H82CPE-E1

The University of Nottingham

Malaysia Campus
DEPARTMENT OF CHEMICAL AND ENVIRONMENTAL ENGINEERING
A LEVEL 2 MODULE, AUTUMN SEMESTER 2013-2014
CHEMICAL AND PHASE EQUILIBRIA
Time allowed FIFTY minutes

Candidates may complete the front cover of their answer book but must NOT write anything
else until the start of the examination period is announced
Answer all FIVE questions
Only silent is permitted in this try-out exam.

DO NOT turn examination paper over until instructed to do so

ADDITIONAL MATERIAL:

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Thermodynamic Formulae
Figure Q1. Enthalpy-concentration diagram for aqueous
sulfuric acid at 1 bar

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1.

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Find the density of 1.4 moles benzene vapor at 500 0C and a pressure of 40 atm. The PV-T properties are given by the van der Waals equation of state with a is 18 liter2atom/mol2 and b is 0.1154 liter/mol. Take R to be 0.0820578 liter-atm/mol-K.
Solution:
Various forms of vdW WoS:

V b RT

Molar Volume:

P 2
V

Volume:

an 2
P 2
V

V nb nRT

2
nRT n a
P
2
V nb V

We can rewrite vdW EoS as f(V) and derivate it with respect to V:

VdW Eos:

an 2

P 2 V nb nRT
V

an 2
f (V ) P 2 V nb nRT
V

an 2 an 3b
f (V ) PV Pnb
2 nRT
V
V
2
3
an
2an b
f ' (V ) P 2
V
V3

(1)
(2)

(3)

We use the Newton-Raphson formula to find the root V:

Vi1 Vi

Vi 1

P = 40 atm
R = 0.08206 liter-atm/mol-K
T = 500 C
2
2
a = 18 liter -atom/mol
b = 0.1154 liter/mol
n

f (V )
f ' (V )

(4)

an 2
P 2 V nb nRT
V
Vi
an 2 2 an 3b
P 2
V
V3

Values
40
0.08206
773.15
18
0.003183
1.4

Vi
2.2206
1.7437
1.5625
1.5679
1.5941
1.5883
1.5895
1.5893

Numerator
15.6777
6.1761
-0.1760
-0.8546
0.1905
-0.0408
0.0088
-0.0019

(5)

Denominato
r
32.8738
34.1012
32.6577
32.7080
32.9446
32.8932
32.9043
32.9019

Density = m/V = (1.4 mol)*(78 g/mol)/(1.5893 liter) = 68.71 g/liter

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Vi+1
1.7437
1.5625
1.5679
1.5941
1.5883
1.5895
1.5893
1.5893

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2.

H82CPE-E1

Using the thermodynamic formulae, calculate the change in Gibbs free energy when 20
moles or nitrogen is compressed from 10 bar to 90 bar at 80oC. Take R to be 8.3144
J/kmol-K. What does the positive value indicate?
Solution:
Starting from thermodynamics formulae for G:

G H TS
G U PV TS
(a)

dG dU d ( PV ) d (TS )
From first and second law:

dU dQ dW rev
dQ TdS
dW rev PdV
Thus,

dU TdS PdV

(b)

Substituting (b) to (a) gives:

dG TdS PdV PdV VdP TdS SdT

dG VdP SdT

G
G
dP
dT
P T
T P

G(P,T) can be expressed as: dG

G
V
P T

From the above form, we know that:

whence

G = V dP = nRT

dP
= nRT ln P2
P
P1

90
G = 20 x8.3144 x353.15 x ln = 128.98 J
10
Positive value indicates that the compression is not a spontaneous process, thus work is
needed.

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3.

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Using the information from the enthalpy-mass composition diagram, estimate how much heat
must be absorbed or released to keep the mixture at 0oC when three moles of water and one
mole of sulfuric acid are mixed isothermally at 0oC.
Solution:
Molar mass of H2O = 18 g/mol
Molar mass of H2SO4 = 98 g/mol

mass of H2O = 54 g
mass of H2SO4 = 98 g

%wt H2SO4 = (98g)/(54g + 98g) = 64.5 %

H mix H w1 H 1 w2 H 2
From Figure Q3:
H1 (T = 0oC) = 0 kJ/kg
H2 (T = 0oC) = 0 kJ/kg
Enthalphy of mixture, H = Hmix

= -320 kJ/kg
= (-320 kJ/kg)(0.152kg)
= -48.64 kJ
Thus, -48.64 kJ of heat must be released in order to keep the mixture at 0oC.

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4.

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Consider the following equilibrium at 25oC, where all the gases taking part behave
ideally:

PC15 g PCl 3 g Cl 2 g
The values of the standard enthalpy and standard free energy of formation are tabulated
below for each gas at 298 K.
at 298.15 K
G 0f kJ kmol-1

PCl5(g)
-305

PCl3(g)
-268

H 0f kJ kmol-1

-375

-287

Cl2(g)
0
0

Using the vant Hoff equation below and assuming that the standard enthalpy change at
298 K remains constant, calculate the equilibrium constant for the reaction at 573 K and
the equilibrium conversion achieved at a pressure of 1 atmosphere.

d G 0
d

(ln K P )
dT RT
dT

H 0

RT 2

Solution:

G o
RT
G o
37

=-0.0149
8.3144298
RT

ln K p
ln K 298

Using integrated form of vant Hoff gives:

K2
H 0 1 1
; where ln K1 = ln K298

K1
R T2 T1
ln K2 = ln K1 - Ho/R (1/T2 1/T1)
ln K573 = -0.0149 10.584 (1/573 1/298)
Therefore, K573 = 1.017 atm.
ln

Consider 1 kmol feed, giving at equilibrium x kmol PCl3, x kmol Cl2 and (1 - x) kmol PCl5.
Writing pi = xiP = (ni/ni)P gives:
x
x
1
1
2
1 + x 1 + x = 1 x = 1.017
KP =
1- x
1 - x2
1
1+ x
1.017
whence x =
= 71% conversion
2.017

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5.

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Acetone (component 1) and methanol (component 2) form an azeotrope boiling at 55.7oC

at 1 atm pressure, with a composition x1 = 0.80. Calculate the van Laar Coefficients for
the system. Using the Antoine and van Laar equations given below, calculate the
constants, A12 and A21 in the van Laar equation for the mixture.
Antoine equations, with P* in mmHg and T in oC, are:
Acetone: log10 P1* = 7.11714 - 1210.595/(T + 229.664)
Methanol :log10 P2* = 8.08097 - 1582.271/(T + 239.726)
The van Laar equations are:

ln 1 =

A12
2

A12 A21 x 2
A21 x 2 + A12 x12

A x
1 + 12 1
A21 x 2

2
2
A21 A12 x1
A21
ln 2 =
=
2
A21 x 2 + A12 x12

A
21 x 2
1 +

A12 x1

Solution:

P1* 749.6464 mmHg

P2* 530.9746 mmHg
P = 1 atm = 760 mmHg
At azeotrope point: x1 = y1 = 0.8 and x2 = y2 = 0.2

ln 1 = ln

y1 P
P
= ln *
*
P1
x1 P1

= 0.014

ln 2 = ln

y2 P
P
= ln *
*
x 2 P2
P2

= 0.36

ln 1
=
ln 2

A12 1.6129 A21

A12 0.77737
A21 0.48197

A21 x2
2
A12 x1

(3)

Substitute (3) into (1) ln 1 =

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2
2
A12 A21 x2 0.014 =
2
2
0.36
A21 A12 x1

A12

A x
1 + 12 1
A21 x2

(1)

(2)

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Thermodynamic formulae
a) Fundamental equation definitions

dU TdS PdV
H U PV
A U TS
G H TS
b) Derived Equations

dH TdS VdP
dA SdT PdV
dG SdT VdP
c) Chemical equilibrium ln K p
0
d) H 298

e)

0
G 298

0
f

) products ( ni H 0f ) reac tan ts

0
f

) products ( ni G 0f ) reac tan ts

(n H
( n G

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G o
RT

End

H82CPE-E1

Figure Q1
Enthalpy-concentration diagram for aqueous sulfuric acid at 1 bar

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