UNIVERSITY OF PRETORIA

DEPARTMENT OF CHEMICAL ENGINEERING

Chemical Engineering CIR 310
June 2021 Semester Test 2 TIME: 48 h
Full Marks {80} Available marks: {80}

Open book exam, take-home examination. Answer all the questions. Derive all equations you
need from first principles. State and justify all assumptions you make and explain in detail the
algorithms you employ. Upload to ClickUP your handwritten answers, black pen on white paper,
as a single pdf document. Please make sure that each page is signed! You must please also
upload, as separate documents, the Excel spread sheets which show the calculations you
performed for each for each question answered. In the event that you experience problems
uploading to ClickUP, please email your answers to walter.focke@up.ac.za

QUESTION 1: Two compounds, labelled M and C form highly non-ideal liquid mixtures. The
system was investigated using differential scanning calorimetry (DSC). The results are presented
in Table 1. Apply the 3-parameter Wilson equation and determine the eutectic composition and
the eutectic temperature. Please also plot the fully annotated phase diagram and report the
parameter values you found for the 3-parameter Wilson equation. (12)

Table 1. DSC heats of fusion for the pure compounds and melting temperatures of mixtures
containing the indicated mol fractions of the two components

Heat of fusion M C
−1
ΔHfusion, kJ⋅mol 13.62 6.32
M C Tm , K
0.00 1.00 452.4
0.20 0.80 356.0
0.40 0.60 290.0
0.60 0.40 238.0
0.80 0.20 261.0
1.00 0.00 309.7

Hint: The activity coefficients for the 3-p Wilson equation are:

The eutectic temperature and composition are determined using the following equation:

These equations can be re-arranged to:

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 √
The solution is obtained in Excel using the following algorithm:
Plot the melting loci predicted by the two equations after minimising the temperature errors
(predicted vs. experimental). Note: One must be careful in deciding which experimental
data points belong to which branch! √
The intersection of the two lines define the eutectic composition and temperature. √
The eutectic composition contains 57.7 mol% M. √
The eutectic temperature is −36.0 °C (237.2 K) √
The 3-p Wilson parameters are: √√√

Λ1 326.541
20.2359
Λ2 3
0.23004
C 5

Figure annotation: √ √ √ √ √

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QUESTION 2: You are a young engineer tasked to help design a plant for the separation of two
components, here labelled 1 and 2. Initially, only the vapour pressure data, shown in Table 1, are
available to you. The Table lists the Antoine vapour pressure constants to be used in the
correlation in which T is the absolute temperature in Kelvin and Psat represents the vapour
pressure in kPa:

Table 1. Antoine constants

A B C
Compound 4.8619 -132.97
(1) 3 559.071 4
6.2077 1233.12
Compound (2) 2 9 -40.953

A literature search revealed that the system features an azeotrope at 68.4 °C with component 1
present at 42 mol%. Based on the molecular structure of the two compounds, your team leader is
confident that the activity coefficients for this system can be represented with the Porter model
with temperature independent parameters. Furthermore, he thinks that it is not necessary to make
corrections for non-ideal vapour behaviour. You accept his suggestions and proceed as follows:

(a) Since the system pressure data is not available, you decide to use the Ψ-method for your
data analysis. In order to refresh your memory of the thermodynamics course which you attended
at University, you approach your task carefully starting with basic concepts. So, you first derive
the Ψ-method equations and consider the activity coefficients defined by the Porter model, before
drawing a schematic plot of Ψ vs. x1. Please draft (and submit for examination) such a rough
sketch using a semi-log plot. Explain why this is necessary to reveal the essence of the
composition dependence of the function Ψ= Ψ(x1) when the system is described by a Porter
model. Annotate this graph fully showing the values of the intercepts at the pure component
composition extremities and the composition where Ψ will take on the value of unity. If possible,
also express the particular points in terms of infinite dilution activity coefficients. (8)

The basic equilibrium relationships are: √

Taking the ratio of these two equations and rearranging leads to √

Where

The activity coefficients for the Porter model are:

Therefore: , i.e. √√

Note that √

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Figure: Showing the expected curve for the Porter model. It is a straight line passing through
the point (0.5, 1) and this becomes clear when plotting log Ψ vs. x1 √ √ √

(b) Now use the available data and generate the actual Ψ= Ψ(x1) curve in Excel on the basis
of the azeotrope and the vapour pressure data that you have available. Please explain in detail the
procedure you follow and provide proper justifications. Please make sure that your x1 intervals
correspond to 0.05 mole fractions. (6)

From (a) we know that the Porter curve of ln Ψ is a straight line passing through the point (0.5,

1). At an azeotrope, α=1 and . Calculate the vapour pressures at the temperature
of the azeotrope. This yields Ψ = 127.48/151.88 = 0.839348. √ √
Next, calculate the slope and intercept of the straight line passing through these points. √ √ √
x1 ln Ψ
0.42 -0.17513
0.5 0
slope = 2.189121
Intercept = -1.09456

The implication is that the constant of the Porter model equals A = -1.09456 √

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(c) Next, you decide to employ the Ψ= Ψ(x1) curve to predict the isothermal y1 - x1 diagram
at 50 °C. Do that and make sure you explain in detail how you managed to do that. (4)

All we have to do, is to evaluate the ratio of the vapour pressures of the two components at the
temperature of 50 °C. √

The calculate α at each x1 value using: . √

The we calculate y1 using: . √

The result is shown in the Figure: √

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(d) Your team leader is quite impressed with this Ψ-approach which you implemented. He
was not aware that this kind of procedure could be used. However, he requests double-checking
the results using the conventional approach, the one that allows you to also generate P-x1-y1 phase
diagram at 50 °C. Please do that and confirm that you get the same results for the y1-x1 curve but
do not forget to also plot the P-x1-y1 phase diagram at 50 °C! (4)

The conventional approach utilises √

Adding these two equations delivers an expression for the system pressure:

The activity coefficients are determined from √

Usually, an azeotrope point allows the determination of the values of two parameters in an
activity coefficient model. In order to get a good average, we do not just use the vapour
pressure for component 1 at the azeotrope temperature to fix the value of A in the Porter
model. Rather, we use the expression: √

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Obtain A = -1.095 √

The results are presented in the Figures below.

Figure: P-x1-y1 phase diagram Figure: Comparing the outcomes of the

conventional- and Ψ-methods

(e) In part (d), you calculated values at discrete compositions spaced 0.05 mol fraction units
apart. Use analytic expressions and calculate the exact values of the azeotrope composition and
the maximum (or minimum) pressure in the P-x1-y1 phase diagram at 50 °C. (4)

The expression for the Porter model-predicted azeotrope pressure in terms of the vapour
pressures of the components is

√ Pazeo = 55.194 kPa √

The azeotrope composition: √ x1,azeo = 0.4101 √

(f) Your team leader believes that you should rather have generated the isobaric y1 - x1
equilibrium diagram for a pressure of 1 atm as the operation of the distillation column will be
closer to isobaric than isothermal conditions. He also wants you to use an analytic expression to
get the exact values for the temperature and azeotrope composition at 1 atm. Do that and, once
again, fully explain the approach you used for achieving this goal. (4)

The same expressions as in (e) applies except that Pazeo = 1atm. √

We find the temperature where this will hold using:

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Tazeo = 67.09 °C = 340.24 K √

The azeotrope composition: x1,azeo = 0.4177 √

Student Excel sheet should explain/show explicitly how they generated the isobaric phase
diagram. √

(g) At a later stage, a sensitivity analysis revealed that accurate VLE data is very important
for your design. A research group is commissioned to measure VLE at 1 atm. Table 2 lists the
values generated by this firm. Plot the data on the Figure you generated in (f) and comment on
the validity of the assertions made by the team leader at the start of the project. (2)

Table 2. Isobaric VLE data at 1 atm

x1 0 0.0546 0.0591 0.0917 0.1005 0.1391 0.2066

y1 0 0.0211 0.0311 0.0442 0.0472 0.0799 0.1358
x1 0.2738 0.3262 0.3518 0.3939 0.4111 0.4294 0.4468
y1 0.2031 0.2776 0.3149 0.3852 0.4044 0.4333 0.4487
x1 0.4487 0.468 0.4757 0.5866 0.6167 0.672 0.7098
y1 0.4545 0.4911 0.5199 0.6973 0.7361 0.8084 0.8483
x1 0.7821 0.818 0.8761 0.9126 0.9652 0.9882 1
y1 0.9058 0.9336 0.9546 0.9686 0.9892 0.9973 1

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The predicted results agree quite well with the experimental values. Therefore, the assumptions
of ideal vapour behaviour and the use of the Porter model were justified! √ √

[32]

QUESTION 3: In theory, the Gibbs-Helmholtz differential equation makes it possible to predict

the excess enthalpy (= heat of mixing) from the excess Gibbs energy. In practice, this is seldom
possible for several reasons. This includes the fact that the current activity coefficient models in
general use are not really up to the task as the correct temperature dependence of the model
parameters have not yet been established. Furthermore, the VLE data quality is usually
insufficient to allow one to deduce useful empirical expressions to describe the temperature
dependence. In this question, you will explore the possibility of using the heat of mixing data for
the benzene (1) – cyclohexane (2) system in order to predict the Margules model parameters
applicable to VLE to within an integration constant. The VLE data for this system was
established in the distant past over a large temperature range. Unfortunately, the data contains
many errors and the fitted parameter values do not vary smoothly with temperature. Fortunately,
this is not the case for the enthalpy of mixing data. Therefore, you are asked to establish a
practically useful temperature dependence of the excess Gibbs energy parameters using the heat
of mixing data set. However, you will have to apply Barker’s data reduction method on the VLE
data as well. The parameters you establish in that way will be necessary in order to determine the
constant of integration that arises when you solve the Gibbs-Helmholtz differential equation
starting from the heat of mixing.

Assume that both the excess enthalpy and the excess Gibbs energy for this binary, the benzene (1)
– cyclohexane (2) system, follow the Margules mixture model, i.e.

Excess Gibbs energy:

Heat of mixing:

Note that the Ai and Bi are considered temperature-dependent model parameters. The activity
coefficients are defined by:

You will be supplied with two seprate spread sheets in which the Margules equation has already
been programmed. Your first task is to optimise the model parameters for each isothermal data set
using the Excel Solver functionality. Once you have those parameters, the analysis can proceed.

(a) Determine the best-fit Ai values at each temperature in the Excel file with the VLE data.
Use Barker’s method where possible. Minimise the sum of square errors in the vapour

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compositions for those data sets that did not report the system pressure. Document the values in
the Excel sheet. (4)

Answer provided in the Excel document: Benzene-cyclohexane-VLE-Margules √ √ √ √

(b) Next focus on the heat of mixing results and determine which of the following possible
temperature functions best describe the variation of the Bi = Bi(T) parameters:

. Please use the correlation

coefficient to determine which temperature function provides the best data representation. (4)

Answer provided in the Excel document: HE-Benzene-cyclohexane-Margules √ √ √ √

A log-log fit gave the best results:
α1 α2
Intercept 12.4560 13.2613
Slope -2.1516 -2.2716
β1 β2
Correlatio
n -0.9995 -0.9983

(c) Select the best temperature model and establish the values of the α and β parameters by a
least squares data fit. Then use the Gibbs-Helmholtz equation to establish an expression for Ai =
Ai(T) based on the Bi = Bi(T) functions. (6)

The integration constant is denoted as “c” √ √ √ √ √ √

(d) Note that the solution of the Gibbs-Helmholtz differential equation delivers a constant of
integration. Establish the value(s) of the constant(s) by comparing all of the best-fit Ai values
determined in (a) with the equation derived in (c). Document the constant(s) you establish in this
way. (4)

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Calculate the difference between the at each VLE isothermal temperature.
Then took the average and obtained: √ √ √ √
Heat of mixing results
ln α1 ln α2
12.4 13.2
Intercept 6 6
Slope -2.15 -2.27

Negative β1 β2
0.06 0.06
2 0
c1 c2

(e) Now use your equation derived from the heat of mixing data together with the integration
constant to predict the VLE P-x1-y1 and y1-x1 phase diagrams at each temperature. Comment in
detail on the success or failure of this exercise. (2)

The predictions are surprisingly good! Exceptions are the data sets for 25 °C and 60 °C √ √

(f) Table 3 lists heat capacity data. Derive a temperature-dependent expression for the heat
capacity of a 1:1 molar mixture of benzene and cyclohexane. Note: Remember that

(8)

√√√√√√√√

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(g) The liquids, water, benzene and cyclohexane are available at a temperature of exactly 50
°C. One mole each of the three liquids are rapidly poured into a Dewar thermos flask and it is
then sealed. What is the temperature of the system when it reaches equilibrium? (8)

The water is immiscible with the benzene and cyclohexane so it is treated separately. The
organic mixture comprises a total of 2 mol. The heat of mixing is therefor equal to:

√√
This quantity must be evaluated at 50 °C, i.e. 323.15 K

The heat capacity of the equimolar organic mixture comprising a total of 2 mol is:

The total heat capacity including the water is:

Energy balance: √ √

Solution shown in Excel: √ √

323.15 Starting temperature
320.11 Final temperature

[36]
Table 3. Heat capacity data with T expressed in Kelvin
Compound Heat capacity Cp, J/mol⋅ K T-range (K)
Benzene 61.20 + 0.252 T 283.78 to 348.47

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Cyclohexane 147.2 + 0.380 T 298 to 313
Water 75.5 273.15 to 373.15

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