Department Mining and Process Engineering

Subject Process Thermodynamics 324

Course code PTD720S

Level NQF Level 7, 12 Credits

Due Date 4th November 2022 16:00

Marks 30 marks

Assignment 2 Memo

Examiners: Prof. Kasonde Maweja

Mr. Thomas Moongo

Moderator: Dr. Richmond K. Asamoah (University of South Australia)

General Instructions and Notes

➢ Answer all questions.

➢ Marks allocated are shown against each question.
➢ Only non-programmable calculators may be used.
➢ Write your initials and student number on each page.
➢ Write neatly and legibly; illegible work will not be considered for marks.
➢ Pay attention to units and show the relevant unit in each calculated answer.
➢ Use well labeled and headed illustrative diagrams and sketches wherever necessary.
➢ No marks will be considered for correct answers in the event that two or more
different undeleted answers are given for the same problem.
➢ No marks will be awarded for correct answers only. Calculations must contain a
minimum number of logically sequenced steps followed by the final answer.
➢ In the event that insufficient information was provided to solve a specific problem,
make realistic assumptions, state, and motivate these and continue solving the
problem based on the assumptions made.
➢ Hard copy assignments should be submitted to Mr. Moongo. Late submission will be
penalized by 10% per day.

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Question 1 [5 marks]
A liquid mixture charged into a distillation column at 100℃ and 30 bar pressure has a molar
volume (in cm3/mol) of components 1 and 2 described by the equation below:
V = 𝑥1 𝑉1 + 𝑥2 𝑉2 - 10𝑥1 𝑥2
Given that the pure component molar volumes at these conditions are 90 and 110 cm 3/mol
for components 1 and 2, respectively. Assuming that the mixture has 30 mol-% component 1,
determine the partial molar volume of component 1 in that mixture.
Answer:
V = 𝑥1 𝑉1 + 𝑥2 𝑉2 - 10𝑥1 𝑥2
= 𝑥1 𝑉1 + (1 − 𝑥1 )𝑉2 - 10𝑥1 (1 − 𝑥1 ) 𝑥1 + 𝑥2 = 1 ∴ 𝑥2 = 1 - 𝑥1
= 𝑥1 𝑉1 + 𝑉2 - 𝑥1 𝑉2 - 10𝑥1 - 10𝑥12
= 90𝑥1 + 110 - 110𝑥1 - 10𝑥1 - 10𝑥12 𝑉1 = 90 cm3/mol & 𝑉2 = 110 cm3/mol
= 110 + (90 - 110 − 10)𝑥1 - 10𝑥12
= 110 - 30𝑥1 - 10𝑥12

Partial molar volumes can be computed using the below equations:

𝑑𝑉
𝑉̅1 = V + 𝑥2 𝑑𝑥1
𝑑𝑉
𝑉̅2 = V + 𝑥1 𝑑𝑥
2

Therefore, for component 1 we have:

𝑑𝑉
= -30 + 20𝑥1
𝑑𝑥1

𝑑𝑉
𝑉̅1 = V + 𝑥2 𝑑𝑥
1

= (110 - 30𝑥1 - 10𝑥12 ) + (1 - 𝑥1 )(-30 + 20𝑥1 )

= 110 - 30𝑥1 - 10𝑥12 – 30 + 20𝑥1 + 30𝑥1 - 20𝑥12
= (-10 -20) 𝑥12 + (-30+20+30)𝑥1 + (110 - 30)
= - 10𝑥12 + 20𝑥1 + 80 𝑥1 = 30%
= - 10(30%)2 + 20(30%) + 80
= 85.1 cm3/mol

Question 2 [5 marks]
The solubility of hydrogen in liquid iron under 1 atm pressure of hydrogen is found to obey
the following equation:

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 1670
log 𝑆𝐻2 = − 𝑇
− 1.68 , where the solubility is expressed in wt%. Can the hydrogen content

be brought down to 1ppm (0.0001%) by reducing the pressure in the vacuum chamber to 1
𝜇𝑚 𝐻𝑔 at 1600°C?

Answer:
According to the reaction
𝐻2(𝑔) ↔ 2⟨𝐻⟩

The Sieverts’ law

ℎ2 2
𝑆𝐻 1
𝐾 = 𝑝𝐻 = 𝑝𝐻2
thus, log 𝑆𝐻2 = 𝐾 ′ + 2 log(𝑝𝐻2 )
𝐻2

Given the solubility under 1atm (760 𝑚𝑚𝐻𝑔 ) pressure at 1600°C:

1670 1670
log 𝑆𝐻2 = − − 1.68 = − − 1.68 = −2.5716
𝑇 (1600 + 273)

𝑆𝐻2 = 10(−2.5716) = 0.0027% = 27𝑝𝑝𝑚

The constant 𝐾 ′ at 1600°C can be obtained using the Sieverts law as:
1
log 𝑆𝐻2 = 𝐾 ′ + log(𝑝𝐻2 )
2
1
−2.5716 = 𝐾 ′ + log(760)
2
1
∴ 𝐾 ′ = −2.5716 − log(760) = −4.012
2
Using the Sieverts’ law, evaluate the solubility at 1600°C under vacuum 1𝜇𝑚𝐻𝑔 =
0.001 𝑚𝑚𝐻𝑔
1 1
log 𝑆𝐻2 = 𝐾 ′ + log(𝑝𝐻2 ) = −4.012 + (0.001) = −4.0115
2 2
𝑆𝐻2 = 10(−4.0115) = 0.000097% = 0.97𝑝𝑝𝑚 < 1𝑝𝑝𝑚

The answer is yes.

Question 3 [5 marks]
For a mixture of 10 mol% methane, 20 mol% ethane and 70 mol% propane at 10°C. Determine
the bubble point pressure.

Answer:
Students will use the De Priester chart of the K-values for distillation of the hydrocarbons.

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Knowing the temperature inside the column 10°C, they choose the first guess value of the
bubble point pressure and draw the straight line connecting the temperature point 10°C to
the guessed bubble pressure.
Read the K-values at the intersections with the respective curves for methane, ethane, and
propane.
Calculate the mole fractions of methane, ethane, and propane in the vapour as
ymet = K met xmet
yeth = K eth xeth
yprop = K prop xprop

Then check that the mole fractions of the constituents in the vapour sum to unit.
ymet + yeth + yprop = 1

If
ymet + yeth + yprop ≠ 1, change the value of the guessed bubble pressure and iterate until
convergence to 1.
The number of iterations depends on the student guess of the bubble pressure.
The bubble pressure is about 2400 kPa. This indicate that the distillation column will
operate under high pressure of 24 bar or about 24 atmospheres.
The first vapour formed will have the composition methane 59 mol%, ethane 21 mol%,
propane 22 mol%.

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First guess

Methane Ethane Propane

x given 0.1 0.2 0.7
1500
kPa K_values 8.5 1 0.42
Y 0.85 0.2 0.294 1.344
Second iteration

Methane Ethane Propane

x given 0.1 0.2 0.7
2000
kPa K_values 6.4 1.2 0.35
Y 0.64 0.24 0.245 1.125
Third iteration

Methane Ethane Propane

x given 0.1 0.2 0.7
2400
kPa K_values 5.9 1.09 0.32
Y 0.59 0.218 0.224 1.032

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Question 4 [3 marks]
Discuss the concepts of:
a) Critical solution temperature in liquid – liquid solutions
b) Reverse osmosis
c) Elevation of boiling point in solution
The answers will contain the following information
a) Temperature at which two liquids become fully miscible. The student can make use of
sketches of binodal curves to indicate the cases of Upper Critical Solution Temperature
(UCST) and Lower Critical Solution Temperature (LCST).
b) The answers must indicate the diffusion of species through a semi-permeable
membrane for the osmosis. Then indicate the effect of external applied pressure to
counteract the natural law of mass action for reverse osmosis.
𝑅𝑇 2
c) The students will discuss the factors in the expression ∆𝑇 = 1000𝑏𝐿 𝑚, where m is the
𝑣
molality of the solute (number of moles of the solute in 1kg of solvent), Tb is the boiling
temperature of the solvent, and L is the latent heat of vaporisation of the solvent.

Question 5 [3 marks]
The electromotive force (e.m.f.) of a cell having the following reaction:
𝑍𝑛 + 2𝐴𝑔𝐶𝑙 ↔ 𝑍𝑛𝐶𝑙2 + 2𝐴𝑔

at atmospheric pressure is 1.005 V at 25°C (298K) and 1.015 V at 0°C (273K). Assuming the
temperature coefficient of e.m.f. to be constant, calculate the changes in thermodynamic
functions of the reaction at 25°C, in:
a) Gibbs free energy
b) Entropy
c) Enthalpy of the reaction
Answer:
(a) ∆𝐺 = −𝑛𝐸𝐹
= −2 𝑥 1.005 𝑥 96485
= − 193 935 𝐽
∆𝐸
(b) ∆𝑆 = 𝑛𝐹 ( )
∆𝑇

1.005 − 1.015
= 2 𝑥 96485 ( )
298 − 273
𝐽
= −77.188
𝑚𝑜𝑙. 𝐾
∆𝐸
(c) ∆𝐻 = −𝑛𝐹 [𝐸 − 𝑇 (∆𝑇 )]

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 1.005−1.015
= −2 𝑋 96485 𝑋 [1.005 − 298 ( 298−273
)]

= −216937 𝐽

Question 6 [4 marks]
Develop the expressions for the mole fractions of reacting species as functions of the reaction
coordinate ε for a system initially containing 3 mol H2S and 5 mol O2 undergoing the following
reaction:
2𝐻2 𝑆(𝑔) + 3𝑂2 (𝑔) ↔ 2𝐻2 𝑂(𝑔) + 2𝑆𝑂2 (𝑔)

Also discuss the effects of the pressure and the temperature of the reactor on the progress
of this reaction.
Answer:
The following is a model answer. The student may choose different expressions for the
reaction coordinate 𝜀
𝐻2 𝑆 𝑂2 𝐻2 𝑂 𝑆𝑂2
Initial 3 5 0 0
After reaction 3 − 2𝜀 5 − 3𝜀 2𝜀 2𝜀
Total after reaction (3 − 2𝜀) + (5 − 3𝜀) + 2𝜀 + 2𝜀 = 8 − 𝜀
Mole fractions 3 − 2𝜀 5 − 3𝜀 2𝜀 2𝜀
8−𝜀 8−𝜀 8−𝜀 8−𝜀
The thermodynamic equilibrium constant can be expressed in function of the reaction
coordinate as follows:

2𝜀 2 2𝜀 2
(8 − 𝜀 ) (8 − 𝜀 ) 16𝜀 4 (8 − 𝜀)
𝐾𝜀 = =
3 − 2𝜀 2 5 − 3𝜀 3 (3 − 2𝜀)2 (5 − 3𝜀)3
( ) ( )
8−𝜀 8−𝜀
The balanced equation of the reaction shows 5 moles in gas phase on the left and 4 moles in
gas phase on the right. Thus, increasing the pressure inside the reactor will favour the direct
reaction, which leads to a decrease in the number of moles in gas phase.

Question 7 [5 marks]
The following data were obtained for the oxidation of niobium in pure oxygen atmosphere
at 200°C.

Time, 20 60 100 120 180

[minutes]
Weight gain, 26.5 45.8 59.2 65.0 80.0
[mg/cm2]

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Calculate the parabolic rate constant of the reaction.
Answer:
In oxidation processes, parabolic kinetics occurs when the mass gain or oxide growth on a
sample is proportional to the square root of time. In general, parabolic kinetics indicates that
diffusion of reactants (such as Nb, O, or electrons) through a growing oxide scale is rate
determining (Kofstad, 1966).
𝑥 ∝ 𝑠𝑞𝑟𝑡(𝑡) or 𝑥 2 = 2𝑘 ′ 𝑡

Thus the parabolic rate constant of the reaction is estimated as follows:

𝑥2
𝑘′ =
2𝑡
From the given data in the table the estimated corresponding values of k’ are:

time[min] 20 60 100 120 180

weigh increase
[mg/cm^2] 26.5 45.8 59.2 65 80
k' 17.6 17.5 17.5 17.6 17.8 17.6

An average value of k’ is obtained

𝑚𝑔2
𝑘 ′ = 17.6
𝑐𝑚4 . 𝑚𝑖𝑛

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