UNIVERSITY OF GUYANA

FACULTY of NATURAL SCIENCES

SEMESTER I FINAL EXAMINATIONS OF 2023-2024

CODE AND NAME OF COURSE: CHM2104 Chemical Thermodynamics

DATE AND TIME: December 20, 2023 DURATION: 2.5 hrs
EXAMINERS: Dr. Dawn I Fox and Mr. Shomere Garnett (Internal) and Mr. Patrick Ketwaru
(Second marker)
INSTRUCTIONS TO CANDIDATES: This paper two sections, A and B. Section A has one
compulsory question worth 40 marks. You must answer the question in section A.

Section B has three (3) questions worth 30 marks each. You are required to answer ANY and ONLY
TWO (2) questions from Section B. Show all steps of calculations and label question parts correctly.

Marks allocated to question sections are given in square brackets at the right-hand margin. Some
useful data and formulae are provided below.

Useful data:

R = 8.314 J K-1 mol-1 = 0.08206 L atm K-1 mol-1; g = 9.81 m s-2; 1 atm = 101 325 Pa = 760

mm Hg; 1 bar = 0.987 atm = 0.1 MPa.

Formulae:

𝑉 𝑛𝑅𝑇 𝑛 2
𝑝𝑉 = 𝑛𝑅𝑇; 𝑍 = 𝑉𝑚𝑜 ; 𝑝 = 𝑉−𝑛𝑏 − 𝑎 (𝑉) ; 𝑑𝑤 = −𝑝𝑑𝑉; 𝑤 = −𝑝𝑒𝑥 𝛥𝑉;
𝑚
1/𝑐
𝑉 𝑇𝑓 𝑉 𝐶𝑉,𝑚 3𝑅 5𝑅
𝑤 = −𝑛𝑅𝑇𝑙𝑛 ( 𝑉𝑓 ) ; 𝑤𝑎𝑑 = 𝐶𝑉 𝛥𝑇; = (𝑉 𝑖 ) 𝑤ℎ𝑒𝑟𝑒 𝑐 = ; 𝐶𝑉,𝑚 = ; 𝐶𝑝.𝑚 = ;
𝑖 𝑇𝑖 𝑓 𝑅 2 2
𝛾
1 𝜕𝑉 1 𝜕𝑉 𝑝𝑓 𝑉 𝐶 𝑉
𝛼 = 𝑉 (𝜕𝑇 ) ; 𝜅𝑇 = − 𝑉 (𝜕𝑝) ; = (𝑉 𝑖 ) 𝑤ℎ𝑒𝑟𝑒 𝛾 = 𝐶𝑃,𝑚; 𝛥𝑆 = 𝑛𝑅𝑙𝑛 ( 𝑉𝑓 );
𝑝 𝑇 𝑝𝑖 𝑓 𝑉,𝑚 𝑖
𝑞𝑟𝑒𝑣 𝑇𝑓 𝑝𝑓
𝛥𝑆 = ; ∆𝑆 = 𝐶𝑝 𝑙𝑛 ( 𝑇 ); 𝑑𝑆𝑠𝑦𝑠 + 𝑑𝑆𝑠𝑢𝑟𝑟 ≥ 0; 𝑑𝐺 = 𝑉𝑑𝑝 − 𝑆𝑑𝑇; ∆𝐺 = 𝑛𝑅𝑇𝑙𝑛 ( 𝑝 );
𝑇 𝑖 𝑖
𝜕 𝛥𝐺 𝛥𝐻
( ) =− ; 𝐺 = 𝐻 − 𝑇𝑆; 𝐻 = 𝑈 + 𝑝𝑉; 𝑝𝐴 = 𝑝𝐴∗ 𝑥𝐴 ; 𝑝𝐵 = 𝑥𝐵 𝐾𝐵 ;
𝜕𝑇 𝑇 𝑃 𝑇2
𝑝𝐴 𝑛𝛼 𝑙
𝑝𝑇 = 𝑝𝐴 + 𝑝𝐵 = 𝑥𝐴 𝑝𝐴∗ + 𝑥𝐵 𝑝𝐵∗ ; 𝑦𝐴 = ; = 𝑙𝛽 ; Π = [𝐵]𝑅𝑇; Δ𝑇 = 𝐾𝑓 𝑏;
𝑝𝑇 𝑛𝛽 𝛼

𝜃 𝜃 𝑑𝑝 ∆𝐻𝑣𝑎𝑝
𝛥𝐺𝑟𝑥𝑛 = −𝑅𝑇𝑙𝑛𝐾; 𝛥𝐺𝑟𝑥𝑛 = 𝛥𝐺𝑟𝑥𝑛 + 𝑅𝑇𝑙𝑛𝑄; = 𝑇∆𝑉
𝑑𝑇 𝑣𝑎𝑝
𝐾2 𝜃
𝛥𝐻𝑟𝑥𝑛 1 1 𝛥𝐻𝑣𝑎𝑝 1 1
𝑙𝑛 (𝐾 ) = − ( ) [𝑇 − 𝑇 ]; 𝑃 = 𝑃 ∗ 𝑒 −𝜒 𝑤ℎ𝑒𝑟𝑒 𝜒 = [𝑇 − 𝑇 ∗ ]
1 𝑅 2 1 𝑅

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Section A This section has one question worth 40 marks. You must answer this question.

Question 1

(a) (i) State the First Law of Thermodynamics. [3]

Give the symbolic relationship (equation) for the First Law, and name each term in the equation.
[3]

(ii) Differentiate between a diathermic boundary and an adiabatic boundary, giving examples.
[4]

(b) (i) A sample of 2.50 mol of an ideal, monatomic gas is expanded reversibly and isothermally at
25 oC until its volume is doubled. Calculate q, w, ∆U and ∆S for this process. [8]

(ii) The same sample of gas in (b) (i) above is expanded reversibly and adiabatically under the same
initial conditions until its volume is doubled. Calculate the final temperature Tf, wad, q, ∆U and ∆S
for this process. [12]

(c) (i) Write a statement comparing the work (w) done by the gas in the two scenarios described in
(b) above. Account for the difference in the values obtained. [5]

(ii) Write a statement comparing the changes in entropy (∆S) of the gas in the two scenarios
described in (b) above. Account for the differences in the values obtained. [5]

Section B This section has three questions worth 30 marks each. Answer any TWO questions from
this section.

Question 2

(a) (i) State the three assumptions for the kinetic theory of gases and explain the rationale for any
one assumption. [5]

(ii) The mathematical model for the kinetic theory of gases is given by:

1⁄ 𝑛𝑀𝑐 2
𝑝= 3
𝑉
Name each term in the equation and state two implications of this relationship. [5]

(b) Calculate the pressure exerted by 1.0 mol of a gas at 500 K in a 150 mL container using

(i) the perfect gas relationship, then [4]

(ii) the van der Waal’s equation (a = 4.484 atm L2mol-2 and b = 4.34 x 10-2 Lmol-1). [6]
2
(iii) Calculate the compression factor for the gas under these conditions, and interpret the result, i.e.,
account for the value obtained. [5]
𝑅𝑇 𝑎
(c) The Berthelot equation of state (𝑝 = 𝑉 − 𝑇𝑉 2 ) is almost identical to the van der Waals
𝑚 −𝑏 𝑚
equation.

Identify the difference, and suggest a reasonable justification for that difference. [5]

Question 3

(a) Use an appropriate form of the Clapeyron equation to explain the slope of solid-liquid boundary
for a substance with a liquid that is denser than the solid. [5]

(b) The Gibbs-Helmholtz relationship shows how Gibbs energy changes with temperature and is
given by:
𝜃 𝜃
∆𝐺𝑇2 ∆𝐺𝑇1 1 1
− = ∆𝐻 𝜃 ( − )
𝑇2 𝑇1 𝑇2 𝑇1

Use this relationship and tabulated thermodynamic data below to determine the Gibbs energy of
reaction (∆𝑟 𝐺 𝜃 ) for the synthesis of ammonia at 375 K from its value at 298 K.

The balanced equation for ammonia synthesis is:

𝑁2 (𝑔) + 3𝐻2 (𝑔) → 2𝑁𝐻3 (𝑔)

Standard thermodynamic data

Species N2 H2 NH3

Standard enthalpy of formation (kJ/mol) 0 0 – 46.11

Standard Gibbs energy of formation (kJ/mol) 0 0 – 16.45

Complete the following steps:

- Calculate the enthalpy of reaction (∆𝐻 𝜃 ) at 298 K [5]

𝜃
- Calculate the Gibbs energy of reaction at 298 K (∆𝐺298𝐾 ) [5]
𝜃
- Hence calculate the Gibbs energy of reaction at 375 K (∆𝐺375𝐾 ) [5]

Question 3 continues on page 4

3
(c) Use the phase diagram in Figure 1 below to answer the following questions:

(ii) State the initial physical state of the substance, and what would be observed when a sample of
carbon dioxide, initially at 1.0 atm and 298 K is subjected to the following cycle:

Step 1: isobaric heating to 320 K,

Step 2: isothermal compression to 80 atm, and
Step 3: isobaric cooling to 210 K [10]

N.B. These steps are done sequentially.

Figure 1. Experimental phase diagram for carbon dioxide (Atkins et al, 2006)

Nothing has been omitted. Question 4 is on page 5.

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Question 4

(a) Differentiate between:

(i) ideal solutions and ideal-dilute solutions, and [4]

(ii) fugacity coefficients and activity coefficients [4]

(b) (i) The standard Gibbs energy of the decomposition reaction

𝐻2 𝑂2 (𝑙) → +𝐻2 𝑂(𝑙) + 1⁄2 𝑂2 (𝑔) is – 116.78 kJ/mol. Calculate the equilibrium constant K for
the reaction at this temperature. [5]

(ii) A hypothetical decomposition reaction 𝐴(𝑔) → 2𝐵 (𝑔) has a hypothetical equilibrium constant
K = 2.00 x 10-3. The degree of dissociation  is defined as the fraction of reactant that has
decomposed.

Estimate the size of  (qualitatively) for this hypothetical reaction. [2]

(iii) Copy and complete the Initial-Change-Equilibrium (ICE) table below to express K in terms of
the degree of dissociation  for the hypothetical reaction in (ii) above. [10]

A B

Initial amount n 0

Amount of change to reach equilibrium (in

terms of )

Amount at equilibrium

Mole fraction (x)

Partial pressure (using p as total pressure)

4𝛼 2 𝑝
(iv) Hence or otherwise, show that 𝐾 = [5]
1−𝛼 2

END OF PAPER