UNIVERSITY OF PRETORIA

DEPARTMENT OF CHEMICAL ENGINEERING

Chemical Engineering CIR 310
May 2022 Semester Test 2 TIME: 90 min
Full Marks {40} Available marks: {55}

Open book exam sit-down 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.

QUESTION 1: The van der Waals equation of state adequately describes the behaviour of the

fluid states for a particular compound:

The temperature dependence of the a-parameter is described by the Adachi-Lu expressions:

The value of the constant m is unity for this compound. The critical temperature, pressure and

volume for this compound are known. Furthermore, you may assume that = constant
for the ideal gas form of this compound. The internal energy of the van der Waals EOS is given
by:

(a) Consider the ideal gas state of your compound. Make use of the information provided and
express the internal energy and the enthalpy of this ideal gas in terms of the absolute
temperature and the ratio of the heat capacities, i.e. γ =Cp/Cv. (7)

Ideal gas: and furthermore, both CV and CP are only functions of temperature.

Now √ √
Choose T = 0 K to be the reference state where U = 0. √

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Then the two constants would be zero too. Since γ is a constant, it follows that

and √√

(b) Derive expressions for the heat capacity (CV) of both the liquid and the vapour phases of
the compound described by the van der Waals EOS. (4)

√√√

(c) Show, via a rigorous mathematical derivation, that the enthalpy of vaporisation predicted
by the van der Waals EOS, is given by:

(6)

The enthalpy is obtained from the internal energy from H = U + PV √

Now, for a van der Waals gas

2
 √

Therefore: √

The vapour pressure is given by: √

Therefore:

√√

(d) Outline an algorithm for calculating the enthalpy of vaporization of your compound at a
given temperature. (3)

Given the critical temperature, the critical pressure and the m-parameter for Adachi-Lu
equation, one can calculate the enthalpy of vaporisation as a function of temperature.

Algorithm:
1. Choose a value for the temperature T
2. Solve for Psat, VV and VL.
3. Calculate ΔHvap √√√

(e) Assume that the classic van der Waals mixing rules apply and that the geometric
combining rule applies for the cross-parameter. How does the critical temperature vary
with composition in a binary mixture of van der Waals fluids? (4)

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Recall: and . Therefore, √

For a pure compound: √

For a binary mixture: √√

(f) Interestingly, experimental data for the acetone-chloroform binary system shows that the
variation of the critical temperature in a binary mixture closely follows the linear blending

rule, i.e. . Derive the conditions that must hold for the equation derived in
(e) to reduce to the linear blending law behaviour. (4)
[28]

Compare coefficients for cross terms: √

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 Therefore, the requirement is that: √√

QUESTION 2: Prove that, irrespective of the activity coefficient model, an azeotrope always
occurs at a maximum or a minimum in the P-x surface for a ternary system. You may assume
that the vapour behaves like an ideal gas.
[7]

An azeotrope is defined as the situation when for all i. The equilibrium conditions are:

for i = 1, 2, 3

This means

Furthermore, at the azeotrope composition, √

The system pressure is given by: √

Keep in mind the Gibbs-Duhem equation: √

Since we want to evaluate dP at the azeotrope composition we substitute ,

and √

√√

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QUESTION 3. Isothermal binary vapour-liquid equilibrium (VLE) data reduction. Assume that
the vapour behaves like an ideal gas and that full sets of P-x1-y1 VLE data points were measured
for the binary systems under investigation. It is believed that a particular binary VLE system will
follow either the Margules or the van Laar activity coefficient models.

(a) Write down the two equilibrium conditions that relate the vapour compositions y1 and y2
to the liquid composition and the relevant pressures. Use them to derive an expression for the
total system pressure that is a function of liquid composition and vapour pressures only.
(2)

The equilibrium expressions are: and (√)

The total system pressure is obtained as follows:

(√)

(b) Write down equations to show how you would determine activity coefficients from
knowledge of an azeotrope composition.
(2)

At an azeotrope point y1 = x1 and y2 =x2.

Consequently and (√) and (√)

(c) Show that, if the van Laar activity coefficient model applies, a plot of
yields a straight line. Link the van Laar activity coefficient parameters to the slope and intercept
of this straight line. (3)

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 (√)

The intercept is and the slope is (√)(√)

(d) What value for the slope would indicate that the system behaviour data is actually
adequately captured by the Porter model?
(1)

The Margules model reduces to the Porter model when A = A12 = A21. In that case the slope will
be equal to −1. (√)

(e) Show that, if the van Laar activity model holds, a plot of the inverse of vs.
x1 should be a straight line. Evaluate the intercepts of this line at the pure component
compositions expressing the values in terms of the van Laar model parameters (2)

(√)(√)

(f) The infinite dilution activity coefficient can be evaluated using the following identity:

. Use this expression and determine for both the Margules and
van Laar models. (2)

Van Laar: (√)

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 Margules: (√)

The function Ψ is defined by where α is the relative volatility. Figure 1 shows

VLE data for the acetone (1) - methanol (2) system plotted as Ψ = Ψ(x1). Remarkably, all the
data, irrespective of the measurement temperature, fall on a straight line when the ordinate axis is
based on a logarithmic scale, i.e. it indicates that the data can be correlated according to ℓnΨ =
Ax1 + Bx2 with A and B taken as temperature-independent parameters.

(g) Express the function Ψ in terms activity coefficients only. (2)

and

⇒ ⇒ (√)(√)

(h) Express A and B in terms of infinite dilution activity coefficients (2)

and (√)(√)

(i) Derive an equation that links these two infinite dilution activity coefficients, i.e. show that
they are not independent quantities. Hint: Consider application of the Redlich-Kister equation!
(2)

Note that the Redlich-Kister test for thermodynamic consistency states that, for constant
pressure and temperature, it holds that:

⇒ A = −B ⇒ (√)(√)

(j) Show that such behaviour is consistent with the Porter activity coefficient model
(2)
[20]
{55}

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 Porter model: and

(√)(√)

Figure 1. VLE data for the acetone (1) – methanol (2) system