CHE 3161 (JUN 10)

CHE 3161: Chemistry & Chemical Thermodynamics

Final Exam - Solution
Date: 06/2010

Total Marks: 100

1) An ideal gas, CP = (7/2)R and CV = (5/2)R, undergoes a cycle consisting of the

following mechanically reversible steps:
(a) An adiabatic compression from state A at P1 , V1 , T1 to state B at P2 , V2 , T2 .
(b) An isobaric expansion from state B at P2 , V2 , T2 to state C at P3 = P2 , V3 , T3 .
(c) An adiabatic expansion from state C at P3 , V3 , T3 to state D at P4 , V4 , T4 .
(d) A constant-volume expansion process from state D at P4 , V4 , T4 to state A at P1 , V1 =
V4 , T1 .
(i) Sketch this cycle on a P V diagram
(ii) On the basis of one mole of ideal gas, what is the heat QBC absorbed in step (b), and
the heat QDA rejected in step (d)?
(iii) If the thermal efficiency is defined as the ratio of the net work output to the heat
absorbed, show that thermal efficiency is
=1+

QDA
QBC

(iv) By defining the compression ratio rc V1 /V2 , and the expansion ratio re V4 /V3 ,
show that,


1 (1/re ) (1/rc )
=1

1/re 1/rc
where, = CP /CV .
(v) Determine its thermal efficiency if T1 = 200 C, T2 = 1000 C, T3 = 1700 C, and T4 =
601 C.
(20 marks)

CHE 3161 (JUN 10)

Figure 1: P V diagram of the cycle undergone by the ideal gas.

Solution:
(i) On a P V diagram, the cycle would appear as shown in the figure above.
(ii) In step (b), the gas undergoes an isobaric expansion. The heat absorbed at constant
pressure is equal to the enthalpy change. As a result, since the ideal gas has constant
heat capacities,
QBC = CP (T3 T2 )
(1)
In step (d), the gas undergoes an isochoric expansion. The heat rejected at constant
volume is equal to the change in internal energy. As a result,
QDA = CV (T1 T4 )

(2)

(iii) Since the gas undergoes a cycle, the internal energy change U = Q + W = 0, where
Q in the net heat absorbed, and W is the net work input. As a result, the net work
output is,
W = QBC + QDA
and the thermal efficiency is,
=

QDA
QBC + QDA
=1+
QBC
QBC

(iv) From eqns (1) and (2),

CV (T1 T4 )
1
=1+
=1+
CP (T3 T2 )

T1 T4
T3 T2


(3)

For the reversible adiabatic expansion, and reversible adiabatic compression of an ideal
gas, we know that, T V 1 = constant. As a result,
T3 V31 = T4 V41

and T2 V21 = T1 V11

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CHE 3161 (JUN 10)

Since the compression ratio rc V1 /V2 , and the expansion ratio re V4 /V3 ,

T4 = T3

1
re

1

 1
1
and T1 = T2
rc

Substituting these expressions into eqn (3) leads to,

 1
 1
1
1
T3
T2

1
re
rc

=1

T3 T2

(4)

We know that,
P2 =

RT2
V2

and P3 =

RT3
V3

Since P2 = P3 ,

T2
V2
=
T3
V3
Diving the numerator and denominator of the right hand side by V1 and V4 , respectively
(since V1 = V4 ), we have,
T2
V2 /V1
re
=
=
(5)
T3
V3 /V4
rc
Combining eqns (4) and (5) leads to,


1 re
=1

1

 1
re 1

rc rc

re

1
rc

Which can be rewritten as,

  
1
1

1 re
rc

=1

1
1

re rc


(v) Substituting the various temperatures into eqn (3), we have,

= 0.591

CHE 3161 (JUN 10)

2) Propylene gas at 127 C and 38 bar (state 1) is throttled in a steady-state flow process
to 1 bar and 90.1 C (state 2), where it may be assumed to be an ideal gas. Estimate the
enthalpy change (H) and entropy change (S) of the propylene for this change of state.
The ideal heat capacity for propylene gas is known to depend on temperature through the
relation, CP /R = A + B T + C T 2 , where T is in degrees Kelvin. The relevant data for
propylene are given in the Tables below:
A
B
1.637 22.706 103
Tc (K)
Pc (bar)
365.6
46.65

C
6.915 106

0.140

Table 1: Values of the coefficients A, B and C, and the critical parameters for propylene.

0
H R /RTc
0.6000

Pr =
Tr

HHH
1.05
1.10
1.15

0.654
0.581
0.523

0.8000

1.000

0.955 1.359
0.827 1.120
0.732 0.968

Pr =
Tr

HHH
1.05
1.10
1.15

1
H R /RTc
0.6000

0.498
0.381
0.296

0.8000

1.000

0.691 0.877
0.507 0.617
0.385 0.459

Table 2: Lee/Kesler generalized-correlation values for residual enthalpy

Pr =
Tr

HHH
1.05
1.10
1.15

0
S R /R
0.6000

0.439
0.371
0.319

0.8000

1.000

0.656 0.965
0.537 0.742
0.452 0.607

Pr =
Tr

HHH
1.05
1.10
1.15

1
S R /R
0.6000

0.8000

0.460
0.350
0.275

0.642 0.820
0.470 0.577
0.361 0.437

1.000

Table 3: Lee/Kesler generalized-correlation values for residual entropy

(20 marks)

CHE 3161 (JUN 10)

Solution: The process undergone by propane can be visualised in the following figure:

Figure 2: The entropy change from the initial to the final state can be calculated by a two-step
process. The first is a change from state 1 at 38 bar and 127 C to an ideal gas at 38 bar and 127 C.
The second is a change from an ideal gas at 38 bar and 127 C to state 2, which is an ideal gas at
90.1 C and 1 bar.

For the initial conditions,

T1
400.15
= 1.095
=
Tc
365.6
P1
38
= 0.815
=
=
Pc
46.65

T1r =
P1r

From the Lee/Kesler generalized-correlation tables

Tr and Pr , using interpolation,

0
H1R
= 0.863, and
R Tc

0
S1R
= 0.565, and
R
As a result, since,
H1R = H1R

0

+ H1R

1

given in the problem, at these values of

1
H1R
= 0.534
R Tc

1
S1R
= 0.496
R

and S1R = S2R

0

+ S1R

1

we have,
H1R = 0.863 8.314 365.6 + 0.140 (0.534 8.314 365.6)
= 2.623 103 + 0.140 (1.623 103 ) = 2.85 103 J/mol
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CHE 3161 (JUN 10)

S1R = 0.5658.314+0.140(0.4968.314) = 4.697+0.140(4.124) = 5.275 J/(mol K)
For an ideal gas (with the coefficient D = 0),


B 2
C
ig
2
3
3
H = R A (T2 T1 ) + (T2 T1 ) +
(T2 T1 )
2
3
It follows that,

22.706 103 
H = 8.314 1.637 (363.25 400.15) +
(363.25)2 (400.15)2
2


6.915 106 
3
3
= 2.85 103 J/(mol K)

(363.25) (400.15)
3


ig

Therefore,
H = H1R + H ig = 0 J/mol
as is expected from a throttling process at steady-state.
In a similar manner,
S ig
= A ln
R

T2
T1

C
+ B (T2 T1 ) +
(T22 T12 ) ln
2

P2
P1

As a result, S ig = 22.774 J/(mol K), and,

S = S1R + S ig = 28.048 J/(mol K)

CHE 3161 (JUN 10)

3)
(a) The following is a rule of thumb: For a binary system in VLE at low pressure, the equilibrium vapour-phase mole fraction y1 corresponding to an equimolar liquid mixture is
approximately,
P sat
y1 = sat 1 sat
P1 + P2
where P1sat is a pure-species vapour pressure. Clearly, this equation is valid if Raoults
law applies. Show that it is also valid for VLE described by the modified Raoults law,
with,
ln 1 = A x22 ; ln 2 = A x21
(b) Assuming Raoults law is an adequate description of the VLE of toluene/ethylbenzene
mixtures,
(i) Compute the bubble point pressure and vapor composition for a liquid mixture
with composition xtoluene = 0.6, xethylbenzene = 0.4 at 450 K.
(ii) Compute the dew point pressure and liquid composition for a vapor mixture with
composition ytoluene = 0.6, yethylbenzene = 0.4 at 450 K.
(iii) Compute the vapor and liquid composition and phase fractions (fraction of the
system that is in each phase) for an overall composition of ztoluene = 0.6, zethylbenzene =
0.4 at 450 K and 3.75 bar.
The vapor pressure of toluene at 450 K is 4.844 bar, and the vapor pressure of ethylbenzene at 450 K is 2.685 bar.
(20 marks)

CHE 3161 (JUN 10)

Solution:
(i) From modified Raoults law,
yi P = xi i Pisat

(i = 1, 2, . . . , N )

and the given equations for ln 1 and ln 2 ,

y1 P = x1 exp(A x22 ) P1sat

and y2 P = x2 exp(A x21 ) P2sat

These equations sum to give:

P = x1 exp(A x22 ) P1sat + x2 exp(A x21 ) P2sat
Dividing the equation for y1 P by the preceding equation yields:
y1 =

x1 exp(A x22 ) P1sat

x1 exp(A x22 ) P1sat + x2 exp(A x21 ) P2sat

For x1 = x2 this equation obviously reduces to:

y1 =

P1sat
P1sat + P2sat

(b) (i) We will call toluene species 1 and ethylbenzene species 2. Raoults law for species 1
and 2 is y1 P = x1 P1sat and y2 P = x2 P2sat , from which P = x1 P1sat +x2 P2sat = 0.6
4.844 + 0.4 2.685 = 3.98 bar. Thus, y1 = x1 P1sat /P = 0.6 4.844/3.98 = 0.730
and y2 = 1 y1 = 0.270.
(ii) From the Raoults law for each species, we have y1 P/P1sat +y2 P/P2sat = P (y1 /P1sat +
y2 /P2sat ) = x1 +x2 = 1 so P = 1/(y1 /P1sat +y2 /P2sat ) = 1/(0.6/4.844+0.4/2.685) =
3.665 bar. Thus, x1 = y1 P/P1sat = 0.6 3.665/4.844 = 0.454, and x2 = 1 x1 =
0.546.
(iii) In this case, we know that there will be 2 phases present, since the total pressure
is between the bubble point and dew point for this overall composition, calculated
in parts (i) and (ii). So, we will start from the flash calculation equation:
yi =

zi Ki
1 + V (Ki 1)

and

N
X
i=1

yi = 1 =

N
X
i=1

zi Ki
1 + V (Ki 1)

For a system that obeys Raoults law, Ki = yi /xi = P1sat /P . So, K1 = 4.844/3.75 =
1.292 and K2 = 2.685/3.75 = 0.716. So, we have
N
X
i=1

yi = 1 =

0.6 1.292 0.4 0.716

0.7752
0.2864
+
=
+
1 + 0.292V
1 0.284V
1 + 0.292V
1 0.284V
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CHE 3161 (JUN 10)

Rearranging this equation leads to,
0.08293 V 2 0.1446 V + 0.0616 = 0
Applying the quadratic formula to this last equation gives the fraction of the
system in the vapor phase as V = 0.740 (or V = 1, which is the trivial solution
that isnt physically meaningful). The fraction of the system in the liquid phase
is then L = 1 V = 0.260. The vapor phase mole fractions are then:
y1 =

z1 K1
0.6 1.292
=
= 0.637
1 + V (K1 1)
1 + 0.740 0.292

Thus, y2 = 1 y1 = 0.363, x1 = y1 /K1 = 0.493, and x2 = 1 x1 = 0.507.

CHE 3161 (JUN 10)

4) A single P x1 data point is available for a binary system at 35 C:
x1 = 0.389,

P = 108.6 kPa

For this system, at 35 C,

P1sat = 120.2 kPa and P2sat = 73.9 kPa
(a) Verify if Raoults law is satisfied
(b) Assume that the excess Gibbs energy obeys the following model:
GE
= A x1 x2
RT
Use the known data and the modified Raoults law to evaluate the constant A.
(c) Find the corresponding value of y1 at 108.6 kPa and 35 C.
(d) Find the total pressure at 35 C for an equimolar liquid mixture.
(c) Is an azeotrope likely at 35 C?
(20 marks)

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CHE 3161 (JUN 10)

Solution:
(a) According to Raoults law,
P = x1 P1sat + (1 x1 )P2sat
From the given data,
P = 0.389 120.2 + (1 0.389) 73.9 = 91.911 kPa
Since this is not equal to the specified pressure, Raoults law is not satisfied.
(b) For the given model for the excess Gibbs energy, we know that the activity coefficients
are given by the expressions,




1 = exp Ax22
and 2 = exp Ax21
From modified Raoults law, P = x1 1 P1sat + (1 x1 ) 2 P2sat , we have,




P = x1 exp Ax22 P1sat + (1 x1 ) exp Ax21 P2sat
Therefore,




108.6 = 0.389 exp A (0.611)2 120.2 + 0.611 exp A (0.389)2 73.9
The only unknown in this equation is A, which can be solved to give,
A = 0.622
(c) We know that from modified Raoults law,

P1sat

 120.2
P sat
y1 = x1 1 1 = x1 exp Ax22
= 0.389 exp 0.622 (0.611)2
= 0.543
P
P
108.6
(d) Since x1 = x2 and 1 = 2 , we know from modified Raoults law that,


P = x1 1 P1sat + x2 2 P2sat = 0.5 exp 0.622 (0.5)2 (120.2 + 73.9) = 113.38 kPa
(e) We need to find the relative volatility, 12 =

y1 /x1
. From the expressions for the
y2 /x2

modified Raoults law, it follows that,

120.2 exp [0.622 x2 2 ]
1 P1 sat
=
73.9 exp [0.622 x1 2 ]
2 P2 sat
This can be simplified further to,
12 =

12 = 1.6265 exp [0.622(1 2x1 )]

Evaluating this expression at x1 = 0 and x1 = 1 leads to the following values for 12 :
x1
12
0.0 3.027
1.0 0.8724
At an azeotrope, since x1 = y1 , and x2 = y2 , the relative volatility 12 = 1. Since from
the table of values it is clear that 12 passes through 1.0 for some x1 in the interval
0 < x1 < 1, an azeotrope can exist.
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CHE 3161 (JUN 10)

5) Consider the hydrogenation of toluene to give methylcyclohexane:
C7 H8 (g) + 3 H2 (g)
C7 H14 (g)
Starting from a stoichiometric mixture of reactants (3 moles of H2 per mole of toluene):
(a) Compute the equilibrium constant at 350 C and 1 bar total pressure. You can assume
that the enthalpy change of reaction is independent of temperature and is equal to its
value at 298.15 K.
(b) Compute the equilibrium composition at 350 C and 1 bar total pressure.
The mixture of the reactants and product can be treated as an ideal gas mixture. Enthalpies
and Gibbs energies of formation for toluene and methylcyclohexane are given in the Table
below.
Gf298
f
H298

C7 H8
C7 H14
(J/mol) 122050
27480
(J/mol) 50170 154770

(20 marks)

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CHE 3161 (JUN 10)

Solution:
(a) First, we need to compute the enthalpy and Gibbs energy change for the reaction at
298 K. For hydrogen, the enthalpy and Gibbs energy of formation are zero because it is
an element in its standard state. We are given that, for methylcyclohexane, Gf298 =
f
27480 J/mol and H298
= 154770 J/mol, and for toluene, Gf298 = 122050 J/mol
f
and H298 = 50170 J/mol. Subtracting the toluene values from the methylcyclohexane

values, we have G298 = 94570 J/mol and H298

= 204940 J/mol. Neglecting the
temperature dependence of the enthalpy of reaction, we can compute the equilibrium
constant for the reaction as K = K0 K1 , where K0 = exp(G298 /(R 298.15)) is the

/(R 298.15) (1 298.15/T )

equilibrium constant at 298 K and K1 = exp(H298
gives the change in the equilibrium constant when the temperature changes from 298
K to T . For this case, we have
K0 = exp(94570/(8.314 298.15)) = 3.71 1016
and
K1 = exp(204940/(8.314 298.15) (1 298.15/623.15)) = 1.88 1019
From which K = 0.00696.
(b) For a mixture of ideal gases, the composition at equilibrium is related to the equilibrium
constant by
 
Y
P
i
(yi ) =
K

P
i
which for this problem becomes
yC8 H14
=K
yC8 H8 yH3 2

P
1 bar

3

If we initially have 1 mole of toluene and 3 moles of H2 , then the number of moles are
related to the reaction coordinate by
nC8 H8 = 1 e
nH2 = 3 3e = 3(1 e )
nC8 H14 = e
n = 4 3e
So, the mole fractions are given by
yC8 H8 =
y H2 =

1 e
4 3e

3(1 e )
4 3e
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CHE 3161 (JUN 10)

yC8 H14 =

e
4 3e

Substituting these into the equilibrium relationship gives:

e (4 3e )3
e (4 3e )3
=
=K
(1 e )(3(1 e ))3
27(1 e )4

P
1 bar

3

Using the value of K from part (a) and a pressure of 1 bar, this is
e (4 3e )3
= 0.00696
27(1 e )4
To solve this iteratively, we can rearrange it as
e =

0.1880(1 e )4
(4 3e )3

Starting from e = 0 and iterating on this gives e = 0.00292. Substituting this back
into the expressions for the mole fractions gives yC8 H8 = 0.2498, yH2 = 0.7495, and
yC8 H14 = 0.00073.

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