CHE2612

JANUARY/FEBRUARY EXAMINATION 2021

UNIVERSITY EXAMINATIONS

Jan / Feb 2021

CHE2612

Physical Chemistry II (Theory)

100 Marks

Duration 2.0 Hours

First Examiner: Dr BS Dladla

Moderator: Dr MG Smith

This is a closed book examination.

Use a ball point pen, preferably black.

This question paper consists of 9 pages.

A Resource section appears on page 8.

The use of non-programmable calculator is permissible.

Guidelines for uploading the answer file on myExams can be found on page 8.

Instructions:

Name all symbols used.

Use ONLY SI units unless instructed otherwise.

Answer ANY FOUR questions. Each question counts 25 Marks.

Connectivity to the internet and the IRIS invigilation system is compulsory.

Upon submission remember to tick the Honesty Declaration.

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Question 1[25]

1.1 Choose one of the words in bold to give the sentence the correct scientific meaning.
a. An equation of state relates pressure, volume, temperature, and mass/amount of
substance. [1]

b. Boyle’s law/Dalton’s law states that the pressure exerted by a mixture of gases is the
sum of the pressures each gas would exert if it alone occupied the container. [1]

c. The Joule-Thomson effect is the cooling of a gas that occurs when it expands through a
throttle with/without the influx of heat. [1]

d. At constant temperature and pressure, change in a system tends to occur in the direction
of increasing/decreasing Gibbs energy. [1]

e. A eutectic is a mixture that freezes and melts without change of

temperature/composition. [1]

1.2 Consider a real gas mixture consisting of 252 mg of methane (Mr/g mol-1 = 16.04), 230 mg
of argon (Mr/g mol-1 = 39.95) and 157 mg of neon (Mr/g mol-1 = 20.18) in a sealed vessel.
The partial pressure of methane is 7.87 kPa. Calculate

a. the partial pressures for argon and neon. [7]

b. the total pressure of the mixture. [3]

1.3 Sketch a graph illustrating the variation with pressure of Gibbs energy for solid, liquid and
gaseous phases of a substance at constant temperature. Identify in your graph,

a. the axes. [2]

b. the phase transition pressures. [2]

c. the most stable phases. [3]

1.4 Identify

a. the equation that describes your graph in 1.3. [2]

b. the state function that represents the slope of your graph in 1.3. [1]

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Question 2[25]

2.1 Illustrate, by means of graphs, how the compression factor varies with pressure at constant
temperature. Draw in the same diagram a) a real gas isotherm higher than Boyle temperature,
b) a Boyle isotherm, c) an ideal gas isotherm, and d) a real gas isotherm lower than Boyle
isotherm. [5]

2.2 Identify the following properties as either extensive or intensive

a. Molar volume [1]

b. Temperature [1]

c. Gibbs energy [1]

d. Enthalpy [1]

e. Mole fraction [1]

2.3 Draw a fully labelled pressure – composition diagram for a binary liquid mixture obeying
Raoult’s law. Assume different pure component vapour pressures. [5]

2.4 Consider an ideal solution of benzene with mole fraction of 0.35 and toluene at 25°C. The
vapour pressure of benzene is 73 Torr and that of toluene is 27 Torr. Calculate

i) The total vapour pressure and [2]

ii) The mole fraction of benzene in the vapour phase that is at equilibrium with
the solution. [2]

2.5 State whether True or False

i) By definition an ideal solution obeys Henry’s law. [1]
ii) A colligative property depends only on the number of solute particles present,
not their identity. [1]

iii) The expression dU = TdS – pdV gives the fundamental equation. [1]
iv) Gibbs energy definition: G = H − TS [1]
v) The chemical potentials of two phases in equilibrium are equal. [1]

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JANUARY/FEBRUARY EXAMINATION 2021
𝜕𝐺
vi) ( ) = −𝑆 [1]
𝜕𝑇 𝑝

Question 3[25]

3.1 Consider a gas with a molar volume 1.5 times that of a perfect gas.

a. Calculate the compression factor. [3]

b. Interpret the value obtained in a. [2]

3.2 Consider the following reactions at 298 K.

2 O3(g) → 3 O2(g) ∆𝑟 𝐻 ⦵ = −427.0 𝑘𝐽/𝑚𝑜𝑙

O2(g) → 2 O(g) ∆𝑎𝑡 𝐻 ⦵ = 495.0 𝑘𝐽/𝑚𝑜𝑙

NO(g) + O3(g) → NO2(g) + O2(g) ∆𝑟 𝐻 ⦵ = −199.0 𝑘𝐽/𝑚𝑜𝑙

Calculate the standard reaction enthalpy for the reaction

NO(g) + O(g) → NO2(g) [14]

3.3 Consider a gaseous mixture consisting of 75.5% nitrogen (N2), 23.2% oxygen (O2), and 1.3%
argon (Ar). Calculate the Gibbs energy of mixing per mole when the ideal mixture is
prepared from the pure gases at 298 K. [6]

Question 4[25]

4.1 Consider a state for which the molar volume is 4.00 × 10-4 m3/mol at 288 K. If the van der
Waals parameters a and b are 0.76 Pa m6 mol-2 and 1.26 × 10-4 m3/mol respectively, calculate
the gas pressure in Pa, using i) the perfect gas law and ii) van der Waals equations of state.
[4]

4.2 Explain the difference in the values obtained in 4.1. [2]

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JANUARY/FEBRUARY EXAMINATION 2021
4.3

The graph in the figure above depicts a temperature-composition solid-liquid phase

diagram.

1. Name the phases in the regions 1-8 [8]

2. At what temperatures do the pure components solidify. [2]

3. Name the line curve marked 9. [1]

4. Write the probable formula for the incongruent-melting compound. [2]

5. Write the probable formula for the congruent-melting compound. [2]

6. Identify the lines marked 4, 5, and 10 as either peritectic or eutectic. [3]

7. Name the phase above line curve marked 9. [1]

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JANUARY/FEBRUARY EXAMINATION 2021
Question 5[25]

5.1 Explain the following statements:

a. Ideal-dilute solution. [2]

b. Azeotrope . [2]

c. Triple point. [2]

d. Spontaneous process. [2]

e. Free expansion. [2]

5.2

Consider 2.50 mol of an ideal gas initially in state 1, shown in the diagram. The ideal gas, with
constant-volume molar heat capacity, CV,m = 20.79 J mol-1 K-1, undergoes a three-step cyclic
transition as shown in the diagram. Calculate in SI units,

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JANUARY/FEBRUARY EXAMINATION 2021
a. for transition state 1 to state 2, the heat (q), the work (w), the change in internal energy
(ΔU), and the change in enthalpy (ΔH). [4]

b. for transition state 2 to state 3, the heat (q), the work (w), the change in internal energy
(ΔU), and the change in enthalpy (ΔH). [4]

c. for transition state 3 to state 1, the heat (q), the work (w), the change in internal energy
(ΔU), and the change in enthalpy (ΔH). [4]

d. for each quantity, the total magnitude after full cycle transition. [3]

END

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JANUARY/FEBRUARY EXAMINATION 2021
RESOURCES SECTION
𝑛𝑅𝑇 𝑛2 𝑎
Van der Waals equation 𝑝= −
𝑉−𝑛𝑏 𝑉2

First law of Thermodynamics ∆U = q + w

Internal energy change ΔU = n CV,m ΔT

Enthalpy H = U + pV
𝑉2
Reversible work 𝑤 = −𝑛𝑅𝑇 ln
𝑉1

Irreversible work 𝑤 = −𝑝𝑒𝑥𝑡 (𝑉2 − 𝑉1 )

Gibbs energy of mixing ∆𝑚𝑖𝑥 𝐺 = ∑ 𝑛𝑖 𝑅𝑇 𝑙𝑛 𝑥𝑖

∆𝑚𝑖𝑥 𝐺
Entropy of mixing ∆𝑚𝑖𝑥 𝑆 = −
𝑇

Ideal gas law pV = nRT

Total volume 𝑉 = 𝑛𝐴 𝑉̅𝐴 + 𝑛𝐵 𝑉̅𝐵

∗
𝑥𝐴 𝑝𝐴
Composition of vapour 𝑦𝐴 = ∗ ∗ ∗ )𝑥
𝑝𝐵 +(𝑝𝐴 −𝑝𝐵 𝐴

Universal gas constant, R 8.3145 J/K mol

Conversion factors
1 atm 101.325 kPa
1 litre 1 dm3
1 bar 105 Pa

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