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 2

Isochoric

Isothermal 3

V
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(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:

P4
W14 = RT1 ln
P1

If the two works have to be the same:

P
RT1 ln 4 = R (T1 − T2 ) (1)
P1
P4 (T1 − T2 )
ln =
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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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 ω = 0.152. [20 marks]

Solution:

For the given conditions:

80 + 273.15 15
Tr = = 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

!! (Tr ) 0.4278! (Tr )

q= = = 5.3403
"Tr 0.08664Tr

We can now solve iteratively for Z using the equation:

(Z ! ! ) (Z ! 0.0320)
Z = 1+ ! ! q! = 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:

1 Z + #$
I= ln = 0.0372
! ! " Z + !$

The derivative is:

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 CHE 3161 (JUN 11)
0.5
d ln ! (Tr ) " T %
= !(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:

HR " d ln ! (Tr ) %
= 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 Raoult’s 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 Raoult’s 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 Raoult’s law,

yi P = xi ! i Pi sat

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At the azeotrope, yi= xi, then,

P
!i =
Pi sat

Therefore,

!1 P2sat
=
! 2 P1sat

Given the conditions,

ln !1 = A x22 ; ln ! 2 = A x12

Then,
!1
ln = A(x22 ! x12 )
!2

Therefore,
!1 P sat
lnln 2sat
! P
A= 2 22 = 2 1 2
x2 ! x1 x2 ! x1

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:

x1 !1P1sat
y1 = = 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) Determine an expression as a function of x1 for [8 marks]

(i) the partial molar volume of species 1, V1 .

(ii) the partial molar volume of species 2, V2 .

(b) Using the expressions obtained in (4a), calculate the values for [12 marks]

(i) the pure-species volumes V1 and V2 .

(ii) the partial molar volumes at infinite dilution V1! and V2! .

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

dV
(i) Using Eq. (11.15), V1 = V + x2
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

dV
(ii) Using Eq. (11.16), V2 = V ! x1
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. [6 marks]

(b) Assume an ideal solution. [14 marks]

For n-C4H10: ω1 = 0.200; Tc,1= 425.1 K; Pc,1= 37.96 bar

For iso-C4H10: ω2 = 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.

1− ε
y1 = = 1− ε
1 + 0(ε )
ε
y2 = =ε
1 + 0(ε )

(a) For an ideal-gas mixture:

−v
⎛ P ⎞
vi
∏i ( yi ) = ⎜⎜ P ⎟⎟ K
⎝ o ⎠
v1 v2
y1 × y2 = K
(1 − ε ) −1 × ε = K
ε
K= = 1.974
1− ε

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 CHE 3161 (JUN 11)

Thus, ε = 0.664
y1= 1 - ε = 0.336
y2= ε = 0.664

(b) For an ideal solution:

−v
⎛ P ⎞
vi
∏i ( yiφi ) = ⎜⎝ P o ⎟⎠ K

For species 1 ≡n-C4H10: ω1 = 0.200; Tc,1= 425.1 K; Pc,1= 37.96 bar

Pr ,1 × Pc ,1 = P Tr ,1 × Tc ,1 = T
15 425
Pr ,1 = = 0.395 Tr ,1 = =1
37.96 425.1

Using Equation (3.65) to determine Bo

0.422
B1o = 0.083 − = −0.339
11.6

Using Equation (3.66) to determine B1

0.172
B11 = 0.139 − = −0.033
14.2

Using Equation (11.68) to determine φ1.

⎡ 0.395
φ1 = exp⎢ {− 0.339 + 0.2(−0.033)}⎤⎥ = 0.872
⎣ 1 ⎦

For species 2 ≡iso-C4H10: ω2 = 0.181; Tc,2 = 408.1 K; Pc,2= 36.48 bar

Pr , 2 × Pc , 2 = P Tr , 2 × Tc , 2 = T
15 425
Pr , 2 = = 0.411 Tr , 2 = = 1.041
36.48 408.1

Using Equation (3.65) to determine Bo

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 CHE 3161 (JUN 11)

0.422
B2o = 0.083 − = −0.313
1.0411.6

Using Equation (3.66) to determine B1

0.172
B21 = 0.139 − 4.2
= −6.29 × 10 −3
1.041

Using Equation (11.68) to determine φ2.

⎡ 0.411 ⎤
φ2 = exp⎢ { }
− 0.313 + 0.181(−6.29 × 10 −3 ) ⎥ = 0.883
⎣ 1.041 ⎦

−v
vi ⎛ P ⎞
∏i ( yiφi ) = ⎜⎝ P o ⎟⎠ K
( y1φ1 ) v1 × ( y2φ2 ) v2 = 1.974
[(1 − ε )(0.872)]−1[ε (0.883)]1 = 1.974

Thus, ε = 0.661
y1= 1 - ε = 0.339
y2= ε = 0.661

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