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Laboratory Manual Physical Chemistry Year 3 PHYSICAL CHEMISTRY YEAR 3 LABORATORY MANUAL Table of Contents

General Information Report Writing

Experiment 1. Bomb Calorimetry 2. Molecular Spectroscopy a. IR Spectroscopy b. NMR Spectroscopy c. UV Spectroscopy 3. The Critical Point 4. Determination of Acid Dissociation Constant For Methyl Red 5. Phase Diagram of A Three Component Partially Immuscible Liquid System 6. The Hydrolysis of Tert Butyl Chloride 7. Influence of Elongation on Surface Activity For Alcohol Chain 8. Determination of Vapour Viscocity Normal Aliphatic

Laboratory Manual Physical Chemistry Year 3 EXPERIMENT 1: BOMB CALORIMETRY Principles of Calorimetry Calorimetry is concerned with determining experimentally the enthalpy change the energy change H or

E accompanying a given isothermal change in state of a system,

normally one in which a chemical reaction occurs. The reaction at temperature T can be written schematically in the form

A(T ) B(T ) initial state

C (T ) D(T ) final state

(1)

In practice it is not necessary to actually carry out the change in state isothermally because H and E are independent of the path. In caloritmetry it is usually

convenient to use a path composed of two steps: Step I. A change of state is carried out adiabatically in the calorimeter vessel to yield the desired products but in general at another temperature T1 :

A(T ) B(T ) S (T )

C (T1) D(T1) S (T1)

(2)

where S represents those parts of the system (e.g., inside wall of the calorimeter vessel, stirrer, thermometer, solvent) that are always at the same temperature as the reactants or products because of the experimental arrangement; these parts, plus the reactants or products constitute the system under discussion. Step II. The products of Step I are brought to the initial temperature T by adding heat to (or taking it from) the system:

C (T1 ) D(T1 ) S (T1 )

C (T ) D(T ) S (T ) .

(3)

If heat capacity data are available, it is not necessary to carry out this step in actuality. By adding Eqs (2) and (3) to obtain Eq (1), it is seen that these two steps describe a complete path connecting the desired initial and final steps. Accordingly, H or E for

the change in state (1) is the sum of values of this quantity pertaining to the two steps:

H E

H1 E1

H II E II

(4a) (4b)

Laboratory Manual Physical Chemistry Year 3 Because there is no change in volume of the system, and hence no work is done, and heat q for Step I being zero,

H1
E1

qp
qv

0
0

(constant pressure) (constant volume)

(5a) (5b)

Thus, if both steps are carried out at constant pressure,

H II E II

(6a)

and if both steps are carried out at constant volume

(6b)

Whether the process is carried out at constant pressure or at constant volume is a matter of convenience. Combustion reactions are conveniently carried out at constant volume in a bomb.

H and

E differ only in the pressure-volume term

(PV ), viz
(7)

( PV )

When all reactants and products are condensed phases, the

( PV ) term is negligible,

but when gases are involved, as in the case of combustion, it is likely to be significant in magnitude. Eq. (7) may be rewritten in the form

H
Where

E RT ( n)

(8)

n is the increase in the number of moles of gas in the system.

Step II can be carried out by adding heat to the system or taking heat away from the system and measuring q for this process. However, if the heat capacity of the system is known or can be determined,

H II or

E II can be calculated, making use of the

temperature change (T1 T ) resulting from Step I.

H II E II

T T1 T T1

C p (C

D S )dT D S )dT

(9a) (9b)

C v (C

An indirect method of determining the heat capacity is to carry out another reaction altogether, for which the heat of reaction is known, in the same calorimeter under the same conditions. This method depends on the fact that in most calorimetric

measurements on chemical reactions the heat capacity contributions of the actual product species (C and D) are very small or negligible, in comparison with the

Laboratory Manual Physical Chemistry Year 3 contribution due to the parts of the system denoted by the symbol S. In a bomb

calorimeter experiment the reactants or products amount to a gram or two, while the rest of the system is equivalent to about 3000 g of water. Thus the value of C(S) can be calculated from the heat of the known reaction and the temperature change produced by it, as follows:

C p (S ) Cv (S )
Experiment

H known T E known T

(constant pressure)

(10a)

(constant volume)

(10b)

The detailed information for performing this bomb calorimeter experiment is provided with the apparatus. (a) (b) Determine the water equivalent of the bomb calorimeter with benzoic acid. Determine the heats of combustion of anthracene OR phenanthrene. Repeat the experiment if necessary. Hence calculate the standard enthalpy of

formation and compare with the literature values. References (1) (2) Finlay, Practical Physical Chemistry, 8th Ed. Mahler-Cook Bomb Calorimeter Manual

Shoemaker and Garland, Experiments in Physical Chemistry, 2nd Edition, McGraw-Hill, 1962.

Laboratory Manual Physical Chemistry Year 3

EXPERIMENT 2: MOLECULAR SPECTROSOPY

(A)

Infra-Red Spectroscopy

This experiment is designed to familiarize you with certain techniques, features and applications of infrared spectroscopy. Specifically, this experiment deals with

intermolecular hydrogen-bonding of phenol in solution. Intermolecular Hydrogen-bonding of Phenol General An O-H bond normally gives rise to a sharp absorption band in the region 3500-3700 cm1

. If, however, the hydroxyl group takes part in a hydrogen bond, the O-H resonance is

shifted to a lower frequency, considerably intensified in terms of band area, and considerably broadened. In cases of intermolecular hydrogen bonding in suitable solutions an equilibrium may exist between molecules with free hydroxyl groups and those with bonded hydroxyl groups. The spectra of the two (or more) types of molecule will be superimposed, giving both sharp O-H absorptions and broader O-H absorptions at lower frequency. Dilution breaks up the hydrogen bonds, and, relatively speaking the sharp peak will increase in intensity while the hydrogen bonding.

The intensity of an absorption may be defined by a molar extinction coefficient,

, based

on measurements of peak heights (or, more strictly, on integrated band areas). If I is the transmitted intensity of radiation in the absence of the absorption band, but I the intensity transmitted at the band absorption maximum, then is given by .. (1)

lC

log10 ( I / I )

Where C is the concentration of the solution in moles per litre and l is the path length in cm.

Suppose an equilibrium exists for phenol in solution in CC14 of the type (N.B. this is but one of several possibilities):-

Laboratory Manual Physical Chemistry Year 3

2PhOH

(PhOH)2

We will refer to the left-hand side species as free phenol and the right-hand side species as bonded phenol. The sharp O-H band at ca. 3620 cm-1 could be assumed to be due solely to free phenol. For a given total concentration of phenol only a proportion of the molecules will be free. Dilution increases this proportion and in theory at infinite dilution all the molecules will be free. If we knew the true extinction coefficient,
of the O-H

absorption of free phenol we could calculate the concentration, C f , of free phenol at any total phenol concentration, C. To obtain, coefficients,
we could measure apparent extinction

a , at several concentrations by means of equation (2).

1 log10 ( I / I ) lC

..

(2)

And then extrapolate to C = 0. It is then possible to obtain values of C f in any solution by means of (3)

Cf

1 log10 ( I / I ) l

.. (3)

It can be seen that the path-length, l , does not affect the final result, provided it remains constant. Tabulate
a

/ 0.1

(0.1 / C ) log10 ( I 0 / I ) 0 / log10 ( I / I ) 0.1 and plot

against C, then extrapolate to C = 0 to find

/ 0.1 . N.B.

0.1 is

a at the 0.1 M

concentration. Values of C f may be obtained from your tabulated data by means of equation (4).

Cf (

0.1

C(

0.1

.. (4)

The concentration, C b , of bonded phenol is then Cb

1 (C C f ) , and the equilibrium 2

constant for dimerisation by hydrogen-bonded is then C b / C 2 f .

Note that a straight line plot is obtained only if the predominant species formed is the dimer. The formation of appreciable amounts of other species, such as trimers,

tetramers and other higher polymers, will cause departure from linearity in the region of higher concentrations. Note also that because of the large uncertainties involved in the measured quantities in this experiment, e.g. the absorbances, especially at very low or

Laboratory Manual Physical Chemistry Year 3 at very high concentrations (why?), or the effect of the presence of water even in trace quantities (why?), you have to exercise considerable judgement in arriving at the result you want. For example, would it be sensible to carry out a least squares treatment if indeed a straight line is obtained. Consequently it may not be possible to obtain high precision in the results.

Experimental You are provided with phenol crystals. Make up 100 mL of a solution in CCl4 of 0.1 M concentration. Then using dilution techniques make 10 mL solutions of 0.09 M and other concentrations in decreasing steps of 0.1 M down to 0.01 M. You are provided with 2 cells with NaC1 windows, of spacing approximately 0.5 mm. Wash the two cells with CC14. Fill one of the cell with your solution and the other with CC14. When filling the sample cell make sure that no solution spills over on to the outside of the NaC1 plates (if it does, wash it off with pure CC14). You will not operate the infrared spectrophotometer yourself. Place the CC14 cell in the sample beam and obtain the spectrum of CC14. The place this cell in the reference beam and the sample cell in the sample beam, and obtain the difference spectrum of phenol in solution. Wash out the sample cell with CC14 and then fill it with another solution. Obtain the spectrum of this solution (with the CC14 cell in the reference beam). The same cell must be used for the solution.

Measure I 0 and I for the free OH absorption as in the figure below, making allowance for the fact that there is some overlapping by the broad bonded OH absorption which lies between 3600 and 3300 cm-1.

Calculate

/ 0.1 for each concentration and plot a / 0.1 against C. Draw as smooth
a

a curve as is possible to fit your data and extrapolate to C = 0 to obtain

/ 0.1 . Note
Then using

the large uncertainty in the value of the intercept (why?). If any point on this plot are wildly off a smooth curve, repeat the spectrum for that concentration.

equation (4) calculate C f , the concentration of free phenol for each total concentration, C. Obtain values for the equilibrium constant for the equation

Laboratory Manual Physical Chemistry Year 3

2PhOH

( PhOH ) 2

A Method for Measuring Absorbance

----- dotted lines indicate what the curves would look like if there were no overlap.

(B) N.M.R. Problem

Study Of Rotational Isomerism In 1,1,2-Trichloroethane

The aim of the experiment is to obtain coupling constants for protons gauche to one another and for those trans to one another in 1,1,2-trichloroethane. The experimentallyobserved coupling constant is a statistical average over all the possible conformations. The values obtained for solutions for which the rotamer populations are known are used to calculated energy differences for the neat liquid.

Laboratory Manual Physical Chemistry Year 3 Theory A molecule of the type X 2 HC

CH 2 X is commonly thought to have three potential

minima with regard to internal rotation about the C-C bond. The chemical and physical behaviour of such a molecule depends considerably upon the relative magnitude with respect to kT of the barrier heights (differences in potential energy between

neighbouring maxima and minima) and the energy differences between various minima. If one or all of the barrier heights are comparable with kT, it will be possible for one stable sonfiguration to be converted into another with rapidity. A dynamic equilibrium is then present which may be described as a mixture of rotational isomers, or stable conformations. There is one rotational isomer or stable conformation for each potential minimum, and these cannot, at this temperature, be isolated from each other. The composition of the mixture will be determined by the relative free energies of the several isomers present. These relatively stable forms have the staggered

configurations shown in the figure:

A schematic three minimum Curve of potential energy, V, Against azimuthal angle of internal rotation, 0, such as Occurs for an unsymmetrically substituted ethane of the type

X 2 HC CH 2 X .

Rotamers I and II are equivalent and may be referred to as the asymmetric form, rotamer III being symmetric. The fractional population of each form may be written Pa and Ps respectively. The internal rotation is rapid compared to the N.M.R. time-scale at room temperature and the observed spectrum is therefore the weighted average of the rotameric forms. The observed coupling constant J12 is given by:

J12

pa J t

pa J g

2 ps J g .

The weighting factors have to be normalized so that

J12

1 pa J t 2

( ps

1 pa ) J g 2

Laboratory Manual Physical Chemistry Year 3 Where J g and J t are the coupling constants between protons mutually oriented gauche and trans respectively.

The chemical shifts of H 2 and H 2 , are equal, so the spin system is classified as AB2 (or, in first order, AX 2 ). The coupling constant J22, thus does not affect the spectrum. If the enery difference between symmetric and antisymmetric form, to the equation:

Ea

E s , is known, then p a and p s may be calculated according

pa ps

G / RT

2e

G / RT

2e

E / RT

The factor 2 appears because of the statistical weight of th asymmetric form. Values of

E may be obtained from measurements of infrared spectra. The absorption at 1211


cm-1, for example, is assigned to the asymmetric form and that at 1238 cm -1 to the asymmetric form. If two different solutions of 1,1,2-trichloroethane, with known values of

E , are studied by NMR and J12 is measured for each, then two simultaneous
equations in Jg and Jt are obtained. Thus the individual values of Jg and Jt may be deduced, and measurements of J12 for other solutions of 1,1,2-trichloroethane may be used to calculate appropriate (which can be checked by IR measurements). Experimental Aspects The N.M.R spectra of 1,1,2-trichloroethane in the following 3 solution with tetramethylsilane as internal reference will be obtained: Neat liquid, 50% V/V solution in carbon tetrachloride, 50% V/V solution in acetonitrile. Obtain an average value of J12 in each case. Calculations and Problems Infrared measurements show that

E values

E is -0.41 and + 0.03 kcal/mole for 50% solutions of E for the neat liquid.

1,1,2-trichloroethane in carbon tetrachloride and acetonitrile respectively. Calculate Jt and Jg from your data. Deduce a value of

Laboratory Manual Physical Chemistry Year 3 Include in your Discussion section answers to the following problems. Why do the values of

E vary in the manner observed?

What effects tell you the NMR spectrum of 1,1,2-trichloroethane is not exactly first-order at 60 MHz? What assumption have been made in this experiment? Suggest further NMR experiments to investigate rotational isomerism in 1,1,2trichloroethane more thoroughly.

Suggested Reading

1.

L.M. Jackman and S. Sternhell, Applications of N.M.R. Spectroscopy in Organic Chemistry, 2nd Ed., Chapter 5-2, 1969, Pergamon Press.

2.

S. Mizushima, T. Shimanouchi, T. Miyazawa, I. Ichishima, K. Kuratani, I. Nakagawa, and N. Shido, J. Chem Phys. 21, 815 (1953).

S. Mizushima, Structure of Molecules and Internal Rotation, Chap. II, 1954,

Academic Press.

Molecular Spectroscopy (C) Spectrophotometric Determination Of An Equilibrium Constant Between A Molecular Complex And Its Free Component Molecules.

Theory The relative weak interactions between an electron donor (D) and an electron acdeptor (A) can lead to the formation of a molecular complex (D,A). The ground and excited states of the complex can best be described1,2 by the wave functions
N

a 0 ( D, A) b 1 ( D

A )

And
E

1(D

A ) b

0 ( D, A).

The term

0 refers to the no-bond wave function and corresponds to the structure in

which the bonding results from coulombic, induction, dispersion, and exchange repulsion forces, while the dative-bond wave function
1 corresponds to the structure where an

electron has been transferred from D to A. Resonance between the no-bond and the

Laboratory Manual Physical Chemistry Year 3 dative structure in the ground state provides additional stability over the usual stability attributed to forces in the no-bond structure. This additional force contributing to the stability of the molecular complex is called a charge-transfer force. The coulombic, induction, and dispersion forces are attractive, whild the exchange repulsion works against them, giving a total net force in the no-bond structure which might be either negative or, if the charge-transfer forces are strong enough, even zero or positive. For weak molecular interaction the ground state energy (W N) is given by the expression

WN
Where W

Hf

G0

X0

W0

X0

is the energy of the two separated molecules,

H f is the enthalpy of

formation of the complex, G 0 is the no-bond energy term and X 0 is the resonance nergy of interaction between no-bond and the dative states of the complex. The energy of the excited state of the complex (W E) is given by the expression

WE

ID

E A G1

X1

W1

X1

Where I D is the ionization potential of the donor, E A is the electron affinity of the acceptor, G1 is the sum of several terms including the large electrostatic energy of interaction between the charges on D and A and X 1 is the resonance energy due to

interaction with the no-bond state. The transition from the ground state to the excited state of the complex can be achieved by the absorption of light and the absorption band associated with this transition is called on intermolecular charge-transfer band. The energy change corresponding to the charge-transfer band is equal to W E

WN . A

diagrammatic representation of the relationship of these various energy terms is given below. Excited state of complex
E ( D, A)

W E __________ _____________ D X1 W1 __________ ______________ D W ____________________ ___ D G0 W0 ____________________ ___ D, A X0 A

A A

D, A

Laboratory Manual Physical Chemistry Year 3

Ground state of complex

N ( D, A)

WN ____________________ D, A

A potential-energy diagram for molecular complexes. Experimental The purpose of this experiment is to evaluate the equilibrium constant ( K c ) at 30oC for molecular complex formation from mesitylene (M) and iodine (I 2). The equilibrium on the basis of 1:1 complex stoichiometry can be written as

M
and

I2
cx c x )(c A

MI 2

Kc

(c D

cx

(1)

where c D is the initial concentration of mesitylene, c A is the initial concentration of the iodine and c x is the concentration of the complex at equilibrium. We have assumed that activaties can be replaced by concentrations in the equilibrium expression (1). The validity of the 1:1 complex stoichiometry will be borne out if the experimental results can be satisfactorily interpreted in terms of the assumed stoichiometry of the complex. The absorbance (A) of an absorbing species is related to its concentration by Beers law, i.e.,

log I 0 / I

c1
is the

where I 0 is the intensity of incident light, I is the intensity of light transmitted,

molar absorptivity, c is the concentration, and 1 is the path length of the cell. If several species absorb at a particular wavelength, then the absorbances are additive. In our case all species participating in the equilibrium absorb in the region of wavelength maximum of the charge-transfer band, however, the molecular complex absorbs strongly while the uncomplexed I 2 and mesitylene do not. wavelength chosen for measurement be AF . absorbances of D, A and D, A., i.e. Let the total absorbance at the

This can be written in terms of the

AT
such that

AD

AA

AD, A .

A considerable simplification in the experimental work results if conditions are chosen,

Laboratory Manual Physical Chemistry Year 3

cD

cA

cX .

This means that AA can be taken as zero, and the absorbance due to the complex is given by

AD, A

AT

AD

AD can be calculated if D is known.


This can readily be obtained by measuring the absorbance of a solution containing only mesitylene at the wavelength chosen for measurement. Upon replacement of c X by AD, A / D, A in the equilibrium expression (1) and rearrangement, one can obtain the expression

AD, A / c D c A

1 D, A K c

AD, A / c A K c

(2)

Absorbancies are masured for a series of solutions made with various known values of

c D and c A , and values of AD, A / c D c A are plotted against AD, A / c A . If the data are
represented by a linear plot, the the gradient and the intercept can lead to the value of
DA and K c . A word of caution is in order here. Linearity of the plot merely indicates

that the equilibrium can be interpreted in terms of the postulated equilibrium and that the approximations used in deriving expression (2) have not been violated. A more

comprehensive analysis of the experimental data is generally required before one can assign a particular model for the equilibrium reaction. Procedure Two solutions are prepared: (a) 100 cm3 of CC14 solution of I2 of molarity in the region of 0.0004 (b)
3 50 cm

of CC14 solution of mesitylene of molarity in the region of 2. The first is prepared

by dilution of a more concentrated solution which in turn is made up by dissolving a weighed quantity of I2 in a measured volume of solution. The second is made up by accurately weighing about 16 cm3 of distilled mesitylene in a 50 cm3 volumetric flask and filling to the mark with carbon tetrachloride. All these solutions are made up to the mark in a thermostat bath at 300C. The concentration of the I2 solution may be checked by standard titration methods. The spectra of the following solutions are to be recorded by the use of UV-VIS spectrophotometer from 320-700 nm. The reference call should have pure CC14.

Laboratory Manual Physical Chemistry Year 3 (a) (b) (c) CCl4 solution of I2 having molarity in the region of 0.0002; CCl4 solution of mesitylene having molarity in the region of 1; 1:1 mixture of solutions (a) and (b).

Let us now for convenience refer to the I2 and mesitylene solutions prepared as S I 2 and

S M respectively. Select a wavelength for measurement at which the complex absorbs


strongly while the uncomplexed mesitylene do not. The absorbencies of the following solutions are to be measured at this particular wavelength.

(1)

Pure S I 2 and make sure that the ab sorbance does not exceed 0.02, if it does, then prepare in fresh solution of I2.

(2) (3) (4) (5) (6) (7)

Pure S M solution. 5 cm3 S M + 1 cm3 S I 2 5 cm3 S M + 6 cm3 S I 2 5 cm3 S M + 11 cm3 S I 2 5 cm3 S M + 16 cm3 S I 2 5 cm3 S M + 21 cm3 S I 2

The absorbencies must be corrected for zero error of cells which can simply be obtained by measuring the absorbance of the solution cell when it is filled with pure CC14 against the reference cell having CC14 . Make sure that the cell compartment is thermostated at 300C for all measurements of absorbances. Calculation and Discussion (1) (2) (3) Calculate for mesitylene in CC14.
D, A

Determine graphically K c and

for the complex.

Check the validity of the approximation c D for the least favourable case.

c X by calculating c D and c X

(4)

Which molecular orbitals are involved in the electron transfer from D to A in the excited state of the complex?

Laboratory Manual Physical Chemistry Year 3 (5) (6) Suggest possible structures for the MI2 complex. What further experiments would you carry out to determine formation? (7) Do your results suggest the nature of bonding involved in the ground state of the complex? References (1) (2) R.S. Mulliken, J. Amer. Chem. Soc., 1952, 74, 811. R.S. Mulliken, and W.B. Person, Molecular Complexes: A Lecture and Reprint Volume, Wiley, New York, 1969. L.J. Andrews and R.M. Keefer Molecular complexes in Organic Chemistry, Holden-Day, San Francisco, 1964.

H f for complex

(3)

Laboratory Manual Physical Chemistry Year 3

EXPERIMENT 3: THE CRITICAL POINT


Introduction

The objective of this experiment is to measure the densities of coexisting carbon dioxide liquid and gas near critical point. At its critical point, the densities of a liquid and its gas phase become equal. Since such a point is difficult to determine directly, an extrapolation method is often used to determine the critical density. This method is based on the law of rectilinear diameters which states that
av

= ( l+

) =

- cT ,

(1) where
av

is the average of the densities of the coexisting liquid and gas phase
o

at a temperature T, c and

are constants for any particular fluid. The plot of


l

av

versus T is a straight line while the plot of

and

is a curve known as the

coexistence curve. They intersect at the critical point and this serves to locate its position. Such a plot is called a Cailletet-Mathias curve. The behaviour of thermodynamic properties near the critical point may be described by the use of critical exponents. The critical exponent associated with density is and is defined by
l c g

Tc T Tc

.
g

(2) ) versus log (Tc - T).

It may be obtained as the gradient in the plot of log ( l +

Method

A set of 8 capillaries filled with carbon dioxide is provided. Data are supplied which will enable you to obtain the cross-sectional area of each capillary and the amount of carbon dioxide that it contains. Set the thermostat at 24.0oC. The temperature of the bath should be read to 0.01oC and the regulator should be adjusted such that the range of temperature fluctuations does not exceed 0.04oC.

Laboratory Manual Physical Chemistry Year 3

While the bath is attaining the temperature, measure l1, l2, and l3 as specified in the following diagrams (Fig. 1 and Fig. 2) for all the capillaries using a catharometer.

l1

l2

l3

FIG.1

FIG. 2

This is to enable you to calculate the internal volume of the capillaries. If the end bits appear conical as in Fig. 1, the volume of the capillary is given by V = A( where A

1 1 l1 + l2 + l3 ) , 3 3

(3)

is the cross-sectional area of the capillary. If the end-bits appear

hemispherical as in Fig. 2, then l1 l2 d/2 ,

where d is the diameter of the capillary. In this case


V A 4 3 A l2

(4)

Laboratory Manual Physical Chemistry Year 3

When the set temperature has been reached, maintain the bath at this temperature for at least 10 minutes. Then measure the level of the meniscus of the liquid carbon dioxide in each of the capillary. Repeat the measurement of the meniscus levels at an interval of 0.5 oC until a temperature of 30.5 oC is reached. You are required to calculate the volume of the liquid phase, Vl , in the capillaries and plot the result versus temperature as the experiment proceeds. In the event that the liquid phase in a particular capillary disappears at the set temperature, lower the temperature slightly until the liquid phase reappears, and measure the meniscus level again at this lower temperature (for this particular capillary only). Obtain two to three readings at an interval of 0.1 oC in this region until the liquid phase disappears again (why?). Try to observe the critical opalescence in carbon dioxide near the critical temperature. This is best seen at right angle to the incident light beam.

Caution

Do not raise the temperature of the bath appreciably above 31 oC as the capillaries may explode. The use of safety glasses in this experiment is mandatory.

Calculations

Calculate the internal volume, V, of each capillary and the mass of carbon dioxide in it. At each temperature, calculate Vl , and obtain the volume of the gas phase, Vg, through the equation Vg = V - Vl . (5) Plot Vl against temperature for a chosen capillary. Extrapolate this plot to V l = 0. Let the temperature at this point be T o. The density of the gas phase at this temperature can be calculated. For the other capillaries which still contain two phases, the density of the gas phase at T o is now known. The volumes of the two phases at this temperature can be obtained by interpolation, and hence the density of the liquid phase at To can also be obtained.

Laboratory Manual Physical Chemistry Year 3

Repeat this process for all the capillaries to obtain the density of the coexisting gas phase and liquid phase at a set of new T o values. Finally construct a Cailletet-Mathias plot and from it obtain the critical temperature Tc. Test the law of rectilinear diameter and finally obtain the critical density
c.

Discussion

Explain why the meniscus in some tubes move down and disappear at the bottom while the meniscus in other tubes may have move up and disappeared at the top. Is it possible for the meniscus to remain stationary as the temperature is raised? What causes the phenomenon of critical opalescence? Relate the parameters a and b in the van der Waals eqn.,
( P a
2 Vm

) ( Vm

b )

RT ,

(6)

to the critical volume and the critical temperature, and hence calculate their values. How do they compare with literature values? The van der Waals equation predict a value of 0.5 for the critical experimental Does your result agree with this? .

References

Shoemaker, Garland and Steinfeld, Experiments in Physical Chemistry, 3 rd ed., pp. 245 -252, McGraw Hill (1974). Rowlinson,Liquids and Liquid mixtures, 2nd ed., pp. 90-94, Butterworth (1969) Moore, Physical Chemistry, 5th ed. Pp. 20-26, 919-922, Longman (1972).

Laboratory Manual Physical Chemistry Year 3 EXPERIMENT 4: DETERMINATION OF ACID DISSOCIATION CONSTANT FOR METHYL RED

The objective of this experiment is to determine the acid dissociation constant for methyl red (a type of dye) using visible spectrophotometry. The constant K, for this equilibrium: H+ MR-

HMR

Methyl red (acidic form)

Methyl red (base form)

Is given as K

[ H ][ MR ] [ HMR ]

Methyl red is a type of dye: acid -(-dimethylamino-phenylazo) benzoic (C15H15N3O2, Molecular weight 269.31)

Methyl red is a weak acid in which its color in aqueous solution depends on the pH. The H+ (or H3O+) in solution determines the ration of MR- to HMR as the following equation:

[ MR ] [ HMR]

Ka [ H 3O ]

At pH 4.2 the solution is red and pH 6.2 the solution is yellow. The human eye is sensitive towards color changes when the ratio of the two colors is between 0.1 and 10. For methyl red in solution:

[ MR ] [ HMR ]

0.1

red solution

[ MR ] [ HMR ]

10

yellow solution

Laboratory Manual Physical Chemistry Year 3 The ratios are equal to 10Ka and 0.1Ka respectively. If we write HMR and MRrespectively as A and B, so

[ H ][ B] [ A]

(1)

For any material which absorbs light, according to Beer-Lambert law, absorption Aobs is given as Aobs = Lc where c is concentration, L is path length and is coefficient of absorption which depends on the type of material which absorbs and to the wavelength of absorption.

For system which is being investigated in this experiment, at one particular wavelength, the absorbing coefficient Aobs is given as Aobs = A [A]L + B [B]L (2)

Equation (2) can be written as Aobs = a ([A] + [B]) L where a is the effective absorption coefficient. From equation (2) and (3), we get,

(3)

[ A] [ B]

[ [

B a

] A]
a

Insert this equation into (1) will obtain

[H ] K

[ B [ a

a] A]

( B

A)

( a

( a A)

A)

Laboratory Manual Physical Chemistry Year 3 Or

1
a A

H K

1
B A B

1
A

(4)

If the initial concentration of methyl red (ci) is constant for all solutions, so [A] + [B] = ci and equation (3) can be written as Aobs = aciL

(5)

A For solutions which has methyl red in acidic form, the absorption, Aobs , will be given as

A Aobs

Aci L

(6)

Combining equation (5) and (6) will produce

1 ( a
A)

ci L ( Aobs
A Aobs )

And by combining the above equation with equation (4) will have

A ci L / (Aobs - A obs )

([H+] / K)

[1 / (

)] + [1 / (

)]

(7)

since ci and L for all solutions are constant, the plot of a straight line where,

1 ( Aobs A )
A obs

versus [H+] will give

Intercept Slope

For methyl red which exists in basic solution, the absorption will be given as

B Aobs

B ci L

(8)

Laboratory Manual Physical Chemistry Year 3 With the same procedures, we will obtain the following expression ciL / (Aobs - A B obs ) And the plot of determined by = (K / [H+]) [1 / ( versus
A

)] + [1 / (

)]

(9)

1 ( Aobs A )
B obs

1 will give a straight line where K can be [H ]

slope intercept

Experimental procedures

100 mL methyl red standard solution is prepared by adding 40 mL stock solution to 30 mL alcohol and diluted with distilled water.

Two solutions will have to be prepared in order to choose a suitable wavelength to measure the absorption of several methyl red solutions which will be needed. One solution consists of methyl red in acidic form (which will be named acidic solution), while another solution consists of the basic form (which will be named basic solution). Record the spectrum from 400 nm to 700 nm for both solutions. You will have to draw a rough plot while performing more measurements to obtain the wavelength region of maximum absorption. With those results, choose the two most suitable wavelengths based on the absorption maximum Aobs with the change of pH. The acidic solution can be prepared by adding 5 mL methyl red stock solution with 10 mL hydrochloric acid (with 0.1 mol dm-3 concentration) and diluting this mixture to 100 mL. The base solution requires the dilution of 5 mL stock solution and 25 mL sodium acetate solution (concentration 0.04 mol dm3) to become 100 mL. You will also have to prepare several methyl red solutions which contain 0.01 mol dm3 sodium acetate and acetic acid concentrations varying from 0.001 mol dm-3 to 0.05 mol dm-3. Make sure that the total methyl red used for each solution are the same as for those prepared for the acidic and basic solution. Determine the pH value and absorption Aobs for the two wavelengths which you have selected earlier for each solution. At least two readings must be taken for each determination.

Laboratory Manual Physical Chemistry Year 3

The pH meter must be calibrated with two standard buffer solutions for pH 4 and pH 7. Results and calculation

1. Plot the spectrum for acidic solution and basic solution. Determine the wavelengths A and B which give maximum absorption for the acidic solution and basic solution. Record AobsA and AobsB which are seen at at A and B. 2. For the methyl red solutions with various concentration of acetic acid, record all pH and Aobs which is determined at A and B. 3. For Aobs which was obtained at A calculate solutions. Record your readings. 4. For Aobs which was obtained at B record
1 ( Aobs
A Aobs )

1 ( Aobs
A Aobs )

and [H+] for each

1 ( Aobs
B Aobs )

and

1 [H ]

in a table.

5. Plot

versus [H+] and determine the slope and intercept by using

the least square method. Determine the K value and its uncertainty. 6. Repeat (5) but plot
( Aobs 1
B Aobs )

versus

1 [H ]

Questions 1. Derive equation (9) starting from equation (8). 2. Compare K values obtained from (5) and (6). Which of these values are accurate. 3. Discuss whether the experiment can be performed using wavelengths other than A and B.

Reference R. Chang, Physical Chemistry, 2nd edition, Macmillan, 1981, Chapter 12.

Laboratory Manual Physical Chemistry Year 3 EXPERIMENT 5: PHASE DIAGRAM OF A THREE-COMPONENT PARTIALLY IMMISCIBLE LIQUID SYSTEM

The composition of a ternary system may be described by one point in a triple coordinate diagram. The phase diagram of a ternary liquid system separating into two phases is given in Figure 1. The points on the dome (curve abcdefg), represent the compositions at which the two phases separate.

C
0.00 1.0

0.25

0.8

0.6 0.50

d c
0.75

0.4

e f
0.2

1.00

a
0.2 0.4 0.6 0.8

g
1.0

0.0

0.0

Figure 1. Phase diagram of a ternary system with two immiscible liquids, A and B.

Above this dome only a single phase, hence complete miscibility exists. At a composition described by a point under this dome, the system will separate into two phases. The a and g positions in Figure 1 indicate that there is slight miscibility between components A and B. If no miscibility existed between components A and B, the a position would coincide with corner A and the g position with corner B. The diagram also indicates that it is the third component, C, that is really miscible with either A or B in all proportions. In such a phase diagram the tie lines have a very important aspect: they connect the concentration of the two phases experimentally found to be in equilibrium with each other. For instance, when a mixture with composition h (Fig. 1) is prepared, it separates into two phases. Phase one (rich in A and C, and poor in B) has the composition

Laboratory Manual Physical Chemistry Year 3 designated on the diagram by b. Phase two (rich in B and C, but poor in A) has a composition designated by point f. The quantitative ratio of the two phases is given by,

Phase _ one Phase _ two

fh bh

and, therefore, once a phase diagram is available it can be used to determine the compositions and proportions of the phases that would result when a mixture of specified overall composition is prepared.

You may notice that the dome in Figure 1 is not symmetrical and the tie lines are not parallel to each other. This is simply because the solubility of C in the two phases (A and B) is not the same. In whatever direction the tie lines are slanted, they connect points of equilibrium compositions. These equilibrium compositions, b vs. f and c vs. e, become increasingly similar with each subsequent tie line, starting from the base of the dome and proceeding upward. Similarly, the tie lines become shorter and finally converge to a composition. This is called isothermal critical point or the plait point.

EXPERIMENTAL The phase diagram of a dimethyl sulfoxide-water-benzene system will be obtained. In order to obtain the points on the miscibility curve dome, one has to titrate different mixtures of DMSO-benzene with water to the point at which cloudiness appears. This can be accomplished in the following manner: Stopper and number 10 to 15 Erlenmeyer flasks of 100 mL capacity. From two burettes (one containing DMSO and one, benzene) prepare mixtures of DMSO and benzene in different proportions. For example, in the first bottle, add 15 mL of DMSO and 0.2 mL of benzene, in the second bottle add 14 mL of DMSO and 1 mL of benzene, and so forth; in the last bottle, combine 1 mL of DMSO and 14 mL of benzene.

Titrate each bottle with water from a third burette to the point of slight turbidity. Be very careful because any over-titration will result in separation of phases.

Measure the refractive index of each titrated mixture. Prepare a table to show your results.

Laboratory Manual Physical Chemistry Year 3 Since the phase diagram to be drawn will represent an isothermal equilibrium, the following precautions must be observed. After the original mixtures of DMSO and

benzene are prepared, they should be thermostated at 30C. The titration must be done slowly as the mixing of DMSO with water is exothermic. Therefore, the water should be added very slowly, with constant swirling of the Erlenmeyer flask in the thermostat so that thermal equilibrium is achieved before the endpoint is reached.

Determine the density of each of the components at 30C. After the endpoint of the titration has been reached and the refractive index of each mixture has been measured, add a slight excess of water to each bottle. Allow sufficient time in the thermostat for the two phases to separate.

After the phases have separated, take a small aliquot from each phase and measure the refractive indices. Again, present your data with a table. Knowing the densities of the components, convert the data collected in table 1 into weight percentage composition. Plot your composition data thus obtained on a three co-ordinate diagram. Connect the points to form the miscibility curve.

Plot the refractive index diagram above the three co-ordinate diagram in a manner similar to that given in figure 2 by drawing vertical lines from the points representing the titration end point compositions. Selecting a proper refractive indices scale as the y-axis, plot the refractive indices obtained at each titration end point composition. Once a diagram such as in figure 2 is obtained, use the refractive index calibration curve to obtain the tie lines.

Laboratory Manual Physical Chemistry Year 3

1.60

1.55

refractive index

1.50

1.45

1.40

1.35
0.0 0.2 0.4 0.6 0.8 1.0

DMSO
0.00
1.0

0.25

0.8

0.6 0.50 0.4 0.75 0.2

1.00

H2O

0.0
0.2 0.4 0.6 0.8 1.0

0.0

C6H6

Figure 2. Three-component phase diagram with the representative refractive indices of the different compositions.

Questions 1. What is the composition at which a plait point (isothermal critical point) may exist in your ternary system? 2. If you start with a complex mixture of 40% benzene, 20% DMSO (or acetone and so forth), and 40% water, what is the estimated composition of the two-phase? In what proportion would you obtain these phases?

Laboratory Manual Physical Chemistry Year 3 EXPERIMENT 6: THE HYDROLYSIS OF TERT-BUTYL CHLORIDE, C4H9Cl The rate of reaction for the hydrolysis of C4H9Cl can be monitored via the measurement of the electrical conductivity. This hydrolysis can neither be catalyzed by the hydrogen ion nor by the hydroxyl ion. Instead, the rate determining step is the slow ionization, given as

C4H9Cl

slow

C4H9+ + Cl-

(1)

followed by the rapid step which involves the reaction of C4H9 with water,

C4H9+ + H2O

rapid

C4H9OH + H+

(2)

Hence, the overall reaction can be written as

C4H9Cl + H2O

C4H9OH + H+ + Cl-

(3)

Here, the electrical conductivity of the solution increases as the reaction proceeds due to the formation of the strong electrolyte, HCl.

OBJECTIVE To determine the order of reaction and the rate constant for the hydrolysis of C4H9Cl. EXPERIMENTAL PROCEDURES Add 50 mL of aqueous alcohol (80% alcohol v/v) into a large boiling tube, stopper the tube, and immerse it into a water bath whose temperature is kept constant at 30C. While waiting for the temperature of the alcohol to equilibrate, prepare a tube with a conductivity probe. When the thermal equilibrium of the alcohol is achieved, pipette 0.3 mL of tertbutyl chloride into the alcohol. Stir the mixture to ensure homogeneity.

Laboratory Manual Physical Chemistry Year 3 Insert the conductivity probe into the mixture and start the stopwatch immediately. The conductivity can be measured with a conductivity meter. However, prior to using the conductivity meter, it has to be calibrated with the standard KCl (0.745 g/L solution, producing 1.41 mS cm-1). The conductivity readings can now be obtained. Initially, the conductivity

readings for this experiment are recorded every 30 s for a period of 5 min, after which the readings are taken every 2 min for a period of 1 h. After taking the readings, transfer the conductivity probe into an empty boiling tube. The boiling tube which contains the reaction mixture is then stoppered and placed in a beaker of water with a temperature of 60C for a period of 15 min in order to complete the hydrolysis. When the hydrolysis is complete, cool the boiling tube by immersing it again in the water bath. The final conductivity reading is taken when the reaction mixture in the boiling tube is at 30C. REPEAT THE ABOVE PROCEDURE using 0.2 mL and 0.4 mL of tert-butyl chloride. CALCULATIONS AND DISCUSSIONS The conductivity of the solution is proportionate with the amount of hydrogen chloride formed. (Alternatively, plot a calibration curve from the successive dilutions of the final reaction mixture with the solvation of 80% alcohol-water, and measure the conductivity for each dilution.)

The rate constant for a first-order reaction can be written as:

1 ln t

o t

(4)

in which

o t

is the conductivity at t = 0, is the conductivity at time t, and is the conductivity when the reaction is complete.

Laboratory Manual Physical Chemistry Year 3

The plot of ln

o t

against time, t, is a straight line with slope, k. The half-life for

this reaction is independent of the initial concentration of tert-butyl chloride, and the value of k is independent of the conductivity units used. Hence, the cell constant for the conductivity probe is negligible. In addition, the results are also not influenced by the existence of a trace foreign electrolyte since the calculation for k depends only on the difference between the two rates.

ATTENTION: If the value of k obtained for the different volume of tert-butyl chloride differs more than 5%, you are required to repeat the experiment.

Show that the rate law is suitable with the mechanism suggested in the reaction.

Laboratory Manual Physical Chemistry Year 3 EXPERIMENT 7: INFLUENCE OF ELONGATION ON SURFACE ACTIVITY FOR NORMAL ALIPHATIC ALCHOHOL CHAIN

Surface activity is defined by the tendency of a particular chemical to adsorb on surface. As a result, the concentration of the chemical on the surface is higher than that of in the solution (bulk concentration). The chemicals that display such kind of property are

called surfactants. Usually, the surfactant molecule has one part of unpolarized chain namely paraffin chain and the other part is a polarized or an ionized moiety. A molecule that has such potential of two different properties will influence the properties of its solution. The polarized chain will contact with aqueous phase but for the hydrocarbon chain, it does not have any affinity with water. Therefore, the surfactant molecule

adsorbs on the surface with its orientation obeying that condition. Adsorption on the surface will cause a decrease in surface tension which the phenomena can be considered as a way to describe the surface activity.

Quantitatively, the surface excess concentration

can be obtained from the surface

tension, and the internal concentration, C, through the absorption Gibbs equation:

1 d RT d ln C
Units in mol m-2; R is 8.314 J K-1 mol-1; in mol N m-1 T in K

Procedure

For the present procedure, all glasses must be washed carefully at first using Chromic acid. 0.1 mol dm-3 alcohol solutions of methyl, ethyl, n-propyl, n-butyl and n-amyl can be prepared in 100 mL volumetric flask from the alcohol solutions of 0.40, 0.58, 0.75, 0.95 and 1.08 mL, respectively. Dilute the alcohol to the marked level with distilled water. The surface tension of each solution can be determined at room temperature using a torsion balance (Procedure for the operation of this equipment can be found from the laboratory assistant).

Laboratory Manual Physical Chemistry Year 3

Prepare solutions of amyl alcohol with concentrations of 0.01, 0.02, 0.04, 0.06, 0.08, 0.10 mol dm-3 whereas solutions of 0.15, 0.18 and 0.2 mol dm-3 have readily been prepared. Shake the solutions to ensure all the alcohols have been diluted and determine the surface tension of each solution as described above.

The surface tension for distilled water must be determined as well.

Repeat the

procedures using t-butyl alcohol. Prepare a stock solution containing 6 g t-butyl alcohol in 100 mL solution in a 100 mL volumetric flask. Dilute solutions of 0.5, 1, 3, 5, 7, 10 and 13 mol dm-3

to 100 mL with distilled water in volumetric flasks. Determine the surface tensions for the solutions. Result and discussion

Plot a graph of

versus the number of carbon atoms in alcohol. Explain the result

obtained. The decreasing of surface tension can be assumed as a measurement of the alcohol surface activity.

Plot

versus lnC as well for the amyl alcohol and draw a tangent on the line curve at C = 0.02, 0.04, 0.06, 0.08, 0.12 and 0.18 mol dm-3.

Calculate

for the concentrations using the adsorption Gibbs equation. Finally, plot

versus concentration and determine the limiting value for the highest concentration. Describe the shape of the graph. Use the limiting value in calculating the average surface area per amyl alcohol molecule. Compare the area with the cross-sectional area of paraffin chain, namely 0.195 cm2.

Repeat the calculation for the t-butyl alcohol and comment it.

Laboratory Manual Physical Chemistry Year 3 EXPERIMENT 8: DETERMINATION OF VAPOUR VISCOSITY

When a gas passes through a tube in a laminar flow, the separating distance between the layers of the flow is called the mean free path. This distance will not be influenced by the intermolecular forces between the molecules because the friction flow in the gas phase as a consequence of momentum transfer from a fast moving layer to a slower moving layer. Therefore this explains why the viscosity of a gas is so much smaller than the viscosity of a liquid. The gas viscosity also depends on the ambient temperature and in the case of a real gas, the viscosity depends on the square-root of the temperature in Kelvin. This change in viscosity is more prominent in the case of an ideal gas. On the contrary, the liquid viscosity decreases when the temperature is increased. For hardsphere molecules, according to molecular kinetic theory, the viscosity is given by the following equation;

5 32
Where, c l = = =

cl

RTM
3 2N

1 2

(1) T = Temperature (K) molecular mass collision cross-sectional area Avogadro number

density of gas mean speed mean free path gas constant

M = =

R =

N =

Equation (1) shows that the viscosity of an ideal gas is indirectly proportional to the pressure. Nevertheless this is not true for a real gas due to the fact that intermolecular interactions exist between the molecules. There are two common methods to determine gas viscosity; (a) viscous reactance method and (b) transpiration method. In the viscous reactance method, two objects in the form of either cylindrical, disc or spherical shapes are placed side-by-side to one another in the gas medium of interest. When one of the objects is swung towards the other in order to move the gas, it would subsequently swing the other object. The gas viscosity is then determined from the rate of oscillation of the second object.

In the second transpiration method, the gas viscosity can be determined in two ways; (a) Time-volume measurement whereby the gas of interest is allowed to flow through a capillary upon certain pressure and

Laboratory Manual Physical Chemistry Year 3 (b) Time-pressure measurement during the vacuuming process through the capillary. However the size and dimension of the capillary must be precisely known in order to determine the absolute gas viscosity value. This can be done by using a standard gas of known viscosity.

Experimental procedure Set the temperature of water bath to about 35oC. Check for leaks by closing all valves and vacuum the manifold. Leakage can be detected by observing the barometer pressure gauge every 10 minutes.

Then introduce dry air through the silica gel into the system. While the capillary is being vacuumed, record the barometer heights at certain time intervals for 20 - 30 minutes. Record readings such as pressure inside the manifold Pm and the air pressure Pa. The difference in the pressure P, is given by P = Pa - Pm. Obtain Pa by using the barometer provided. Introduce 5 -10 mL of pentane into the manifold by using a round bottom quick-fit reservoir flask. Secure and seal with silicon grease. Vacuum until almost all the pentane evaporates. Immediately close the valve and let the temperature equilibrate with the room temperature. Make sure that all the pentane completely evaporates. Then vacuum through the capillary and record your barometer readings at certain time intervals. Repeat the experiment with diethyl ether and methylene dichloride respectively.

Result and calculation Use your data to prove the following Poiseuille equation,

1 P
where P = Po = r = V = L k and t = = =

r 4t 16VL

1 Po

kt

1 Po

(2)

pressure at time t initial pressure at time t = 0 capillary radius volume of the system capillary length manifold constant time

Laboratory Manual Physical Chemistry Year 3 Plot 1 P

against t for dry air and all the three gases investigated. Given that the

viscosity of air at 35oC is 188.6 microPoise, determine the viscosities for all gases. Assuming that the volume of the system and the length of the capillary are 700 cm3 and 81 mm respectively, determine the radius of the capillary using the data obtain from the dry air.

Discuss your results with respect to the boiling point of pentane, diethyl ether and methylene dichloride respectively. Questions 1. Derive equation (2) from the Poiseuille equation and the ideal gas equation. Poiseuille equation, Q where

r 4 P1 P2 8L

Q = the volume flow rate in the laminar flow and (P1 - P2) = differential pressure at both ends of the capillary.

2. 3.

At what pressure will the mean free path be equal to the length of the capillary? Is equation (2) valid when the mean free path is greater than the length of the capillary tube?

References 1. 2. P.W. Atkins, "Physical Chemistry", ed. 6, Oxford 1998. I.N. Levine, "Physical Chemistry", ed. 4, McGraw-Hill, 1995.

3. R.A. Alberty & R.J. Silbey, "Physical Chemistry", ed. 2, John Wiley, 1996.

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