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 :

C 3 H 8(g)
8(g)→ C 2 H 4(g)
4(g) + CH 4(g)
4(g)  v = 1

Basis: 1 mole C 3 H 8feed. By Eq. (13.4) nC   H 

3 8
 1     

n0  nC   H  1 (1
    )
Fractional conversion of C 3 H 8= 3 8
     
n0 1

1       
By Eq. (13.5)  yC   H      yC   H      yCH    
1    1    1   
3 8 2 4 4

From data in Table C.4.

 J   J 
 H 298    82670   G298    42290  
mol  mol 

V :=
1 ∶= (1.1.472402) (14.9.038194)
( 11 )   ∶=(
 
1. 213 28. 785  B := -3
 .10   C :=
8.
(4. 8
324
92 )  .10-6
2.164
end := rows(A) i := 1.. end

 A  
  vi. Ai    B    Bii  
  vi. B C   
  vi.Ci  
i i i

 A  1.913 
 
 B    5.31x 10 3   C   2  .268  x10 6  

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

T 
C  po  B C   D       1 
 dT    AT 0     1    T 02    2  1  T 03   3  1     
T 0
 R 2   3 T        
0

(Van Ness, Eq. 4.19)

T 
C  po dT        D        1 
   A ln      BT 0     CT 02  2 2 
 
     1
 
T 0
 R T        T 
0  
2
  

(Van Ness, Eq. 5.15)

 

T 
Where,      
T 0
625
C  po   625
 
   5.31  10
3  
2   625  
2
  2.268  106  
3   625  
3
   
 dT   1,913  298.15    1    .15  
298   1  298.15     1
 298.15       298.15  
298,15
 R 2   298.15    3    
625
C  po  
   dT    11.2997
298,15
 R

    625    

    1 
625
C  p dT  0
625 2   298.15    625    
  1.913  ln   5.31 10  298.15   2.268  10  298.15 
   3   6
    1
 R T  298.15   2  298.15  
298,15
  
    
625
C  p0 dT 
  0.0022506  
298,15
 R
  T 

G 0 G00   H 
  0
 H 00 1
T 
C  p0 T 
 C  p0 dT 
 RT 
 0

 RT 0

 RT 
 
T  T 0  R
dT   
T 0
 R T 
 

(Van Ness, Eq. 13.18)

0
G  42290  82670  82670  1 (11.2997)  0.0022506  
 R
 RT 
T  (8.314)(625) (8.314)(625) 625

0
G
 2187.9  
 RT 
 RT 

(Van Ness, Eq.13.11a)

   G 0  
exp 
 K   exp   1.52356  
   R
 RT 
T   
(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   )
0
 G 0  J   
 ln  K    G  4972
  .3  
 R
 RT 
T  mol 

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

Its not dificult to find T by trial. This lead
le ad 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 carboncarbon monoxide
monoxide and hydrogen in the

stoichiometric
a.  What isproportions.
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 ,)

∆H298 = - 90135
  ∆G298 = - 24791
 
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 

T 
C  po  B C   D       1 
 dT    AT 0     1    2
T 0    
2
 1  3
T 0 
  
3
 1     
T 0
 R 2   3 T        
0

(Van Ness, Eq. 4.19)

 

T 
C  po dT        D        1 

T 0
 R T 
  A ln      BT 0     CT 02  2 2 
      0   
T  2
     1
   

(Van Ness, Eq. 5.15)

T 
Where,      
T 0

C  po     2
   3.45  10 6   3  300  1 
   0.135  105  
 10 3
923,15
  300   10.815 2    300    3    300     298,15 
 dT   -7.663 298,15    1 
 298,15  
298,15 

  1 

298,15 

  1 
  300 
298,15
 R 2
  298,15    3
  298,15    298,15
 
  298,15  
923,15
C  po  
   dT   - 9.043
298,15
 R

       300    

      1 
923,15
C  p 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 
2
2      1
298,15
 R T  298,15
    300   2 
2
   298,15  
   298 ,15  
    298,15      
 
923,15
C  p dT 
0

298,15
  R
  T 
 -0.03024
0 0   0 0 T  0 T  0

0 0 0
G  G   H    H   
1 C  dT   C  dT   

 p  p

 RT   RT 0  RT  T  T   R

0 T 
 R T  0

(Van Ness, Eq. 13.18)

0
G - 24791  (- 90135 ) - 90135  1
   (9.403)  (0.03024)  
 R
 RT 
T  (8,413)(298,15) (8,413)(300) 300
0
G
 -2.439 x 104  
 RT 
 RT 
0
G
ln  K     2.439 x 104  
 RT 
 RT 
(Van Ness, Eq.13.11a)

   G 0  
 K   ex
exp
p   1.762 x 104  
   R T   
 RT 

By Equation (13.5), with the species numbered in the order in which they
appear in the reaction,
− ℰ   −  .ℰ ℰ  
y1 =
− .ℰ ℰ − .ℰ
By Equation (13.28),
y2 =
 = 0.8
 
(guess) → P = 1
− .ℰ
y3 =
; P0 = 1 
ℰ. − .ℰ  =  P . ℰ ℰℰ
Given
ℰ .  − ℰ P K  = Find ( ) ;  = 0.9752

y3 =   → y3 = 0.9291

− .ℰ
 

(b)  y3 = 0.5 By the preceding equation 

ℰ ..+  
 = → ℰ  = 0.75
Solution of the equilibrium equation for K gives
ℰ. − .ℰ  
K=
. − ℰ → K = 27

Find by trial the value of T for which this is correct.

correct. It turns out to be :
T = 364.47 Kelvin
(c)  For P = 100 bar , the preceding equation Becomes

ℰ. − .ℰ  .

K=
. − ℰ 100-2  → K = 2.7 x 10-3 
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 :

© For CO(1) : Tr =   ; Tr =
Pr =
.


.   ;
3.973
Pr = 2.858
 

By using the formula:

Tr = T / Tc
Pr = P / Pc
B0 = 0.083-(0.422/(Tr 1.6))
B1 = 0.139-(0.172/(Tr 4.2))
ln = (Pr/Tr) x (B0 + (ω
(ω x B1))

The results of calculations are tabulated in the following table

Tc(K) Pc(atm) ωi* Tri  Pri  B0  B1  ɸi  
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)
ed-4)
 


© For CH3OH(3) : Tr =
.  ; Tr = 1.03

Pr =
.  ; Pr = 1.235

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.

ɸ  =
.(.)
Therefore ; i = 1....3

  ; v=

( )  ; ∏   ɸ vi
  = 0.593
.
The expression used for K in part (c) now becomes :
ℰ. − .ℰ  .
K=
. − ℰ
K= 1.6011 x 10-3 
100-2 . 0.593

Another solution by trial for T yields :

T = 528.7 Kelvin