; this enabled y o u to compare the tendencies of other couples to reduce C u to C u . Is this a valid procedure? Explain y o u r answer. 2. Using y o u r measured data, calculate the free energy change AG w h i c h w o u l d occur in the cell Zn|0.5A/ Z n S O | | 0 . 5 A f S n C l | S n , if 0.5A/ of S n were reduced while the concentrations of Z n and S n remained at 0.5M.
2 + 2 + 2 + 4 2 2 + 2 +
REFERENCE
Yoder, C.H., Suydam, F . H . , and Snavely, F . A . Chemistry. New Y o r k : Harcourt Brace Jovanovich, Inc., 1975. Chapter 17.
Experiment 25 Electrochemistry: An Electrolytic Cell

Introduction
In an electrolytic cell, an o x i d a t i o n - r e d u c t i o n reaction that does not proceed spontaneously can be forced to occur by using an external device to pull electrons from one electrode (the anode), causing o x i d a t i o n to occur, and to p u m p them i n t o another electrode (the cathode), causing reduction to occur. The process that occurs in the cell is called electrolysis. This experiment deals w i t h the relationship between the amount of o x i d a t i o n and reduction that takes place during electrolysis and the q u a n t i t y of electricity that passes through the cell. Figure 25-1 is a diagram of a cell for the electrolysis of a concentrated C u C l solution; here, a strip of copper is the cathode and a strip of platinum is the anode. Platinum is a fairly inert metal and undergoes no reaction in this cell; it serves only as an electron-transfer medium. The reactions at the electrodes in Fi mi re 25-1 are
2
Anode: 2C1 Cathode: C u

2 +
>-Cl2(g)
+ 2e~
2t' ( o x i d a t i o n )
(25-1) (25-2)
Cu(s) (reduction)
If the current (in amperes) is k n o w n and the time of electrolysis (in seconds) is recorded, then the q u a n t i t y of electricity (in coulombs) passing through the cell can be calculated: - amp X sec = coul/sec X sec = coul (25-3)
Faraday's First law states that the quantity of a metal deposited at an electrode in an electrolytic cell is proportional to the number of coulombs of charge passing
254
Experiment 25
through the electrical c i r c u i t . Thus, the greater the amount of charge that passes through the cell, the greater the weight of metal deposited o n t o the cathode. Faraday's second law states that the weights of different substances produced by the passage of a given a m o u n t of charge are p r o p o r t i o n a l to the equivalent weights of those substances. For example, the passage of 96,500 coul of charge w o u l d deposit different weights of silver, copper, and lead. Of course, the laws describing electrolysis can also be applied to cells in w h i c h reactions do not involve the plating out of a metal onto a cathode. It is simply that the use of such cells in the laboratory provides a convenient way to measure the amount of reduced material (in this case, the metal). In this experiment, y o u w i l l electrolyze a solution o f C u S 0 (copper sulfate), so that copper is deposited o n t o the cathode. In a d d i t i o n , o x i d a t i o n at the anode must occur. Y o u w i l l use copper for b o t h electrodes. Depending on the voltage supplied by the batteries, any of these three o x i d a t i o n reactions might occur:
4
Sulfate ion might be oxidized: 2S0 "

2 4
0 ^ %Je
(25-4)
The copper anode itself m i g h t be o x i d i z e d : Cu Water might be o x i d i z e d : 2H 0

2
Cu
2 +
+ 2c"
(25-5)
0 + 41F + 4e
2
(25-6)
Y o u must determine which of these three reactions occurs by observing the anode during and after the electrolysis. Reaction (25-5) w o u l d cause the anode to lose weight; weighing the anode before and after the electrolysis will determine whether this has occurred. Reaction (25-6) w o u l d result in bubbles of oxygen gas being given o f f around the anode. If there is no evidence of anode weight loss or oxygen gas emission, then reaction (25-4) must be occurring (assuming that there is no other u n k n o w n material present that can be oxidized). The increase in the mass of the cathode where copper w i l l plate out serves as a measure o f the q u a n t i t y o f the reaction taking place at this electrode. This mass increase can he related to the number of moles of electrons f l o w i n g through the cell (calculated from the total electric charge and the charge of 1 mole of electrons). The equivalent weight of copper (that is, the weight deposited b y . l mole of electrons) can then be calculated easily. It is best to plate metals by electrolysis under conditions of long plating time and low current. The currents used in this experiment will be substantially higher than o p t i m u m to save t i m e ; consequently, some inaccuracies will be introduced. But your results w i l l probably be w i t h i n 10-15% o f the theoretical results.
EQUIPMENT NEEDED
alligator clips ammeter beakers
direct-current power supply sandpaper variable resistance
255
Electrochemistry: An Electrolytic Cell
CHEMICALS NEEDED
acetone \M C u S 0 Cu strips
PROCEDURE
Clean t w o copper strips w i t h medium or fine sandpaper. Bend each strip about 2 cm from the end, so that it can be hooked over the side of a beaker. Handle the cleaned strips o n l y by the edges to keep them as free from contamination as possible. Weigh each strip as accurately as possible on the analytical balance. Be sure that you can distinguish between the two strips. One w i l l be the anode and one will be the cathode. Y o u must k n o w w h i c h is w h i c h , so that y o u can compare the weight of each strip after the electrolysis w i t h its weight before the electrolysis. Place the copper electrodes over opposite sides of a 100-ml beaker; be sure that the strips remain parallel to one another. Assemble the electrical equipment as shown in Figure 25-2. Be careful to connect the cathode to the negative terminal of the power source. Before proceeding further, ask y o u r i n s t r u c t o r to check your apparatus. Pour 60 ml of C u S 0 solution i n t o the beaker. Adjust the variable resistance to its m a x i m u m value. T u r n on the power-supply s w i t c h ; note the time. Immediately adjust the resistance so that a current of about 100 m i l l i a m p (read on the ammeter dial) flows in the cell.
4
256
Experiment 25
A l l o w the current to flow for 25 minutes to carry out the electrolysis. Check and record in y o u r notebook the current reading once a minute. If necessary, readjust the resistance to maintain the current of 100 m i l l i a m p . At the end of 25 minutes, t u r n o f f the power supply. Then disconnect the clips to the electrodes. L i f t each electrode by the edge and hang it over the lip o f a dry, 250-ml beaker. Wash each electrode carefully by dipping it i n t o a beaker of distilled water or w i t h water f r o m y o u r wash bottle. Do not squirt the water directly onto the metal deposited during the electrolysis, because this might cause the metal to fall from the surface of the electrode. Instead, direct the water at the upper p o r t i o n of each stip and allow it to run d o w n the strip. Be sure to wash both sides of each strip. Then repeat this washing procedure using acetone. A l l o w the electrodes to d r y for about 15 minutes, and then weigh them. Be careful to handle the electrodes o n l y by the edges and above the area where the metal has been deposited. Y o u r instructor may ask y o u to make a second t r i a l .
D A T A AMD
RESULTS
1. To obtain the average value of the current, add all the current readings ( i n amp) and divide by the number of readings. 2. F r o m E q u a t i o n (25-3), calculate the a m o u n t of charge (in coul) that passed through the cell, using the average value of current (in amp) and the time ( i n sec) o f y o u r electrolysis. 3. Since the charge is carried by electrons, y o u can calculate the number of moles of electrons needed to carry the charge that passed through y o u r cell. (The charge on one mole of electrons is 96,500 coul.) 4. F r o m the cathode weight gain and the atomic weight of copper, determine the number of moles of copper that plated out o n t o the cathode. 5. The number of grams of copper deposited per mole of electrons passing through the cell is the equivalent weight of copper.
QUESTIONS
1. Compare y o u r experimental value for the equivalent weight of copper w i t h the theoretical value. 2. If y o u lost some of the copper deposit on the cathode before weighing i t , how w o u l d y o u r value of the equivalent weight be affected?
REFERENCE
Yoder, C . H . , Suydam, F . H . , and Snavely, F . A . Chemistry. New Y o r k : H a r c o u r t Brace Jovanovich, Inc., 1975. Chapter 17.
Write an equation for the reaction that occurred at the anode in the electrolytic cell.
Describe the physical evidence on w h i c h y o u based y o u r conclusion about the anode reaction.
Answer the questions from page 256 in the space below. (If necessary, attach a separate sheet of paper to the Report Sheet.) ^
Experiment 26 An Oxidation-Reduction Titration

Introduction
/{J U
In one type of chemical reaction, electrons are transferred between the reactants. These reactions are called oxidation-reduction (or redox) reactions. An electron transfer reaction between the enzyme cytochrome a ( w h i c h contains F e ) and oxygen enables living organisms to use atmospheric oxygen to support life. The energy released in fuel-cell redox reactions has provided power for A p o l l o space flights. The energy of ordinary automobile and dry-cell batteries is released by spontaneous redox reactions. Experiment 24 was concerned w i t h electrical energy supplied by these reactions.
3 2 +
In a d d i t i o n to being sources of energy, o x i d a t i o n - r e d u c t i o n reactions are useful for analytical purposes. This experiment is designed to study a redox reaction used in chemical analysis. A l t h o u g h y o u have used redox reactions before in this c o u r s e for example, in the synthesis of S n l and in studying the solubility product of C u ( I 0 ) t h e focus has often been only on the stoichiometric relationships i n volved. This experiment will examine in detail some features o f titrations in which the reactants are oxidizing and reducing agents. The goal o f this experiment w i l l be to use a redox t i t r a t i o n to report the percentage of F e in an u n k n o w n sample (to be provided by y o u r i n s t r u c t o r ) .
4 3 2 2 +
Whether any- particular species tends to be reduced is reflected in the value of the standard electrode potential E for the reduction half-reaction. Equation (26-1) shows that the ferric ion F e has a tendency (in comparison to H 0 ) to be reduced to the ferrous ion F e :
3 + + 3 2 +
Fe (aq) + e
3+
Fe (aq)
2+
E = +0.77 volts
2
(26-1)
Similarly, Equation (26-2) shows that the dichromate ion C r 0 ~ is easily reduced toCr :
2 7 3 +
C r 0 ' ( a q ) + 1 4 H + 6e
2 + 2 7
>2Cr
3 +
+7H 0
2
E = +1.33 volts
(26-2)
A l t h o u g h the E values in Equations (26-1) and (26-2) indicate a tendency for b o t h F e and C r 0 " to be reduced (in comparison to the tendency of FT to be reduced to y H ) , it is obvious that C r 0 ~ has a considerably greater tendency to be reduced than F e . The dichromate C r 0 ~ w i l l even abstract electrons from F e ( a q ) and oxidize it to F e ( a q ) , because C r 0 " has a very great tendency to be reduced. When C r 0 ~ and F e are allowed to react in an acidic aqueous s o l u t i o n , the reaction that occurs can be obtained by combining Equations (26-1) and (26-2) in such a way that the number of moles of electrons to be supplied to C r 0 is exactly provided by the F e :
3+ 2 2 7 2 2 2 7 3 + 2 2 7 2+ 3+ 2 2 7 2 2 + 2 7 2 _ 2 7 2 +
6 F e ( a q ) + C r 0 " ( a q ) + 14H (aq)

2+ 2 + 2 7
6Fe (aq) + 2Cr (aq) + 7 H 0

3+ 3+ 2
(26-3)
259
260
Experiment 26
Equation (26-3) shows that 6 moles o f F e react w i t l i 1 mole o f C r 0 " . Because of this simple relationship, it is convenient to use a dichromate solution of k n o w n m o l a r i t y to titrate a solution that contains i r o n as F e . The number of moles of i r o n present can easily be determined from Equation (26-3) and from the volume and m o l a r i t y of dichromate solution used in the t i t r a t i o n . T w o problems are encountered when this simple procedure is actually carried o u t . f i r s t , it is necessary to be sure that all the iron in the sample is actually present as F e . Second, some way must be devised to detect the endpoint; that is, the p o i n t when exactly 6 moles of C r 0 ~ have been added for each mole of F e present. These problems and their solutions will be discussed in t u r n . Oxygen in the air can oxidize F e to F e and the 0 can be reduced to H 0 in aqueous solutions, as indicated by the f o l l o w i n g reduction potentials:
2 + 2 2 7 2 + 2+ 2 2 + 2 7 2 + 3 + 2 2
0 + 4 H + 4<f
+ 2
2 H 0 E = +1.23 volts
2 2 +
(26-4) (26-1)
3 +
Fe
3 +
+ e
Fe
2+
E = +0.77 volts
2 +
Thus, in any solution containing F e , some F e may be oxidizsd to F e by the oxygen present in the air; sometimes, the pale-yellow color characteristic of a small amount of F e can be seen. Because F e does not react w i t h dichromate ions, whatever iron is present as F e instead of as F e cannot be detected in the d i chromate t i t r a t i o n , and low results for iron w i l l be obtained. T o avoid this, any iron that is present as F e must be converted to F e before the t i t r a t i o n begins; this is done by adding S n C l to the hot s o l u t i o n :
3 + 3 + 3 + 2 + 3 + 2 + 2
Sn Fe
4 +
+ 2e + e"
3 +
>Sn >Fe
2 + 2 +
2 +
E = +0.15 volts E = +0.77 volts

2 +
(26-5) (26-1) (26-6)

2 +
3 +
2Fe
+ Sn
-* 2 F e
+ Sn
4 +
E = +0.62 volts
However, this a d d i t i o n , in t u r n , generates another d i f f i c u l t y ; any remaining S n in excess of the q u a n t i t y needed to reduce the F e can be oxidized by the dichromate i o n , as can be seen from the standard electrode potentials E for reactions (26-2) and (26-5). Because it is n o t possible to distinguish the dichromate that reacts w i t h F c from the dichromate that reacts w i t h S n , the calculated amount of F e w o u l d be high. Therefore, the next step is to remove the excess Sir " "; this is accomplished by adding a solution of H g C l . A n y remaining S n w i l l immediately be oxidized by H g to S n while the H g is reduced. The relevant equations are
3 + 2 + 2 + 2+ 2 1 2 + 2 2 + 4 + 2 +
2Hg 2Hg
2 +
+ 2C1" + 2e + Sn
2 +
Hg Cl (s)
2 2
E = +1.44 volts
4 +
(26-7) (26-8)
2 +
+ 2CP
Hg Cl (s) + Sn
2 2
E = +1.29 volts
The insoluble H g C l precipitates from the solution as a small q u a n t i t y of white solid. An examination of the standard electrode potentials E in Equations (26-7) and (26-1) indicates that H g C l should react w i t h the F e that is produced in the dichromate t i t r a t i o n of F e . Fortunately, this reaction is quite slow; if the t i t r a t i o n
2 2 3 + 2 2 2 +
251
An OxidationReduction Titration
is carried out at a reasonably rapid pace, no interference from this source is encountered. To summarize the procedure discussed in the last several paragraphs: Only i r o n present as F e w i l l react w i t h the C r 0 ~ solution that is used as the t i t r a n t . Therefore, S n C l solution is added to reduce any F e to F e . Excess S n C l is removed by adding H g C l solution to oxidize S n to S n . It is theoretically possible for various mercury species to react w i t h other solution components, but these reactions are slow enough that the t i t r a t i o n can be completed before they occur. Using an indicator to detect the endpoint in a redox t i t r a t i o n presents a different problem than the one y o u encountered in acid-base titrations. There, the indicator was a species w i t h protonated and deprotonated forms that exhibited different colors:
2 + 2 2 7 3 + 2 + 2 2 2 + 4+ 2
HIn
Color I
+ H O^H 0
2 3
In
C o l o r II
(26-9)
As [ H 0 ] changes during a t i t r a t i o n , the e q u i l i b r i u m shifts to the left or to the right, and the solution displays color I or color I I , respectively. An e q u i l i b r i u m shift also occurred when y o u t i t r a t e d iodine using thiosulfate as a reducing agent and starch as an indicator (Experiments 14, 15, 19). In the presence of iodine, starch forms a deep-blue complex if some iodide is also present:
+ 3
I + I" + starch < * deep-blue complex

2
(26-10)
The disappearance of the blue color, resulting from an extensive shift to the left, means that the iodine was just consumed in the t i t r a t i o n . For most r.edox reactions, no indicator substances are available that form different colored species w i t h oxidized and reduced forms of a couple (as starch does w i t h iodine). Consequently, some substance that can be oxidized is used: In
Color I
In*
C o l o r II
+e
(26-11)
The position of this e q u i l i b r i u m (and therefore the color of the solution) depends on the potential of the solution at the endpoint. A suitable indicator for the t i t r a t i o n of F e by C r 0 ~ is diphenylamine sulfonic acid, w i t h E - 0.85 volts, which changes from colorless to purple at the endpoint. In other words, the indicator is oxidized to the purple I n form when the endpoint is reached. The essential point of the preceding discussion is that the electron-accepting ability of a t i t r a t i o n solution at e q u i l i b r i u m can be measured. An indicator w i t h an E close to this value is chosen, so that i t w i l l be oxidized at e q u i l i b r i u m . I f I n and I n e x h i b i t different colors, the endpoint can be detected visually. This i n t r o d u c t o r y discussion has dealt p r i m a r i l y w i t h t w o i m p o r t a n t problems normally encountered in redox titrations in general: (1) how to be sure that all the titratable material is in the same o x i d a t i o n state, and ( 2 ) h o w to select a visual indicator. These t w o points have been applied to the i r o n - d i c h r o m a t e t i t r a t i o n . The simple conclusion is that it is possible to carry out such a t i t r a t i o n to determine the percentage of iron in a sample, if the amount of dichromate required for the titrat i o n is k n o w n , by using the stoichiometry of E q u a t i o n (26-3).
2 + 2 2 7 + +
262
Experiment 26
EQUIPMENT NEEDED
50-ml buret burner 10-ml graduated cylinder Erlenmeyer flasks
250-ml volumetric flask medicine dropper ring stand wire gauze
CHEMICALS
NEEDED
diphenylamine sulfonate indicator 6A/HC1 H g C l solution

2
H P0 K Cr 0 SnCT solution
3 4 2 2 7 2
PROCEDURE
In c o n d u c t i n g this experiment, y o u w i l l prepare a potassium dTchromate s o l u t i o n of accurately k n o w n m o l a r i t y and then use this solution to titrate weighed samples of your unknown.
Preparation of K C r 0 Solution
; 2 7
On the analytical balance, weigh out about 1.3 g of K C r 0 i n t o a clean, dry beaker or weighing pan; record the weight that y o u actually take as precisely as the balance permits. Transfer all the salt to a clean (see I n t r o d u c t i o n , p. 2 8 ) , 250-ml volumetric flask; y o u do not have to dry the flask if there is only distilled water in i t . Rinse the beaker several times w i t h a few ml of distilled water to be sure that all the K C ' r 0 is washed into the flask. A d d about 50 ml of distilled water to the flask anil swirl the flask u n t i l the potassium tlichromate is completely dissolved. Then dilute the solution w i t h distilled water to the mark on the neck of the flask. Stopper the flask and invert it several times to m i x the solution completely. If necessary, this solution may be stored in y o u r desk u n t i l the next laboratory p e r i o d , provided it is t i g h t l y stoppered.
2 2 7 2 2 7
Titration of Samples
O b t a i n an u n k n o w n and record its i d e n t i f i c a t i o n number. Clean a buret, rinse it w i t h three 10-ml portions of your standard K C r 0 s o l u t i o n , and then fill the buret w i t h this s o l u t i o n . The buret should be filled early in the procedure, because the samples must be titrated rapidly once they are prepared. On the analytical balance, weigh o u t about 1.4 g of y o u r u n k n o w n ; record the weight that you actually take. Dissolve the sample in 15 ml of 6M HC1 and then add 35 ml o f distilled water. The solution w i l l probably have a yellow color because o f the presence of F e . Heat the solution almost to boiling and add S n C l solution dropwise u n t i l the yellow color just disappears; then add 1 or 2 extra drops. If very
2 2 7 3 + 2
263
An Oxidation Reduction Titration
little F e is present, o n l y 1 or 2 drops of S n C l solution may dispel the y e l l o w color. Even if no yellow color is apparent, you should still add 1 or 2 drops (no more) of S n C l solution to be sure that any trace of F e is reduced to F e . Cool the s o l u t i o n under running water to room temperature. Then measure 10 ml of saturated H g C l solution in a graduated cylinder and q u i c k l y add this to the flask as y o u swirl i t . The appearance of a silky, white I I g C l precipitate indicates that the reduction has proceeded satisfactorily. If the precipitate is gray, indicating the presence of metallic mercury, y o u have added too much S n C l and must discard the sample, because the mercury will react w i t h C r 0 ~ . If the precipitate is white and silky, add 5 ml of 85% H P 0 and 5 drops of diphenylamine sulfonic acid indicator. Titrate at once w i t h your standard K . C r 0 to the purple endpoint; the solution may appear green just before the endpoint is reached because of the presence of intermediate o x i d a t i o n products of the indicator. Weigh out a second sample of your u n k n o w n , dissolve it and treat it as described above, and then titrate i t . Y o u may want to adjust the sample size so that a more convenient volume of the dichromate solution is required. Prepare and titrate a third sample. Because it takes a non-negligible amount of dichromate to react w i t h the indicator and oxidize it to the purple f o r m , y o u must determine what volume of d i chromate solution is required to achieve this effect and then subtract this required volume from the volume used in each t i t r a t i o n . Y o u can do this by using K C r 0 solution to titrate a solution containing all the components mentioned previously except your u n k n o w n ; that is, y o u can m i x 15 ml of (vVl H C l , 35 ml of distilled water, 2 drops of S n C l solution, 10 ml of H g C l solution, 5 ml of H P 0 , and 5 drops of indicator. Then titrate this solution w i t h dichromate. The volume required is the blank correction. In the absence of F e , the reaction of C r 0 ~ w i t h d i phenylamine sulfonate is quite slow. Be sure y o u allow enough time for each drop to react before adding the next drop. The blank correction should be less than 1 m l .
3 + 2 3 + 2+ 2 2 2 2 2 2 2 7 3 4 2 2 7 2 2 7 2 2 3 4 2+ 2 2 7
CALCULATIONS
Using the exact weight of K C r 0 that y o u t o o k , the formula weight of the salt, and the fact that the volumetric flask contains 250.0 m l , calculate the m o l a r i t y of y o u r standard potassium dichromate solution to the proper number of significant figures. For each t i t r a t i o n , determine the volume of standard K C r 0 solution that reacted w i t h F e by subtracting the blank correction from the total volume used. For each t i t r a t i o n , calculate the number of moles of K C r 0 used. From Equation (26-3), determine the number of moles of iron in the sample. Calculate the number of grams of iron in each sample. Convert this figure to the percentage of iron in the sample. Be sure to use the correct number of significant figures.
2 2 7 2 2 7 2 + 2 2 7
QUESTION
H o w w o u l d y o u r calculated percentage of iron compare to the true value (high, l o w , same) if each of the f o l l o w i n g blunders were made?
264
Experiment 26
(a) N o t all of the K C r 0 flask.

2 2
that was weighed out was transferred to the volumetric
(b) Some of the iron-containing sample was spilled after it was weighed. (c) No S n C l solution was added to the iron-containing sample solution, even though the solution had a yellow color. (d) No H g C l solution was added after the S n C l solution was added to the y e l l o w , iron-containing sample solution. (e) After the a d d i t i o n of H g C l , a gray precipitate indicating presence of metallic mercury appears and the solution is titrated instead of discarded.
2 2 2 2
REFERENCES
1. Yoder, C.H., Suydam, F . H . , and Snavely, F . A . Chemistry. New Y o r k : Harcourt Brace Jovanovich, Inc., 1975. Chapter 17. 2. K o l t h o f f , I . M . , and Belcher, R. Volumetric Analysis, V o l . I I I . New Y o r k : Interscience Publishers, John Wiley & Sons, Inc., 1957. Chapter V. 3. Quane, D. Journal of Chemical Education 48, A105 (197 1).
Show a sample calculation of moles of K . , C r . , 0
reacting w i t h F e :
2+
Show a sample calculation of grams of iron present in a sample:
Show a sample calculation of the percentage of iron in a sample:
(Answer the questions from pages it to the Report Sheet.)
263-264
on
a separate sheet of paper and attach *
Experiment 27 Metal Chelate Complexes

Introduction
Even before studying transition metal complexes in y o u r t e x t b o o k , y o u encountered several such species in your laboratory w o r k . The first of these was [ C o ( N H ) ] C l , which y o u synthesized in Experiment 5. As y o u may recall, this compound contains a C o ion bound to six ammonia molecules that are arranged in octahedral fashion around the ion (see Figure 5-1, page 61). These surrounding groups are called ligands. Each ammonia ligand has only one atom ( N ) that can bond to a metal cation. In some possible ligands, more than one atom is capable of bonding to a metal cation. One example of such a ligand is N H C H C H N H (ethylenediamine). Here, the t w o N atoms can b o t h be bonded to the same metal ion simultaneously; the ligand is said to be bidentate. The resulting complex contains rings of atoms and is called a chelate. An ion such as C o can be surrounded in octahedral fashion w i t h six coordinated N atoms by forming a complex w i t h six N H molecules (refer again to Figure 5-1) or by forming a complex w i t h three ethylenediamine molecules (see Figure 27-1).
3 6 3 3 + 2 2 2 2 3 + 3
Chelating ligands f o r m complexes that are especially stable thermodynamically. In other words, the e q u i l i b r i u m constants for the f o r m a t i o n of these complexes are extremely large in comparison to the e q u i l i b r i u m constants for the f o r m a t i o n of similar complexes that contain ligands w i t h only one donor a t o m . For example, reaction (27-1) has an e q u i l i b r i u m constant K = 1 0 :
3 4
268
Experiment 27
This difference is especially surprising when we consider that the C o is in substantially the same environment in both complexes; that is, the C o ion is surrounded octahedrally by six coordinated N atoms. The greater stability of complexes containing chelating ligands, compared to the stability of similar complexes containing nonchclating ligands, is called the chelate effect.
3 + 3 +
The essential reason for the added stability of chelate complexes is a statistical ( e n t r o p y ) one. Once the first N of ethylenediamine attaches itself to the metal cation, the second N atom is held nearby. The metal cation is far more likely to find this second N and coordinate w i t h it than to encounter and react w i t h an entirely different ligand molecule in the solution. This statistical effect shows up in the entropy of complex f o r m a t i o n . A n o t h e r way of viewing the particularly favorable entropy change in the f o r m a t i o n of chelates is to note that seven particles are produced from four in Equation (27-2), while a monodentate ligand produces seven particles from seven [see Equation ( 2 7 - 1 ) ] . The chelate effect occurs w i t h many ligands besides ethylenediamine. To produce this effect, the only requirement is that each ligand molecule must have more than one atom that can coordinate to one metal cation. v. The purpose of this experiment is to study the consequences of chelate formation compared to the f o r m a t i o n of complexes w i t h monodentate ligands. The chelating ligands that y o u w i l l study in this experiment appear in Figure 27-2. The behavior o f these ligands w i l l be compared w i t h the behavior o f the monodentate ligands water, ammonia, and chloride. Note that the ligands ethylenediamine and oxalate are bidentate; each ligand has t w o atoms that are capable of c o o r d i n a t i n g
269
Metal Chelate Complexes
simultaneously w i t h one metal i o n . Ethylenediaminetetraacetate ( E D T A ) is sexadentate; it has six atoms for coordinating (2 N and 4 O ) . Figure 27-3 shows how an ethylenediaminetetraacetate ligand can coil itself around a cation so that all six of the octahedral coordination positions are filled. Acetate may be either monodentate or bidentate; it is probably bidentate w i t h P b , which you w i l l use in this experiment.
2 +
One of the main practical uses of chelate f o r m a t i o n is in the dissolution of nearly insoluble salts. This aspect o f chelate behavior w i l l be emphasized here. Consider the e q u i l i b r i u m representing complex formation between a metal cation M and a monodentate or chelating ligand L, where n is the number of ligands coordinated t o M
2 + 2 +
2 +
+ L^ML
2 +
(27-3)
As w i t h any e q u i l i b r i u m , reaction (27-3) can be described by an e q u i l i b r i u m constant; for this type of reaction, the e q u i l i b r i u m constant is called a formation constant: [ML ]
2+ f
[M
2 +
] [L]'
By adding sufficient L, the e q u i l i b r i u m of Equation (27-3) can be shifted to the right and essentially all the M can be converted to M L . If M L has a characteristic color, i t w i l l be easy to determine when this shift occurs. Because chelating ligands have especially large values o f K -, a lower concentration o f L w i l l be required to shift the e q u i l i b r i u m of Equation (27-3) to the right if L is chelating than if L is monodentate (assuming that the same k i n d of atom is bonded to the metal ion in each case, so that the ligands are as much alike as possible).
2 + 2 + 2 + ;
N o w consider the process of dissolving a salt MX in a solution of some ligand L. If MX is only slightly soluble, it w i l l dissolve according to Equation (27-5): M X ( s ) ^ M ( a q ) + X ~(aq)
2 + 2
(27-5)
The salt w i l l stop dissolving when [ M ] and [ X ] are large enough that their
2 + 2 -
270
Experiment 27
product is equal to K
sp
for the salt: K = [ M ( a q ) | [X "(aq)]

2 + 2 sp 2 +
(27-6)
I f the solution also contains L , then the concentration o f M ( a q ) w i l l constantly be diminished by conversion to M L and the solubility e q u i l i b r i u m w i l l be shifted to the right by removal of M ( a q ) :
2 + 2 +
MX(s) * M (aq) + X (aq) +

2+ 2 _
(27-7)
nL
It
ML
2 + 2 +
The more effective L is at complexing M ( a q ) (that is, the larger the f o r m a t i o n constant for M L ) , the less L w i l l be required to shift the e q u i l i b r i u m o f l i q u a t i o n (27-7) to the right by removal of M ( a q ) to dissolve MX(s) completely.
2+ 2 +
In more mathematical terms, the solubility of a nearly insoluble salt in the presence of a complexing ligand L can be determined as follows. The equilibria in solution are MX(s) - M (aq) + X "(aq)
2+ 2
(27-5) (27-3) I
M (aq) + n L - M L
2 +
2 +
Assume that the s o l u b i l i t y of MX is s moles/liter. Then when e q u i l i b r i u m is established for b o t h Equations (27-5) and (27-3) and when MX stops dissolving (that is, when the solution is saturated), s = [ X ~ ] and
2
[M (aq)] s = K
2 + 2 +
sp
(27-8)
The concentration of M ( a q ) is determined by the e q u i l i b r i u m of Equation (27-3) as well as of Equation (27-5) _

f
[ML 1
2+
_ [LI"
|ML +1
2
f n
[M (aq)l
2 +
(K /s) [L]
sp
A rearrangement indicates h o w s, the e q u i l i b r i u m concentration of X mined: - ^sp [ML, |

2 +
2 -
, is deter-
C7-10)
Equation (27-10) shows that the solubility of MX in the presence of a complexing ligand L depends on how effectively L complexes (depends on Kf and [ L ] ) as well as on how soluble MX is in pure water (depends on K ). In this experiment, y o u w i l l study how solubility depends on each o f these factors.
sp
271
medicine droppers test-tube rack test tubes
CHEMICALS NEEDED
l.OA/Cu(N0 ) 0.1A/EDTA 3.OA/ H C H 0 l.OA/ K C 0 l.OA/NaBr l.OA/NaCl

3 2 3 2 2 4
l.OA/Nal 6.0/1/NH 3.OA/ N H C H C H N H 3.0M N H C l i 0 1.OA/Ni(N0 ) l.OA/Pb(N0 )

3 2 2 2 4 2 3 2 3 2 3 2
PLAN
In the first part of this experiment, y o u w i l l investigate the complexing a b i l i t y of monodentate and bidentate ligands w i t h the N i and C u c a t i o n s . Complexing ability w i l l be reflected by the ease w i t h which solutions o f the ligands dissolve precipitates o f N i C 0 (nickel oxalate) and C u C 0 (copper oxalate). I f y o u begin w i t h several test tubes containing equal amounts of precipitate, only a small amount of the ligand that is the best complexing agent (that is, the ligand w i t h the largest Kf for complex f o r m a t i o n ) w i l l be required to dissolve the precipitate. If Kf is small, you w i l l have to'add a large amount o f L to shift the solubility e q u i l i b r i u m to the right. By measuring the volume of each L required to dissolve the precipitate, y o u can order the ligands according to the size of Kf for c o m p l e x a t i o n w i t h each metal.
2 + 2+ 2 4 2 4
In the second part o f this experiment, y o u w i l l work w i t h a sexadentate ligand, E D T A , w h i c h is an excellent complexing agent, to determine how the A^p of a low-solubility salt influences the ability of a chelating ligand to dissolve the precipitate. The nearly insoluble compounds that y o u w i l l attempt to dissolve are P b C l , P b B r , and P b l . Y o u w i l l then compare these E D T A results w i t h the results y o u obtain by dissolving the lead halides as acetate complexes. Acetate is most likely a bidentate ligand toward lead, rather than a monodentate. Whether acetate is monoor bidentate, E D T A coordinates several more atoms to P b than acetate does.
2 2 2 2 +
Finally, y o u w i l l make a few observations on the f o r m a t i o n o f complexes in s o l u t i o n .
PROCEDURE
A. V a r y i n g the Ligands
In this part of the experiment, y o u w i l l use a single metal i o n at a time. A f t e r forming a precipitate of the low-solubility metal oxalate, y o u w i l l try to dissolve it in solutions of various ligands by complex f o r m a t i o n .
272
Experiment 27
In labeled test tubes, obtain about 10 ml each of the ligand solutions 6.0/1/ N H . 3.OA/ N H C H C H N H , 1.0/1/ K C 0 , 0.1A/ E D T A , and 1.0A/ NaCl. Also obtain about 10 ml of 1 .OA/ N i ( N 0 ) . Prepare six test tubes containing N i C 0 precipitate by adding to each test tube 0.5 ml ( 10 drops from a medicine dropper) of the N i ( N 0 ) solution f o l l o w e d by 7 drops (no more) of 1 .OA/ K C 0 solution. A f t e r the tubes stand for a few minutes, you should see a precipitate of nickel oxalate. If y o u do not, add one or t w o more drops of potassium oxalate and wait t w o or three more minutes for the precipitate to f o r m . Do not add any more potassium oxalate than y o u need to obtain a precipitate; be sure to add the same amount of potassium oxalate to each of the tubes so that your comparisons will be valid.
3 2 2 2 2 2 2 4 3 2 2 4 3 2 2 2 4
To each test tube, add one of the five ligand solutions dropwise. (Be sure to use a different dropper for each ligand s o l u t i o n . ) Shake each tube to m i x the contents thoroughly after the addition of each drop of the ligand solution. A d d water to the sixth tube. For each ligand solution, count and record the number of drops required to dissolve the precipitate and form a clear solution. Note and record the color of each s o l u t i o n . A d d several more drops of the particular ligand solution to each test tube. Note and record whether any further color change develops, as well as the number of drops required to produce any color change that does occur. A dissolution or a color change may result simply from the effect of the water in the s o l u t i o n , rather than from the effect of adding more drops of a particular ligand. To the sixth test tube, add distilled water dropwise to match the total volume in each of the other five tubes. Some of the solubility equilibria are established slowly. If the first 30 or so drops of a ligand solution do not dissolve the precipitate, set the test tube aside and shake it occasionally, adding 10 drops of ligand solution each time. The ligands provided may not all dissolve the precipitate. I f an entire test tube full o f a m i x t u r e does not produce a clear solution, y o u can conclude that the ligand y o u are testing w i l l not dissolve the precipitate. Next prepare six test tubes containing copper oxalate by combining 10 drops of 1.0A/ C u ( N 0 ) and 1 1 drops of 1.0/1-/ K C 0 in each tube. Investigate the a b i l i t y of each ligand solution to dissolve this precipitate, f o l l o w i n g the same procedure y o u used in examining nickel oxalate.
3 2 2 2 4
B. V a r y i n g the Precipitate for One Metal Ion
Obtain 5 ml of P b ( N 0 ) solution, 1 ml each of NaCl, NaBr, and Nal solutions, and 5 ml of E D T A solution. Prepare three test tubes containing P b C l , P b B r , and P b l by adding 2 drops of lead nitrate solution and 4 drops of the sodium halide solution to a test tube. A t t e m p t to dissolve each of the three precipitates in 3.OA/ N H C F I 0 s o l u t i o n ; record the number of drops required to dissolve each precipitate. Then repeat this procedure using E D T A to dissolve the precipitates. When making comparisons between E D T A and a m m o n i u m acetate, it is i m p o r t a n t to recognize that the E D T A solution is o n l y one-thirtieth as concentrated as the a m m o n i u m acetate solution.
3 2 2 2 2 4 2 3 2
Prepare a precipitate of P b C l as before. Dissolve this precipitate in 3.OA/ H C H 0 and compare the number of drops required to dissolve P b C l w i t h the
2 2 3 2 2
273
number of drops of a m m o n i u m acetate solution that were required to dissolve this precipitate. A c c o u n t for the difference.
C. Shifting E q u i l i b r i a in S o l u t i o n : Monodentate vs. Chelating Ligands
Prepare a set of test tubes for color comparison as follows. A d d 2 drops of 1.04/ C u ( N 0 ) to each of three test tubes. Then, to the first tube, add 10 drops of distilled water; to the second tube, add 10 drops of 6.0/17 N H ; and to the third tube, add 10 drops o f E D T A solution. The tubes w i l l contain C u ( H 0 ) , Cu(NH ) , and C u ( E D T A ) , respectively, and w i l l be used to observe the color characteristic of each complex. Prepare a test tube containing the copper-ammine complex by adding 2 drops of C u ( N 0 ) solution to a test tube followed by enough 6.047 N H to produce the color of the C u ( N H ) complex. T h e n add a 200% excess of N H to be sure that essentially all the C u is present as C u ( N H ) rather than as C u ( H 0 ) . To this s o l u t i o n , add E D T A dropwise u n t i l the complex is converted to C u ( E D T A ) " , as evidenced by the color change. Record the number of drops required. Prepare a solution of C u ( E D T A ) " by combining 2 drops of C u ( N 0 ) solut i o n and enough E D T A to produce the color of this complex. A d d a 200% excess of E D T A . Then add 6.04/ N H dropwise t o t r y t o convert the E D T A complex t o the ammine complex. Record the number of drops required.
3 2 3 2 + 2 + 2 6 3 4 2 3 2 3 2 + 3 4 3 2 + 2 + 2 + 3 4 2 6 2 2 3 2 3
1.
The ligand solutions that y o u used in this experiment were n o t all of the same concentration. The ligand concentrations were varied for reasons that include s o l u b i l i t y difficulties ( E D T A ) and the necessity to avoid the side reactions that w o u l d occur w i t h more dilute solutions of ammonia and ethylenediamine. Therefore, to obtain an effective comparison of the c o m p l e x i n g abilities of the ligands y o u used here, y o u must make some concentration and statistical corrections in the volumes y o u measured. It is convenient to convert all the volumes to the comparison basis of 1.04/ N H solution. Such a s o l u t i o n w o u l d contain 1.0 mole/liter of N atoms that could coordinate. Each d r o p of 6.047 N H that y o u used w o u l d then be equivalent to 6 drops of 1.047 N H .
3 3 3
Each molecule of ethylenediamine contains t w o N atoms that can coordinate. Thus, a 3.04/ N H C H C H N H solution contains 6.0 moles/liter of N atoms that are capable of metal c o o r d i n a t i o n ; 1 drop of this solution is then equivalent to 6 drops of 1.04/ N H .
2 2 2 2 3
The 1.04/ solution of oxalate contains bidentate ligands that have t w o O atoms for coordination, whereas each E D T A i o n has six atoms that can coordinate. ( I t is likely that only five o f these six atoms w i l l coordinate w i t h N i and that only four o f these six atoms w i l l coordinate w i t h C u , b u t y o u can ignore this refinement for the purposes of this experiment.)
2 + 2 +
Use the reasoning o u t l i n e d here to convert the volumes of all the solutions y o u used in Part A of this experiment to the comparison basis of a 1.047 concentrat i o n o f coordinating atoms.
274
Experiment 27
2.
Assume that all complexes of a particular metal i o n have the same number of ligand atoms coordinated f r o m the added ligands. Y o u can then rank the ligands that coordinate w i t h N i and C u according to their f o r m a t i o n constants for metal complexes by n o t i n g w h i c h requires the smallest corrected volume to dissolve precipitates. Do this separately for the ligands reacting w i t h nickel oxalate and w i t h copper oxalate. Write the series w i t h the best coordinating ligand first: A > B > C
2 + 2 +
A l t h o u g h the assumption that all complexes of a particular metal i o n have the same number of ligand atoms coordinated from the added ligands is not s t r i c t l y true, departures from this assumption w i l l not significantly affect y o u r results and y o u do n o t have to account for t h e m here. 3. Explain how y o u r observations for the N H and NH2CH2CH2NH2 reactions w i t h N i and C u illustrate the chelate effect. Why is this a better comparison than the reactions o f N H and C 0 " w i t h N i and C u ?
3 2 + 2 + 2 2 + 2+ 3 2 4
4.
A c c o u n t for the relative volumes of a m m o n i u m acetate s o l u t i o n required to dissolve P b C l , P b B r , and P b l . A c c o u n t for the relative volumes of E D T A solution required to dissolve the lead halide precipitates. Refer t6 Equation (27-10) in y o u r discussion.
2 2 2
5.
Compare the corrected volume of E D T A required to dissolve each lead halide precipitate w i t h the corrected volume of a m m o n i u m acetate required to dissolve each of these precipitates. What does this tell y o u about the f o r m a t i o n constants of the E D T A and acetate complexes of P b ?
2+
6. 7.
A c c o u n t for the different quantities of 3.OA/ a m m o n i u m acetate and 3.OA/ acetic acid solutions required to dissolve lead chloride as the acetate complexes. Explain the results y o u obtained in Part C. Can the E D T A - c o m p l e x ^ amminecomplex e q u i l i b r i u m be shifted b o t h f r o m left to right and f r o m right to left? Explain w h y this is the case.
REFERENCE
Yoder, C . H . , Suydam, F . H . , and Snavely, F . A . Chemistry. New Y o r k : Harcourt Brace Jovanovich, Inc., 1975. Chapter 2 2 .
Experiment 28 Synthesis of an Organometallic Compound
Introduction
Organometallic compounds contain metal atoms bonded to carbon atoms of organic groups. Transition metals form a large number of such compounds. In this experiment, y o u w i l l use one organometallic c o m p o u n d as a starting material to prepare another. The starting compound that y o u w i l l use is shown in Figure 28-1. This c o m p o u n d is composed of t w o identical halves bonded together and is therefore called a dimer (di: t w o ) . Each Fe atom is bonded to a C H " ring. The dashed circle inside each ring indicates that several Lewis structures can be w r i t t e n for the ring, as depicted in Figure 28-2. The delocalized 7r-orbital system of the ring is involved in bonding to the Fe a t o m . Each Fe atom is also bonded to CO groups, t w o of which bridge the Fe atoms. F i n a l l y , the t w o Fe atoms f o r m a covalent bond. The o x i d a t i o n state for Fe in this c o m p o u n d is + 1 .
5 5
The i r o n atoms in this molecule can be easily oxidized to the +2 state that is more c o m m o n for i r o n . Iodine, like the other halogens, is a good o x i d i z i n g agent and reacts readily w i t h the dimer just described to produce (C H )Fe(CO)2L depicted in Figure 28-3. In this product, there is a covalent bond between Fe and I. Iodine is reduced to its very stable -1 o x i d a t i o n state, and iron is oxidized to the +2 state. The equation for the reaction is
5 s
[(C H )Fe(CO) ] + I
s s 2 2
-2(C H )Fe(CO) I
5 5 2
(28-1)
278
Experiment 28
279
Synthesis of an Organometailic Compound
iodine mineral oil
0.5A/ N a S 0
2 2
TECHNIQUE
Both of the reactants and also the product are nearly insoluble in water, so the reaction cannot be carried out in this solvent. In this experiment, y o u w i l l use the polar organic solvent dichloromethane ( C H C 1 ) in which all three materials are quite soluble.
2 2
A n excess o f iodine w i l l be used t o make sure that the organometallic starting material reacts w i t h i n a fairly short time. Before y o u come to the laboratory, calculate the approximate amount o f iodine that y o u will use in the experiment. Check y o u r figures w i t h y o u r instructor before y o u begin. After the reaction, the excess iodine must be removed so that only the product remains in the dichloromethane solution. This is done by shaking the dichloromethane solution w i t h an aqueous solution of sodium thiosulfate ( N a S 0 ) . Iodine and sodium thiosulfate react to form sodium iodide and sodium tetrathionate, b o t h of which are water soluble:
2 2 3
I + 2Na S 0
2 2 2
2NaI + N a S 0
2 4
(28-2)
Water and dichloromethane are immiscible; consequently, the t w o solutions can be easily separated from one another using a separatory funnel. A f t e r treating the,dichloromethane solution w i t h sodium thiosulfate, the solut i o n should confain only the product ( C H ) F e ( C O ) I . The solution w i l l be wet w i t h water and must be dried before the product can be isolated. This is done by m i x i n g a l i t t l e anhydrous sodium sulfate ( N a S 0 ) i n t o the s o l u t i o n . This d r y i n g agent absorbs water by f o r m i n g hydrated crystals that are insoluble in dichloromethane; these crystals can be removed from the dried solution by f i l t r a t i o n .
5 5 2 2 4
To isolate the product, hexane ( C H ) is added to the s o l u t i o n , which is then concentrated by removing solvent under reduced pressure. Of these t w o organic solvents, dichloromethane is more volatile; as the m i x t u r e of the t w o solvents boils under reduced pressure, the vapor w i l l contain a higher p r o p o r t i o n o f dichloromethane than it will o f hexane. The solution w i l l become richer in hexane and the product, which is nearly insoluble in this nonpolar solvent, w i l l precipitate. The solution cools considerably during this concentration, so it may be helpful to place the tlask in a beaker of warm water. The precipitate can be collected by f i l t r a t i o n .
6 1 4
Iodine, [ ( C H ) F e ( C O ) ] , and ( C H ) F e ( C O ) I are all dark-colored crystalline materials. To convince yourself that the material y o u isolate is actually different from the t w o starting materials, y o u w i l l examine some physical properties o f the three materials. A l t h o u g h the crystals of these materials look similar, they have noticeably different colors when they are powdered. Concentrated solutions of all three substances are quite dark and may be indistinguishable, but their dilute solutions have distinctively different colors. Their melting points are also different. A l l three substances melt above 1 0 0 C ; you w i l l need t o use a mineral-oil bath to measure their melting points. The melting point of the p r o d u c t , if it is pure, should be fairly sharp; melting should occur over not more than a 2 range. Make a p r e l i m i 5 5 2 2 5 5 2
280
Experiment 28
nary determination w i t h one sample of the product by rapidly heating the bath. Then, w i t h a second sample, heat the bath very slowly to make a precise determinat i o n . The melting point o f the organometallic starting material w i l l not be sharp; report a range for i t . To determine the m e l t i n g point of iodine, the open end of the capillary tube must be sealed in a l o w burner flame after the iodine is put i n t o i t ; if this is not done the iodine can vaporize out of the tube w i t h o u t melting.
PROCEDURE
C a u t i o n ! Both the starting material [ ( C H ) F e ( C O ) ] 2 and the product ( C H ) F e ( C O ) I can decompose and liberate carbon monoxide. In this experiment you w i l l w o r k w i t h small quantities o f these materials, from which there should be no danger. However, to avoid any possibility of liberating carbon m o n o x i d e i n t o the laboratory atmosphere, handle these materials only as described in this experiment. Do not attempt any other reaction or investigation of the properties of these compounds. Caution! Hexane is extremely flammable. Be sure that y o u are n o t near a lighted burner when y o u pour i t .
5 5 2 5 s 2
A. The Reaction
Measure out 50 ml of dichloromethane. Place 2 0 - 3 0 ml of it in a 125-ml Erlenmeyer flask, and dissolve 1.0-1.5 g of [ ( C H ) F e ( C O ) ] in the dichloromethane. Record the weight of this starting material that y o u actually use. This weighing (and all others in the experiment) can be made on the triple-beam balance. To the solut i o n , add a 200% excess of iodine. Stopper the flask, and swirl it gently for at least 1 5 minutes. Occasionally wash d o w n the sides of the flask w i t h a few ml of the remaining dichloromethane.
5 s 2 2
B. R e m o v a l of Unreacted Iodine
Pour the solution i n t o a separatory funnel; to i t , add about 50 ml of 0.5A/ sodium thiosulfate s o l u t i o n . Stopper the funnel and shake the m i x t u r e vigorously; occasionally open the stopcock (while holding the stoppered funnel upside d o w n ) to release the pressure that builds up from the vaporization of dichloromethane. Support the funnel in a metal ring on a ring stand, and allow the funnel and its contents to stand for several minutes. The m i x t u r e will separate i n t o t w o layers; the more dense dichloromethane solution w i l l settle to the b o t t o m . Unstopper the funnel and drain o f f and collect the dichloromethane layer. Discard the water layer. Return the dichloromethane solution to the funnel, and repeat this sodium t h i o sulfate treatment to be sure that all the iodine has been removed. Drain the dichloromethane layer i n t o a flask.
C. Drying the D i c h l o r o m e t h a n e S o l u t i o n
A d d 3-5 g of anhydrous sodium sulfate to the dichloromethane solution and vigorously swirl the m i x t u r e to ensure contact between the sodium sulfate and any
281
Synthesis of an Organometallic Compound
water that may be present. Set up a funnel and a piece of filter paper for gravity filtration. In the b o t t o m of the paper place a small amount of sodium sulfate; filter the dichloromethane solution through this i n t o a clean, dry suction f i l t r a t i o n flask. Use a few ml of the remaining dichloromethane to wash o u t the flask and to wash as much solution as possible out of the sodium sulfate in the funnel.
D. Precipitating and Collecting the Product
To the dichloromethane solution, add 100 ml of hexane. Put a broken wooden stick i n t o the flask to provide a rough surface on which small bubbles may form to prevent " b u m p i n g " of the solution when it boils. Stopper the flask and connect it to a trap b o t t l e ; connect the trap bottle to the water aspirator. T u r n on the aspirator and continue the suction u n t i l the solution is reduced to less than 50 m l . If not all of the [ ( C H ) F e ( C O ) ] has reacted, it w i l l precipitate first as a dark red film on the sides o f the flask. Then the product w i l l precipitate as tiny crystals. Collect these crystals by gravity f i l t r a t i o n ; reuse the filtrate to wash crystals o u t of the flask; be careful not to scrape out any [ ( C H ) F e ( C O ) ] if it is present. Open the filter paper and let the crystals stand u n t i l they are d r y .
5 s 2 2 s 5 2 2
E. D e t e r m i n i n g Properties
Using a mineral o i l bath and a thermometer graduated to at least 2 0 0 C , determine the melting points of iodine, [ ( C H ) F e ( C O ) 1 , and ( C H ) F e ( C O ) I . Determine the color of each of these materials in its crystalline f o r m and the color of each when a small crystal is crushed on white paper to a very fine powder. Determine the color of a very dilute dichloromethane s o l u t i o n of each of the materials. Be sure that each solution is sufficiently dilute that y o u can describe it by a single color such as " y e l l o w , " rather than by a m i x t u r e of colors such as " y e l l o w brown."
5 5 2 2 5 5 2
Report gram and molar quantities of b o t h starting materials and of the product. Calculate the percentage y i e l d of the product. Provide the requested i n f o r m a t i o n on the physical properties of iodine, [ ( C H ) F e ( C O ) ] , and ( C H ) F e ( C O ) I . T u r n in your product in a labeled bottle.
5 5 2 2 5 5 2
QUESTIONS
1. E x p l a i n , in terms of sound chemical principles, why it is desirable to make the dichloromethane solution of the reactants as concentrated as possible. Why is an excess of iodine used? 2. Write an equation to show what happens to sodium sulfate when it is used as a d r y i n g agent. 3. L o o k up the normal b o i l i n g points of dichloromethane and hexane. Which
282
Experiment 28
should have the higher vapor pressure at r o o m temperature? If the atmospheric pressure over these liquids drops, what will happen to their boiling points? Can these liquids b o i l at 2 0 C ? Why does the m i x t u r e of liquids cool as it boils?
REFERENCES
1. Yoder, C . H . , Suydam, F . H . , and Snavely, F . A . Chemistry. New Y o r k : Harcourt Brace Jovanovich, Inc., 1975. Chapter 22. 2. K i n g , R.B. Organumetallic Syntheses, V o l u m e I. New Y o r k : Academic Press, 1965,p.175.
Introduction II Inorganic Qualitative
Analysis
A. Chemical Systems for Study
Qualitative analysis is the study of how to identify the components of a m i x t u r e . The particular kinds o f mixtures that w i l l concern y o u are aqueous solutions o f inorganic salts. It w o u l d be impossible in this section to study all the k n o w n i n organic ions, so we shall confine our a t t e n t i o n to 28 cations and 7 anions. Most o f the cations y o u will study here are metallic. This is n o t surprising i f y o u recall that the most characteristic feature of metals is their electropositivitythe ease w i t h which they give up electrons. It is also w o r t h n o t i n g that b o t h cations and anions probably exist in aqueous solution as more complex species than the formulas used in this section indicate. F o r example, the C o ion is k n o w n to be closely surrounded by exactly six molecules of water, arranged in a regular fashion w i t h the negative end of the water dipole pointing toward the positively charged cobalt cation. Other cations are also surrounded by several water molecules, but the exact number is n o t always k n o w n . A n i o n s are also surrounded by water molecules, but these molecules are arranged so that the positive end of the water dipole points toward the negatively charged anion. Again, the precise number of water molecules bound in this way is n o t always k n o w n . F o r this reason, it is more convenient to refer to the ions as C o or Br", for example, even when they are in s o l u t i o n . Sometimes anions and cations are labeled C o ( a q ) , as an example, if emphasis is to be placed on the surrounding water molecules.
2 + 2 + 2+
B. Identifying Ions
The cations and anions y o u w i l l be asked to identify can be recognized by the characteristic reactions that they undergo. For instance, a s o l u t i o n containing silver ions w i l l react w i t h chromate ions to form a dark maroon c o m p o u n d , silver chromate. This c o m p o u n d is n o t very soluble in water, and so it precipitates f r o m solut i o n . The reaction between silver and chromate is represented by the equation 2Ag (aq) + Cr0 -(aq)
+ 2 4
Ag Cr0 (s)
2 4
(1)
The (s) indicates that the c o m p o u n d is a solid precipitate. The silver solution could not be composed merely of dissolved silver cations; enough anions must also be present to balance the positive charge. In fact, solutions containing A g ions are usually made by dissolving silver nitrate
+
AgN0 (s)
3
Ag (aq) + N 0 - ( a q )
+ 3
(2)
285
286
I n t r o d u c t i o n II
I,
Because the nitrate ion remains in solution and does not participate in reaction ( I ) , it is of no interest. The nitrate ion is therefore o m i t t e d from the equation showing the reaction of silver ion w i t h chromate i o n . For the same reason, the cation in the chromate s o l u t i o n is o m i t t e d f r o m the reaction, and we speak of the solution as if it contained o n l y chromate. To summarize, one reaction characteristic of the silver ion is the formation of a dark maroon c o m p o u n d w i t h chromate i o n . Thus, if y o u have a solution that forms such a precipitate when y o u add chromate, y o u can conclude that the solution contains Ag*. This reaction can serve as a test for the presence of the i o n . Similarly, the barium ion forms a bright y e l l o w precipitate of barium chromate when chromate ion is added, by the reaction Ba (aq) + Cr0
2+ 2 _ 4
(aq)
BaCr0 (s)
4
(3)
This reaction can serve as a test for barium. The procedure explained here shows y o u the reasoning used in qualitative analysis: A solution that is k n o w n to contain some ion is found to give a characteristic reaction, such as the precipitation of B a C r 0 . If some other solution of an u n k n o w n composition behaves similarly, then this behavior is regarded as evidence that the B a ion is present. Obviously, if no reaction is observed w i t h C r 0 ~ , B a must be absent. But suppose that a s o l u t i o n contains b o t h B a and A g ; if we t r y to confirm the presence of either of these ions by adding chromate, both maroon silver chromate and yellow barium chromate w i l l precipitate at the same time
4 2+ 2 2 + 4 2 + +
2Ag (aq) + C r 0 " ( a q ) - + A g C r 0 ( s )

+ 2 4 2 4
(maroon) (yellow)
(1) (3)
B a ( a q ) + C r 0 " ( a q ) -> B a C r 0 ( s )
2+ 2 4 4
The resulting precipitate w i l l be brownish in color, and the test w i l l be indeterminate. Here, silver and barium are said to " i n t e r f e r e " w i t h each other. To c o n f i r m the presence of either ion using the chromate test, the two ions w o u l d have to be separated, and the chromate test w o u l d have to be performed on each. It is easy to see, then, that the i d e n t i f i c a t i o n of ions in solution requires (1) the separation of interfering ions, and (2) the c o n f i r m a t i o n of each ion using a separate test reaction for each (usually the f o r m a t i o n of a precipitate).
C. G r o u p Separation
To make it easier to detect the 28 cations, they are separated i n t o more manageable groups that have some s o l u b i l i t y similarities; each ion in a group is then separated from the others. As an example, all the ions in Group I ( A g \ H g , and P b ) form insoluble chlorides. A s o l u t i o n of all 28 cations can be treated w i t h h y d r o chloric acid; this treatment immediately precipitates the insoluble chlorides of Group I cations, leaving the ions of all the other groups in solution. The white chloride precipitate can then be tested for A g , H g , and P b by separating each ion from the others and then c o n f i r m i n g the presence of each ion i n d i v i d u a l l y .
2 + 2+ 2 + 2 + 2 + 2
Group II ions all f o r m sulfides that are insoluble in acidic solutions. Thus, treating an acidic s o l u t i o n containing ions in Groups IIV w i t h hydrogen sulfide
1 ..
1
287
Inorganic Qualitative Analysis
produces a black precipitate of Group II sulfides while the ions in Groups I I I , I V , and V remain in solution. Ions in Groups I I I , I V , and V can be separated from one another by similar precipitation techniques.
D. T e c h n i q u e
Y o u r laboratory work in qualitative analysis w i l l be carried out on a somewhat smaller scale than in most of the other experiments in this manual. In addition to the obvious saving in quantities o f reagents, w o r k i n g on a smaller scale will allow y o u to complete the qualitative experiments in less time, because y o u w i l l not have to wait for large quantities of precipitate to f o r m , transfer large volumes of l i q u i d , and so f o r t h . This small-scale w o r k is called semimicro qualitative analysis. The special laboratory techniques and equipment used in semimicro w o r k will be described in this section. 1. Equipment. Y o u r set of desk equipment includes a micro burner, several semimicro test tubes in a rack, a metal test-tube support, and a set of dropping bottles for reagent solutions. V o l u m e measurements are conveniently made by counting numbers of drops instead of by ml when w o r k i n g on a semimicro scale. Unless the dropping bottles have been filled in the s t o c k r o o m , y o u r instructor w i l l tell y o u w h i c h reagent solutions to place in these dropping bottles. Be sure that the bottles have been washed and thoroughly rinsed twice w i t h distilled water. Label each b o t t l e . In addition to the.droppers provided in these bottles, y o u should have a few droppers for w i t h d r a w i n g liquids from small test tubes. The most convenient k i n d of dropper is a capillary pipet, a piece of glass tubing drawn to a very long and narrow constriction on one end and equipped w i t h a rubber bulb for suction (see Figure i i - 1 ) . These may be supplied by y o u r instructor, or y o u can make y o u r o w n . To make a capillary pipet, heat the center of a 5-in. length of glass t u b i n g . Rotate the tubing and heat it u n t i l it begins to sag in the m i d d l e ; then remove the tubing from the flame and pull it out to a small diameter. When the glass is c o o l , cut it i n t o t w o pi pets. Y o u should also make four or five stirring rods, each not longer than 4 i n . (the technique for breaking and fire-polishing glass is described on page 9). Y o u w i l l be
288
Introduction II
using these stirring rods c o n t i n u a l l y for several weeks, so be sure to fire-polish the ends to avoitl i n j u r y . 2. A v o i d i n g C o n t a m i n a t i o n . The anions and the cations that y o u w i l l w o r k w i t h in qualitative analysis will be supplied in concentrations o f only < 10 m g / m l . I f you do not clean y o u r glassware carefully and completely, y o u can introduce quantities of contaminants that are almost this large in themselves i n t o y o u r analysis. A d d e d reagents could then react w i t h contaminants to produce spurious results. Tap water is a particularly c o m m o n source of contaminant ions. A f t e r washing any glassware to be used in qualitative analysis, rinse the equipment at least twice w i t h distilled water. Capillary pipets should be rinsed twice w i t h distilled water after each use; if y o u develop the h a b i f of automatically washing y o u r glassware after each use, y o u w i l l be certain t o pick up a clean pipet whenever y o u need one. Keeping a beaker o f distilled water on y o u r desk w i l l provide a convenient way to rinse y o u r pipets. It is almost unnecessary to say that any water y o u add to solutions must be distilled water.,. ^ A clean towel on y o u r w o r k i n g area w i l l provide a place to lay stirring rods and pipets so that they w i l l n o t pick up any contaminants from the desk surface. As before, remember never to introduce y o u r pipets i n t o c o m m u n i t y vessels. Most o f these vessels w i l l be equipped w i t h their o w n droppers for removing solutions. The droppers y o u use to add reagents to test tubes should be held above the tube and not inserted i n t o i t . 3. A d d i n g Reagents. When w o r k i n g on a semimicro scale, l i q u i d reagents are added f r o m droppers or capillary pipets, and volumes are measured by c o u n t i n g the number of drops. A good rule of t h u m b is that 1 drop = 0.05 m l ; this means, of course, that 1 ml = 20 drops. Occasionally, y o u will need to measure small volumes accurately. For this purpose, y o u w i l l need to calibrate t w o capillary pipets. T o do this, fill a 10-ml graduated cylinder to the 5.0-ml mark w i t h distilled water, and count the number of drops of distilled water required f r o m the pipet to bring the level up 2 ml to the 7.0-ml mark on the cylinder. Obviously, half this number o f drops w i l l equal 1 m l . Label the pipet w i t h this calibration i n f o r m a t i o n . 4. M i x i n g Solutions. Several techniques are available for m i x i n g solutions in semimicro test tubes. The most obvious one is to use a stirring r o d . This is really not an efficient stirring technique, however. It is more satisfactory ( i f the tube is not t o o f u l l ) to h o l d the test tube in the t h u m b and forefinger of one hand and flick the b o t t o m of the tube w i t h the forefinger of the other hand. A l t e r n a t i v e l y , the contents may be partially sucked up in a capillary pipet ( b u t not up to the b u l b ) and then squirted back i n t o the tube. This procedure should be repeated t w o or three times for each m i x i n g . 5. Centrifuging. Many tests in qualitative analysis produce precipitates that must be separated from the remaining s o l u t i o n (called the supernatant liquid). This is c o m m o n l y done by placing the test tube in the head of a centrifuge and spinning it at high speed. The centrifugal force packs the precipitate at the b o t t o m
289
Centrifuge tube.
of the tube many times faster than it would take if y o u allowed the precipitate to settle naturally. When you centrifuge, be sure to balance the revolving head by placing a similar test tube that is filled to the same level w i t h distilled water opposite y o u r test tube in the centrifuge. I f y o u do not do this, the centrifuge w i l l be damaged and fewer centrifuges w i l l be available for y o u r laboratory w o r k i f some must be removed to be repaired. Once the centrifuge is turned on, it should spin at top speed for 30 seconds or so. Then t u r n o f f the switch and let the centrifuge come to a stop by itself. Do not attempt to slow it d o w n or stop it w i t h y o u r hand. Sometimes special test tubes called centrifuge tubes are supplied. These tubes have a narrow b o t t o m that helps to pack the precipitate (sec Figure i i - 2 ) . However, an ordinary semimicro test tube is adequate for centrifuging. 6. Testing for Completeness of Precipitation. A f t e r y o u remove a tube from the centrifuge, y o u should always test to be sure the precipitation is complete. To do this, add an additional drop of the precipitating reagent and note whether more
290
Introduction II
precipitate forms. If it does, add a few more drops of the reagent u n t i l precipitation seems to stop. Then centrifuge and test again. 7. Separating the Supernatant Liquid from a Precipitate. A capillary pipet can be used to draw o f f the solution above a precipitate (see Figure i i - 3 ) . Before y o u insert the pipet i n t o the test tube, be sure to squeeze the air out of the bulb. Some precipitates flocculate (remain partly dispersed in solution) even after centrifuging. If this happens, y o u can insert a t i n y plug of c o t t o n i n t o the capillary pipet, and then filter the supernatant l i q u i d through the c o t t o n plug. 8. Washing Precipitates. A f t e r a supernatant l i q u i d has been w i t h d r a w n as completely as possible w i t h a pipet, some o f the liquid w i l l still cling to the precipitate. This l i q u i d w i l l contain ions that can interfere w i t h further tests y o u w i l l make on the precipitate. Thus, this solution must be removed by washing. The wash l i q u i d is usually distilled water; sometimes another solution may be specified. The wash l i q u i d is added to the precipitate, and the packed precipitate is broken up by stirring it u n t i l it is completely dispersed in the l i q u i d . The tube is then centrifuged, and the l i q u i d is drawn off. This wash l i q u i d is usually discarded, but if it contains an appreciable q u a n t i t y of ions, y o u may be directed to add it to the first solution y o u removed from the precipitate. 9. Heating Solutions. Test tubes containing solutions are usually heated in a water bath, as shown in Figure i i - 4 . Some test-tube holders are constructed to sit inside the beaker instead of to fit over the top (as shown in the figure here).
291
10. Evaporating Solutions. When the volume of a solution is to be reduced appreciably or when a solution is to be taken to dryness, it is placed in a porcelain casserole or crucible and heated under a hood, so that any t o x i c fumes can be expelled from the laboratory. This heating must be conducted in such a way that the solution does not spatter. This can be accomplished by using a y - i n . flame from the micro burner; such a flame is referred to as a " m i c r o f l a m e . " The gas level can be adjusted properly by using a screw clamp on the burner hose. During heating, the crucible (held w i t h tongs) or casserole should be continuously swirled in the microflame. As dryness approaches, the b o t t o m o f the vessel w i l l dry first. Keep bringing fresh solution to the dry b o t t o m by swirling and t i l t i n g the vessel. Just before complete dryness is reached, remove the casserole or crucible from the flame and let the heat of the vessel complete the evaporation. If the residue is baked in the flame after it is d r y , volatile substances may be lost or the residue may be converted to an insoluble f o r m .
E. Y o u r L a b o r a t o r y Work in Qualitative A n a l y s i s
A f t e r so many general instructions, it w o u l d probably be helpful to comment more specifically on exactly what y o u w i l l do in the laboratory. 1. First Qualitative Analysis Period. y o u w i l l need to: Before y o u can w o r k in the laboratory,
(a) Clean your semimicro test tubes (and dropping bottles, if they are e m p t y ) , rinsing each twice w i t h distilled water. (b) Make five or six capillary pipets (unless these arc to be supplied), and obtain squeeze bulbs for them. (c) Make four or five stirring rods, each 4 i n . or so in length; fire-polish the ends. (d) Calibrate t w o capillary pipets. (e) Label and fill your dropping bottles w i t h the solutions provided by y o u r instructor. If the stockroom provides these reagents, be sure to obtain a complete set. 2. Subsequent Laboratory Periods. Y o u w i l l analyze each group o f ions separately. Before coming to class, carefully study the I n t r o d u c t i o n to each qualitative experiment. Y o u w i l l be expected to k n o w the analytical procedure for each group and to be able to write an equation for each separation and c o n f i r m a t o r y test. (Naturally, y o u do not need to memorize quantities of reagents to be used.) In the laboratory, you can obtain a so-called " k n o w n " solution containing ~ 1 0 m g / m l of each o f the group ions. Y o u w i l l conduct the group analysis procedure using this k n o w n solution to observe the reactions and to practice y o u r skills. A f t e r y o u complete y o u r analysis o f the k n o w n solution, y o u r instructor w i l l provide y o u w i t h an u n k n o w n solution that may contain any of the group ions. By f o l l o w i n g the analytical procedure, y o u w i l l decide and report which o f the possible ions arc present in y o u r u n k n o w n solution and which are absent. Finally, after all individual groups have been studied, y o u w i l l receive a general u n k n o w n that contains cations and anions from any o f the groups. Y o u w i l l report all ions present in this u n k n o w n , w h i c h may be a solution or a solid. I
I
292
I n t r o d u c t i o n II
3. Keeping a N o t e b o o k . Unless y o u are specifically directed to do otherwise by y o u r instructor, y o u are to keep a record of each step in the analysis of b o t h y o u r k n o w n and y o u r u n k n o w n in a notebook, f o l l o w i n g the example below: Solution or precipitate Group I k n o w n
Operation Added HCl
Observation White precipitate Some precipitate dissolved
Conclusion Ag , Pb , H g possibly present

+ 2+ 2 + 2
Precipitate 1.1
A d d e d hot water
P b probably present
2 +
A complete record w i l l help y o u r instructor to surmise where y o u may have made any errors and w i l l assure y o u that y o u have reached warranted conclusions. If y o u r notes are to be of any value, they must be recorded d u r i n g the experimentno/ at the end of the period or later in the day. Y o u may find it helpful to consult more complete treatments of qualitative analysis. [ F o r example, see E.J. K i n g , Ionic Reactions and Separations: Experiments in Qualitative Analysis (New Y o r k : Harcourt Brace Jovanovich, Inc., 1973); and C.H. Sorum, Introduction to Semimicro Qualitative Analysis, F o u r t h E d i t i o n (Englew o o d Cliffs, N . J : Prentice-Hall, 1967).]
Experiment 29 Qualitative Analysis of the Group I Cations

Introduction
The separation of the three Group I cations A g , P b , and H g from other cations in later groups depends on the fact that chlorides of G r o u p I cations are insoluble in acidic s o l u t i o n . This is a rather unusual occurrence, as y o u can see from the general solubility rules given on page 374. A l l other cations (Groups IIV) form soluble chlorides and remain in solution.
+ 2+ 2 + 2
S E P A R A T I O N OF G R O U P I CATIONS
The precipitate consisting of white, insoluble A g C l , P b C l , and H g C l forms when 6M HC1 is added to 10 or so drops of the s o l u t i o n . O n l y a slight excess of h y d r o c h l o r i c acid is added to obtain the precipitate.
2 2 2
A g + CP - AgCl(s)
f 2 +
(29-1)
A l t h o u g h Equation (29-1) and similar equations that can be w r i t t e n for P b and Hg suggest that the e q u i l i b r i u m can be shifted as far to the right as desired by adding sufficient C I " ions, the solubilities of the chlorides begin to increase after a large enough [ C P ] is reached, because of complex ion f o r m a t i o n :
2 + 2
AgCl(s)+ C I " - A g C l "

2
PbCl (s) + C I " ^ P b C l "

2 3
(29-2)
H g C l ( s ) + 2C1" * H g C l " + Hg(l)

2 2 2 4
Even a slight excess o f C I " w i l l cause the essentially complete removal o f these cations as their chlorides. In the solutions used here, [ A g ] = 0.02 before the addit i o n of HC1. At the conclusion of the G r o u p I p r e c i p i t a t i o n , sufficient C I " is s t i l l present so that [ C P ] = 0.35. The m a x i m u m amount of A g that can remain in solution then is given by
+ +
[ A g 1 (0.35) = K, = 1.8 X 1 0 "

+ p
1 0
(29-3)
w h i c h gives [ A g ] = 5 X 1 0 " . Thus, 5 X \0~ M; this is certainly complete A l t h o u g h H g i s also completely sufficiently soluble that a high enough precipitate w i t h G r o u p I I .
+ 10 l0 2 + 2
[ A g ] has been reduced from 0.02A/ to enough removal of A g for practical purposes. precipitated under these conditions, P b C l is [ P b ] remains in solution to give a PbS
+ + 2 2 +
294
Experiment 29
S E P A R A T I O N AND C O N F I R M A T I O N OF T H E C A T I O N S
The PbCU can be separated From the other chloride precipitates by taking advantage of a diFFerence in s o l u b i l i t y characteristics. A l l three chlorides increase in solubility as the temperature oF the water is raised; however, since P b C l is much more soluble than the other chlorides, even at room temperature, a given q u a n t i t y oF hot water will dissolve sufficient P b C l to separate it From AgC'l and H g C l :
2 2 2 2
|i PbCl (s)-^Pb H 0
2 2 2 +
+ 2C1"
v'"*' O
( "4)
2 9
A f t e r the precipitates are heated and stirred and the P b C l has dissolved, the AgCI and H g C I must be q u i c k l y centrifuged to the b o t t o m oF the test tube. The supernatant l i q u i d containing P b is drawn o f f before the solution cools and the P b C l reprecipitates.
2 2 2 2 + 2
The presence of P b is confirmed by adding K C r 0 . A yellow precipitate of lead chromate (K = 2 X 1 0 " ' ) forms if P b i s present:
2 + 2 4 lf 2 + sp
Pb
2 +
+Cr0
2 4
"^PbCr0 (s)
4
\*
V i
(29-5)
The precipitate of AgCI and H g C I is treated w i t h cone. (15/17) N H , and the silver and mercurous ions are confirmed by the different behaviors of these chlorides with N H .
2 2 3 3
Silver chloride (AgCI) dissolves in N H by forming the complex ion A g ( N H ) :

+ 3 3 2
AgCl(s) + 2 N H ( a q ) ^ A g ( N H ) * + C I "
3 3 2
(29-6)
This same effect was noted in Experiment 28 when insoluble compounds were dissolved by f o r m i n g complexes. Mercurous chloride undergoes a d i s p r o p o r t i o n a t i o n reaction w i t h N H . In a disproportionation reaction, there is simultaneous o x i d a t i o n and reduction of different atoms of one k i n d . In this case, mercurous ions H g are oxidized to the mercuric ion H g and reduced to metallic mercury H g ( l ) :
3 2 + 2 2 +
H g C l ( s ) + 2 N H ^ H g ( N H ) C l ( s ) + Hg(l) + N H C 1
2 2 3 2 4 2 + 2
(29-7)
The H g forms a white precipitate of H g ( N H ) C l (mercuric amidochloride), while the metallic mercury in finely divided form is black. The mixture of these t w o precipitates appears gray. The appearance of this gray color is taken as c o n f i r m a t i o n o f the presence o f H g . The supernatant l i q u i d contains A g ( N H ) * ions, and their presence is confirmed b y acidifying this solution w i t h H N 0 . Protons combine w i t h N H t o form N H , destroying the silver ammine complex in the process:
2 + 2 3 2 + 3 3 4
Ag(NH )
3
+ 2
+ 2 H 0 - Ag + 2NH/+ 2H 0
+ + 3 2
(29-8)
The Ag* ions then form a precipitate of white AgCI ( w h i c h confirms the presence of Ag*) by reacting w i t h the C I " ions in s o l u t i o n : A g + C l " - AgCl(s)
+
(29-9)
295
Qualitative Analysis of the Group I Cations
A possible complication can result if a large amount of mercury is present. Th metallic mercury formed via the reaction given in Equation (29-7) may reduce A to metallic silver:
:
2AgCl(s) + 2Hg(l) -* 2Ag(s) + H g C l ( s )

2 2
(29
I f this happens, the silver w i l l remain w i t h the gray mercury precipitate, instead o f dissolving via the reaction of Equation (29-6). Then no positive confirmatory test for A g w i l l be seen. I f y o u do not detect the presence o f Ag* via the reactions o f Equations (29-8) and (29-9), y o u should try to find it in the gray precipitate. The precipitate is treated w i t h aqua regia, a m i x t u r e of cone. HCl and cone. H N 0 , w h i c h dissolves almost any salt. The H g ( N H ) C l and Hg are oxidized and converted to chloro complexes:
+ 3 2
2Hg(NH )Cl(s) + 6N0 " + 6 C P + 8H 0 ->+ 2 3 3
2 I I g C l - - + N ( g ) + 6 N O , ( g ) + 141 UO
4 2
(29-1 1 ) (29-1 2)
H g ( l ) + 2 N 0 - + 4 C I " + 4 I I 0 - H g C I " + 2 N 0 + 6 I I 0
+ 2 3 3 4 2 2
Ag is oxidized and converted to a chloro complex by the large excess of cone. HCl: Ag + NO3-+ 2 C T + 2 H 0 ^ AgCI " + N 0 ( g ) + 3 I I 0
+ 3 2 2 2
(29-13)
The solution is evaporated to remove any excess aqua regia. When the remaining solution is diluted wi.th water, [ C I " I is decreased sufficiently that white AgCl precipitates; e q u i l i b r i u m [ E q u a t i o n (29-14)] is shifted to the right when [ C I " ) is lowered. AgCl "(aq) -> AgCl(s) + Cl"(aq)
2 2 _
(29-14)
The H g C l i o n remains in solution. If desired, its presence can be confirmed after centrifuging by adding S n ( I I ) chloride solution, which produces a gray precipitate by first reducing H g C l " to white H g C l and then to black Hg:
4 2 4 2 2
2HgCl " + Sn -> Hg Cl (s) + SnCl "

2 2+ 2 4 2 2 6
(29-15)
2
H g C l ( s ) + 4C1" + S n
2 2
2 +
- 2 H g ( l ) + S n C l "
6
(29-16)
CHEMICALS
NEEDED
(Solutions
+
without
specified
concentration
2
are
prepared as
4
indicated
in
Appendix
V.)
Ag (2mg/ml) 6A/ H C H 0 (acetic acid) 6M HCl" 12.1/ HCl Hg (10 m g / m l ) 6M H N 0 16M H N 0

2 3 2 2 + 2 3 3
K C r 0 solution litmus paper 6M N H 15yV/NH P b (15 m g / m l ) S n C l solution

3 3 2+ 2
296
Experiment 29
PROCEDURE
A n a l y s i s o f K n o w n and U n k n o w n S o l u t i o n s
1. Use 5 drops of a k n o w n or practice solution that contains about 15 m g / m l P b , 10 m g / m l H g , and 2 m g / m l A g . 2. The u n k n o w n solution may contain the ions of this and possibly other groups. If it is basic, acidify w i t h 6M HC1. If the u n k n o w n is a solid, take a representative sample and dissolve about 20 mg in a few drops of 6M H N 0 . The directions for the analysis are given in Outline 1. The superscript numbers in the instructions direct y o u r a t t e n t i o n to the notes that f o l l o w the outline for explanations, precautions, and further instructions. Consult y o u r instructor for the type of notebook record that y o u should keep for the analysis.
2+ 2 + + 2 3
297
298
Experiment 29
Notes to Outline 1
1. Small quantities of reagents are usually required. One drop (0.05 m l ) of 6A1 HC1 contains 6 X 0.05 = 0.3 m m o l . If a sample contains 20 mg of Ag (a very large a m o u n t ) , this is equivalent to 0.19 m m o l . Thus, 1 drop of 6A1 HC1 supplies more than enough Cl~ for complete precipitation. 2. Consult the technique section if y o u are in d o u b t as to how to perform any operations. 3. T h o r o u g h m i x i n g is d i f f i c u l t in a centrifuge tube because it has a narrow b o t t o m . Work the glass rod up and d o w n , and rub the inner wall to induce the crystallization of P b Q , w h i c h often forms supersaturated solutions. 4. If no precipitate forms, A g a n d H g ions are definitely absent, but P b ions may be at too l o w a concentration to precipitate w i t h Group I (and w i l l then appear in Group I I ) or P b C l may have supersaturated. Supcrsaturation can be overcome by vigorous stirring and rubbing the inner walls of the tube w i t h a rod. A l l o w five minutes before y o u conclude that G r o u p I is absent. 5. A large excess of reagent may dissolve the chlorides. 6. In these directions, "a f e w " is interpreted as 1 to 3 drops; "several," as 3 to 6 drops. Learn to judge for yourself from the size of the precipitate how much reagent to add. Use the least amount of reagent necessary to produce the required result. 7. The residue is washed w i t h very dilute HQ to minimize the loss of P b C I . Dilute 1 drop of 6M HQ w i t h about 10 drops (0.5 m l ) of water in a test tube and m i x well. 8. Use distilled water from a tube suspended in the water bath. Start heating this tube before beginning the analysis, so that it w i l l be ready when y o u need i t . Do not use water directly from the water bath. 9. Acetic acid prevents the precipitation of other chromates, such as C u C r 0 or ( B i O ) C r 0 , that may appear at this point if the group precipitate was not washed carefully enough. 10. Centrifuge to determine the btdk of the precipitate. It is useful to observe the size of tests on k n o w n solutions, for these help y o u to distinguish between normal and trace amounts in u n k n o w n solutions. Traces are generally caused by contamination and should not be reported. When large amounts of bismuth are present, it may sometimes carry through to this point because of careless technique. If y o u suspect the presence of bismuth, test the s o l u b i l i t y of the y e l l o w precipitate in 6AI N a O H ; P b C r 0 w i l l dissolve, but ( B i O ) C r 0 w i l l not. 1 1. If the lead is not almost completely removed from the precipitate, the chlorides can become coated w i t h insoluble P b ( O H ) when ammonia is added; this w i l l prevent their reaction w i t h the reagent. 12. It is better to use a test tube when acidifying S o l u t i o n 1.3, because it is easier to m i x in such tubes. 13. This is a more d i f f i c u l t operation than the beginning student may realize. Silver is often missed because the solution and the n i t r i c acid are not mixed well enough to obtain a definite acidic reaction. If y o u see a cloudy white layer floating on top of a clear one, y o u have not mixed the solution vigorously enough. Note particularly that a false acidic reaction can be obtained if the stirring rod touches an upper part of the tube that is wet w i t h acid. F o l l o w the m i x i n g procedure described in the technique section. Test for acidity by suspending a drop of the stirred solution on y o u r stirring rod and touching it to wet litmus.
2 + 2 + 2 + 2 2 2 4 2 4 4 2 4 2
299
14. The purpose of evaporation is to remove excess HC1 and to destroy nitric acid that w o u l d otherwise interfere w i t h the test for mercury. But if y o u permit too much solution to evaporate, some H g C l can be lost. Use a microflame, and h o l d the crucible in a pair of tongs. Wave the crucible back and f o r t h above, not i n , the flame; withdraw the crucible momentarily if boiling becomes vigorous. Stop heating when a drop or t w o o f solution remains; further evaporation w i l l occur as the hot solution stands.
2
RESULTS
Submit a 3 X 5 i n . card for your u n k n o w n s o l u t i o n , giving y o u r name, desk number, ions present, and ions absent. Have y o u r notebook available for y o u r instructor to examine on request.
REFERENCE
K i n g , Edward J. Ionic Reactions and Separations: Experiments in Qualitative Analysis. New Y o r k : Harcourt Brace Jovanovich, Inc., 1973, pp. 1 2 9 - 4 2 .
Experiment 30 Qualitative Analysis of the Group II Cations

Introduction
Group I I has many cations: H g , Pb + B i , C u , C d , A s ( l I I ) , A s ( V ) , S b ( I H ) , S b ( V ) , S n , and S n ( I V ) . Y o u w i l l undoubtedly find it more d i f f i c u l t to separate and c o n f i r m the G r o u p II cations than y o u did the G r o u p I cations. If y o u are to obtain good experimental results, y o u should be thoroughly familiar w i t h the material in this section before coming to the laboratory. Y o u r w o r k must be done carefully, and y o u should be sure that y o u understand exactly what is happening as y o u perform each step.
2 + 2 3 + 2 + 2 + 2+
Y o u w i l l notice that some o f the cations are identified by their o x i d a t i o n states (in Roman numerals) rather than w i t h values of the positive ionic charge. In these cases, the free cations do not exist in solution. Rather, some more complex species is present; for example, A s ( V ) is found as the arsenate ion A S O 4 in basic solutions and as H2ASO4 in acidic solutions.
3
Some of the cations may be present in more than one o x i d a t i o n state, depending on what compounds are used to prepare solutions or solid unknowns [ f o r example, A s ( I I I ) and A s ( V ) ] . : T n the course o f the analysis, b o t h o x i d a t i o n states w i l l be converted t o the same c o m p o u n d , which can then be reported merely as B i , A s ( V ) , S b ( I I I ) , or S n . Note that the t w o o x i d a t i o n states of mercury can be separately identified: the mercurous ion H g appears i n G r o u p I , while the mercuric ion H g appears i n G r o u p I I .
3 + 2+ 2 + 2 + 2
S E P A R A T I O N OF G R O U P II CATIONS
The G r o u p II cations have the c o m m o n property that they all form insoluble sulfides in acidic solutions. Table 30-1 below shows the s o l u b i l i t y products for several insoluble sulfides, including those in G r o u p I I .
302
Experiment 30
Other cations that form insoluble sulfides include several from Group I I I . The i m p o r t a n t question to be considered here is how the Group II cations can be cleanly separated by p r e c i p i t a t i o n as sulfides from the Group I I I cations that also form slightly soluble sulfides. The answer is that solution acidity must be carefully cont r o l l e d . Suppose that the solution of cations has [ M ] = 0.01 for the divalent cations. If C d is to be precipitated as CdS, then the [S ~] must be large enough that
2 + 2 + 2
[ C d ] [S -] = ( O . O l ) l S ] > K = 1 X 1 0 "
2 + 2 2 sp 2 26
28
(30-1)
or, solving Equation (30-1 ), [ S " [ must be > 1 X 1 0 ^ to precipitate CdS. A n y concentration greater than 1 X 1 0 ~ is sufficient. If [S ~] were 1 X 10~ yV/ and the solution also contained [ C o ] = 0 . 0 1 , then
26 2 21 2 +
[ C o ] [ S ] = (0.01)(1 X l C T ) = 1 X 1 0 ~
2 + 2 _ 2 1
23
(30-2)
Since this is only one-tenth as large as the K for CoS, by c o n t r o l l i n g [ S ~ [ , a large enough concentration can the less soluble G r o u p I I sulfides) w i l l precipitate. This small enough that CoS (and all the more soluble Group solution.
sp 2
no cobalt precipitates. Thus, be attained that CdS (and all concentration can also be I I I sulfides) will remain in
The sulfide concentration can be c o n t r o l l e d by adjusting the p H . Sulfide ions for precipitations are supplied by c o n t i n u a l l y saturating the solution w i t h H S , a weak acid. This gas dissolves in water to give [ H S ] = 0.1 and participates in the same k i n d of equilibria as any d i p r o t i c acid:
2 2
H S ( a q ) + H 0 - H 0 + US"
+ 2 2 3
(30-3) (30-4)
HS" + H 0 - H 0 + S "
+ 2 3 2
The e q u i l i b r i u m constants are [H3O+HHS-] [H S]

2
= R
] Q
1 Q
5 )
^ H s ' r
'~'
These t w o equilibria take place in the same solution. Hence, only one concentration of each species can be characteristic of the solution. If equations (30-5) and (30-6) are m u l t i p l i e d together, [ H S ] is cancelled in b o t h the numerator and the denominator:
-
[H o-][Hs-i
3
[H o*ns -i
2 3
[H O*] [S -]
3 2 2
2 0
[H S]
2
[HS ]
-
[H S]
a
Equation (30-7) can be considered merely a statement of the mathematical relationship among concentrations that must hold because of Equations (30-5) and (30-6).
303
Qualitative Analysis of the Group II Cations
If the solution remains saturated w i t h H S during the precipitation, [ H S ] = 0.1 and

2 2
[H 0 ] [S
+ 2 3
2 _
] = (0.1) X 1.3 X 1 0 ~ = 1.3 X 10~

2
21
(30-8)
As in any e q u i l i b r i u m , the species involved do not all need to come from the same source. Here, the [ H 0 1 of the solution can be adjusted by adding HC1. If [ H 0 ] of the solution is made eqtial to 0.3/W and the solution is kept saturated w i t h H S , then
+ + 3 3 2
(0.3)
[ S ] = 1.3 X 10~ [ S ] = 1.4 X 1 0 "

2 _ 2 _
21
2 0
(30-9)
This sulfide concentration is large enough that the ion product of the Group II sulfides exceeds their solubility product constants, causing them to precipitate. At the same time, the concentration is sufficiently small that no ion product of the G r o u p I I I sulfides exceeds its respective K ; therefore no Group II sulfides precipitate.
sp
Y o u should note from the i n f o r m a t i o n in Table 30-1 that SnS is relatively soluble and could precipitate w i t h Group I I I . To avoid this, S n is oxidized to S n ( I V ) before the p r e c i p i t a t i o n , because S n S , like the other G r o u p II sulfides, is very insoluble. Hydrogen sulfide is supplied to the reaction by generating it in the test tube. A solution of the organic c o m p o u n d thioacetamide ( T A ) is added, and the solution is heated. Thioacetamide breaks d o w n on heating to generate H S :
2 + 2 2
CH C(S)NH + H 0
3 2 2
H S(g) + C H C ( 0 ) N H
2 3 2
(30-10)
Thus, the solution can be kept saturated w i t h H S during the course of the precipit a t i o n . During the p r e c i p i t a t i o n , A s ( V ) is reduced to A s ( I I I ) by thioacetamide solution.
SUBDIVISION OF G R O U P II CATIONS
There are so many ions to test for in Group II that this group is separated i n t o t w o subgroups after precipitation. The separation is possible because of the amphoteric nature of some of the metal sulfides. As y o u may recall, an amphoteric compound can function b o t h as a base and as an acid. When treated w i t h K O H , A s S , S b S , and SnS behave as acids and dissolve w i t h the f o r m a t i o n of the complex ions
2 3 2 3 2
A s S ( s ) + 6 0 H ^ AsS ~ + A s 0
3 2 3 3
3 3
"+ 3H 0
2 2
(30-1 1 ) (30-12) (30-13)
Sb S (s) + 6 0 H " - * S b S
2 3 2
3 _ 3
+ Sb0 ~+ 3 H 0
3 3 2
SnS (s) + O H ^ S n S O H "
304
Experiment 30
HgS is weakly acidic, and some HgS may also dissolve. The remaining precipitate consists of the very weakly acidic sulfides HgS, PbS, B i S , CdS, and CuS. These subgroups are referred to as the arsenic subgroup and the copper subgroup of G r o u p I I , respectively.
2 3
Separation and Confirmation of Copper Subgroup Ions
Mercury. A l l the copper subgroup sulfides except HgS can be dissolved by heating them w i t h H N 0 . N i t r i c acid oxidizes sulfide to elemental sulfur:
3
S '+ 2 N 0 " + 4 H 0 - S(s) + 2 N 0 ( g ) + 6 H 0

2 + 3 3 2 2 2
(30-14)
The o x i d a t i o n of sulfide shifts the s o l u b i l i t y equilibria to the right as S ~ is c o n t i n u ously removed and the ion product drops below the value of K . For example
ip
CdS(s) ^ C d ( a q ) + S ( a q )
2+ 2_
J N0 ~
3
(30-15)
S HgS does not dissolve in H N 0 , because its s o l u b i l i t y product is so small (~ 1 0 ~ ) that sufficient S ~ is not removed by o x i d a t i o n to S. After separating the solution containing P b , B i , C d , and C u , the black precipitate of HgS can be dissolved in aqua regia. This reagent not only oxidizes S ~, but also removes H g by converting it to H g C l ~ and shifting the solubility equil i b r i u m to the right:
52 3 2 2+ 3 + 2 + 2 + 2 2 + 2 4
HgS - H g ( a q ) + S " CI" | N0 "
2+
(30-16)
HgCl 2 4 + 2 3 3 4
S
2
HgS + 2 N 0 - + 4C1 + 4 H 0 - > I l g C l ~ + S(s) + 2 N O , ( g ) + 6 H 0
(30-17)
The solution is evaporated to remove excess HC1 and H N 0 , and the residue is dissolved. To this s o l u t i o n , S n C l is added to c o n f i r m the presence of H g :
3 2 + 2
2HgCl ~+ S n
2 4
2 +
^ Hg CT (s) + SnCl ~
2 2 2 6 2+ 2
(30-18) (30-19)
H g C l + 4 C T + S n - - 2Hg(l) + S n C l "
2 2 6
The gray precipitate of H g C l and Hg confirms the presence of Hg.

2 2
Lead. The lead ion is separated from the solution o f P b , B i , C d , and C u by precipitation as white P b S 0 . This sulfate is somewhat soluble in H N 0 , so the nitric acid must be destroyed. Because H N 0 is volatile, it can be removed by evaporation after the addition of I I S 0 :
2+ 3 + 2 + 4 3 3 2 4
2 +
N0 " + H S0
3 2
H N 0 ( g ) + HS0 3 4
(30-20)
305
Q u a l i t a t i v e Analysis of the G r o u p II Cations
When all the H N 0 be discontinued.
has evaporated, dense white S 0
w i l l appear and the heating can
H S0 -^-*S0 (g) + H 0(g)

2 4 3 2 3 +
(30-21)
2 +
The lead sulfate residue is then separated from the solution containing B i , C d , and C u . Because the residue may be contaminated w i t h small quantities of bism u t h and copper sulfates, it is dissolved in h o t a m m o n i u m acetate:
2 +
P b S 0 + 3 C H 0 " * P b ( C H 0 - ) " + S 0 2 4 2 3 2 2 3 2 3 4
(30-22)
Impurities are left behind as solids. Potassium chromate is added to the solution to produce a precipitate of y e l l o w lead chromate, w h i c h confirms the presence of Pb: Pb(C H Q -)
2 3 2 3
+ C r 0 - * P b C r 0 + 3 C H 0 "
2 4 4 2 3 2 3 + 2 + 2 +
(30-23)
Bismuth. The separation o f B i from C d and C u can be achieved by the precipitation o f B i ( O H ) . B o t h C d and C u also form insoluble hydroxides; but i f the base used is N H , these ions w i l l remain in solution as ammine complexes:
2 + 2 + 3 3
Cd Cu
2 +
+ 4NH ^Cd(NH )
3 3
2 + 4
A'= 3 X 1 0
(30-24)
1 3
2 +
+ 4NH -Cu(NH )
3 3
2 + 4
AT= 1.1 X 1 0
2 + 2 +
(30-25)
The f o r m a t i o n of these complex ions reduces [ C u ] and [ C d ] to the point where [Cu | [ O H " l < K
2 + 2 tp
(30-26)
sp
[Cd
2 +
][OfT]
< K
(30-27)
The precipitate of white B i ( O H ) can be reduced to black metallic Bi by a basic stannite s o l u t i o n :

3
2 B i ( O H ) ( s ) + 3 S n ( O H ) " + 3 0 H " -> 2Bi(s) + 3 S n ( O H ) "

2 3 3 6
(30-28)
The black Bi confirms the presence of b i s m u t h . Cadmium and copper. The copper tetraammine complex C u ( N H ) is deep blue. Thus, the presence of C u can usually be detected from the color of the solution after the precipitation of B i ( O H ) . If this test seems inconclusive, a p o r t i o n of the solution can be used to form a maroon copper ferrocyanide precipitate. The ammine complex is first destroyed
2 + 3 4 2 + 3
Cu(NH )
3
2 + 4
+ 4 H C H 0 * C u
2 3 2 2 + 4 6
2 +
+ 4NH
2
+ 4
+ 4C H 0 "
2 3 2 6
(30-29) (30-30)
2Cu
+ F e ( C N ) " + C u F e ( C N )
Cadmium is confirmed by reprecipitating y e l l o w CdS: Cd(NH )

3 2 + 4
+ H S -* CdS(s) + 2 N H + 2 N H
2 3
+ 4
(30-31)
306
Experiment 30
If no C u is present, this test can be made by using the solution from the B i ( O H ) p r e c i p i t a t i o n . If C u is present, the black precipitate of CuS that forms when the solution is treated w i t h H S w i l l mask the y e l l o w CdS. In this case, the C u is first removed from solution by reduction w i t h d i t h i o n i t e ion S 0 ~ . This i o n w i l l not reduce C d :
2 + 3 2 + 2 + 2 2 2 4 2 +
Cu(NII )
3
2 + 4
+ S 0
2
2 4
+ 4 N H + 2 H 0 - > Cu(s) + 2 S 0
3 2
2 _ 3
+ 4NH + 4NH
3
+ 4
(30-32)
Separation and C o n f i r m a t i o n of A r s e n i c S u b g r o u p Ions
The cations of the arsenic subgroup are first reprecipitated as A s S , S b S , and SnS by acidifying the solution containing complex ions. This simply reverses the reaction that occurs when these cations are dissolved in K O H :
2 3 2 3 2
A s S " + A s 0 " + 6 H 0 * -* A s S ( s ) + 911 0

3 3 3 3 3 2 3 2
(30-33) (30-34) (30-35)

2 3
SbS
3 _ 3
+ S b 0 " + 6 H ( y ^ Sb S (s) + 9 H 0
3 3 3 2 3 2 + 2 3 2 2
S n S O i r + H 0 ^ SnS (s) + 2 H 0
The m i x t u r e of sulfide precipitates is then reacted w i t h dilute HC1 to dissolve S b S and SnS as the chloro complexes:
2
S b S ( s ) + 6 H 0 + 8Cl~-> 2SbCl ~ + 3 H S ( g ) + 6 H 0
+ 2 3 3 4 2 2
(30-36) (30-37)
SnS (s) + 4 I I 0 + 6CP -* SnCl ~ + 2 H S ( g ) + 4 I I 0

+ 2 2 3 6 2 2
Note that here these sulfides display the basic side of their amphoteric behavior in the reactions given by Equations ( 3 0 - 3 3 ) - ( 3 0 - 3 5 ) and the acidic side in the reactions given by Equations (30-36) and (30-37). A s S does not dissolve in dilute HC1.
2 3
Arsenic. The precipitate of A s S (after removal of the supernatant solution containing S b C l and SnCl ~) is oxidized w i t h hydrogen peroxide in ammonia solution:
2 3 2 4 6
A s S + 5 0 f T + O H " -> 2 A s 0 " + 3S + 3 H 0

3 2 3 2 4 2 4
(30-38)
The arsenate ion A s 0 " is precipitated by the a d d i t i o n of a magnesia m i x t u r e , a solution o f M g ( N 0 ) and N H N 0 i n aqueous ammonia:
3 2 4 3
As0
3 _ 4
+ Mg
2 +
+ NH
+ 4
+ 6 H 0 -> M g N H A s 0 6H 0(s)
2 4 4 2 3 4
(30-39)
This solid is redissolved in acetic acid, w h i c h converts much of the basic A s 0 ~ ion t o H A s 0 and H A s 0 " :
_ 2 2 4 4
M g N H A s 0 - 6 H 0 ( s ) + 2 H C H 0 -> H As0 '+ Mg

4 4 2 2 3 2 2 4
2 +
+ NH
+ 4
+ 2C H 0 - + 6H 0
2 3 2 2
(30-40)
Arsenic is finally confirmed by adding silver nitrate solution to precipitate reddish-
307
b r o w n silver arsenate:
ff
& // f
+ 3
<A- o .
TA
* \ % \ ,
:
H A s 0 " + 3Ag + 2 H 0 - Ag As0 (s) + 2 H 0

+ 2 4 2 3 4 2 4 6
( f c l )
\]
j| j
A n t i m o n y . The solution containing SbCl ~and S n C l ~ i s divided i n t o t w o v > parts: one part for the a n t i m o n y test and one part for the tin test. The a n t i m o n y \ > r } ; ^ test solution is allowed to react w i t h oxalic acid; both S b ( I I I ) and S n ( I V ) form oxalate complexes: SbCl "+ 3 H C 0
4 2 2 2 6 2 2 4
+ 6H 0->Sb(C 0 ) ~ + 4 C r + 6 H 0
3 2 2 4 3 3 4
(30-42)
+
SnCl " + 3 H C 0
+ 6H O^Sn(C 0 )
2 2 4
2 3
"+6Cl"+6H 0
3
(30-43) U g r o ^ A * ,
The formation constant for the reaction given in Equation (30-43) is so large that when thioacetamide is added and the solution is heated, no SnS w i l l precipitate because of the l o w [ S n ( I V ) ] . Reddish-orange S b S is the precipitate, and it confirms the presence of a n t i m o n y :
2 2 3
2Sb(C 0 )
2 4
3 3
+ 3 H S * S b S ( s ) + 6 H C 0
2 2 3 2 4
(30-44)
2_ 6
T i n . The S n ( I V ) in the second p o r t i o n of the SbCl ""/SnCl reduced to S n by the reaction w i t h Al wire
2 +
solution is first
3 S n C l " + 2 A l ( s ) - > 3 S n + 2 A J + 18C1"

2 2 + 3 + 6
(30-45)
Sb w i l l be reduced to the metal S b C l + Al(s) - Sb(s) + A l

4 3 +
+ 4CP
(30-46)
A side reaction w i l l also reduce some S n

2 +
2 +
to Sn:
3 +
3 S n + 2Al(s) h . 3Sn(s) + 2 A 1
(30-47)
However, Sn (but not Sb) can be reoxidized by hot HCl once the Al reduction is complete: Sn(s) + 2 H 0 ^ S n
+ 3 2+ 2 +
+ H (g) + 2 H 0
2 2
(30-48)
When all the tin is in the form of S n , it is confirmed by the familiar reaction w i t h Hg
2 +
Sn
2 +
+ 2Hg
2 +
+ 8Cr-> S n C l " + H g C l ( s )
4 6 2 2 2 + 2 +
(30-49)
This reaction was used earlier to confirm the presence of H g . Because S n is not in excess this time, H g w i l l be reduced only as far as the white precipitate H g C l .
2 + 2 2
CHEMICALS
NEEDED
AgN0 A l wire
A s ( l I I ) ( 2 mg/ml) B i (2 mg/ml)
3 +
308
C d (8 m g / m l ) Cu (2mg/ml) 6M H C H 0
2 + 2 + 2 3 2
magnesia m i x t u r e 6A/ NaOH N a S 0 4 (solid)

2 2
3% H 0 18A/H S0 2A/HC1 6M HC1 1 2M HC1 H g (2 m g / m l ) HgCl

2 2 2 4 2 + 2
6M N H 15A/NH NH C H 0 NH C1 NH N0 oxalic acid pH indicator paper

3 3 4 2 3 2 4 4 3
6A/HNO3
16A/HN0 K Cr0 O.SM K O H litmus paper
3 2 4
Pb (4mg/ml)
2 +
Sb(III) (2 mg/ml) Sn(IV) (8 mg/ml) SnCl thioacetamide ( T A )

2
PROCEDURE
Analysis of Known and Unknown Samples
1.
2.
Use 5 drops of a k n o w n or a practice solution that contains 2 m g / m l each of H g , B i , C u , A s ( I l I ) , and S b ( I I I ) , 4 m g / m l o f P b . and 8 mg/ml each o f C d and S n ( I V ) . If the solution contains a sediment, shake it well and then q u i c k l y w i t h d r a w the sample solution. The u n k n o w n may be (1) a solution containing the ions of this and possibly other groups, or (2) a solid m i x t u r e . If it is Solution 1.1 from Outline 1 (see Experiment 29), use all of i t . If it is a special u n k n o w n solution containing only Group II ions, treat it as y o u w o u l d the practice solution. If it is a solid, dissolve about 20 mg of a representative sample in 10 drops of 6/W HC1 and use half of this solution for the analysis.
2 + 3 + 2 + 2+ 2 +
Preliminary
Preparation
Calibration of a test tube. Measure 2.5 ml of water i n t o a clean, dry test tube. Mark the position of the b o t t o m of the meniscus w i t h a strip of label. O x i d a t i o n of t i n ( I I ) . Transfer the solution to be analyzed (which should be acidic) to a small casserole or crucible. A d d 2 drops of 3% H 0 , and b o i l the solution u n t i l only a few drops remain. Do this by swirling the solution constantly in a microflame and w i t h d r a w i n g the dish from this flame just before the final volume is reached (the solution w i l l continue to evaporate as i t cools). The chlorides o f A s ( V ) , S b ( V ) , S n ( I V ) , and H g are sufficiently volatile that some of these compounds may be lost if evaporation is excessive. Dilute the remaining solution w i t h 3-5 drops of water, and transfer this solution to the calibrated test tube. Rinse the casserole walls and b o t t o m twice w i t h 3-5 drops of water, and transfer b o t h rinses to the test tube. Do not be concerned if the
2 2 2 +
309
solution is t u r b i d . This is usually caused by SbOCl or BiOCl, w h i c h are readily converted to the sulfides in a later step.
A d j u s t m e n t of A c i d i t y
A d d 6M N H to the solution u n t i l it is basic to litmus or wide-range indicator paper. If C u ion is present, the formation of the deep-blue ammonia complex also acts as an indicator, but the blue color may be obscured by colored precipitates or complex ions of G r o u p I I I cations. To the basic solution, add 2M HC1 dropwise u n t i l the pH is between 2 and 3, according to wide-range indicator paper. If the solution is too acidic, adjust it w i t h a fraction of a drop of 6M N H . Then use your calibrated pipet to add exactly 0.35 ml of 2M HC1. Then add 4 drops of 13% thioacetamide solution (hereafter abbreviated T A ) and enough water to make the total volume 2.5 m l . M i x w e l l . Check the acidity of the solution w i t h short-range indicator paper. It should have a pH of 0.5, corresponding to a hydrogen ion concentration of 0.3A/. To treat the s o l u t i o n further, see Outline 2, w h i c h follows.
3 2 + 3
310
Experiment 30
311
4. Use water f r o m a test tube in the hot water bath or add cold water and heat in the water bath for a few minutes. Washing is necessary to remove any excess H S , which increases the solubility of HgS in K O H , as well as ions of other groups, if present. 5. A m m o n i u m chloride prevents the sulfides from turning to a colloidal suspension. 6. This evaporation is necessary to remove H S and T A , which are slowly o x i dized by atmospheric oxygen to sulfur and even to sulfate. Sulfate w o u l d precipitate B a and S r ions, causing them to be lost. 7. If a colloidal suspension persists despite the presence of N H N 0 , add a few crystals of the solid salt. Sometimes it is necessary to repeat this treatment; if so, add o n l y the m i n i m u m amount of N H N 0 that is required to coagulate the c o l l o i d . 8. If y o u cannot analyze the copper subgroup of Group II cations immediately, cover the sulfides w i t h water and a drop of TA and stopper the tube w i t h a cork or the bulb of a medicine dropper. If possible, it is better to conduct the analysis as far as the separation of Precipitate 3.1 from S o l u t i o n 3.1 in Outline 3 before storing the sulfides. 9. The complete separation of solution and precipitate is d i f f i c u l t to achieve in a test tube. Therefore, a second centrifugation and separation are made in a centrifuge tube. If a c o l l o i d persists, add a few crystals of N H N 0 or a drop of 0.2M N I I N 0 solution and warm to coagulate the precipitate. 1 0 . I f this solution cannot b e analyzed immediately, add a drop o f T A and reserve it in a t i g h t l y stoppered tube. A precipitate sometimes appears if the solution stands for a day or more. If the precipitate is colored, it is a sulfide. Its formation is not harmful; y o u can keep it w i t h the solution.
2 2 2+ 2+ 4 3 4 3 4 3 4 3
312
Experiment 30
313
Notes to Outline 3 1. There is an i n d u c t i o n period during which no apparent change occurs. When bubbling starts, the bubbles often carry sulfur and sulfides to the surface. Absence of bubbling does not mean there is no reaction. 2. As these formulas and colors i m p l y , a black precipitate at this stage is not necessarily an indication of the presence of mercury, nor is the formation of a white or a y e l l o w precipitate p r o o f of the absence of mercury. The precipitate must always be dissolved, and the mercury must be sought in solution. 3. In drawing o f f the s o l u t i o n , leave behind any particles of sulfur. 4. M e r c u r y ( I I ) chloride is somewhat volatile and should not be heated too strongly. ' 5. Evaporation destroys nitrate and removes excess HC1. The concentration of acid is further decreased by d i l u t i o n , because the reaction between H g C l and the S n ion is slow if the concentration of HC1 is high. 6. The f o r m a t i o n of S 0 indicates that nitrate has been removed as molecular H N 0 . Once seen, S 0 fumes are easy to recognize thereafter. They are heavier than the fumes of nitric acid that are given o f f first. Failure to evaporate u n t i l copious fumes are evolved may cause a sufficient amount of lead to remain in solution to spoil subsequent tests. Y e t evaporation should not be carried to dryness, because the anhydrous sulfates return to solution slowly. If dryness does occur, add 2 drops of 6A/ H S 0 and 3 drops of water, and then warm the casserole on the water bath for several minutes. Stir to disperse the residue in the solution. 7. The f o r m a t i o n of a precipitate at this point is not a certain indication of the presence of P b . Occasionally, other sulfates such as ( B i O ) S 0 precipitate here. The bismuth c o m p o u n d is less soluble than P b S 0 in N H C H 0 ; ( B i O ) C r 0 is more soluble than P b C r 0 in H C H 0 , and is insoluble in N a O H . 8. If a large q u a n t i t y of bismuth is found, check the s o l u b i l i t y of this precipitate in N a O H . 9. If the blue color is faint and further c o n f i r m a t i o n is required, acidify a drop o f the solution w i t h H C H 0 and add a drop o f K F e ( C N ) solution. C o p p e r ( I I ) forms a red ferrocyanide, whereas cadmium forms a white ferrocyanide. 1 0 . Beginning students may find it hard to see a small, gelatinous precipitate of B i ( O H ) , particularly when it is suspended in a blue solution.
2 2 + 3 3 3 2 4 2+ 2 4 4 4 2 3 2 2 4 4 2 3 2 2 3 2 4 6 3
314
Experiment 30
11. T o a drop o f S n C l reagent, add 6 M N a O H dropwise w i t h careful m i x i n g u n t i l the precipitate S n ( O H ) redissolves. This w i l l require at least 2 drops o f N a O H solution. If y o u doubt the effectiveness of the S n C l solution, which does gradually oxidize in air, prepare some stannite from the solution and test its effect on B i ( O H ) made from the standard solution of B i i o n . 12. Sodium d i t h i o n i t e is a powerful reducing agent and is unstable. Keep it dry and away f r o m heat. Use a dry spatula to measure the solid. One-half of a spatulafull, or about 50 mg, should reduce 12.5 mg o f C u ion. The blue color o f the copper ammonia complex should permanently disappear when d i t h i o n i t e is added. 13. Precipitated copper is red. Black or b r o w n residues frequently obtained here are colored by other metals. This is not h a r m f u l ; in fact, it is advantageous to remove traces of other metals before the cadmium test. 14. If the solution remains in contact w i t h copper too long, some of the copper can redissolve. 15. A f t e r prolonged treatment w i t h d i t h i o n i t e , a yellow color may appear; this is cadmium sulfide. If this occurs, add TA at once and w a r m . The sulfide apparently results from the decomposition of the d i t h i o n i t e after the copper is removed.
2 2 2 3 3 + 2 +
16. Occasionally a buff, green, or black precipitate is obtained at this p o i n t . This is a restdt of careless separations in previous steps of the analysis. If the precipitate is large, remove the solution and discard i t . Dissolve the precipitate as far as possible in one drop of 6M HC1. Centrifuge and transfer the clear solution to a test tube. Dilute w i t h 1 ml of water, add T A , and w a r m to reprecipitate the sulfide. 17. Cadmium may also be identified during the precipitation of the group (see note 3 to Outline 2).
315
316
Experiment 30
Notes to Outline 4 1. Thioacetamide is required to supply the H S that is lost by vaporization. 2. If the solution becomes too acidic, some SnS may be lost. Thus, 24/ rather than 647 HC1 is used. M i x thoroughly after each addition of HC1. 3. The sulfides y o u are w o r k i n g w i t h in this section are all highly colored. A white t u r b i d i t y that does not settle readily upon centrifugation is sulfur in its collodial f o r m . When y o u obtain o n l y this, the arsenic subgroup is absent.
2 2
4. The sulfides are precipitated in a test tube to permit careful neutralization and thorough m i x i n g . Because sulfides do not pack w e l l , the separation of precipitate and solution is improved if a centrifuge tube is used. 5. The extraction w i t h 1247 HC1 in the next step w i l l fail i f the acid becomes diluted w i t h excess water in the precipitate. 6. Note any change in the character of the precipitate during this treatment. A bright y e l l o w residue is usually A s S ; a black precipitate may contain HgS. A colorless solution and a white t u r b i d i t y of S indicate the absence of arsenic. Do not heat the m i x t u r e for a prolonged period of time, for some A s S may dissolve slowly.
2 3 2 3
7. Draw o f f the supernatant solution through a wisp of c o t t o n wrapped around the tip of a pipet. If the pipet or the casserole contains water, this may decrease the concentration of HC1 to such an extent that S b S reprecipitates. This is not harmful. 8. A black residue is probably HgS. It can be identified by the procedure given in Outline 3 for Precipitate 3 . 1 . A m m o n i a readily dissolves A s S , but does not dissolve HgS; the H 0 oxidizes A s ( I I I ) to A s ( V ) . 9. Solutions of M g N H A S 0 - 6 H 0 often become supersaturated. Give the precipitate time to form before y o u report a negative result. 10. A washing here removes traces of chloride that would precipitate w i t h A g N 0 in the next step. 1 1 . I f a white precipitate o f AgCl forms, add more A g N 0 . 12. If the solution is permitted to evaporate beyond this point, some S n C l may be lost. 13. A l u m i n u m can reduce S n ( l V ) and S n ( I I ) to gray Sn that will dissolve in HC1 after the A l has been consumed; Sb will not dissolve. 14. If the regular a n t i m o n y test is indecisive, y o u may make a c o n f i r m a t o r y test on this residue. Wash it w i t h water and dissolve it in a drop of 647 H N 0 . Dilute w i t h water, add T A , and warm the solution to precipitate S b S . 15. Since S n is oxidized by oxygen in the air, the addition of H g C l should not be delayed.
2 3 2 3 2 2 4 4 2 3 3 4 3 2 3 2 + 2
317
Qualitative Analysis of the G oup II Cations
16. The precipitate is frequently orange at first and then darkens because of the postprecipitation of impurities. If the precipitate is yellow, it may be A s S because the treatment of Precipitate 4.1 w i t h HC1 was too prolonged. Test the solubility of the precipitate in 12/W HC1 and in N H + H 0 . On the other hand, if the precipitate in the a n t i m o n y test is very dark, it may be contaminated w i t h HgS. In this case, remove the solution, add 6/V/ HC1 to the precipitate, and warm the solution for one or t w o minutes. Centrifuge and discard the residue. Then dilute the s o l u t i o n , add T A , and warm to reprecipitate S b S .
2 3 3 2 2 2 3
RESULTS
Submit a 3 X 5 i n . card for your u n k n o w n s o l u t i o n , giving y o u r name, desk number, ions present, and ions absent. Have your notebook available for your instructor to examine on request.
REFERENCE
Experiment 31 Qualitative Analysis of the Group III Cations

Introduction
The cations o f G r o u p I I I ( A l \ C r , F e , F e , M n , C o , N i , and Z n ) form insoluble hydroxides or sulfides in basic solutions. A l l of these cations except A l and Z n are transition metals; thus (except for A l and Z n ) , they form many highly colored complex ions that can be easily identified and that indicate the presence of G r o u p I I I ions in some preliminary tests even when ions from other groups are present in solution.
3 3 + 3+ 2+ 2 + 2 + 2 + 2 + 3 + 2 + 3 + 2 +
S E P A R A T I O N O F G R O U P III C A T I O N S
Group I I I cations can be separated from the cations of Groups IV and V by precipitation as sulfides or hydroxides. The precipitation is carried o u t w i t h thioacetamide in an ammoniaammonium chloride buffer. This buffer maintains the pH of the solution at ~ 9 . 3 ; this means, of course, that [ H 0 ] = 5.3 X 1 0 " and [ O H ] = 1.8 X 10~ . F r o m Equation (30-8) in the preceding experiment, we can compute the sulfide concentration in this buffered solution when it is saturated w i t h H S:
+ 1 0 3 5 2
[ H 0 ] [ S " ] = (5.3 X 1 0 - ' ) [ S - ] = 1.3 X 1 0 " [ S ] - 5 X 10~

+ 2 2 2 2 3 2 _ 3
21
(31-1)
If the metal ions are 0.0!/>/, then [M

2 +
] I S ' ] = 5 X 10"
2
(31-2)
and the ion product is larger than K for CoS, FeS, MnS, N i S , and ZnS. Thus, all these ions w i l l precipitate as sulfides. A l , C r , F e , F e , and M n also form insoluble hydroxides, as Table 31-1 indicates. Because the sulfides of F e and M n are less soluble than the hydroxides, these ions will precipitate as FeS and MnS even though the [ O F T ] is fairly substantial. F e , w h i c h has a very insoluble h y d r o x i d e , is reduced to F e by H S , and precipitates as FeS:
sp 3 + 3 + 3 + 2 + 2 + 2 + 3+ 2 + 2
2 +
2 F e + I I S + 2 H 0 -> 2 F e + S + 2 H 0
3 + 2 + 2 2 3
(31-3)
The purpose of the buffer is to maintain a sufficiently high concentration of O H " to precipitate A l ( O H ) , C r ( O H ) , and M n ( O H ) , b u t a l o w enough concentration to prevent the G r o u p V cation M g ( O H ) from precipitating. The i o n products for
3 3 2 2
319
320
Experiment 31
divalent and trivalent hydroxides are [M [M

2 +
][OrT] ] [OH"]
= (0.01)(1.8 X 1 0 ~ ) = 2 . 2 X 1 0 "
5 2 5 3
12
(31-4) (31-5)
3 +
= (0.01)(1.8 X 1 0 " ) = 3.0 X 1 0 "

sp
17
respectively. These values are obviously larger than A^ for Group I I I hydroxides, yet smaller than K for M g ( O H ) , so that its precipitation is prevented. An additional reason for maintaining [ O H ] at a reasonably low level is that C r ( O H ) and A l ( O H ) are amphoteric and w o u l d dissolve as C r ( 0 H ) and A l ( O H ) ~ i f [ O H ] were t o o large.
sp 2 _ 3 3 4 4 -
Separation and Confirmation of Group III Ions
Manganese. A f t e r the supernatant l i q u i d containing Group IV and G r o u p V ions is removed, the G r o u p I I I precipitate is dissolved in H N 0 . The amphoteric hydroxides display basic behavior. For example
3
Al(OH) (s) + 3 H 0 + A l
+ 3 3 3
3 +
+ 6H 0
2
(31-6)
The sulfides dissolve because H N 0 oxidizes the sulfide ion to sulfur and shifts the solubility e q u i l i b r i u m to the right (as in Experiment 30 w i t h the copper subgroup ions i n G r o u p I I ) : FeS(s) + 3NO-T+ 6 H 0 -> F e
+ 3 2 + 3 + 3 +
+ S + 3N0 (g) + 9 H 0
2 2
(31-7)
Note that F e is reoxidized to F e by N 0 . The solution is then treated w i t h C10 ". M n is oxidized to insoluble b r o w n M n 0 , w h i c h can be separated.
_ 3 2 + 3 2
Mn
2 +
+ 2C10J -> M n 0 ( s ) + 2C10 (g)

2 2
(31-8)
321
Qualitative Analysis of the Group I I I Cations
In a d d i t i o n , the chlorate ion oxidizes C r and C I " is oxidized to C l by N 0 :

_ 2 3 3 +
3 +
to yellow-orange dichromate ( C r 0
2
2 7
),
2Cr +6C10 - + 3 H 0 - > C r 0

3 2 2
2 7
- + 6C10 + 2 H 0
2 3
(31-9) (31-10)
3 C r + N 0 - + 4 H 0 * - * C l + NOC1 + 61UO
3 3 2
The precipitated M n 0 to M n :
2 +
is dissolved in acidic hydrogen peroxide and again reduced
Mn0 (s) + I I 0
2 2 2 +
+ 2 I l 0 * M n
+ 3
2 4
+ 0 ( g ) + 411 0
2 2
(31-1 1 )
The M n is oxidized to deep-purple permanganate w i t h sodium bismuthate to con firm manganese: 4Mn
2 +
+ 5 B i 0 + 1 8 H 0 ^ 4Mn0 - + 10Bi
+ 2 5 3 4
3 +
+ 27H 0
2
(31-12)
Division of G r o u p III Ions
Further advantage can be taken of the amphoteric behavior of some of the hydroxides to separate the remaining G r o u p I I I ions i n t o t w o subgroups: (1) F e , C o , N i , and (2) A l , Z n , C r ( V I ) . When the solution is treated w i t h N a O H , hydroxides precipitate for all ions except C r , w h i c h has been oxidized to C r 0 . As excess base is added, the amphoteric Z n ( O H ) and A l ( O H ) redissolve:
3+ 3+ 2 + 3 + 2 + 3 + 2 2 7 2 3
Z n ( O H ) ( s ) + 2 0 F T -* Z n ( O H )
2
2 _ 4
(31-13) (31-14)
AI(OM) + O F T ^ Al(OH) 3 4
Dichromate is converted to chromate: Cr 0

2 2 7
" + 2 0 F T -> 2 C r 0 " + H 0

2 4 2
(31-15)
N i ( O H ) and F e ( O H ) are not affected by the addition of excess base. Because C o ( O H ) is somewhat soluble, it is oxidized w i t h H 0 to less soluble C ' o ( O H ) .
2 3 2 2 2 3
C o n f i r m a t i o n of i r o n , cobalt, and nickel. The precipitate of F e ( O H ) , C o ( O H ) , and N i ( O H ) is then dissolved in HC1. The hydroxides act as bases, and the H 0 ions of the acid shift the s o l u b i l i t y equilibria to the right by removing OH":
3 3 2 + 3
Ni(OII) (s) ^
2
Ni
2 +
+ 2 0 t r |H O II 0
3 2 +
322
Experiment 31
The C o ion is unstable and spontaneously oxidizes water to 0 , so that C o reduced t o C o :

3 + 2 2 +
3 +
is
4Co
3 +
+ 6 H 0 - 4 C o
2
2 +
+ 0 (g) + 4H 0*
2 3 2 +
(31-17)
3 +
One p o r t i o n of the solution can be used to c o n f i r m the presence of C o and F e ; another p o r t i o n can be used to c o n f i r m N i . To h a l f of the solution, a crystal of N H N C S is added. A blood-red F e ( N C S ) complex confirms the presence of F e :
2 + 2+ 4 3+
Fe
3 +
3 +
+NCS"-Fe(NCS)
2+
2 +
(31-18)
2 +
If F e is present, the color of F e ( N C S ) must be destroyed before testing for C o . This is done by adding NaF, w h i c h converts F e ( N C S ) to colorless FeF ~:
2+ 3 6
Fe(NCS) + 6 F - ^ F e F
2 + 4
3 6
" + NCS
2+
(31-19)
A solution of N H N C S in a l c o h o l e t h e r is added and C o , if present, forms a blue complex in this solvent, c o n f i r m i n g the presence of Co: Co
2 +
+ 4NCS" > Co(NCS) ~ alcohol ether

2 4 2 +
(3 1-20)
T o test for N i , all F e and C o must be removed from the other p o r t i o n o f solut i o n . A d d i n g N H precipitates F e ( O H ) and C o ( O H ) , which are discarded. N i remains in solution as the blue-purple complex ion N i ( N H ) . D i m e t h y l g l y o x i m e is added to the s o l u t i o n , and a red precipitate whose structure appears in Figure 3 1-1 confirms the presence of nickel.
2 + 3 + 2 + 3 3 2 2 + 3 6
C h r o m i u m . The basic solution containing C r 0 A 1 ( 0 H ) ~ , and Z n ( O H ) " can n o w be tested for the presence of these ions. The presence of C r 0 " is indicated by the y e l l o w color of the s o l u t i o n C r 0 ~ a n d can be confirmed by making one p o r t i o n of the solution acidic and adding P b to precipitate yellow lead chromate:
2 2 4 4 4 2 4 2 4 2 +
Pb(C H 0 )
2 3 2
+Cr0 '-*Pb(Cr0 )(s) +2C H 0 "

2 4 4 2 3 2
(31-21)
323
FIGURE 31-2
Zinc complex with dithizone.
Aluminum. A n a m m o n i a - a m m o n i u m chloride buffer is added to a second p o r t i o n of the C r 0 ~ , A l ( O H ) " , Z n ( O H ) ~ solution, as in the i n i t i a l precipitation of the group. As shown earlier, this buffer provides a sufficient [ O H " | to precipitate A l ( O H ) . The presence o f N H retains Z n i n solution a s the complex ion Z n ( N H ) . The A l ( O H ) precipitate is separated by centrifugation and then dissolved in an acidic buffer of acetic acid and a m m o n i u m acetate. A l u m i n o n reagent is added, and A l ( i f present) produces a red precipitate A l ( C H 0 ) . This reaction occurs o n l y around the pH provided by the buffer.
2 2 4 4 4 2 + 3 3 2 + 3 4 3 3 + 2 2 1 3 9 3
Zinc. The solution that remains after the precipitation of A l ( O H ) must be freed of C r 0 , so that it cannot interfere w i t h the Z n test. This is done by adding BaCl] to precipitate B a C r 0 , which is discarded. Zinc sulfide is then precipitated by the a d d i t i o n of T A . The white color characteristic of ZnS confirms the presence of Z n . A final c o n f i r m a t o r y test is the formation of a purple-red complex between Z n and dithizone. The ZnS precipitate is dissolved in H N 0 , w h i c h oxidizes S " to S. The resulting solution is made basic and applied to a piece of dithizone paper. The purple-red complex whose structure appears in Figure 31-2 confirms the presence of Zn .
3 2 _ 2 + 4 4 2 + 2 3 2 +
2 +
324
Experiment 31
N H N C S (solid) N i ( 2 mg/ml) Pb(C H 0 ) SnCl

4 2 + 2 3 2 2 2
sodium bismuthatc (solid) thioacetamide Zn (4mg/ml)

2 +
PROCEDURE
Analysis of Known and Unknown Samples
1. Use 5 drops of a k n o w n or practice solution that contains 2 m g / m l each of A l , C r , N i , C o , and M n , and 4 m g / m l o f Z n . Note that the practice solution contains no i r o n . Carry out the tests for i r o n , and note the faint colorations that may appear caused by impurities. Then add 1 drop of F e solution to the test s o l u t i o n , and observe the appearance of a bona fide test.
3 + 3 + 2 + 2 + 2 + 2 + 3 +
2.
If the u n k n o w n is S o l u t i o n 2.1 from Outline 2 (Experiment 30), use all of the solution in the systematic analysis. If the u n k n o w n solution contains o n l y Group I I I ions, use 5 drops in the systematic analysis (more must be available for preliminary tests). If the u n k n o w n is a solid, take a representative sample and dissolve about 50 mg in water or in 64/ HC1; use about a t h i r d of this solution in the systematic analysis.
Always note the color of the k n o w n or u n k n o w n sample. Compare the colors of the u n k n o w n samples w i t h the colors of k n o w n ions. Some of the most c o m m o n ions and colors are: C r , violet; N i ( N H ) , blue-purple; C o C l and C o C l , blue; C r C l a n d C r ( O H ) , deep green; F e , pale green; F e C l , y e l l o w ; F e ( I I I ) - O H complexes, yellow to red; C o , red; M n , very pale pink (almost colorless); A l and Z n , colorless. In the solid state, combinations of colors must be considered; green nickel and red cobalt salts produce a gray m i x t u r e .
3+ 2 + 2 _ 3 6 2 4 + 2+ 2+ 2 4 2 + 2 + 3 + 2 +
Preliminary Tests
It is possible to make specific tests for all of the ions in this group (except a l u m i n u m and c h r o m i u m ) on the original sample, even when it contains ions from other groups. These tests are given here. It is wise to c o n f i r m each test by systematic analysis, according to Outline 5. Tests for i r o n . In a general analysis, all F e ioiis are reduced to F*e by H S or T A . Tests for the o x i d a t i o n state of iron must be made on the original sample.
3 + 2+ 2
Test for Fe : Dissolve one small crystal of K F e ( C N ) in about 20 drops of water. A d d a drop of this solution to a drop of the test solution. A blue color or a blue precipitate of K F e F e ( C N ) indicates the presence of F e . If the solution turns green, y o u may have used t o o much ferricyanide so that its yellow color masks the blue. In this case, add 1 d r o p of ferricyanide reagent to 5 drops of distilled water, m i x w e l l , and use this reagent to t r y the test again. Other ions produce colored precipitates w i t h this reagent, but o n l y F e forms a blue precipitate.
2+ 3 6 2+ 6 2 +
325
Test for Fe *: Dissolve a few crystals of N H N C S in a l i t t l e water, and add a few drops of this reagent to the test solution. The dense red color of F e N C S {not a precipitate) indicates the presence of F e i o n . Pink or light red colorations are caused by traces of i r o n , a c o m m o n i m p u r i t y in reagents. A l l aged solutions of F e contain F e , because the i r o n ( I I ) is slowly oxidized by the oxygen in the air. Do not report traces. If y o u are not sure that the color of y o u r test solution is deep enough to indicate the presence of F e , test a few drops of a solution that contains 0.1 m g / m l of F e (dilute one drop of the standard ion solution w i t h 5 ml of water and m i x well.) An indication of the presence of i r o n is also obtained in the test for cobalt.
3 4 2+ 3 + 2 + 3 + 3+ 3 +
Test for nickel. Dilute one drop of the test solution w i t h a few drops of water; then add 154/ N H u n t i l the solution is strongly alkaline. Centrifuge and draw o f f the clear solution to another tube. To the solution add several drops of d i m e t h y l glyoxime solution. A deep-red precipitate of nickel d i m e t h y l g l y o x i m a t e indicates the presence o f N i . I f a b r o w n coloration caused by C o forms instead, add more reagent. This test w i l l fail when o n l y a small amount o f nickel is present, because N i ( O H ) coprecipitates w i t h the larger precipitate of the gelatinous hydroxides of aluminum and iron ( I I I ) , which is centrifuged and discarded.
3 2 + 2 + 2
Test for manganese. Test a drop of the solution for chloride by acidifying the solution w i t h nitric acid ( i f necessary) and then adding A g N 0 s o l u t i o n .
3
If chloride is absent, add a drop of 164/ H N 0 and one-quarter spatula-full of sodium bismuthate. Centrifuge to see the color. The purple color of M n 0 indicates the presence of manganese. 2. If chloride is present, add A g N 0 solution u n t i l no more precipitate forms. Then test the solution w i t h H N 0 and sodium bismuthate, as before.
3 _ 4 3 3
1.
Test for cobalt. To a drop of the acidic solution, add a few drops of water and several crystals of N H N C S . If a red color ( F e N C S ) appears, add solid N a F , a l i t t l e at a time, u n t i l the color disappears. Then add 5 - 1 0 drops of a s o l u t i o n of N H N C S in alcohol-ether. A blue upper layer containing Co( N C S ) indicates the presence of Co. A green upper layer indicates the presence of low concentrations of either C o or N C S . If the color is indistinct or if it fades when the solution is shaken, add a spatula-full of solid N H N C S . If the color is red, add more NaF. A dark, m u d d y green color may be caused by the presence of C u ; add a drop of S n C l to reduce C u ( I I ) to C u ( I ) .
2+ 4 4 2 _ 4 2 + 4 2 + 2
Test for zinc. To 1 drop of the test s o l u t i o n , add 64/ N a O H u n t i l the solution is basic and then add 1 or 2 drops in excess. T o u c h a pipet to this m i x t u r e without squeezing the b u l b . Some o f the solution w i l l rise in the t i p o f the pipet by capillary action. Then bring the t i p d o w n vertically on the center of a square of dithizone paper. A purple-red spot indicates the present of Z n . An orange ring is caused by NaOH alone. M e r c u r y ( I or I I ) and lead(II) produce purple-blue spots, and S n ( I I ) produces a pink spot. N o w touch the pipet to some water and bring the t i p d o w n on the center o f the spot. The zinc spot w i l l spread as the water flows out o f the pipet; a spot produced by another ion w o u l d not spread.
2 +
326
Experiment 31
327
328
Experiment 31
329
6. If a purple color appears but then fades rapidly, chloride is present and y o u should add more bismuthate. 7. The o x i d a t i o n of M n ( I I ) to M n 0 by chlorate requires b o i l i n g , the presence of 16/17 H N 0 , and the absence of chloride. A v o i d adding too much K C 1 0 at one time, or the e v o l u t i o n of C 1 0 may become too violent. 8. I f the side test shows the absence o f manganese, no precipitate w i l l be obtained. Even so, the potassium chlorate treatment is used to oxidize C r to Cr 0 7 9. The first bismuthate that is added will oxidize 1 1 0 to 0 . A n excess is present when the layer of b r o w n or black, solid on the b o t t o m is several millimeters thick and no bubbles are evolved. 10. The hydrogen peroxide oxidizes C o ( O I l ) to C o ( O H ) , , and a better separation o f C o from A l and Z n results. Warming accelerates the reaction and decomposes the excess I I 0 . 1 1. A double centrifugation is advisable to ensure the complete separation of F e , C o , and N i from C r ( V I ) , A l , and Z n . 12. The thiocyanate reagent contains ether and a m y l alcohol, which are volatile solvents. I f the solution is warm when the reagent is added, most o f the solvents will evaporate. 13. The preliminary test is a more reliable indicator of F e than a red color at this stage. A certain amount of iron is frequently picked up during the analysis from impurities in the reagents or through careless technique. Therefore, even when no iron is detected in the preliminary test, a pink color is sometimes observed here. 14. If the blue color fades after m i x i n g , add a spatula-full of solid N H N C S . A large water layer extracts so much thiocyanate from the upper layer that the sensit i v i t y of the test is reduced. 15. A large, false nickel test may be found here if the solution was stirred w i t h a nickel spatula at any earlier stage. Glass rods should always be used for stirring. 16. If cobalt is present, it combines w i t h d i m e t h y l g l y o x i m e to produce a brown solution before any d i m e t h y l g l y o x i m e reacts w i t h nickel. If a b r o w n color forms, be sure to add a sufficient excess of reagent. 17. If the a l u m i n u m hydroxide is brownish in color, it may contain i r o n . Dissolve the A l ( O H ) in a drop or t w o of 6A7 NaGTI and centrifuge to remove the b r o w n F e ( O H ) . Neutralize the solution w i t h 6A/ HC1, and add N H C 1 and N H to reprecipitate A l ( O H ) . 18. The best lake is formed if the pH of the.acidic solution containing the aluminon is raised to between 5 and 7.2 by the addition of a m m o n i u m acetate. A precipitate may form in this weakly acidic solution i f large amounts o f A l * are present. Otherwise, the precipitate w i l l not appear u n t i l the solution is made weakly basic. An excess of N H is harmful. Silica from glass storage vessels does not produce a red lake, but F e , C r , P b , and other metals do give a red lake. Only silica could be present here if earlier separations were made carefully.
2 3 3 2 3 + 2 2 7 2 2 2 2 3 + 3 + 2 + 2 2 3+ 3 + 2 + 3 + 2 + 3 + 4 3 3 4 3 3 3 3 3+ 3+ 2+
RESULTS
For y o u r u n k n o w n solution, t u r n in a 3 X 5 i n . card giving y o u r name, desk number, ions present, ions absent. Have y o u r notebook available for y o u r instructor to examine on request.
330
REFERENCE
King,
Edward
J. Ionic Reactions and Separations:
Experiments in
Qualitative Anal-
ysis. New Y o r k : Harcourt Brace Jovanovich, Inc., pp. 163-82.
Experiment 32 Qualitative Analysis of the Group IV Cations

Introduction
The cations of Groups IV and V are those of the alkali and alkaline-earth families of the periodic table. Many of the cations of Groups IV and V can be identified by the flame-test m e t h o d y o u used in Experiment 8. However, flame tests are less satisfactory for analyzing samples in w h i c h several different ions may be present. This is because some flames tend to mask those of other ions. For this reason, a m e t h o d of chemical analysis that can be used to identify these cations is presented in Experiments 32 and 33. Y o u may still wish to use the procedure in Experiment 8 to make some flame tests in the preliminary analysis of y o u r u n k n o w n solution.
S E P A R A T I O N OF T H E GROUP
The G r o u p IV cations, C a , S r , and B a have very similar chemical behaviors in that each forms only a +2 i o n that has the noble gas c o n f i g u r a t i o n . Thus, no redox reactions occur to permit separation and i d e n t i f i c a t i o n . The analytical scheme depends p r i m a r i l y on s o l u b i l i t y differences between salts of o x o acids. The ions are precipitated as insoluble carbonates from a buffer m i x t u r e of ammonia, a m m o n i u m chloride, and a m m o n i u m carbonate. Carbonate precipitation is particularly advantageous, because carbonates can easily be redissolved in an acidic solution. The acid dissociation constants given in Table 32-1 show that C 0 ~ and HC0 ~are b o t h strong enough bases t o react essentially completely w i t h protons and to shift the s o l u b i l i t y equilibria to the right by the removal of C 0 ions:
2+ 2+ 2 + 2 3 3 2 _ 3
331
332
Experiment 32
Before precipitating the group, the a m m o n i u m salts that y o u have added to the sample as y o u separated the G r o u p I I I cations are removed by evaporation and baking. Then the concentrations o f N H , N H C 1 , and ( N H ) C 0 are adjusted precisely. After this adjustment, [ C 0 ~ ] w i l l be about 3 X 10 /W. Again i f y o u suppose that all the metal ions are present in 0 . 0 \ M concentrations, y o u can see from Table 32-2 that the i o n products w i l l be large enough to precipitate all the Group IV carbonates, but not the fairly insoluble M g C 0 from G r o u p V.
3 4 4 2 3 2 -2 3 3
Separation and C o n f i r m a t i o n of the Ions
B a r i u m . A f t e r removing the supernatant solution that contains Group V ions, the carbonate precipitate is dissolved in an a m m o n i u m acetate-acetic acid buffer that has a pH of ~ 4 . 7 . Some chromate ion is added to precipitate yellow B a C r 0 . In an acidic solution, the chromate ion participates in t w o i m p o r t a n t equilibria:
4
Cr0 - + I1 0 ^ HCr0
2 + 4 3
+ I1 0
2 2
(32-2) (32-3)
2 4
2Cr0 + 2 H 0 - Cr 0
+ 4 3 2
2 7
" + 3H 0
At the pH of the buffer used, o n l y about 1% of the chromate is present as C r 0 ~ ; the other 99% is converted to H C r 0 " or C r 0 " by the reactions of Equations (32-2) and (32-3). Thus, [ C r 0 ] is kept small enough that B a C r 0 (A' = 1 X 1 0 ' ) precipitates and C a C r 0 ( A ' = 7 X 1 0 " ) and S r C r 0 ( A ' = 3 X 10~ ) do not.
2 4 2 7 2 _ 4 4 S|) 1 0 4 s 4 s p 4 sp
The B a C r 0 precipitate can be dissolved in the strong acid H Q , which w i l l shift the equilibria reactions in Equations (32-2) and (32-3) far to the right:
4
BaCr0 (s) # B a
4
2 +
+ Cr0
2 _ 4
(32-4)
+ 3 2 _ 7
I H 0 HQCV+ Cr 0
2
Ba
2 +
is confirmed by precipitation from this solution as insoluble B a S 0 .

4
Calcium and s t r o n t i u m . The chromate that remains after the precipitation of B a C r 0 must be removed. This can be done by precipitating C a C 0 and S r C 0 and
4 3 3
333
Qualitative Analysis of the Group IV Cations
then washing the precipitate. Since there is no longer a possibility of precipitating the M g that was carried i n t o the G r o u p V solution, no buffer is needed to c o n t r o l [ C 0 ~ ] . N a C 0 can be used as the carbonate source. The carbonate i o n is eliminated when the precipitate is allowed to react w i t h concentrated H N 0 :
2 + 2 3 2 3 3
CaC0 (s) + 2 H 0 -+ C a ^Ca

+ 3 3
2+
2 +
+ H C0 + 2H 0 + C0 (g) + 3 i l 0
2 3 2 2 2
(32-5)
S t r o n t i u m carbonate ( S r C 0 ) dissolves similarly; but S r ( N 0 ) is insoluble in cone. H N 0 and precipitates immediately. Since C a ( N 0 ) is soluble, this procedure separates C a from Sr . The S r ( N 0 ) precipitate can then be dissolved in water:
3 3 2 3 3 2 2 + 2+ 3 2
Sr(N0 ) (s)
3 2
Sr (aq) + 2N0 (aq)

2+ _ 3 4 2 4
(32-6)
4
S t r o n t i u m is confirmed by the a d d i t i o n of ( N H ) S 0 to precipitate white S r S 0 . A n y traces o f C a ( N 0 ) that have precipitated w i t h S r ( N 0 ) w i l l form a precipitate of C a S 0 , as the A^p values given in Table 32-2 show. Thus, before precipitat i o n , some triethanolamine is added to f o r m a complex w i t h C a :
3 2 3 2 4 2+
Ca
2 +
2 +
+ 2 N ( C H O H ) - C a [ N ( C H O H ) 1
2 4 3 2 4 3
2 + 2
(32-7)
2 + 2 _
This reduces [ C a ] by converting it to the complex, so that [ C a ] [ S 0 ] < 2 X 1CT , and no precipitate o f C a S 0 w i l l form. Finally, Ca * is confirmed by the precipitation of C a C 0 T I 0 from a h o t , weakly alkaline solution. The solution must be weakly alkaline because C 0 ~ is a good base (see Table 31-1) and w o u l d be converted to H C 0 " in an acidic solution, thus reducing [ C 0 ~ ] to the point where [ C a ] [ C 0 ~ ] < A ' and preventing precipitation. The solution is heated so that a precipitate o f larger particle size w i l l form.
4 5 4 2 2 4 2 2 2 4 2 4 2 2 + 2 2 4 2 4 sp
334
Experiment 32
PROCEDURE
A n a l y s i s o f K n o w n and U n k n o w n S a m p l e s
1. A k n o w n or practice solution for G r o u p IV should contain 3 m g / m l of B a , S r , C a , and M g ions, and about 30 m g / m l of N H * i o n . Use 10 drops for the analysis. Remove the a m m o n i u m salts, and analyze the group according to Outline 6. To check y o u r technique, add 1 drop of a m m o n i u m sulfate and 1 drop of a m m o n i u m oxalate to Solution 6 . 1 . No more than a trace of precipitate should appeur, even after warming. To this solution, add N a H P 0 solution to precipitate magnesium a m m o n i u m phosphate and to verify that magnesium d i d not precipitate w i t h Group I V . 2. The u n k n o w n may contain only the ions of G r o u p IV or a c o m b i n a t i o n of G r o u p IV and G r o u p V ions. If it is a s o l u t i o n , use 10 drops for the analysis, according to Outline 6. If it is a solid, take a representative sample, dissolve 2 0 - 3 0 mg in water or in 6M HC1, and use this solution for the analysis. Remove the a m m o n i u m salts only if a positive test for the a m m o n i u m ion is obtained (see the Preliminary Test, Outline 7, Experiment 3 3 ) . If the u n k n o w n is Solution 5.1 ( E x p e r i m e n t 3 1 , Outline 5, Cation Group I I I ) , be sure it has been evaporated w i t h h y d r o c h l o r i c acid as directed in Outline 5 (Experiment 3 1) to remove thioacetamide and hydrogen sulfide before any nitric acid is added. (Otherwise, n i t r i c acid can oxidize sulfide to sulfate and cause the premature precipitation of barium and s t r o n t i u m . )
2+ 2+ 2+ 2 + 4 2 4
335
336
Experiment 32
337
9. The precipitates of this group are more densely packed than the sulfides and hydroxides of preceding groups; although they appear to be small, it is possible to obtain a satisfactory test w i t h t h e m . 10. Disregard the f o r m a t i o n of any precipitate after the a d d i t i o n of N a O H . Sodium hydroxide solution is frequently contaminated w i t h carbonate, so any additional precipitate may be the carbonates of s t r o n t i u m and calcium or it may be magnesium hydroxide if some magnesium carbonate was carried into the Group IV solution. 1 1 . Dissolve a heaping spatula-full (~ 0.1 5 g) of solid N a C 0 in 10 drops of water. When such solutions are stored in glass bottles, they etch the glass and dissolve some silica. This w o u l d precipitate w i t h the carbonates of s t r o n t i u m and calcium and make it d i f f i c u l t to judge the quantity of these substances. It is best to use a fresh solution of the reagent.
2 3
12. The solid nitrate settles rapidly. Unless the m i x t u r e is poured q u i c k l y , only the supernatant solution is decanted; the precipitate is left behind in the casserole. Examine the casserole if no precipitate is obtained, to see if any crystals are adhering to the walls. 13. For a satisfactory separation of S r ( N 0 ) , the concentration of H N 0 must not be below 70% (16/W); ideally, it should be close to 80%. Thus, the i n t r o d u c t i o n of water must be avoided by (1) using a dry tube, (2) pouring instead of pipetting, and (3) using a dry r o d . Dry the tube either w i t h a clean t o w e l or in an oven. C A U T I O N : 16A/ H N 0 is very corrosive. I t w i l l produce yellow stains on skin that take a week to wear (or peel) off. F l o o d all spills of n i t r i c acid w i t h water, whether they arc on the skin or on the desk. The use of plastic gloves is recommended.
3 2 3 3
14. S t r o n t i u m nitrate tends to form supersaturated solutions. Stirring, rubbing, and letting the solution stand are the usual ways of coping w i t h supersaturation. Cooling also h e l p s - n o t because the solubility is appreciably decreased, but because the supersaturated solution becomes more unstable. 15. S t r o n t i u m sulfate also tends to form supersaturated solutions. A l l o w at least 5 minutes for a precipitate to f o r m . 16. If desired, a flame test can be made for c o n f i r m a t i o n . The sulfate must be converted to carbonate and dissolved in h y d r o c h l o r i c acid. Remove the solution above the precipitate, and treat the precipitate w i t h a m m o n i u m carbonate solution. Stir up the caked precipitate and w a r m it b r i e f l y . Centrifuge and wash the precipitate several times to remove sulfate. Then dissolve the precipitate in a few drops of 12:1/ HC1 and make the flame test. 17. Since 10 drops o f 16A/ H N 0 were used t o separate S r ( N 0 ) , it w i l l take at least this much 1 5M N H to achieve neutralization. The nitric acid was diluted w i t h water to make the reaction less violent. Failure to make the solution basic is a c o m m o n error at this stage. Be particularly careful when m i x i n g , and test the solution w i t h litmus.
3 3 2 3
RESULTS
Submit a 3 X 5 i n . card for y o u r u n k n o w n , giving y o u r name, desk number, ions present, and ions absent. Have y o u r notebook available for y o u r instructor to examine on request.
338
Experiment 32
REFERENCE
Experiment 33 Qualitative Analysis of the Group V Cations

Introduction
The four G r o u p V cations (Na , K , M g , and N H ) present a special problem in qualitative analysis. W i t h the exception of M g . practically all the compounds of these ions are soluble. Therefore, no single reagent precipitates the G r o u p . The salts that do precipitate are often complex ones that are subject to the interference of other ions.
+ + 2 + + 4 2 +
Flame tests produce somewhat more definitive results w i t h G r o u p V than w i t h Group IV ions, especially when used in conjunction w i t h chemical evidence from the analysis scheme. This is because only t w o ions remain that color a flame: N a and K . The N a flame test is so sensitive that even the minute amounts of N a that leach into s o l u t i o n from glass bottles produce a yellow flame. When t r y i n g to determine whether y o u r u n k n o w n contains Na , y o u should compare the color intensity of the flame w i t h that of a k n o w n solution containing about 4 m g / m l of Na . The shortlived violet color of the K flame is masked by the y e l l o w of N a and should be viewed through t w o thicknesses of blue cobalt glass.
+ + + + + + + +
Separation and C o n f i r m a t i o n of the Ions
S o d i u m and potassium. Use two-thirds of the s o l u t i o n left from the Group IV precipitation to test for N a and K . The N H ion that may have been present in the original solution and that has been added in great quantities d u r i n g analysis is first destroyed by evaporating the solution to dryness. N F I w o u l d interfere w i t h the K* test by f o r m i n g a precipitate w i t h the reagent used, if a m m o n i u m salts were not first thermally decomposed. The residue is then redissolved and divided into t w o parts. One part is treated w i t h magnesium uranyl acetate to give a greenish-yellow crystalline precipitate that confirms the presence of N a :
+ + + 4 + 4 +
Na + M g
+
2 +
+ 3U0
2 + 2
+ 9 C H 0 - + 9 H 0 - > N a M g ( U 0 ) ( C H 0 ) - 9 H 0 ( s ) (33-1)
2 3 2 2 2 3 2 3 3 2 +
It is i m p o r t a n t that the volume of solution be very small; otherwise, [ N a ] w i l l be too small for this precipitate to f o r m . Therefore, o n l y a m i n i m u m volume of water should be used to dissolve the residue after evaporation. The other p o r t i o n of the solution is treated w i t h N a [ C o ( N 0 ) ] to give a yellow precipitate of dipotassium sodium c o b a l t i n i t r i t e that confirms the presence of K :
3 2 6 +
2 K + Na + Co(N0 ) " + H 0 -+ K N a [ C o ( N 0 ) ] -H 0(s)

+ + 3 2 6 2 2 2 6 2
(33-2)
339
340
Experiment 33
Magnesium. The second p o r t i o n of the supernatant l i q u i d from the Group IV precipitation is used to test for M g . In the presence of N H i o n and N H , some N a M P 0 solution is added to form a white precipitate of magnesium a m m o n i u m phosphate:
2 + + 4 3 2 4
Mg
3
2 +
+ NH
+ 4
+ 4
+ P 0 " + 6 H 0 -> M g ( N H ) ( P 0 ) - 6 H 0 ( s )
3 4 2 4 4 2
(33-3)
The N H and N H ion act as a buffer system to provide a sufficiently high I O H " ] t o convert H P 0 " t o P0 ~, but not enough [ O H ] t o precipitate M g ( O H ) . The presence of M g is confirmed by the formation of a blue lake. The precipitate is first dissolved in acid:
2 3 4 4 2 2 +
M g ( N H ) ( P 0 ) - 6 H 0 ( s ) + 2 I I 0 - M g
+ 4 4 2 3
2 +
+ NH
+ 4
+ H P0 + 8H 0
_ 2 4 2 2
(33-4)
A colored lake is then formed by precipitating M g ( O H ) in the presence of a dye that the precipitate adsorbs, coloring it blue. The dye is called "S and O" reagent, ( H O ) C H N = N C H ( N 0 ) . Its chemical name isp-nitrobenzenazoresorcinol.
2 6 3 6 4 2
A m m o n i u m i o n . The test for a m m o n i u m ion ( N H * ) is carried out on a p o r t i o n of the original solution. This is done because many N H salts are added in the course of group precipitations, and a solution w o u l d test positively for N H after Groups I , I I , I I I , and I V had been removed.
4 + 4 + 4
The reaction of ammonia w i t h water is the basis for the N H NH + H O^NH

3 2 + 4
+ 4
test: (33-5)
+ Oir
A strong base is added to the solution, shifting the equilibrium of l i q u a t i o n (33-5) to the left. The solution is heated, and N H gas is given off, because of the s o l u b i l i t y of gases decreases at high temperatures. A watch glass w i t h a piece o f wet, red litmus paper is placed above the test s o l u t i o n . As the escaping ammonia hits the watch glass and dissolves, the reaction of Equation (33-5) occurs and the red litmus turns blue.
3
CHEMICALS NEEDED
6M HC1 16yV/HN0 K ( 4 mg/ml) magnesium uranyl acetate Mg (2mg/ml) N a ( 4 mg/ml) Na Co(N0 ) Na HP0 N a N 0 solid
3 + 2 + + 3 2 6 2 4 2
6M N a O H Na S 6M N H N H ( 2 mg/ml) NH C1 (NH ) C 0 (NH ) S0 litmus paper "S and O" reagent

2 3 + 4 4 4 2 2 4 4 2 4
341
Qualitative Analysis of the Group V Cations
PROCEDURE
A n a l y s i s of K n o w n and U n k n o w n Samples
1. Use 10 drops of a k n o w n or practice solution that contains about 2 m g / m l of M g , 2 m g / m l of N H , 4 m g / m l of K , and 4 mg/ml of Na . 2. The u n k n o w n may be:
2 + + + + 4
(a) A solution containing only the ions of Group V: Use 10 drops of the solution to test for M g , K\ and Na , and a separate p o r t i o n of the solution to test for N H * . (b) A solid mixture containing only the ions of Group V: Take a representative sample, and use 20 mg to test for M g , Na , and K . Dissolve in 8-10 drops o f water. I f the solution is acidic, make it slightly alkaline w i t h 6M N I I (check w i t h l i t m u s ) . If the solution is alkaline, acidify w i t h 64/ HC1 and then make it barely alkaline w i t h 64/ N H . (c) Solution 6.1 (Experiment 32, Outline 6, Cation Group IV) obtained in a general analysis after removal of Groups HIV: Use the entire solution to test for M g , K \ and Na*. A d d 1 drop each o f ( N H ) C 0 and ( N H ) S 0 solutions and 64/ N H ( i f necessary) to make the solution alkaline. Centrifuge to settle the precipitate, which will contain traces o f the ions o f Group IV that escaped precipitation. Withdraw the solution, and use it for the analysis; discard the residue. The test for the a m m o n i u m ion must be made on a separate p o r t i o n of the original unknown.
2 + + 4 2 + + + 3 3 2 + 4 2 2 4 4 2 4 3
342
Experiment 33
343
Qualitative Analysis of the Group V Cations
344
Experiment 33
10. These tests are based on the f o r m a t i o n of fairly soluble precipitates and require that concentrated solutions and excesses of reagents be used. If y o u add t o o much water here, y o u may fail to obtain precipitates. 1 1 . The sodium c o b a l t i n i t r i t e reagent is unstable. It should have a deep reddishamber color. Pale y e l l o w or p i n k solutions should be discarded. Test the reagent w i t h a standard solution o f K i f its potency i s d o u b t e d . 12. If the a m m o n i u m salts have not been completely removed, a v o l u m i n o u s precipitate at this p o i n t is often ( N H ) N a C o ( N 0 2 ) 6 ' H 0 , w h i c h is indistinguishable f r o m the potassium c o m p o u n d . Warming w i l l remove a small amount o f the a m m o n i u m c o m p o u n d , but n o t a large q u a n t i t y . 13. Dissolve the precipitate in 1 drop of 6M HC1. V i e w the flame through t w o thicknesses of cobalt-blue glass to filter o u t the sodium color. The potassium flame appears red. 14. B o t h the potassium and the sodium precipitates supersaturate easily (see note 6 above).
+ 4 2 2
RESULTS
Submit a 3 X 5 i n . card for y o u r u n k n o w n , giving y o u r name, desk number, ions present, and ions absent. Have y o u r n o t e b o o k available for y o u r instructor to examine on request.
REFERENCE
K i n g , Edward J. Ionic Reactions and Separations: Experiments in Qualitative Analysis. New Y o r k : Harcourt Brace Jovanovich, Inc., 1973, pp. 1 9 8 - 2 0 9 .
Experiment 34 Qualitative Analysis

Introduction
of Anions
In this experiment, y o u w i l l learn to test for seven different anions (Cl~, Br", I " , N 0 " , N 0 ~ , S0 ~, and C 0 " ) by chemical analysis. In general, anion tests are subject to interference, and each test should be performed on a fresh p o r t i o n of the original sample unless y o u are instructed otherwise. Directions as to h o w to e l i m i nate any possible interfering ions are given w i t h each test. Y o u may recall from Experiment 9 that some of these anions can be detected by infrared spectroscopy. This technique can also be applied to a solid sample. H o w ever, in a m i x t u r e of anions overlapping bands can cause confusion. Moreover, CI". Br", and 1" cannot be detected in this way.
2 2 3 2 4 3
Identification of A n i o n s
Chloride, bromide, and iodide ions. A preliminary test w i l l show whether any of these ions are present. An ammoniacal solution of A g N 0 is added, which forms insoluble A g C l , AgBr, and A g l w i t h any halide ions present. Of course, if no precipitate forms, then no halides are present. The A g N 0 . s o l u t i o n contains ammonia, so that most of the silver ion is present as A g ( N H ) . [ A g 1 is so small that o n l y the least soluble salts of silver precipitate and A g S 0 remains in solution, since
3 3 + + 3 2 2 4
[Ag l [S0
+ 2
2 4
"|<A'
s p
= 2 X 10"
(34-1)
The precipitate of A g C l , AgBr, and A g l is dissolved by heating w i t h Zn metal, which reduces A g to Ag and forms soluble zinc halides. For example
+
2AgCl(s) + Zn + 2Ag(s) + Z n ( a q ) + 2Cl"(aq)

2+
(34-2)
The Br" and I" ions are then oxidized one by one to halogens. The reduction potential I + 2<f
2
-> 2 1 " + 2Br" - * 2C1"
E = +0.54 E = +1.06 E=+1.36

2
(34-3) (34-4) (34-5)
B r + 2e
2
Cl +2f
2
show that I" is most easily oxidized. Thus an o x i d i z i n g agent ( N 0 ~ ) is chosen that can oxidize I " but not Br". The I i s extracted i n t o CC1 and identified b y its violet color. A f t e r adding additional N 0 " to be sure that all the I" is removed, Br" is
2 4 2
345
346
Experiment 34
oxidized to B r by M n 0 ~ , w h i c h is not a strong enough oxidizing agent to react w i t h C I " . B r is also extracted i n t o C C 1 and identified by its orange-brown color. A i l the remaining Br" is oxidized w i t h additional M n 0 " , and the C I " is identified by its f o r m a t i o n o f a w h i t e AgCl precipitate w i t h A g N 0 .
2 4 2 4 4 3
Nitrite ion. sulfamic acid:
N i t r i t e ( N 0 " ) is identified by its reaction in acid solution w i t h

2
N0 " + NH S0 "
2 2 3
N (g) + S0 " + H 0
2 2 4 2 2
(34-6)
The N gas can be seen bubbling o f f , and the S 0 " produced can be detected by the a d d i t i o n o f B a C l , w i t h w h i c h S 0 " forms a white precipitate o f B a S 0 . Obviously, any sulfate already present in the original solution w o u l d interfere w i t h this test for N 0 " . Therefore, any sulfate present is removed by precipitating it w i t h B a C l and discarding the precipitate before testing for n i t r i t e .
2 4 2 2 4 4 2 2
Nitrate ion. Nitrate ( N 0 " ) is identified by detecting the ammonia produced when it is reduced w i t h Al in basic s o l u t i o n :
3
3 N 0 " + 8A1 + 5 0 K T + 1 8 H 0 -> 3 N H ( g ) + 8 A 1 ( 0 H ) "

3 2 3 4
(34-7)
The N H is detected by allowing it to contact a piece of wet red litmus, w h i c h the the N H turns blue because o f the e q u i l i b r i u m :
3 3
N H + H 0 =^ N H
3 2
+ 4
+ OH"
(34-8)
Al is supplied in the form of Devarda's alloy (45% A I , 50% Cu, 5% Z n ) . The a m m o n i u m ion w o u l d interfere w i t h this test by producing N H via the reverse of the reaction given in Equation (34-8) in basic solution. N 0 " is also reduced by Al to N H . If these t w o ions are present, they are removed before the N 0 " test is begun.
3 2 3 3
Sulfate ion. Sulfate ( S 0 " ) is easy to detect because it forms a white precipitate o f B a S 0 w i t h B a C l . N o other ions y o u deal w i t h here will interfere w i t h this reaction.
2 4 4 2
Carbonate ion.
When C 0 " is acidified, C 0 ( g ) is evolved:

2 3 2
C0
2 3
"+2H 0 ^C0 (g) + 3H 0

+ 3 2 2 2 +
(34-9) ions, a
If the carbon dioxide is allowed to contact a basic solution that contains B a white precipitate of B a C 0 forms, w h i c h confirms the presence of C 0 ~ .
2 3 3
Ba
2 +
+ 2 0 H " + C 0 ( g ) -> BaC0 (s) + H 0

2 3 2
(34-10)
If y o u r instructor has supplied a k n o w n or an u n k n o w n solution, this test can be made d i r e c t l y on the s o l u t i o n . Otherwise, it should be made on a p o r t i o n of the solid sample.
347
Qualitative Analysis of Anions
CHEMICALS NEEDED
0.2M A g N 0 BaCl Ba(OH) boiling chips CC1 Devarda's alloy 6AfHC H 0

3 2 2 4 2 3 2
'
KMn0 k n o w n solid (1 part K B r ; 1 part K I ; 2 parts K N 0 2 parts N a C 0 , 1 part K C l ) N a ( C 0 ) anhydrous N a N 0 solid 6M NaOH 6M N H
4 2 3 2 3 2 3 r e
6M HCl iîi-****^ H N H S 0 (sulfamic acid) (solid) 6M H N 0 3% H 0 6M H S 0

2 3 3 2 2 2 4
d litmus paper Solution A : 3.3/W A g N 0 Solution B : ammoniacal ( N H ) C 0 Zn granules

3 4 2
PROCEDURE Preparing a S o l u t i o n for A n a l y s i s
Y o u r instructor may supply k n o w n and u n k n o w n solutions for anion analysis. If a solid sample is supplied, y o u must prepare a s o l u t i o n . First, t r y dissolving about 20 mg of the solid in 1 ml of distilled water. If necessary, heat the m i x t u r e in a water bath. If all of the sample dissolves, y o u can prepare a larger q u a n t i t y of solution for anion testing by dissolving 100 mg of the solid in 5 ml of distilled water. If all of the solid does not dissolve in the preliminary test for s o l u b i l i t y , place 100 mg of the sample in a small flask and add 5 ml of water, 500 mg of anhydrous N a C 0 , and a b o i l i n g chip. B o i l the contents for at least 10 minutes, occasionally adding water to keep the t o t a l volume constant. Divide the contents of the flask between t w o semimicro test tubes and centrifuge. Combine the solutions; wash each precipitate, and add the wash water to the s o l u t i o n .
2 3
Combine the precipitates and add 6M H C H 0 u n t i l gas ceases to evolve. I f any residue remains, it must be B a S 0 , A g C l , AgBr, or A g l . The test outline gives procedures for testing the residue. Only the first solution (the one w i t h o u t acetic acid) and the residue are needed for the anion tests. The analysis should f o l l o w Outline 8.
2 3 2 4
348
Experiment 34
349
Qualitative Analysis of Anions
volume of 6/W N a O H , being careful not to wet the upper walls of the tube w i t h base. Have a small c o t t o n plug and a piece of wet, red litmus paper ready. A d d several granules of Devarda's alloy, and insert the c o t t o n plug about a t h i r d of the way i n t o the tube. Bend the litmus paper i n t o a V-shape and place it in the m o u t h of the tube (see Figure 34-1). A l l o w the tube to stand for several minutes. The litmus turns blue from evolving N H , indicating the presence oT N 0 " .
3 3
S 0 ~ test. To 5 drops of the test s o l u t i o n , add B a C l u n t i l a precipitate no longer forms. Centrifuge and wash the precipitate. A d d a few drops of 6M HC1. The white precipitate of B a S 0 is insoluble in HC1 and indicates the presence of S 0 .
2 4 2 2 _ 4 4
C 0 ~ test. To a 30-mg p o r t i o n of the original solid (or the solution supplied by y o u r i n s t r u c t o r ) , add 2 drops of 6/W H S 0 . Have ready a medicine dropper containing B a ( O H ) solution, and place the dropper, supported by a piece of rubber tubing, in the m o u t h of the tube (see Figure 34-2). Do not squeeze the bulb of the dropper. The t u r b i d i t y in the dropper is due to B a C 0 and indicates the presence of C 0 .
2 3 2 4 2 2 3 3
Note on Outline 8
1. Zn reduces A g to the metal and yields a solution that contains Z n , C I " , Brand P, and a gray Ag precipitate. A n y insoluble residue that is present after making up the anion test solution can be treated by this m e t h o d . Silver halides w i l l dissolve, but B a S 0 w i l l not. Even i f all the precipitate does not dissolve (indicating the presence of B a S 0 ) , the solution should be tested for halide ions after combining it w i t h Solution 8 . 1 .
+ 2 + 4 4
350
Experiment 34
RESULTS
Submit a 3 X 5 in. card for y o u r u n k n o w n , giving y o u r name, desk number, ions present, and ions absent. Have y o u r notebook available for your instructor to examine on request.
REFERENCE
K i n g , Edward J. Ionic Reactions and Separations: Experiments in Qualitative Analysis. New Y o r k : Harcourt Brace Jovanovich, Inc., 1973, pp. 5 9 - 1 0 6 .
Experiment 35 Analysis of a General Unknown

Introduction
Y o u w i l l be issued a general u n k n o w n which may contain any o f the cations in Groups IV and any of the seven anions in Experiment 34. Y o u should carry o u t the group separations and ion identifications according to Outlines 1-8 given in Experiments 2 9 - 3 4 . If y o u r u n k n o w n is supplied in solution, y o u may use this solution for b o t h cation and anion analyses. I f your u n k n o w n is a solid, y o u w i l l need t o prepare separate solutions for the cation and the anion analyses. Directions for preparing a solution for anion analysis have already been given in Experiment 34. To prepare the solution for cation analysis test the s o l u b i l i t y of separate small portions of the sample successively in cold and hot portions of H 0 , 64/ HC1, 1247 HC1, 647 H N 0 , 1647 H N 0 , and aqua regia (in this order). T h o r o u g h l y m i x 5 - 1 0 drops of each solvent w i t h about 10 mg of sample, and allow time for a reaction to occur. Centrifuge to determine if a small residue remains undissolved. When concentrated acids are used, dilute the m i x t u r e slowly w i t h an equal volume of water after the reaction ceases. Certain salts are only sparingly soluble in concentrated acid. When y o u find a solvent in the list that w i l l dissolve the solid, do not test any more solvents.
2 3 3
Weigh 100 mg of the sample, and treat it w i t h the solvent y o u select. If no solvent dissolves the sample completely, use the solvent that produced the greatest effect or, if there is l i t t l e difference among the solvents, use aqua regia. ( I f an insoluble residue forms, use the procedure described in the f o l l o w i n g discussion.) If the solution was originally obtained by using one of the acid solvents, evaporate the solution to a volume of a few drops to remove any excess acid. Do not evaporate to dryness, because this may cause decomposition or the f o r m a t i o n of basic salts that are d i f f i c u l t to redissolve. Take about one-fourth of the solution (the equivalent of 25 mg of the original sample) for the systematic analysis of the cations. If there is a residue insoluble in acid, special treatment is required. The c o m m o n substances the residue may contain are P b S 0 , B a S 0 , S r S 0 , C a S 0 ( i f a largeamount is present); the ignited sulfates o f F e ( I I I ) , A l ( I I I ) , or C r ( I I I ) ; AgCl, AgBr, A g l ; AUO3, C r 0 , S n 0 , S b 0 , S i 0 , o r silicates; C ; o r S . First the residue is treated w i t h sodium carbonate solution to convert the sulfates to carbonates; the residue is then treated w i t h zinc and acid to reduce the silver halides to metallic silver. 1. Wash the residue twice w i t h a moderately d i l u t e solution of the acid used to dissolve the sample. Then suspend the residue in 1 ml of water and add t w o heaping spatula-fulls of sodium carbonate. Heat the m i x t u r e in b o i l i n g water for 10 minutes, stirring frequently. Centrifuge, discard the s o l u t i o n , and wash the precipitate three
4 4 4 4 2 3 2 2 5 2
351
352
Experiment 35
times w i t h hot water to remove the sulfate. A d d a few drops of 6M H N 0 to the residue and, after the reaction ceases, d i l u t e the m i x t u r e w i t h several drops o f water. Centrifuge and w i t h d r a w the s o l u t i o n ; add it to the acidic solution of the sample to be used in the general analysis. If a residue still remains, repeat the sodium carbonate treatment.
3
2. The residue f r o m the conversion of the sulfates may be silver salts, oxides, silicates, C, or S. A d d 1 ml of water, 1 d r o p of 1 8M H S 0 , and some Zn granules to reduce the silver halides to free silver. Warm for several minutes, and break apart and disperse the residue w i t h a r o d . Centrifuge and discard the solution. Wash the precipitate twice. A d d several drops of 6M H N 0 to dissolve the silver and excess zinc. I d e n t i f y silver in the solution by precipitating the chloride, dissolving it in ammonia, and reprecipitating the chloride w i t h n i t r i c acid (see Outline 1, Experiment 2 9 ) . In y o u r n o t e b o o k , record y o u r procedures and observations on dissolving the sample.
2 4 3
PRELIMINARY
TESTS
It is useful to test a solution of the sample w i t h various reagents that react w i t h sizable numbers of ions. The f o r m a t i o n of a precipitate or the absence of an apparent reaction indicates the presence or the absence of certain groups of ions. The s i m p l i c i t y of the tests makes them w o r t h t r y i n g , but the results must be confirmed by other tests. For each test, dilute 1 drop of the solution of the sample w i t h a few drops of water to obtain a convenient v o l u m e ; then add the particular reagent dropwise, m i x i n g t h o r o u g h l y after each a d d i t i o n , u n t i l no further change is observed.
A. Action of Excess Sodium Hydroxide
A d d 6M N a O H u n t i l an excess is present; the final m i x t u r e should be strongly basic (check w i t h l i t m u s ) . Centrifuge to consolidate any precipitate; the w h i t e , gelatinous hydroxides of magnesium and a l u m i n u m are d i f f i c u l t to see when dispersed. If no precipitate remains, the f o l l o w i n g cations are absent: A Bi(lII) Cd Co
+ 2 + 2 +
Cu Fe Fe Hg
2 +
2 +
3 +
2 +
Hg Mg Mn Ni
2 + 2 2 +
2 +
2 +
If there is a precipitate, its color may be significant; examples: blue C o ( O H ) or C u ( O H ) ; reddish-brown F e ( O H ) ; y e l l o w FlgO; b r o w n A g 0 . Consult a chemical handbook for the colors of other oxides and hydroxides. Other observations may or may not be made, depending on the circumstances. Oxides or hydroxides o f the f o l l o w i n g cations w i l l precipitate at first, and then redissolve in excess base:
2 2 3 2
353
Analysis of a General Unknown
Al As(III) Cr
3 + 3 +
Pb Sb(III) Sn
2 + 2 +
Sn(IV) Zn
2 +
Whether or not y o u observe this depends on the rate at w h i c h the base is added. It is easy to add too much base and overshoot the precipitation step. The c h r o m i u m h y d r o x o complex is green: C r 0 - 3 H 0 ( s ) + 2 0 H " * 2 C r ( O H ) 2 3 2 4
(35-1)
C o p p e r ( I l ) and c o b a l t ( I I ) hydroxides may dissolve if a large excess of base is used. Pink manganese(II) h y d r o x i d e w i l l not dissolve, but w i l l darken in time, since it oxidizes to b r o w n manganese(lll) o x y h y d r o x i d c : 0 + 4 M n ( O H ) ( s ) - 4MnO(OH)(s) + 2 H 0
2 2 2
(35-2)
B. A c t i o n of E x c e s s A q u e o u s A m m o n i a
Use 15A/ N H ; again, check w i t h litmus to be sure that the final solution is strongly alkaline. If no precipitate forms, all cations are absent except
3
Group A : A g ; C u (deep-blue s o l u t i o n ) ; C d ; C o Ni (blue solution); Z n . Group B: Na ; K*j N H * .

+ 2 + 2 + 2 + 2 + + 4
2 +
( y e l l o w - b r o w n solution);
The cations in Group A f o r m weakly dissociated ammonia complexes: Ag + 2 N H ^ Ag(NH )

+ 3 3 + 2
(35-3)
2 + 6
Co Zn
2 +
+ 6 N H +- C o ( N H )
3 3
(35-4) (35-5)
2+
2 +
+ 4 N H *- Z n ( N H )
3 3
2 + 4
The cations in Group B do not f o r m insoluble hydroxides. The hydroxides of B a , S r , and C a are also moderately soluble and should not precipitate, but ammonia solution often absorbs sufficient carbon dioxide from the air to produce small precipitates of the carbonates of these ions. The w h i t e , gelatinous hydroxides of magnesium and a l u m i n u m are d i f f i c u l t to see when they are dispersed in solution. Always centrifuge before y o u decide whether a precipitate is present or absent.
2+ 2 +
C. A c t i o n of S u l f u r i c Acid
Use one drop of 6A/ H S 0 , and add several drops of 95% e t h y l alcohol to decrease the solubility of the sulfates, particularly calcium sulfate. Stir vigorously
2 4
354
Experiment 35
for a minute to overcome supersaturation. If a precipitate forms, P b , B a , S r , or C a may be present. Be sure to record the results of any preliminary tests in y o u r notebook.
2+ 2+ 2+ 2 +
RESULTS
The u n k n o w n should be analyzed according to Outlines 1-8 given in Experiments 2 9 - 3 4 . Submit a 3 X 5 i n . card for y o u r u n k n o w n solution, giving y o u r name, desk number, cations and anions present, and cations and anions absent. Have y o u r notebook available for y o u r i n s t r u c t o r to examine on request.
REFERENCE
Appendix I Sample Laboratory Report: Density Determination
356
Appendix I
best, this estimation is accurate to 0 . 0 0 0 1 g (and may be only to 0.001 g depending on the type of balance). The last figure in the volume measurement must also be estimated; this estimation is accurate to 0.1 m l . The volumes are measured to o n l y three significant figures; the weights are measured to five significant figures. The calculated densities can therefore be accurate to o n l y three significant figures. This means that the weighings are really more accurate than they need to be. They could have been made on a triple-beam balance to o n l y three significant figures; for these weights, this w o u l d have been to an accuracy of 0 . 1 g. However, one purpose of the experiment is to gain experience using the analytical balance, w h i c h is w h y the measurements were made on the analytical balance rather than the triple-beam balance. Considering the inherent uncertainties in the estimation procedures, the weight Of the sulfur sample is actually 24.597 0.002 g and the volume is 1 2.0 0.1 m l . Hence, the m a x i m u m value that the density c o u l d have w o u l d result if the true weight were 24.599 g and the actual volume were 11.9 m l . Then _ 24.599 g _ . , p = - = 2.07 g/ml 11.9 m l
nn
The m i n i m u m value for the density w o u l d result if the true weight were 24.595 g and the volume were 12.1 m l . Then 24.595 g , . p = = 2.03 g/ml 12.1 m l
M
Thus, there is an uncertainty of 0 . 0 2 g / m l in the density of the sulfur. This uncertainty should be expressed as 2.05 0.02 g / m l . By the same m e t h o d , the uncertainty of the l i q u i d density is p = 1.00 0.01 g/ml. A c c o r d i n g to the CRC Handbook of Chemistry and Physics, the density of sulfur is 2.07 g / m l . Therefore, the percentage of error in the experimental determination of the density of sulfur is Correct value - Experimental value ^ Correct value or 2 07 - 2 05 0 02 ^ X 1 0 0 = ^ ^ X 100= 1 % 2.07 2.07
QUESTIONS
No questions to answer.
Appendix II Graphing Experimental Data
Many scientific experiments consist of measuring what happens to one property of a system as another property is varied. For example, it is possible to observe h o w the volume V of a sample of gas changes as the pressure P on the gas is increased. The f o l l o w i n g data could be obtained: Pressure (atm) 1.0 2.0 5.0 10.0 Volume (liters) 16.0 8.0 3.2 1.6
The data make it clear that the volume decreases as the pressure increases. However, a graph provides a more striking presentation of the data (see Figure I I - 1 , which illustrates just h o w fast the volume drops w i t h increasing pressure). In an experiment f r o m w h i c h such data w o u l d be obtained, the experimenter can control the amount of pressure on the gas. Thus, P is said to be an independent variable; thevalues of the independent variable are usually p l o t t e d on the horizontal or x axis of a graph. The size of V depends on h o w large or small the experimenter chooses to make P. Thus, V is a dependent variable; the values of the dependent variable are usually p l o t t e d on the vertical ox y axis of a graph. Dots are placed at the points that correspond to measured values of P and V, and these points are connected by a smooth curve. We draw a continuous s m o o t h curve to connect the points (rather than, for example, several straight-line segments) because we recognize that one property should vary smoothly and regularly as some other property on w h i c h it is dependent varies. Circles may be d r a w n around the experimental points
358
Appendix II
FIGURE 11-2
so that the values can be easily located and are n o t " l o s t " on the line or mistaken for normal imperfections in the paper. When t w o or more different sets of data are p l o t t e d on one graph, one set of points can be enclosed in small squares or triangles instead of circles, so that it is i m m e d i a t e l y apparent w h i c h data belong together and were used for a particular line. Because of the smooth variation of a dependent variable w i t h an independent variable, a graph also permits us to estimate what the value of one variable should be from a particular value of the other variable w i t h o u t making laboratory measurements. For example, we might choose a particular pressure (say, 4.0 atm) and determine what volume corresponds to the p o i n t on the curve at this value of P. F o r P= 4.0 atm, the corresponding volume is 4.0 liters. The preceding set o f data is more accurate than the data y o u will usually obtain in the laboratory. A c t u a l laboratory measurements (whether made by y o u or by a professional chemist) are subject to experimental error. This simply means that in spite of efforts to be as accurate as possible, some random errors inevitably affect a measurement; this usually results f r o m problems encountered in estimating the Final significant figure. For example, some laboratory balances measure a mass to the nearest m i l l i g r a m , but the last significant figure must be estimated. In a weighing, the optical scale might appear as shown in Figure I I - 2 . Here, the pointer is between 1.02 and 1.03 g, and the experimenter must estimate how close the weight is to 1.02. A good guess w o u l d be 1.026. But estimates of 1.025 or 1.027 w o u l d also be acceptable; in fact, one of these weights might be recorded if the object were reweighed. Thus, the last figure in a weight or in any other measurement is subject to uncertainty, w h i c h is called experimental error. Of course, experimental error does not include blunders (such as spilling some of the substance to be weighed) or systematic errors (such as making an incorrect scale reading because the balance is broken). Random experimental errors are unavoidable and remain after accidents, mistakes, and systematic errors have been eliminated. It is useful to note that random errors are just as l i k e l y to be positive as negative. Random errors produce a set of data points that are more scattered on the graph than ideal data points w o u l d be. Real data points for an experiment in w h i c h P and F a r e measured for a gas sample might be similar to those plotted in Figure 11-3. The curve drawn is not the wiggly one that w o u l d connect all the points. Instead, the best smooth and continuous curve is drawn through the set of points, leaving an almost equal number of points above and below the curve. This counterbalances positive and negative experimental errors and produces a curve that represents an average of the experimental results. , .
359
Graphing Experimental Data
360
Appendix II
Assuming that a linear relationship exists between t w o properties, a straight line results when the numerical values of one p r o p e r t y (say, volume) are plotted along the v axis, called the ordinate, and numerical values of the other property (say, temperature) are plotted along the x axis, called the abscissa. The m is constant for a particular line and is called the slope of the line. The b is also constant for a particular line and is called the y intercept. The slope of the line shows h o w rapidly y changes when x is varied. Consider the straight lines shown in Figure I I - 5 . The arrows on the axes indicate the directions of increasing values of x and y. It is obvious y increases more rapidly w i t h x for line A than for line B; line A has a greater slope than B. For line C, y decreases as x increases; this line therefore has a negative slope. At the point where x = 0 (that is, on the y axis) the general equation for a straight line reduces to y = (mX0) + b = b (11-2)
The intercept I) is exactly the value of y at which the line crosses the y axis. Note that in all the graphs in this A p p e n d i x a particular distance along the .v axis does not have the same value as the same distance along the y axis. When y o u first learned to construct graphs in a mathematics class y o u probably made one square on the graph paper represent the same number of units along each axis. However, this is not at all necessary. A graph should fill as m u c h o f the graph paper as possible, so that the experimental data can be p l o t t e d w i t h the greatest possible accuracy and so that any characteristic curvature or linearity w i l l be obvious. To accomplish this, each axis can be scaled in the most convenient manner, perhaps hundreds of units per square along one axis and o n l y a fraction of a unit per square along the other axis. N o r is it necessary for either scale to start at zero. For example, experimental data relating temperature changes to time changes might cover only the temperature range of 7 2 - 1 0 7 C . In this case, it might be convenient to scale the temperature axis f r o m 7 0 C to 1 1 0 C ; if the scale began at 0 C , most of the graph w o u l d be a blank space containing no experimental points. If, on the other hand, the y intercept is to be determined, the x axis must include the p o i n t x = 0 and the y axis must extend far enough that they intercept can be found. In experimental w o r k , values are usually obtained in the laboratory for at least four or five points, these points are p l o t t e d , and the best smooth curve is drawn. If
361
Graphing Experimental Data
this curve is a straight line, the constants m and b can be evaluated from the graph. The advantage of doing this is that we then have an algebraic expression w h i c h enables us to calculate the value of y corresponding to any x w i t h o u t having to make actual measurements of these values. N o r is it necessary to retain the graph and read it each t i m e such i n f o r m a t i o n is desired if the equation for the particular line has been recorded. The slope of a line tells h o w rapidly y changes w i t h x. To evaluate the slope, we choose t w o points on the line (say, points I and II on line A shown in Figure I I - 6 ) . At point I, y = 2.1 and x = 1.0; at point I I , y - 4.3 and x = 3.0. Between points 1 and I I , the value of y changes by an amount Ay = 4 . 3 2.1 = 2.2, and x changes by an amount Ax = 3.0 - 1.0 -2.0. The slope of this line is then given by = *y = Ax
ll=U
2.0
(II-3)
The value calculated for the slope of line A should be the same, regardless of w h i c h t w o values of x and y are chosen on the line. For example, t r y evaluating m using point I I I (y = 5.4; x = 4.0) and point I. Occasionally, using different sets of points to determine a slope may result in slightly different values; this is because of slight errors in reading the values for the points that are used and inaccuracies arising f r o m loss of significant figures in the calculation. To minimize these problems, the t w o points should be as far apart as possible on the line; for example, the use of points y = 27.8 and>', = 1.2, so that Ay = 26.6 (rather than the use of points y = 27.8 and y = 21.6, so that Ay = 6.2) allows for retention of more significant figures. It is also advantageous to choose points on the line that fall exactly at the intersection of lines on the graph paper, so that there is as l i t t l e doubt as possible in assigning values. T h e y intercept b can be easily read from the graph. In Figure I I - 6 , the line crosses the y axis (that is, at the point x - 0) at the value y = 1.0; this, by d e f i n i t i o n , is the y intercept. Thus, the equation for line A in Figure II-6 is
2 2 x
y= \ .\x+ 1.0
(II-4)
362
Appendix II
W i t h this equation, we can calculate the values of y corresponding to any value of x, or vice versa. We will now use this procedure w i t h the straight line obtained earlier by p l o t t i n g Vvs. T for a gas sample (Figure 11-4). We choose t w o points on the line w i t h which to evaluate the slope. Let p o i n t I be V- 16.0 liters, T= 2 0 0 K . Let p o i n t II be V = 36.0 liters, T = 4 5 0 K . Note that the points used to calculate m are chosen f r o m the points on the line and are not experimentally determined points that may lie slightly above or below the best straight line. Using these points Ay m=-= Ax AV (36.0 - 16.0) liters = AT (450 - 2 0 0 ) degrees , . (Ho)
T T c
= 2 ^ = 0.0800 liter/degree 250 The slope o f the line w i l l have units i f either or both o f the quantities p l o t t e d along the x and y axes have units. The difference term that has the fewest significant figures limits the accuracy of the slope. When the line is extrapolated (that is, when the line is extended beyond the region for w h i c h actual experimental values are p l o t t e d ) , we see that the p o i n t at w h i c h the line crosses the y axis is the origin. F o r this particular line, the intercept is 0 (however, this is often not the case). This means that V = 0 when T - 0. The equation for this line is V= (0.0800 liter/degree) T+0 = (0.0800 liter/degree) T (II-6)
Appendix III Infrared Spectrophotometers

A spectrophotometer for use in the infrared region consists of a source of infrared radiation (a glower), a m o n o c h r o m a t o r for selecting a single wavelength at a time, and a detector for measuring the intensity of radiation before and after it passes through the sample. In addition, a recording device is provided for displaying the o u t p u t of the detector. This A p p e n d i x contains photographs and schematic diagrams of some infrared spectrophotometers that may be available for first-year laboratory use. The purpose of presenting this i n f o r m a t i o n is to allow interested students to learn how these instruments w o r k . Y o u r instructor w i l l provide y o u w i t h operating instructions that pertain to the spectrophotometer available in your laboratory. A schematic diagram of the optical system of the Beckman IR 33 appears in Figure I I I - l ; Figure 111-2 is a photograph o f the instrument itself. A n o t h e r spectrophotometer often found in first-year laboratories is the PerkinElmer 735, shown in Figure 111-3.
Appendix II I
FIGURE 111-2
Beckman IR 33 Spectrophotometer. (Courtesy of Beckman Instruments, Inc.)
FIGURE 111-3
Tlie Perkin-Elmer Model 735 Infrared Spectrophotometer. (Courtesy of the Vci în-Eter Corporation.) ,];(:, ..UvU>'tA
Appendix IV Visible and Ultraviolet Spectrophotometers

The parts of a spectrophotometer for use in the visible and ultraviolet regions of the electromagnetic spectrum are similar in function to those of an infrared spectrophotometer. The principal differences lie in the nature of the light source (a tungsten lamp instead of a glower) and the systems for selecting monochromatic radiation (the grating) and for detecting intensity (phototubes), all of which must generate and interact w i t h light of shorter wavelength (higher energy) than infrared. Y o u r instructor w i l l provide you w i t h operating instructions that pertain to the instrument available in your laboratory. Figure I V - 1 is a schematic diagram of the Bausch and L o m b Spectronic 2 0 . A photograph of this instrument, which is capable of measuring the spectrum of solutions in the 3 4 0 0 - 9 5 0 0 A region, appears in Figure I V - 2 . Various controls are labeled in the photograph. A slightly more sophisticated instrument, the Bausch and L o m b Spectronic 70, is shown in Figure I V - 3 . The Spectronic 70 is capable of measuring 3 2 5 0 - 9 2 5 0 A and has a range that is further toward the ultraviolet regions of the spectrum than the Spectronic 2 0 . The Sargent-Welch Chem Anal appears in Figure I V - 4 . The cover of this instrument may be opened to display its optical system.
365
Appendix IV
Visible and Ultraviolet Spectrophotometers
FIGURE IV-4 The Sargent-Welch Chcm-Anal System. (Courtesy of Sargent-Welch Scientific Company.)
Appendix V Reagents and Constants for Qualitative Analysis

REAGENT SOLUTIONS
Reagent * A c i d , acetic * A c i d , hydrochloric * A c i d , hydrochloric * A c i d , hydrochloric * A c i d , nitric * A c i d , nitric * A c i d , sulfuric * A c i d , sulfuric *Aluminon * Ammonia * Ammonia * A m m o n i u m acetate * A m m o n i u m carbonate * A m m o n i u m chloride * A m m o n i u m nitrate * A m m o n i u m oxalate * A m m o n i u m sulfate * A m m o n i u m thiocyanate Barium chloride
:i:
Use B C C
('
Bottle 30 30 30 30gs 30 30gs 8 30gs 8 30 30 8 8 8 8 8 8 8 8
Cone. 6M 2M 6M \2M 6M 164/ 6M ISM 0.1% 6M 15M 3M satd. o.:.i/ 0.2M \M satd. 0.2,1/
Method
of Preparation
B C A
('
C B C C
c c c c c
('
li
Dilute the cone. (17A/) acid. Dilute the cone. (12A/) acid. Dilute the cone. (12A/) acid. Use the cone, reagent. Dilute the cone. (16A7) acid. Use the cone, reagent. Dilute the cone. (18A/) acid. Use the cone, reagent. 1.0 g/liter a m m o n i u m salt of aurintricarboxylic acid. Dilute t h e cone. (15A/) base. Use the cone, reagent. 231.2 g/liter See page 369. 321 g/liter (approx. 6A/) 16.0 g/liter 28.4 g ( N H ) C 0 - H 0 per liter 132 g/liter See page 369. 48.8 g B a C l - 2 H 0 per liter; store in bottle of borosilicate
4 2 2 4 2 2 2
'"Barium h y d r o x i d e *Dimethylglyoxime *] lydrogen peroxide *Lead acetate Magnesia m i x t u r e "Magnesium uranyl acetate *Mercury(II)chloride *Potassium C h r o m a t e * Po t assi u in f e rr o c y a n i d e Potassium hydroxide
A C 1 ?
c
8 8 8 am 8 8 8 8 8 8 30p
0.2A/ 1% 3% 0.24/
('
c c c
glass. Satd. solution [approx. 6 3 g B a ( O H ) - 8 H 0 per l i t e r ] . 10 g/liter of 95% e t h y l alcohol. Use USP solution. 76.0 g P b ( O A c ) - 3 H 0 p e r liter See page 369.
2 2 2 2
(
c
0.1 M 0.5 M 0.2M 0.5 M
See page 369. 27.2 g/liter 97.1 g/liter 84.5 g K F e ( C N ) - 3 H 0 p e r lifer

4 6 2
28.0 g / l i t e r
VJ
\
o?
368
369
Reagent *Potassium permanganate *Silver nitrate *S. and 0. reagent

3 :
Use A B C
Bottle 8am 8 am 8 SS 8 30p SSam SS 30 8 8
Cone. 0.02/W 0.2 A/ 0.05% 0.3 3 M 0.53/ 6A/ 3.3 A/
Method
of Preparation
M-i, Sodium c o b a l t i n i t r i t e * < C *Disodium hydrogen phosphate ( *Sodium h y d r o x i d e Solution A Solution B "Thioacetamide * T i n ( I I ) chloride *Triethanolamine B A A C C
c
3.2 g/liter 34.0 g/liter 0.500 g p-nitrobenzeneazoresorcinol in 1 liter of 0 . 0 2 5 A / N a O H . 135 g/liter; keep cool. 1 i ^ U ^ w A d d 71.0 g anhyd. N a H P 0 gradually to H 0 ; dilute to 1 liter. 240 g/liter 170 g A g N 0 in 300 ml 11,0.
2 4 2 3
13% 20%
25-ml satd. ( N H ) C 0 + 10 ml 15A/ N l l + 100 ml H 0 . See below. See below. 20% by volume w i t h water.
4 2 3 3 2
Key: Asterisks indicate solutions suggested for the reagent k i t . A: solutions used only for anion analysis; B: solutions used in both anion and cation analysis; C: solutions used only in cation analysis. 8: 8-nil size; 30: 30-ml size;SS: side-shelf reagent (250-ml); am: amber; gs: glass-stoppered; p: polyethylene. Although 8 ml is an ample supply of most reagents, refill stock solutions should be available. Like side-shelf reagents, stock solutions may be kept in 250-ml bottles fitted w i t h droppers. Unless otherwise indicated, the weight in the last column of the table is dissolved in distilled water and diluted to a final volume of 1 liter.
S O L U T I O N S : D I R E C T I O N S AND COMMENTS
Ammonium carbonate: Dissolve 192 g powdered reagent in 500 ml of water and 80 ml 15A/ N H . Dilute to 1 liter. Ammonium thiocyanate: Saturate a m i x t u r e of equal volumes of e t h y l ether ami isoamyl alcohol w i t h solid N H S C N . Magnesia mixture: Dissolve 130 g M g ( N 0 ) - 6 H 0 and 240 g N H N 0 in 500 ml water. A d d 150 ml 15A/ N H , and dilute to 1 liter. Store in a polyethylene bottle. Magnesium uranyl acetate: Dissolve 30 g U 0 ( C H 0 ) - 2 H 0 in a mixture of 120 ml of water and 100 ml glacial acetic acid. Also prepare a solution of magnesium acetate by adding 148.5 g M g ( C H 0 ) - 4 I I 0 slowly to a hot m i x t u r e of 40 ml of water and 320 ml glacial acetic acid. M i x the magnesium and uranyl solutions while they arc still w a r m , and allow the m i x t u r e to stand overnight. Filter through cotton or sintered glass.
3 4 3 2 2 4 3 3 2 2 3 2 2 2 2 3 2 2 2
Thioacetamide: Dissolve 130 g in a liter of water; the solution is almost saturated. A f t e r being stored for more than a year in a clear glass b o t t l e , the solution is still effective in precipitating sulfides. Decomposition occurs on standing (indicated by the precipitation of sulfur); this is not harmful. More serious is the gradual formation of sulfate. If the reagent gives a precipitate w i t h barium chloride, a fresh o l u t i o n should be prepared. Tin(II) chloride: Let 45.0 g SnCl - H 0 stand w i t h 1 70 ml 1 2M HC1 u n t i l the SfiHipS disir grate. Dilute slowly to 1 liter. Keep tin shot in the solution.
2 2
370
Appendix V
371
Reagents nd Constants for Qualitative Analysis
372
Appendix V
ont il.
373
374
Appendix V
Reaction Fe Hg Hg Ni Pb Zn
3 +
K
2 +
2 +
2 +
2 +
2 +
2 +
+SCN +4Cr +4I" +6NH (aq) + Cl~ + 4NH (aq)

3 3
=Fe(NCS) =HgCl = Hgl = Ni(NH ) =PbCl = Zn(NH )

2 4 2 4 3 + 3
1.1 5.0 1.9
X X X X
2 +
2.0
11
10 10 10 10 10
15
30
2 + 4
2.8
GENERAL SOLUBILITY RULES
The f o l l o w i n g generalizations indicate the relative solubilities of c o m m o n i n organic salts in water. Cation refers to a m m o n i u m ion or to any of the m o n o a t o m i c , c o m m o n metal ions. 1. The nitrates, chlorates, and acetates of all cations are soluble. Silver acetate is only moderately soluble, however. 2. The chlorides, bromides, and iodides of all cations are soluble, except those of silver and m e r c u r y ( I ) . The halides of lead(II) are only slightly soluble in cold water, but are moderately soluble in hot water. M e r c u r y ( I I ) i o d i d e is insoluble. The water-insoluble halides are also insoluble in dilute acid. 3. The sulfates of all cations are soluble, except those of barium and lead. The sulfates of silver, calcium, and m e r c u r y ( l ) are slightly soluble. The waterinsoluble sulfates are also insoluble in dilute acid. The carbonates, phosphates, borates, chromates, and sulfites of all cations are insoluble, except those of sodium, potassium, and a m m o n i u m . Magnesium chromate is soluble, and magnesium sulfite is slightly soluble. Waterinsoluble salts of these anions are generally soluble in dilute acid because of anion hydrolysis. The hydroxides and sulfides of all cations are insoluble, except those of sodium, potassium, and a m m o n i u m . Those of magnesium, calcium, and barium arc moderately soluble.
4.
5.
6. A l l sodium, potassium, and a m m o n i u m salts are soluble. 7. A l l silver salts are insoluble, except the nitrate and chlorate salts. Silver acetate is moderately soluble. 8. A n t i m o n y and bismuth salts h y d r o l ' z e . i t e r . dv i iluble basic salts; however, these salts are soluble in In e aci 9. I r o n ( I I I ) , lead(II), t i n ( I I ) , t i n ( I V . ~ r c u r y ( I I ) , coppe.(L ), ?r }. a l u m i n u m tend to hydrolyze in neutral or i i ; , . i n l y b sic solw.ic ~ . s 3 givs insoluble hydroxides or basic salts; these SL -S are soluble in - i i re iX'yl
: 1

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Chemistry in the Laboratory

The Ohio State University Marion Campus

San Diego New York Chicago London Sydney Toronto

Line Spectra of Elements

Experiment 11 Experiment 12 Experiment 13 Experiment 14

Experiment 15 Experiment 16 Experiment 17

Experiment 18 Experiment 19 Experiment 20 Experiment 21 Experiment 22 Experiment 23 Experiment 24 Experiment 25 Experiment 26

Gravimetric Determination of Iron Acid-Base Titration Antacids 229 221

Experiment 27 Metal Chelate Complexes

293 301 319 331 339

Experiment 35 Analysis of a General Unknown Appendix I Appendix II Appendix I I I Appendix IV Appendix V

Visible and Ultraviolet Spectrophotometers

Reagents and Constants for Qualitative Analysis

WHAT Y O U ' L L DO IN THE L A B O R A T O R Y

YOUR LABORATORY RESPONSIBILITIES

Safety in the Laboratory

Some Laboratory Protocol

Laboratory Equipment and Technique

Laboratory Equipment and Technique

Laboratory Equipment and Technique

Bunsen-type burners: {left) a Bunsen burner; (right) a T i r r i l l burner.

CUTTING A N D BENDING GLASS

FIGURE i-2 Flame of a properly adjusted Bunsen burner.

Breaking glass tubing.

Inserting glass tubing into a stopper.

INSERTING G L A S S T U B I N G INTO A STOPPER

Laboratory Equipment and Technique

FIGURE -9 Folding filter paper into a cone.

FIGURE i-10 Gravity filtration.

Laboratory Equipment and Technique

FIGURE -12 Clean and dirty glassware.

U n c e r t a i n t y and Significant Figures

FIGURE i-13 Measuring the length of a table w i t h a meter stick.

0 . 0 1 ml 0 . 0 2 ml 0.1 ml 1 ml 0 . 0 0 1 , or better* 0.01 g

Measuring volume w i t h a graduated cylinder.

Control liquid level with index

Making up a standard solution using a volumetric flask.

Experiment 1 The Use of Balances: Hydrated Compounds

BRIEF BALANCE INSTRUCTIONS

Triple-Beam Balance (Figure 1-1)

The Uses of Balances: Hydrated Compounds

analytical balance asbestos square beaker tongs

Bunsen burner clay triangle porcelain crucibles and lids

ring ring stand

The Uses of Balances: Hydrated Compounds

(Answer the questions from pages 33-34 on

the back of the Report Sheet.)

Express each of the above numbers in scientific n o t a t i o n .

(d) 2476 + 0.1207 + 0.0214 + 0.0081 (e) 417 X 2.1 (0 628.718-8.72

(g) 31 - 0.0671 (h) (5.16 X 1 0 ) X (2.1 X 10~ ) X (1.07 X 10~ )

(j) 0.5761 X 0.0821 X 373 * 0.976 * 0.2824 ( k ) 12.01 1 15 + (1.66 X 1 0 "

( Use the back of this page for your calculations, if necessary.)

Experiment 2 Properties of Substances

beakers Bunsen burner capillary tubes copper wire cork

cork borer paring knife 5-ml pipet ring ring stand

l-chloro-4-nitrobenzene methanol mineral oil

naphthalene u n k n o w n l i q u i d ( f r o m list on page 45) unknown solid ( f r o m list on page 45)

Cork with vent.

F I G U R E 2-2 Determining the boiling point of methanol.

Determining the melting point of a solid.

0.684 0.792 2.279 1.145 1.527 0.807 0.785

m.p. m.p. m.p.