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Chemistry 1C

Name:

Titration Curves of Strong and Weak Acids and Bases


OBJECITVES
To learn about the effect that acid and base strength has on the shape of a titration curve. To learn how to use a titration curve to determine: the equivalence point of a titration Ka and Kb values for weak acids and weak bases the relative strengths of acids and bases To learn about the function and selection of appropriate acid-base indicators for titrations.

INTRODUCTION
A titration curve is a graph showing the pH of an acid or base solution as a function of the volume of titrant (base or acid solution) added. In this experiment titration curves for the following acids and bases will be recorded and analyzed: 1. 2. 3. 4. Hydrochloric acid, HCl, (strong acid) titrated with sodium hydroxide, NaOH (strong base). Acetic acid, CH3 COOH, (weak acid) titrated with sodium hydroxide, NaOH. Chloroacetic acid, CH2 ClCOOH, (weak acid) titrated with sodium hydroxide, NaOH. Ammonia, NH3, (weak base) titrated with hydrochloric acid, HCl.

Each of these titrations will exhibit a titration curve characteristic of the acid and base used. Each pair of students will be assigned one of the titrations and will collect data on Day 1 of the experiment. The data will be collected using a pH electrode connected to a LabPro and then transferred into Graphical Analysis using a computer located in the lab room. On Day 2, you will analyze and complete calculations for all four titration curves. You are responsible to complete the analysis and calculations for all four titration curves even though you collect data for only one titration. Your instructor will determine and inform you as to how the four data sets will be distributed to the class.

Titration 1: HCl titrated with NaOH


The shape of this titration curve is characteristic of a strong acid-strong base titration. When an HCl solution is titrated with a NaOH solution, the pH of the acidic solution is initially low. As the base is added, the change in pH is quite gradual until close to the equivalence point, when equimolar amounts of acid and base have been mixed. Near the equivalence point, the pH increases very rapidly. The change in pH then becomes more gradual again, before leveling off with the addition of excess base. At the equivalence point only a neutral salt, NaCl, remains in solution so the pH is 7.00.

Titration 2: CH3COOH titrated with NaOH


The titration of acetic acid with NaOH is a typical weak acid-strong base titration and serves to help us learn about the characteristic shape of weak acid-strong base titration curves. When a CH3 COOH solution is titrated with a NaOH solution, the pH of the acidic solution is initially low. As the base is added, the change in pH rises initially and then becomes almost constant until close to the equivalence point, when equimolar amounts of acid and base have been mixed. Near the equivalence point, the pH increases very rapidly. The change in pH then becomes more gradual again, before leveling off with the addition of excess base. At the equivalence point a basic salt, NaCH3 COO, remains in solution so the pH is greater than 7.00.

Titration 3: CH2ClCOOH titrated with NaOH


The titration of chloroacetic acid with NaOH is very similar to the titration of acetic acid with NaOH. However, the replacement of one of the three non-acidic hydrogen atoms with a chlorine atom changes the strength of the acid dramatically. Thus, this titration serves to illustrate how the shapes of weak acid-strong base titration curves are affected by the strength of the weak acid.

January 14, 2008

Chemistry 1C

Titration Curves of Strong and Weak Acids and Bases

Titration 4: NH3 titrated with HCl


The titration of ammonia with HCl is a typical weak base-strong acid titration and serves to help us learn about the characteristic shape of weak base-strong acid titration curves. When an NH3 solution is titrated with a HCl solution, the pH of the basic solution is initially high. As the acid is added, the change in pH drops initially and then becomes almost constant until close to the equivalence point, when equimolar amounts of base and acid have been mixed. Near the equivalence point, the pH decreases very rapidly. The change in pH then becomes more gradual again, before leveling off with the addition of excess acid. At the equivalence point an acidic salt, NH4Cl, remains in solution so the pH is less than 7.00.

Acid-Base Indicators
Acid-base indicators change color over a small pH range. The change in color and the pH range vary depending upon the indicator. An indicator you are familiar with is phenolphthalein. Phenolphthalein is colorless in solutions of pH < 8.2. At pH 8.2 phenolphthalein begins to turn pink and by pH 10 the color change is complete. To choose an appropriate acid base indicator for a titration, the pH at the equivalence point of the titration should be known. In order to determine the equivalence point accurately using an indicator, the indicator must change color over a pH range that is within the steep vertical region, near or at the equivalence point, of the titration curve. Analysis of the titration curves in this experiment should convince you that within this steep region, the volume of added titrant changes very little as the pH changes dramatically. The class will study three different indicators in this experiment, recording the pH range where they color change.

MATERIALS
LabPro System TI Graphing Calculator Vernier pH Electrode TI-Graph Link magnetic stirrer magnetic stirring bar 250-mL beaker 50-mL buret 25 mL pipet pipet pump ring stand 2 utility clamps 0.1 M NaOH (standardized by stockroom)* 0.1 M NH3 0.1 M HCl 0.1 M CH3COOH 0.1 M CH2ClCOOH (chloroacetic acid) distilled water wash bottle Phenolphthalein indicator Methyl red indicator Bromthymol blue indicator

*The actual concentration of the standardized NaOH solution will be written on the bottle. All students should record this concentration in their lab notebook.

PROCEDURE
Note: DO NOT dispose of any of the solutions in this experiment down the drain! All rinse, left over and titrated solutions are to be collected in a beaker and then disposed of in the appropriately labeled waste container.
1. 2. 3. Obtain and WEAR GOGGLES. Obtain approximately 5 mL of pH 4 and pH 10 buffers in large, clean, dry test tubes. Set up the calculator and LabPro with a pH sensor and calibrate with pH 4 and 10 Buffers. See the LabPro Quick Start Guide for details. Record the slope and intercept values for the calibration in your notebook. These will be displayed on the calculator screen after calibration. Later in the experiment if your LabPro system malfunctions and you need to start again, select MANUAL ENTRY from the CALIBRATION menu and enter your recorded intercept and slope values. This saves some time since you do not have to recalibrate the pH probe with buffer solutions. Record the molarity of the standardized NaOH solution (written on the bottle). The molarity if the standard NaOH solution must be known by all students, regardless of which titration you are assigned!

4.

January 14, 2008

Chemistry 1C

Titration Curves of Strong and Weak Acids and Bases

Titrations 1-3: Acid titrated with standard NaOH Titration 1: Acid is HCl, phenolphthalein as the indicator Titration 2: Acid is CH3COOH, methyl red as the indicator Titration 3: Acid is CH2ClCOOH, phenolphthalein as the indicator
1. Obtain about 60 mL of the standardized ( 0.1 M) NaOH solution. CAUTION: Sodium hydroxide solution is caustic. Avoid spilling it on your skin or clothing. Rinse with water if it comes in contact with skin or clothing. 2. Obtain a 50-mL buret and rinse the buret with a few mL of the NaOH solution. Fill the buret to above the 0.00-mL mark then drain to the 0.00-mL mark. 3. Obtain about 30 mL of the 0.1 M acid solution. CAUTION: Avoid spilling the acid on your skin or clothing. Rinse with water if it comes in contact with skin or clothing. 4. Pipet 25.00 mL of the acid solution into a clean, dry 250-mL beaker. Add two to three drops of the assigned indicator. Buret Use a utility clamp to suspend the pH electrode on a ring stand as shown in Figure 1. Situate the pH electrode in the acid solution and adjust its position toward the outside of the beaker so that the stirring bar does not strike it. Turn on the magnetic stirrer 5. Set up the calculator and LabPro for EVENTS WITH ENTRY data collection. See the LabPro Quick Start Guide for more details. 6. Press 2:START on the LabPro. Before adding NaOH titrant, monitor the pH value on the LabPro screen. Once the pH has stabilized, press [ENTER] and enter 0.00 (the buret volume, in mL) in the TI calculator as your value. You Stirring bar have now saved the first data pair for this experiment. Record the volume, pH (to nearest 0.01), and indicator color in your notebook as well! 7. You are now ready to begin the titration. This process goes faster if one Magnetic stirrer person manipulates and reads the buret while another person operates the calculator and enters volumes. As you titrate, watch for the color change of Figure 1 the indicator, record any changes in the color and corresponding pH in your notebook. DO NOT wash the buret tip with water at any time during the titration! Add an increment of NaOH titrant (enough to raise the pH by 0.3 to 0.4 units). When the pH stabilizes, press [ENTER] and enter the current buret reading (to the nearest 0.01 mL). You have now saved the second data pair for the experiment. Record the volume, pH (to nearest 0.01), and indicator color in your notebook as well! Continue adding NaOH solution in increments that raise the pH by about 0.3 to 0.4 units and enter the buret reading after each increment. As the equivalence point is approached less NaOH will be required to obtain a pH change of 0.3 units. Be careful, you will be adding the base in one-drop increments through the equivalence point. Enter a new buret reading after each increment. Note: It is important that the pH change by at least 0.2 pH units for every addition of base. Record the volume, pH and indicator color in your notebook. Continue adding NaOH solution until the buret reaches the 50.00 ml mark. Do not go below this mark! 8. Enter [STO] to stop when you have finished collecting data. Examine the data points along the displayed graph of pH vs. NaOH volume. As you move the cursor right or left, the volume (X) and pH (Y) are displayed below the graph. 9. Exit the DataMate program. THIS MUST BE DONE BEFORE ATTEMPTING TO TRANSFER THE DATA TO THE COMPUTER OR THE COMPUTER MAY HANG. 10. Use the TI-Graph Link cable and the Graphical Analysis program to transfer the data of pH vs. volume to a computer in the lab.

Titration 4: NH3 titrated with HCl, bromthymol blue as the indicator


1. 2. 3. Obtain about 60 mL of the same HCl solution that is used for titration 1. CAUTION: Avoid spilling the acid on your skin or clothing. Rinse with water if it comes in contact with skin or clothing. Obtain a 50-mL buret and rinse the buret with a few mL of the HCl solution. Fill the buret to above the 0.00-mL mark then drain to the 0.00-mL mark. Obtain about 30 mL of the 0.1 M NH3 solution. CAUTION: Avoid spilling the ammonia on your skin or clothing. Rinse with water if it comes in contact with skin or clothing.

January 14, 2008

Chemistry 1C

Titration Curves of Strong and Weak Acids and Bases

4.

Pipet 25.00 mL of the NH3 solution into a clean, dry 250-mL beaker. Add two to three drops of indicator. Use a utility clamp to suspend the pH electrode on a ring stand as shown in Figure 1. Situate the pH electrode in the NH3 solution and adjust its position toward the outside of the beaker so that the stirring bar does not strike it. Turn on the magnetic stirrer 5. Set up the calculator and LabPro for EVENTS WITH ENTRY data collection. See the LabPro Quick Start Guide for more details. 6. Press 2:START on the LabPro. Before adding HCl titrant, monitor the pH value on the LabPro screen. Once the pH has stabilized, press [ENTER] and enter 0.00 (the buret volume, in mL) in the TI calculator as your value. You have now saved the first data pair for this experiment. Record the volume, pH (to nearest 0.01), and indicator color in your notebook as well! 7. You are now ready to begin the titration. This process goes faster if one person manipulates and reads the buret while another person operates the calculator and enters volumes. As you titrate, watch for the color change of the indicator, record any changes in the color and corresponding pH in your notebook. DO NOT wash the buret tip with water at any time during the titration! Add an increment of HCl titrant (enough to lower the pH by 0.3 to 0.4 units). When the pH stabilizes, press [ENTER] and enter the current buret reading (to the nearest 0.01 mL). You have now saved the second data pair for the experiment. Record the volume, pH (to nearest 0.01), and indicator color in your notebook as well! Continue adding HCl solution in increments that lower the pH by about 0.3 to 0.4 units and enter the buret reading after each increment. As the equivalence point is approached less HCl will be required to obtain a pH change of 0.3 units. Be careful, you will be adding the acid in one-drop increments through the equivalence point. Enter a new buret reading after each increment. Note: It is important that the pH change by at least 0.2 pH units for every addition of base. Record the volume, pH and indicator color in your notebook. Continue adding HCl solution until the buret reaches the 50.00 ml mark. Do not go below this mark! 8. Enter [STO] to stop when you have finished collecting data. Examine the data points along the displayed graph of pH vs. HCl volume. As you move the cursor right or left, the volume (X) and pH (Y) are displayed below the graph 9. Exit the DataMate program. THIS MUST BE DONE BEFORE ATTEMPTING TO TRANSFER THE DATA TO THE COMPUTER OR THE COMPUTER MAY HANG. 10. Use the TI-Graph Link cable and the Graphical Analysis program to transfer the data of pH vs. volume to a computer in the lab.

Clean-up
1. 2. Collect all rinse, left over and titrated solutions in a 600-mL beaker and discard in the appropriately labeled waste container. Rinse the pH electrode, place it back in its storage solution and then return it to the stockroom.

January 14, 2008

Chemistry 1C

Titration Curves of Strong and Weak Acids and Bases

Name: Partners Name

PROCESSING THE DATA: The data analysis through titration 2 will be done in
class on day 2 of the experiment. You will turn in your titration curves and answers to the remaining questions. It is strongly recommended that any points needed along a titration curve be determined using the interpolate function in graphical analysis.

Observed Indicator Color Changes and pH


In the space below record the pH range where each indicator was observed to change color. (These should also be recorded in your lab notebook for reference during a lab exam!)

Titration 1: HCl(aq) Titrated with NaOH(aq)


1. Using the titration curve, find the equivalence point for the titration. This occurs at a pH of 7.00 since this is a strong acidstrong base titration. (Mathematically, this should occur at the inflection point of the curve.) Clearly mark and label the equivalence point on the graph. Record the volume of NaOH used to reach the equivalence point. Using the equivalence volume of NaOH and precise molarity of NaOH, calculate the precise molarity of the HCl solution you titrated.

2.

Precise molarity of HCl 3. The equivalence point for this titration occurs at a pH of 7. Why will an acid-base indicator that changes color between pHs 5 and 9 work just as well to accurately determine the equivalence point for this titration as one that changes color at a pH of 7?

4.

Which of the indicators tested could be used to accurately determine the equivalence point for this titration? List all that apply.

January 14, 2008

Chemistry 1C

Titration Curves of Strong and Weak Acids and Bases

Titration 2: CH3COOH(aq) Titrated with NaOH(aq)


1. Mathematically, the equivalence point of this titration occurs at the inflection point of the titration curve. We will assume that the inflection point occurs at the midpoint of the region where the pH change is the greatest as the base is added. Using the titration curve, determine the equivalence volume of NaOH and the pH at the equivalence point. This occurs at a pH above 7.00 since this is a weak acidstrong base titration. Clearly mark and label the equivalence point on the graph. Record the volume of NaOH used to reach the equivalence point. Record the pH at the equivalence point. Give it some thought: Which of these values has the greatest uncertainty associated with it, the equivalence point volume or the equivalence point pH?

2.

Using the equivalence volume of NaOH and precise molarity of NaOH, calculate the precise molarity of the acetic acid solution you titrated.

Precise molarity of CH3 COOH

Determination of Ka for acetic acid. Three methods.


1. From the initial pH: Using the pH of the acetic acid before addition of any base and the calculated concentration of the acetic acid solution, determine Ka. (Look at the actual data in graphical analysis to get pH at 0.00 mL for this, do not just estimate it from your printed graph!) Determine and report the percent error in this value.

Calculated Ka from initial pH Percent Error 2. From the pH at one-half the equivalence point volume: For a weak acid titrated with a strong base, the pH at one-half the equivalence point volume is related, in a very simple way, to pKa of the weak acid. In the space below, derive the mathematical relationship between pH and pKa at this point. (HINT: Use the Henderson-Hasselbalch equation.)

January 14, 2008

Chemistry 1C

Titration Curves of Strong and Weak Acids and Bases

a)

Using your graph, determine the pH at one-half the equivalence volume. Clearly mark and label this point on the graph. pH at one-half the equivalence volume Give it some thought: Which of your values has the greatest uncertainty associated with it, the equivalence point pH or the pH at half the equivalence point?

b) From the pH at one-half the equivalence volume, determine Ka for acetic acid. Determine and report the percent error in this value.

Ka for acetic acid from pH at half-equivalence point volume Percent Error 3. From the pH at the equivalence point: At the equivalence point all the acetic acid has been neutralized. The solution now contains the product of the neutralization, sodium acetate. This is a basic salt. Hydrolysis occurs so the pH at the equivalence point rises above 7. The extent of hydrolysis will determine the pH. (Make sure you understand this!) a) Using the total volume of solution (NaOH + acetic acid) calculate the concentration of acetate ions produced at the equivalence point.

Concentration of acetate ions at equivalence point b) At the equivalence point, equimolar amounts of acetic acid and sodium hydroxide have been mixed, yielding a solution of sodium acetate. The acetate ion undergoes hydrolysis, producing a basic solution. Write the hydrolysis reaction for the acetate ion.

c)

From the pH at the equivalence point calculate Kb for the acetate ion.

Kb for the acetate ion d) From Kb determine Ka for acetic acid. Report the percent error in this value.

Ka for acetic acid from equivalence point pH Percent Error

January 14, 2008

Chemistry 1C

Titration Curves of Strong and Weak Acids and Bases

4.

Of your three Ka values: a) Which one is the least accurate? b) Which one is the most accurate? Can you explain why?

5.

Based upon our results, is a) phenolphthalein a good indicator for this titration? b) bromthymol blue a good indicator for this titration? c) methyl red a good indicator for this titration?

Titration 3: CH2ClCOOH(aq) Titrated with NaOH(aq)


1. Using the titration curve, determine the equivalence volume of NaOH and the pH at the equivalence point. Clearly mark and label the equivalence point on the graph. Record the volume of NaOH used to reach the equivalence point. Record the pH at the equivalence point. Using the equivalence volume of NaOH and precise molarity of NaOH calculate the precise molarity of the chloroacetic acid solution you titrated.

2.

Precise molarity of CH2 ClCOOH 3. By comparing the pH at the equivalence point for titrations 2 and 3, determine which is the stronger acid; acetic or chloroacetic. Clearly explain how you come to your conclusion.

a)

How can you explain this difference in acid strength? Hint: Draw Lewis structures and think inductive effect.

January 14, 2008

Chemistry 1C

Titration Curves of Strong and Weak Acids and Bases

4.

Using data from our titration curve, determine Ka for chloroacetic acid. (You choose the method, but clearly label the point used on the titration curve and show your work below. Attach additional work if more space is needed) Determine and report your percent error.

Ka for chlororacetic acid Percent Error 5. Is this Ka value consistent with your answer to the previous question regarding relative strengths of acetic and chloroacetic acid. Explain why or why not.

6.

Based upon our class results, is a) phenolphthalein a good indicator for this titration? b) bromthymol blue a good indicator for this titration? a) methyl red a good indicator for this titration?

Titration 4: NH3 titrated with HCl


1. Using the titration curve, determine the equivalence volume of HCl and the pH at the equivalence point. Clearly mark and label the equivalence point on the graph. Record the volume of HCl used to reach the equivalence point. Record the pH at the equivalence point. a) Is the pH equal to, above, or below 7.00 for this titration? Clearly explain what causes this to occur.

2.

Using the equivalence volume of HCl and precise molarity of HCl (see titration 1 results), calculate the precise molarity of the ammonia solution we titrated.

Precise molarity of NH3

Determination of Kb for ammonia. Three methods.


1. From the initial pH: Using the pH of the ammonia before addition of any acid and the calculated concentration of the ammonia solution, determine Kb. (Look at the actual data in graphical analysis to get pH at 0.00 mL for this, do not just estimate it from
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Chemistry 1C

Titration Curves of Strong and Weak Acids and Bases

your printed graph!) Determine and report the percent error in this value.

Calculated Kb from initial pH Percent Error 2. From the pH at one-half the equivalence point volume: Using your graph, determine the pH at one-half the equivalence volume. Clearly mark and label this point on the graph. pH at one-half the equivalence volume a) From the pH at one-half the equivalence volume, determine Kb for ammonia. (Careful here! What is the pH at half the equivalence point equal to?) Determine and report the percent error in this value.

Kb from pH at half-equivalence point volume Percent Error b) From the pH at the equivalence point: At the equivalence point all the ammonia has been neutralized. The solution now contains the product of the neutralization. From the pH at the equivalence point calculate Kb for ammonia. Clearly show all work/steps in this calculation below. Report the percent error in this value.

Kb for ammonia from equivalence point pH Percent Error 3. Of your three Kb values which one is the most accurate? Based upon our class results, is a) phenolphthalein a good indicator for this titration? b) bromthymol blue a good indicator for this titration? b) methyl red a good indicator for this titration?
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7.

Chemistry 1C

Titration Curves of Strong and Weak Acids and Bases

General Questions:
1. Consider 25.0 mL of a 0.10 M strong acid solution and 25.0 mL of a 0.10 M weak acid solution, both titrated with a 0.20 M KOH(aq) solution. List at least three differences between the appearance of the titration curves for the two different acid solutions.

2.

Observe the titration curves for acetic acid and chloroacetic acid. The region along the curve that is around 1 pH unit from the pH at half the equivalence point volume is referred to as the buffer region. a) Explain why the solution is a buffer within this region.

b) Is the region around the half equivalence point volume for the titration of HCl with NaOH a buffer region? Explain why or why not.

c)

Is the region around the half equivalence point volume for the titration of NH3 with HCl a buffer region? Explain why or why not.

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January 14, 2008

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