UNIVERSITY EXAMINATIONS

October/November 2023

CHE2612

Physical Chemistry II (Theory)

100 Marks

Duration 2.00 hours

First Examiner: Dr BS Dladla

Second Examiner: Dr ME Aphane

Instructions:

This is a closed book examination.

Use ONLY ball point pen, preferably black.

This question paper consists of 10 pages.

A Resource section appears on page 8.

Use ONLY SI units unless instructed otherwise.

Answer ANY FOUR questions. Each question counts 25 Marks.

The use of non-programmable calculator is permissible.

Guidelines for uploading the answer file on myExams can be found on page 9.

Additional student instructions

1. Students must upload their answer scripts in a single PDF file (answer scripts must not be password
protected or uploaded as “read only” files)
2. Incorrect file format and uncollated answer scripts will not be considered.
3. NO emailed scripts will be accepted.
4. Students are advised to preview submissions (answer scripts) to ensure legibility and that the correct
answer script file has been uploaded.
5. Incorrect answer scripts and/or submissions made on unofficial examinations platforms (including
the invigilator cell phone application) will not be marked and no opportunity will be granted for
resubmission. Only the last answer file uploaded within the stipulated submission duration period
will be marked.
6. Mark awarded for incomplete submission will be the student’s final mark. No opportunity for
resubmission will be granted.
7. Mark awarded for illegible scanned submission will be the student’s final mark. No opportunity for

1
 resubmission will be granted.
8. Submissions will only be accepted from registered student accounts.
9. Students who have not utilised the proctoring tool will be deemed to have transgressed Unisa’s
examination rules and will have their marks withheld. If a student is found to have been outside the
proctoring tool for a total of 10 minutes during their examination session, they will be considered to
have violated Unisa’s examination rules and their marks will be withheld. For examinations which
use the IRIS invigilator system, IRIS must be recording throughout the duration of the examination
until the submission of the examinations scripts.
10. Students have 48 hours from the date of their examination to upload their invigilator results from
IRIS. Failure to do so will result in students deemed not to have utilized the proctoring tools.
11. Students suspected of dishonest conduct during the examinations will be subjected to
disciplinary processes. Students may not communicate with any other person or request
assistance from any other person during their examinations. Plagiarism is a violation of
academic integrity and students who plagiarise, copy from published work or Artificial
Intelligence Software (eg ChatGPT) or online sources (eg course material), will be in
violation of the Policy on Academic Integrity and the Student Disciplinary Code and may
be referred to a disciplinary hearing. Unisa has a zero tolerance for plagiarism and/or any
other forms of academic dishonesty
12. Listening to audio (music) and making use of audio-to-text software is strictly prohibited
during your examination session unless such usage of the software is related to a student’s
assistive device which has been so declared. Failure to do so will be a transgression of
Unisa’s examination rules and the student's marks will be withheld
13. Students are provided 30 minutes to submit their answer scripts after the official
examination time. Students who experience technical challenges should report the
challenges to the SCSC on 080 000 1870 or their College exam support centres (refer to the
Get help during the examinations by contacting the Student Communication Service Centre
[unisa.ac.za]) within 30 minutes. Queries received after 30 minutes of the official
examination duration time will not be responded to. Submissions made after the official
examination time will be rejected according to the examination regulations and will not be
marked. Only communication received from your myLife account will be considered.
14. Non-adherence to the processes for uploading examination responses will not qualify the
student for any special concessions or future assessments.
15. Queries that are beyond Unisa’s control include the following: a. Personal network or
service provider issues
b. Load shedding/limited space on personal computer
c. Crashed computer
d. Non-functioning cameras or web cameras
e. Using work computers that block access to the myExams site (employer firewall
challenges)
f. Unlicensed software (eg license expires during exams)

Postgraduate students experiencing the above challenges are advised to apply for an
aegrotat and submit supporting evidence within ten days of the examination session.
Students will not be able to apply for an aegrotat for a third examination opportunity.
Postgraduate/undergraduate students experiencing the above challenges in their second
examination opportunity will have to reregister for the affected module.
16. Students suspected of dishonest conduct during the examinations will be subjected to disciplinary
processes. UNISA has a zero tolerance for plagiarism and/or any other forms of academic
dishonesty.
Students experiencing network or load shedding challenges are advised to apply together with supporting
evidence for an Aegrotat within 3 days of the examination session.

2
Question 1 [25]

1.1 Consider the variation of molar Gibbs energy with temperature at constant pressure

and

1.1.1 Write the correct expression for the slope of the graph. [1]

1.1.2 Draw a sketch depicting sublimation, according to the expression in 1.1.1. [4]

1.1.3 Show in your sketch the temperature of phase transition. [1]

1.1.4 Show in your sketch the region where solid is most stable. [1]

1.1.5 Show in your sketch the region where gas is most stable. [1]

1.2 Consider the dissolution of sodium chloride in water and show whether the process

occurs spontaneously under the mentioned conditions. Find relevant data in Resource

section. HINT: First write the pertinent reaction equation. [4]

1.3 Consider the constant molar heat capacity below and calculate the amount of heat

required to raise the temperature of 2.30 mol of water vapour from 100.00C to

500.00C [4]

Cp,m = 30,54 J K-1 mol-1 + (0.01029 J K-2 mol-1)T

1.4 Consider the decomposition of 103.5 g calcium carbonate to solid calcium oxide and

carbon dioxide gas upon heating at standard temperature and pressure and calculate

the change in volume. Mr (CaCO3) = 100.09 g/mol. [4]

1.5 Consider the temperature dependence of the vapour pressure of solid sulphur dioxide

by the relation log(p/Torr) = 10.5916 – 1871.2/(T/K) and that of liquid form by

log(p/Torr) = 8.3186 – 1425.7/(T/K). Estimate the temperature and pressure at the

triple point of sulphur dioxide [5]

3
Question 2 [25]

2.1 Consider the temperature – composition of the KN binary solid – liquid phase
diagram below and draw for each of the following x(N) compositions a sketch
depicting the cooling curve:

2.1.1 0.00 [1]

2.1.2 0.20 [2]

2.1.3 0.66 [1]

2.1.4 0.90 [2]

2.2 Consider two initially separate metal blocks of aluminium (Mr = 26.98 g/mol) and
lead (Mr = 207.19 g/mol) in a chamber with adiabatic walls. The lead block of mass 3
g is initially at 1000C and that of aluminium of mass 4 g is initially at 250C. The blocks

4
 are then placed in contact and allowed to thermally equilibrate. The molar heat
capacities of the metals are considered constant over the temperature of
experiment. At 1 bar, C p,m(Al) = 24.35 JK-1mol-1 and Cp,m(Pb) = 26.44 JK-1mol-1

Calculate

a. the final temperature. [4]

b. the change in the entropy of the blocks in contact. [4]

c. provide evidence that the process occurred spontaneously or not. [2]

2.3 Consider the following reactions at 298 K.

2 O3(g) → 3 O2(g) ∆𝑟𝑟 𝐻𝐻 ⦵ = −427.0 𝑘𝑘𝑘𝑘/𝑚𝑚𝑚𝑚𝑚𝑚

O2(g) → 2 O(g) ∆ 𝑎𝑎𝑎𝑎 𝐻𝐻 ⦵ = 495.0 𝑘𝑘𝑘𝑘/𝑚𝑚𝑚𝑚𝑚𝑚

NO(g) + O3(g) → NO2(g) + O2(g) ∆𝑟𝑟 𝐻𝐻 ⦵ = −199.0 𝑘𝑘𝑘𝑘/𝑚𝑚𝑚𝑚𝑚𝑚

Apply Hess’s law to calculate the standard reaction enthalpy for the reaction

NO(g) + O(g) → NO2(g) [9]

Question 3 [25]

3.1 The mass density of a 20% by mass ethanol/water solution is 968.7 kg/m3 at 200C.
Calculate the partial molar volume of the water in a solution with 52.2 cm3/mol
ethanol partial molar volume. [10]

Mr(H2O) = 18.015 g/mol; Mr(C 2H5OH) = 46.069 g/mol

3.2 Consider the isothermal expansion of a 1.00 sample of ideal gas at 370C from the
initial pressure of 3.00 atm to a final pressure of 1.00 atm and calculate

3.2.1 the heat transferred in the process. [2]

3.2.2 the work done by the system on the surroundings. [2]

3.2.3 the change in internal energy of the system. [2]

3.2.4 the change in enthalpy. [2]

5
3.2.5 the change in entropy of the system. [2]

3.3 Consider the normal boiling point of methanol of 64.10C at which 35.27 kJ/mol of
energy is transferred as into the system as heat and calculate

3.3.1 the entropy of vaporization of methanol at this temperature. [2]

3.3.2 the entropy change of the surroundings. [2]

3.4 Explain the term critical temperature. [1]

Question 4 [25]

4.1 Calculate total vapour pressure above an ideal liquid mixture for which the vapour
composition of one component is 5.32. The vapour pressures of the pure components
at 298 K are 75 Torr and 21 Torr. [7]

4.2 A certain gas obeys the van der Waals equation with a = 0.5 Pa m6 mol-2 and its
volume was found to be 5.00 × 10-4 m3 /mol at 273 K and 3.0 MPa.

i. Express constant a with unit MPa dm6 / mol-1 [2]

ii. Express the volume with the unit dm3 / mol [2]

iii. Calculate the van der Waals constant b. [4]

Express your answers in 5 significant figures

4.3 A 125 mg sample of benzoic acid, (Mr/g mol-1 = 122.13), was burnt in a bomb
calorimeter and an increase in temperature of 4.15 K was observed.
∆cH⦵(C 7H6O2,s) = –3227 kJ/mol, ∆cH⦵(C5H12, g) = –3537 kJ/mol at 298,15 K.

Calculate

i. The calorimeter constant. [6]

ii. The change in temperature upon combustion in the same bomb calorimeter of 125
mg pentane (Mr/g mol-1 = 72.15) [4]

Express your answers in 5 significant figures.

6
Question 5 [25]

5.1 Consider the following data obtained for oxygen at 273.15 K and calculate the best
value of the universal gas constant R. [4]

p/atm 0.750 000 0.500 000 0.250 000

Vm/(dm3 /mol) 29.8649 44.8090 89.6384

5.2 Consider a sample of argon at 100 kPa and is allowed to expand to twice its

initial volume. Calculate the final pressure when the process occurs

5.2.1 Adiabatically (γ = 5/3). [2]

5.2.2 Isothermally. [2]

5.2.3 Explain the difference. [3]

5.3 A certain power station operates with superheated steam at 3000C and

discards waste heat at 200C. Calculate the theoretical efficiency. [3]

5.4 Consider the combustion of 1.000 mol of solid glucose, C 6H12O6, at 250C to

liquid water and gaseous carbon dioxide. Calorimetric measurements give -

2808 kJ/mol as energy released. Calculate

5.4.1 The energy available at constant pressure. [4]

5.4.2 Available maximum work. [3]

5.5 Consider a mixture of benzene and methylbenzene the vapour pressures of

which in pure state are 75 Torr and 25 Torr respectively. If the total vapour

pressure of the mixture is 48 Torr,

5.5.1 Calculate the mole fraction for each component. [2]

5.5.2 Show by calculation that benzene is the more volatile in the mixture. [2]

END

7
 RESOURCES SECTION
𝑛𝑛𝑛𝑛𝑛𝑛 𝑛𝑛2 𝑎𝑎
Van der Waals equation 𝑝𝑝 = 𝑉𝑉−𝑛𝑛𝑛𝑛 − 𝑉𝑉2

First law of Thermodynamics ∆U = q + w

Internal energy change ΔU = n C V,m ΔT

Standard reaction enthalpy ∆𝑟𝑟 𝐻𝐻 ⊖ = ∑ 𝜈𝜈∆𝑓𝑓 𝐻𝐻 ⊖(𝑃𝑃𝑃𝑃) − ∑ 𝜈𝜈∆𝑓𝑓 𝐻𝐻 ⊖ (𝑅𝑅𝑅𝑅)

Standard reaction Gibbs energy of reaction ∆ 𝑟𝑟 𝐺𝐺 ⊖ = ∑ 𝜈𝜈∆𝑓𝑓 𝐺𝐺 ⊖ (𝑃𝑃𝑃𝑃) − ∑ 𝜈𝜈∆𝑓𝑓 𝐺𝐺 ⊖ (𝑅𝑅𝑅𝑅)

Dalton’s law 𝑝𝑝 = ∑ 𝑝𝑝𝑖𝑖

Partial pressure pi = xi ptot

𝑉𝑉2
Reversible work 𝑤𝑤 = −𝑛𝑛𝑛𝑛𝑛𝑛 ln 𝑉𝑉1

Irreversible work 𝑤𝑤 = −𝑝𝑝𝑒𝑒𝑒𝑒𝑒𝑒 (𝑉𝑉2 − 𝑉𝑉1 )

∆ 𝑚𝑚𝑚𝑚𝑚𝑚 𝐺𝐺
Entropy of mixing ∆𝑚𝑚𝑚𝑚𝑚𝑚 𝑆𝑆 = − 𝑇𝑇

𝜕𝜕𝜕𝜕
Partial molar volume definition 𝑉𝑉𝑋𝑋 = �𝜕𝜕𝑛𝑛 �
𝑋𝑋 𝑝𝑝,𝑇𝑇,𝑛𝑛𝑌𝑌

Ideal gas law pV = nRT

𝑉𝑉𝑓𝑓
Reversible expansion entropy ∆𝑆𝑆 = 𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛 𝑉𝑉𝑖𝑖

𝑇𝑇 𝐶𝐶𝑝𝑝
Entropy variation with temperature 𝑆𝑆�𝑇𝑇𝑓𝑓 � = 𝑆𝑆(𝑇𝑇𝑖𝑖 ) + ∫𝑇𝑇 𝑓𝑓 𝑑𝑑𝑑𝑑
𝑖𝑖 𝑇𝑇
at constant pressure
𝑇𝑇
Temperature dependence of enthalpy ∆𝐻𝐻 = ∫𝑇𝑇 𝑓𝑓 𝑛𝑛 𝐶𝐶𝑝𝑝,𝑚𝑚 𝑑𝑑𝑑𝑑
𝑖𝑖

Universal gas constant, R 8.3145 J/K mol

𝑝𝑝𝑐𝑐𝑉𝑉𝑐𝑐 3
Critical compression factor 𝑍𝑍𝑐𝑐 = 𝑅𝑅𝑇𝑇𝑐𝑐
= 8

Total volume 𝑉𝑉 = 𝑛𝑛𝑀𝑀 𝑉𝑉�𝑀𝑀 + 𝑛𝑛𝑁𝑁 𝑉𝑉�𝑁𝑁

Composition of vapour in equilibrium

𝑥𝑥𝐴𝐴 𝑝𝑝∗𝐴𝐴
with an ideal liquid mixture 𝑦𝑦𝐴𝐴 = 𝑝𝑝∗𝐵𝐵+�𝑝𝑝𝐴𝐴
∗
−𝑝𝑝∗𝐵𝐵�𝑥𝑥𝐴𝐴

Boyle’s law pV = const

Adiabatic expansion pVγ = const

Carnot efficiency η = 1 – Tc / Th .

8
 Conversion factors

1 atm 101.325 kPa

1 litre 1 dm3

1 bar 105 Pa

Thermodynamic data

Gravitational acceleration for free fall, g 9.80665 m/s2

Liquid water density at 293 K 0.997 g/cm3

At 298 K ∆𝑓𝑓 𝐻𝐻⊖/kJ mol-1 ∆𝑓𝑓 𝐺𝐺 ⊖/kJ mol-1

H2 (g) 0 0
O2 (g) 0 0
H2 O(l) -285.83 -237.13
H+(aq) 0 0
Cl-1 (aq) -167.16 -131.23
NaCl(s) -411.15 -384.14

9
 GUIDELINES FOR UPLOADING THE ANSWER FILE ON myEXAMS

1. Access myExams at https://cset.myexams.unisa.ac.za/my/ and login using your

student number and myUnisa password.
2. Go to the "CHE2612 Exam Oct/Nov 2023" examination site through the site tabs
on the horizontal navigation bar.
3. Once the site has loaded, select the eAssessment tool from the left navigation
menu.
4. Select the ‘CHE2612 Examination’ file by clicking on the title of the assessment in
the list. A new page will open.
5. Scroll down to Submission
6. Under Attachments, click on the Choose File button to browse for a file on your
device.
Once you have attached your answer file, the name of the file, as well as the file size
and upload time stamp will be displayed under Attachments.
7. Click the honour pledge.
8. Submit your examination answer file.

© UNISA 2023

10