Question

The formation of ethyl chloride was studied using a zirconium oxide catalyst (on silica gel) in
the presence of inert methane.
C 2 H 4 + HCl↔ C2 H 5 Cl

If the surface reaction between adsorbed ethylene and adsorbed hydrochloric acid
(adjacent) controls the overall kinetics, derive an expression for the rate. Neglecting
external and internal transport resistances, evaluate the constants in the rate equation at
350 oF for the following data. The equilibrium constant for the overall reaction at 350 oF is
35.

r × 104 Partial Pressure (atm)

gmoles/(h)(lbcat) CH4 C2 H 4 HCl C2H5Cl

2.62 7.005 0.300 0.370 0.149

2.60 7.090 0.416 0.215 0.102

2.52 7.001 0.343 0.289 0.181

2.16 9.889 0.511 0.489 0.334

2.63 10.169 0.420 0.460 0.175

SOLUTION
The reaction for the formation of ethyl chloride is
C 2 H 4 + HCl↔ C2 H 5 Cl (1)

If A, B and C refer to C2H4, HCl and C2H5Cl

A+ B ↔C (2)
A . X +B . X ↔C . X + X (3)
If the surface reaction between adsorbed A and adsorbed B (adjacent) controls the overall
kinetics, the surface rate is given as
r
s=¿
ks
( 2
¿ K A K BC A C B C v−
Cm
KC
Ks
2
)
CC C v ¿ (4)

Note
{( C¿A )eq =K A C A C v ( C ¿B ) eq=K B C B C v ( C¿C ) eq=K C C C C v }
(5)
C m=¿ C +C
¿
v
¿
A
+C ¿B + C ¿C+C ¿I ¿ (6)

Where I denotes methane which is assumed to be inert.

As in equation (5)
¿
(C I )eq =K I C I C v (7)
¿
Cm
C v= (8)
1+ K A C A + K B C B + K C CC + K I C I

r =k s C ¿m
K A K B CA CB−
( )
KC
C
Ks C (9)
2
[ 1+ K A C A + K B C B + K C C C+ K I C I ]
Note
KA KB
K= Ks (10)
KC

¿
r =k s C K A K B
CA CB− ( K1 ) C C

m 2
[ 1+ K A C A + K B C B+ K C C C + K I C I ]
(11)
Equation 11 can be written in terms of partial pressure
From PV = nRT; P = CRT, this implies, C = P/RT (12)

¿
r =k s C m K A K B
[( )
PA PB
( RT ) 2
−
1 PC
K ( RT ) ]
[ ]
2
P P P P
1+ K A A + K B B + K C C + K I I
RT RT RT RT
(13)
In terms of pressure,
KA
K AP=
RT
KB
K BP=
RT
KC
K CP =
RT
 KI
K IP=
RT
K
Therefore, K P=
RT
and
PC
C C=
RT
Equation 12 now becomes

[ ][ ( )]
¿
K s Cm K A K B 1
2
P A P B− ( P C )
( RT ) KP
r= 2
[ 1+ K AP P A + K BP P B + K CP PC + K IP P I ]
(14)

¿
K s Cm K A K B
Let Z=
( RT )2
Therefore,

r=
[
Z P A P B− ( P C )
( K1 )]
P
2
[ 1+ K AP P A + K BP P B + K CP PC + K IP P I ]
(15)

[ ]
1 /2

1+ K AP P A + K BP PB + K CP P C + K IP P I
=
P A P B− ( P C ) ( )
1
KP
=R
1/ 2
Z r
(16)

r × 104 Partial Pressure (atm) R

gmoles/(h)(lbcat) CH4 C2 H 4 HCl C2H5Cl

PI PA PB PC

2.62 7.005 0.300 0.370 0.149 20.2

2.60 7.090 0.416 0.215 0.102 18.2

 2.52 7.001 0.343 0.289 0.181 19.3

2.16 9.889 0.511 0.489 0.334 33.4

2.63 10.169 0.420 0.460 0.175 26.7

From equation 16,

1/ 2
1+ K AP P A + K BP P B+ K CP PC + K IP P I =R Z
1 /2
1+0.3 K AP +0.37 K BP+ 0.149 K CP +7.005 K IP=20.2 Z
1 /2
1+0.416 K AP +0.215 K BP+ 0.102 K CP +7.090 K IP =18.2 Z
1/ 2
1+0.343 K AP +0.289 K BP + 0.181 K CP +7.001 K IP =19.3 Z
1/ 2
1+0.511 K AP +0.489 K BP+ 0.334 K CP + 9.889 K IP =33.4 Z
1/ 2
1+0.420 K AP +0.460 K BP+ 0.175 K CP +10.169 K IP =26.7 Z

Solving these five equations simultaneously, we have

KA = 27.4 atm-1, KB = 34.5 atm-1, KC = 36.8 atm-1, KI = 2.20 atm-1 and Z = 4.45 gmoles/(hr)
(lbcat.)(atm)2
Substitute these values into equation (15), we have

r=
[
4.45 P A PB − ( 351 ) P ]
C

2
[ 1+27.4 P A +34.5 P B +36.8 PC +2.20 PI ]