13.

16 For the cracking reaction,

C3H8(g)→ C2H4(g) + CH4(g)

The equilibrium conversion is negligible at 300 K, but becomes appreciable at
temperaturesabove 500 K. For a pressure of 1 bar, determine :
a. The fractional conversion of propane at 625 K.

b. The temperature at which the fractional conversion is 85%.

Solution :

C3H8(g)→ C2H4(g) + CH4(g) v = 1

Basis: 1 mole C3H8feed. By Eq. (13.4) nC3 H 8  1  

n0  nC3 H8 1  (1   )
Fractional conversion of C3H8=  
n0 1

1   
By Eq. (13.5) yC3H8  yC2 H 4  yCH 4 
1  1  1 

From data in Table C.4.

J J
H 298  82670 G298  42290
mol mol

−1 1.213 28.785 −8.824

V := ( 1 ) 𝐴 ∶= (1.424) B := (14.394) .10-3 C := (−4.392) .10-6
1 1.702 9.081 −2.164
end := rows(A) i := 1.. end

A   vi. Ai B   vi.Bi C   vi.Ci

i i i

A  1.913 B  5.31x10 3 C  2.268 x10 6

a. T := 625 kelvin T0 := 298.15 kelvin

C po B 2 2 C 3 3 D    1 
   
T

 dT  AT0   1  T0   1  T0   1   
T0
R 2 3 T0   
(Van Ness, Eq. 4.19)

T
C po dT   D    1 
T R T           
2 2     1
2
A ln BT  CT

0 0
0
  T0  2   

(Van Ness, Eq. 5.15)

 T
Where,  
T0
625
C po  625   5.31  10
3   625  2  2.268  106   625 3 
 dT  1,913  298.15    1  298.152     1  298.153    1
R  298.15  2   298.15   3   298.15  
298,15    
625
C p
o


298,15 R
dT   11.2997

   625  
    1 
C p0 dT
 5.31  10 3  298.15  2.268  10 6  298.152   298.15   625  1
625
625

298,15 R T
 1 .913  ln 
298.15   2  298.15 
  
  
625
C p0 dT
 R T  0.0022506
298,15

G 0 G00  H 00 H 00 1 C p C p dT
T T 0 0

    dT  
RT RT0 RT T T0 R T0
R T
(Van Ness, Eq. 13.18)
G 0 42290  82670 82670 1
   (11.2997)  0.0022506
RT (8.314)(625) (8.314)(625) 625

G 0
 2187.9
RT

(Van Ness, Eq.13.11a)

  G 0 
K  exp    1.52356
 RT 
(Van Ness, Eq.13.28)  := 0.5 (guess)
2
Given K  := Find (  )
(1   ).(1   )
 = 0.777

2
b.  = 0.777 K K  2.604
(1   ).(1   )
 G 0 J
 ln K G 0  4972.3
RT mol

The problem is now to find the T which generates this value.

Its not dificult to find T by trial. This lead to the value T = 646.8 K
13.21 For the methanol synthesis reaction,

CO(g) + 2H2(g) → CH3OH(g)

The equilibrium conversion to methanol is large at 300 K, but decreases rapidly with
increasing T . However,reaction rates become appreciable only at higher
temperatures. For a feed mixture of carbon monoxide and hydrogen in the
stoichiometric proportions.
a. What is the equilibrium mole fraction of methanol at 1 bar and 300 K

b. At what temperature does the equilibrium mole fraction of methanol equal

0.50 for a pressure of 1 bar?

c. At what temperature does the equilibrium mole fraction of methanol equal

0.50 for a pressure of 100 bar. Assuming the equilibrium mixture is an ideal
gas ?

d. At what temperature does the equilibrium mole fraction of methanol equal

0.50 for a pressure of 100 bar, assuming the equilibrium mixture is an ideal
solution of gases?

Solution :
CO(g) + 2H2(g) = CH3OH(g)
The sthochiometric numbers are
 CH 3OH  1
 2 H 2  2
 CO  1
 gas  1  (2)  1  2
Basis : 1 mol CO , 2 mol H2 feed n0 = 3
( From the data of Table C. 4 ,)

𝐉 𝐉
∆H298 = - 90135 𝑴𝒐𝒍 ∆G298 = - 24791 𝑴𝒐𝒍

This is the reaction of Ex. 4.6, Pg. 139, from which :

∆A = -7.663 ∆B = 10.815x10-3 ∆C = -3.45x10-6 ∆D = -0.135x10-5

(a) T = 300 Kelvin T0 = 298.15

C po B 2 2 C 3 3 D    1 
   
T

 dT  AT0   1  T0   1  T0   1   
T0
R 2 3 T0   
(Van Ness, Eq. 4.19)
 T
C po dT   D    1 
T R T  A ln   BT0   CT0   2T02  2   1
2

0  

(Van Ness, Eq. 5.15)

T
Where,  
T0
 300 
    5   1
C po
2 3
 300  10.815  10 3     6
   
923,15

298,152  
300
  1 
3.45 10
298,153  
300
  1 
0.135 10  298,15 
 R
dT  -7.663  298,15    1 
 298,15  2   298,15   3   298,15   298,15  300 
298,15      
 298,15 
923,15
C po

298,15 R
dT  - 9.043

    300  
      1 
923,15
C dT 0
300    0,135  10 5
  298,15   300 

3 6
 7.663  ln  10.815  10  298,15    3.45  10  298,15   298,15  1
p 2
2 
 300   
R T 298,15  2
   298,152 
298,15

    
  298,15   

923,15
C p0 dT
 R T  -0.03024
G 0 G00  H 00 H 00 1 C p C p dT
298,15 T T 0 0

    dT  
RT RT0 RT T T0 R T0
R T
(Van Ness, Eq. 13.18)
G 0 - 24791  (- 90135 ) - 90135 1
   (9.403)  (0.03024)
RT (8,413)( 298,15) (8,413)(300) 300
G 0
 -2.439 x 104
RT
G 0
ln K    2.439 x 104
RT
(Van Ness, Eq.13.11a)

  G 0 
K  exp    1.762 x 104
 RT 

By Equation (13.5), with the species numbered in the order in which they
appear in the reaction,
1− ℰ 2− 2 .ℰ ℰ
y1 = y2 = y3 =
3−2 .ℰ 3−2 .ℰ 3−2 .ℰ
By Equation (13.28), ℰ = 0.8 (guess) → P = 1 ; P0 = 1
ℰ.( 3−2 .ℰ )2 P 2
Given = ( ) .K ℰ = Find (ℰ) ; ℰ = 0.9752
4.( 1− ℰ)3 P0
ℰ
y3 = → y3 = 0.9291
3−2 .ℰ
 (b) y3 = 0.5 By the preceding equation

3.𝑦3
ℰ= → ℰ = 0.75
2.𝑦3+ 1
Solution of the equilibrium equation for K gives
ℰ.( 3−2 .ℰ )2
K= → K = 27
4.( 1− ℰ)3

Find by trial the value of T for which this is correct. It turns out to be :
T = 364.47 Kelvin
(c) For P = 100 bar , the preceding equation Becomes

ℰ.( 3−2 .ℰ )2
K= . 100-2 → K = 2.7 x 10-3
4.( 1− ℰ)3
Another solution by trial for T yields, T = 516.48 kelvin

(d) Equation (13.27) applies, and requires fugacity coefficients. Since iteration
will be necessary, assume a starting T of 528 K, for which :

528
© For CO(1) : Tr = ; Tr = 3.973
132.9
100
Pr = ; Pr = 2.858
34.99
By using the formula:
Tr = T / Tc
Pr = P / Pc
B0 = 0.083-(0.422/(Tr1.6))
B1 = 0.139-(0.172/(Tr4.2))
ln = (Pr/Tr) x (B0 + (ω x B1))

The results of calculations are tabulated in the following table

Tc(K) Pc(atm) ωi* Tri Pri B0 B1 ɸi
CO
132,9 34,99 0,048 3,965388 7,550729 0,036435 0,138472 1,085494
2H2 -
33,19 13,13 0,216 15,87828 20,12186 0,077941 0,138998 1,062606
CH3OH
512,6 80,97 0,564 1,028092 3,262937 -0,3207 -0,01411 0,352364
* Price ωi obtained from Appendix B (Smith & Van Ness ed-4)
 528
© For CH3OH(3) : Tr = ; Tr = 1.03
512.6
100
Pr = ; Pr = 1.235
34.99

By equation (11.64) and data from Tables E.15 & E.16.

ɸ3 = 0.6206 x (0.9763)0.564
ɸ3 = 0.612
For H2(2), The reduced temperature is so large that it may be assumed ideal
; ɸ = 1.
Therefore ; i = 1....3
𝟏. 𝟎𝟑𝟐 −𝟏
ɸ = (𝟏. 𝟎𝟎𝟎) ; v = (−𝟐) ; ∏𝒊 ﴾ɸ ﴿vi = 0.593
𝟎. 𝟔𝟏𝟐 𝟏

The expression used for K in part (c) now becomes :

ℰ.( 3−2 .ℰ )2
K= . 100-2 . 0.593
4.( 1− ℰ)3
K= 1.6011 x 10-3
Another solution by trial for T yields :
T = 528.7 Kelvin