CHE 3161 (JUN 11)
Solution for CHE3161_S1_2011
Question 1.
(20 Marks)
One mole of ideal gas with Cp = (5/2)R and Cv = (3/2)R undergoes the following two sequential
steps: (i) Heating from 200 K to 600 K at constant pressure of 3 bar, followed by (ii) Cooling at
constant volume. To achieve the same amount of Work produced by this two-step process, a single
isothermal expansion of the same gas from 200 K and 3 bar to some final pressure, P can be
performed.
(1) Draw all the processes on a P-V diagram.
[4 marks]
(2) What is the final pressure, P of the isothermal expansion process assuming mechanical
reversibility for both the processes?
[14 marks]
(3) Comment on the value of P of the isothermal expansion process assuming mechanical
reversibility for the two-steps process while mechanical irreversibility for the isothermal
expansion process.
[2 marks]
Solution:
(1)
P
1
Isobaric
Isochoric
Isothermal
V
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CHE 3161 (JUN 11)
(2) For the two-steps process:
!
!!" =
! !"
!
= !!
= !! (!! !! )
= !! !! + !! !!
Since P1 = P2, hence
W12 = P2V2 + P1V1
Applying Ideal Gas Law:
W12 = RT2 + RT1
= R(T1 T2 )
W23 = 32 PdV
=0
Therefore,
Total W13 = W12 + W23
= R(T1 T2 )
For the isothermal expansion process:
W14 = RT1 ln
P4
P1
If the two works have to be the same:
P
RT1 ln 4 = R (T1 T2 )
P1
ln
(1)
P4 (T1 T2 )
=
P1
T1
(T T2 )
P4 = P1 exp 1
T1
(200 600)
= 3 exp
200
= 0.406bar
(3) P increases since the left hand term of Eqn (1) will be multiplied by a factor of less that 1 (1
=100% efficiency).
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CHE 3161 (JUN 11)
Question 2.
(20 Marks)
Calculate the compressibility (Z), residual enthalpy (HR), residual entropy (SR), and residual Gibbs
energy (GR) of propane at 80oC and 15 bar using the Soave/Redlich/Kwong equation of state. The
critical properties of propane are Tc = 369.8 K, Pc = 42.48 bar, and = 0.152.
[20 marks]
Solution:
For the given conditions:
Tr =
80 + 273.15
15
= 0.9550 Pr =
= 0.3531
369.8
42.48
The dimensionless EOS parameters for the R/K EOS are:
! =!
Pr
P
= 0.08664 r = 0.0320
Tr
Tr
2
! (Tr ;" ) = "#1+ (0.480 +1.574" ! 0.176" 2 ) (1! Tr1/2 )$% = 1.0328
q=
!! (Tr ) 0.4278! (Tr )
=
= 5.3403
"Tr
0.08664Tr
We can now solve iteratively for Z using the equation:
Z = 1+ ! ! q!
(Z ! ! )
(Z ! 0.0320)
= 1+ 0.0320 ! 0.1709
Z(Z + ! )
Z(Z + 0.0320)
Starting with an initial guess of Z = 1, and iterating gives,
Z = 0.8442
Then the integral I is:
I=
1
Z + #$
ln
= 0.0372
! ! " Z + !$
The derivative is:
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CHE 3161 (JUN 11)
0.5
" T %
d ln ! (Tr )
= !(0.480 +1.574" ! 0.176" 2 ) $ r ' = !0.6877
d lnTr
# ! (Tr ) &
Next, we can use these values to calculate the residual enthalpy and entropy from:
" d ln ! (Tr ) %
HR
= Z !1+ $
!1' qI = !0.4915
RT
# d lnTr
&
SR
d ln " (Tr )
= ln(Z ! ! ) +
qI = !0.3448
R
d lnTr
Therefore,
H R = !1443.031 J.mol-1;
S R = !2.867 J.mol-1.K-1
Knowing these,
G R = H R ! TS R = !430.572 J.mol-1
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CHE 3161 (JUN 11)
Question 3.
(20 Marks)
(1) Prove: An equilibrium liquid/vapour system described by Raoults law cannot exhibit an
azeotrope.
(2) A liquid mixture of cyclohexanone(1)/phenol(2) for which x1 = 0.6 is in equilibrium with its
vapour at 144oC. Determine the equilibrium pressure P and vapour composition y1 from the
following information:
ln !1 = A x22 ; ln ! 2 = A x12
At 144oC, P1Sat = 75.20 and P2Sat = 31.66 KPa
The system forms an azeotrope at 144oC for which x1az = y1az = 0.294
Solution:
(1) For a binary system obeying Raoults law,
y1P = x1 P1sat
(1)
y2 P = x2 P2sat
(2)
equations (1) + (2) give,
y1P + y2 P = x1 P1sat + x2 P2sat
As y1 + y2 =1 and x1 + x2 = 1, therefore
P = P2sat + x1 (P1sat ! P2sat )
(3)
Equation 3 predicts that P is linear in x1. Thus no maximum or minimum can exist in this
relation. Since such an extremum is required for the existence of an azeotrope, no azeotrope
is possible.
(2) Based on the known information, we can first determine the value for A, and then calculate
equilibrium pressure and vapour composition.
From modified Raoults law,
yi P = xi ! i Pi sat
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CHE 3161 (JUN 11)
At the azeotrope, yi= xi, then,
!i =
P
Pi sat
Therefore,
!1 P2sat
=
! 2 P1sat
Given the conditions,
ln !1 = A x22 ; ln ! 2 = A x12
Then,
ln
!1
= A(x22 ! x12 )
!2
Therefore,
!1
P sat
ln 2sat
!
P
A= 2 22 = 2 1 2
x2 ! x1 x2 ! x1
ln
Putting in the known numbers for satuation pressures and compositions at the azeotrope:
A = -2.0998
Next, at x1 = 0.6, x2 = 1-x1 = 0.4,
!1 = exp(A x22 ) = 0.7146
! 2 = exp(A x12 ) = 0.4696
P = x1 !1P1sat + x2! 2 P2sat = 38.1898 kPa
The vapour composition y1 is:
y1 =
x1 !1P1sat
= 0.8443
P
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CHE 3161 (JUN 11)
Question 4.
(20 Marks)
The molar volume (cm3 mol-1) of a binary liquid system of species 1 and 2 at fixed T and P is given
by the equation V = 120x1 + 70x2 + (15x1 + 8x2) x1x2.
(a)
(b)
Determine an expression as a function of x1 for
(i)
the partial molar volume of species 1, V1 .
(ii)
the partial molar volume of species 2, V2 .
Using the expressions obtained in (4a), calculate the values for
(i)
the pure-species volumes V1 and V2 .
(ii)
the partial molar volumes at infinite dilution V1! and V2! .
[8 marks]
[12 marks]
Solutions:
(a)
V = 120x1 + 70x2 + (15x1 + 8x2) x1x2
But x1 + x2 = 1
x2 = 1 x1
V = 120 x1 + 70(1 x1) + [15x1 + 8(1 x1)] x1(1 x1)
Reagreement and simplification of equation will lead to:
V = -7x13 x12 + 58x1 + 70
dV
= 21x12 2 x1 + 58
dx1
(i)
Using Eq. (11.15),
V1 = V + x2
dV
dx1
V1 = !7x13 ! x12 + 58x1 + 70 + (1! x1 )(!21x12 ! 2x1 + 58)
Reagreement and simplification of equation will lead to:
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CHE 3161 (JUN 11)
V1 = 14x13 ! 20x12 ! 2x1 +128
(ii)
Using Eq. (11.16),
V2 = V ! x1
dV
dx1
V2 = !7x13 ! x12 + 58x1 + 70 ! x1 (!21x12 ! 2x1 + 58)
Reagreement and simplification of equation will lead to:
V2 = 14x13 + x12 + 70
(b)
(i)
For pure species volume, V1
x1 = 1
Thus, V1 = 14(1)3 20(1)2 2(1) + 128
V1 = 120 cm3 mol-1
For pure species volume, V2
x2 = 1 or x1 = 0
Thus, V2 = 14(0) + 02 + 70
V2 = 70 cm3 mol-1
(i)
For partial volume at infinite dilution, V1!
x1 = 0
Thus, V1! = 14(0)3 20(0)2 2(0) + 128
V1! = 128 cm3 mol-1
For partial volume at infinite dilution, V2!
x2 = 0 or x1 = 1
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CHE 3161 (JUN 11)
Thus, V2! = 14(1) + 12 + 70
V2! = 85 cm3 mol-1
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CHE 3161 (JUN 11)
Question 5.
(20 Marks)
Equilibrium at 425 K and 15 bar is established for the gas-phase isomerisation reaction:
n-C4H10(g) iso-C4H10(g)
If there is initially 1 mol of reactant and K = 1.974, calculate the compostions of the equilibrium
mixture (yn-C4H10 and yiso-C4H10) by two procedures:
(a)
Assume an ideal-gas mixture.
(b)
Assume an ideal solution.
[6 marks]
[14 marks]
For n-C4H10: 1 = 0.200; Tc,1= 425.1 K; Pc,1= 37.96 bar
For iso-C4H10: 2 = 0.181; Tc,2 = 408.1 K; Pc,2= 36.48 bar
Solutions:
Given T = 425 K, P = 15 bar, K = 1.974, no = 1,
v = vi = 1 1 = 0
Assume species 1 n-C4H10, species 2 iso-C4H10.
y1 =
y2 =
(a)
1
= 1
1 + 0( )
1 + 0( )
For an ideal-gas mixture:
v
P
i ( yi ) = P K
o
v1
v2
y1 y2 = K
vi
(1 ) 1 = K
K=
= 1.974
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CHE 3161 (JUN 11)
Thus, = 0.664
y1= 1 - = 0.336
y2= = 0.664
(b)
For an ideal solution:
v
P
i ( yii ) = P o K
vi
For species 1 n-C4H10: 1 = 0.200; Tc,1= 425.1 K; Pc,1= 37.96 bar
Pr ,1 Pc ,1 = P
Pr ,1 =
Tr ,1 Tc ,1 = T
15
= 0.395
37.96
Tr ,1 =
425
=1
425.1
Using Equation (3.65) to determine Bo
0.422
= 0.339
11.6
B1o = 0.083
Using Equation (3.66) to determine B1
B11 = 0.139
0.172
= 0.033
14.2
Using Equation (11.68) to determine 1.
0.395
{ 0.339 + 0.2(0.033)} = 0.872
1
1 = exp
For species 2 iso-C4H10: 2 = 0.181; Tc,2 = 408.1 K; Pc,2= 36.48 bar
Pr , 2 Pc , 2 = P
Pr , 2 =
15
= 0.411
36.48
Tr , 2 Tc , 2 = T
Tr , 2 =
425
= 1.041
408.1
Using Equation (3.65) to determine Bo
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CHE 3161 (JUN 11)
B2o = 0.083
0.422
= 0.313
1.0411.6
Using Equation (3.66) to determine B1
B21 = 0.139
0.172
= 6.29 10 3
4.2
1.041
Using Equation (11.68) to determine 2.
0.411
0.313 + 0.181(6.29 10 3 ) = 0.883
1.041
2 = exp
P
i ( yii ) = P o K
( y11 ) v1 ( y22 ) v2 = 1.974
vi
[(1 )(0.872)]1[ (0.883)]1 = 1.974
Thus, = 0.661
y1= 1 - = 0.339
y2= = 0.661
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