1

Langmuir-Hinshelwood Hougen-Watson (LHHW) Kinetics Example

2 CHCl
3
+ 2 H
2
O + O
2
2 CO
2
+ 6 HCl
A A P P
A
3
C K C K 1
kC
s cm
g
rate
+ +
= |
.
|

\
|

where:
k (s
-1
) = 0.372 x 10
9
e
(-21,700/RT)

K
P
(cm
3
/mol) = 0.597 x 10
7
e
(+2440/RT)

K
A
(cm
3
/mol) = 0.123 x 10
7
e
(+5330/RT)

C
A
(mol/cm
3
) = concentration of CHCl
3

C
P
(mol/cm
3
) = concentration of HCl

Aspen LHHW kinetics formulation: The rate expression for catalytic reactions can be
modeled using the Langmuir. Isotherm which consists of three fundamental steps.
1. The adsorption of the reactants to the catalyst surface. This term is proportional to
the surface available for adsorption.
2. The surface reaction for reactants to form products. This term can be represented
by a simple power law expression.
3. The desorption of the products from the catalyst surface to the surrounding
environment. This term is proportional to the surface already adsorbed.
At steady state, the rate of adsorption of reactants is equal to the rate of desorption of
products. From this information the following generic expression can be developed.
( )
( )
( ) term adsorption
expression force driving
factor kinetic rate =
The kinetic factor represents the surface reaction, and is represented by the expression.
(
(

|
|
.
|

\
|

|
|
.
|

\
|
=
o
T
1
T
1
R
E n
o
e
T
T
k factor kinetic
The driving force expression representing step 3 (desorption of product from the catalyst
surface, whose rate is directly proportional to the global rate of reaction) is given by.

=
j
i
b
j 2
a
i 1
C K C K force driving
The adsorption term represents step 1 ( the adsorption of reactant to the catalyst surface,
which is indirectly proportional to the global rate). It is expressed by the following:
( )
m
j i
j
C K term dsorption a


=
Both the driving force expression and adsorption term are defined by equilibrium
constants. For example the equilibrium constants for the adsorption term help define the
chemisorption of reactants to the surface of the catalyst (chemisorption being
characterized as an exothermic reaction between surface site and the adsorbate). These
equilibrium constants are of the form: ln(K) = A + B/T + C ln(T) + D T

2
Specifics for this example:

1) kinetic factor
kinetic factor = k [(T/To)
n
] e
[(E/R)(1/T-1/T
o
)]

If T
o
is not specified then kinetic factor = k[T
n
] e
(E/RT)

For n=0, kinetic factor= k exp (E/RT)

For this problem, kinetic factor = 0.372 x 10
9
e
(-21,700[cal/mol]/RT)


This kinetic expression needs to be converted to SI units since the pre-exponential factor
is always in SI units. The expression also needs to be converted from a weight of catalyst
to a mole of reaction basis. Here 5 g of catalyst produces a kmol of reaction.

kinetic factor = [0.372 x10
9
e
(-21,700[cal/mol]/RT)
] / (1000 g/kg) x (100
3
cm
3
/m
3
) / (5g / kmol)
kinetic factor (m3/kg-s) = 0.372 x10
9
e
(-90854000[J/kmol]/RT)
x 200
kinetic factor (m3/kg-s) = 7.44x10
10
e
(9.0854E7/RT)


In Aspen Plus, the form of the equation is
kinetic factor = k exp (E/RT)

Hence, the inputs are as follows:
the preexponential factor k = 7.44 x10
10

and the Activation Energy E = 90854000 J/kmol

2) Driving Force
Aspen Plus calls the first product sum term1 and the second term2.
driving force expression = term1 - term2
For this problem,
driving force expression = (Ca)

In the Aspen Plus form of the driving force expression:
driving force expression = K
1
(C
A
) - K
2
(C
A
)
Term1 = C
A
where K
1
= 1
Term2 = 0 where K
1
=0

driving force expression = 1 (C
A
) - 0 (C
A
)

Since K is in a log form ln(K) = A + B/T + C ln(T) + D T
For term 1: ln 1 = 0 where A = 0
For term2: ln 0 = -infinity
Since cannot be entered, it is approximated as -100. (ln 0 ~ -100 where A = -100)

3) Adsorption term
Any number of terms are possible. For this problem there are three terms and the
adsorption expression exponent m = 1.
adsorption term = (term1 + term2 + term3)
m

3

For term1:
K = 1
ln 1 = 0
ln K = A

For term2:
K
P
= 0.597x10
7
e
(+2440/RT)

ln(K
P
) = ln (0.597 x10
7
) + (2440/1.9872/T)
= 15.602 + 1228/T
ln K = A + B / T

For term3:
K
A
= 0.123 x10
7
e
(+5330/RT)

ln(K
A
) = ln (0.123 x10
7
) + (5330/1.9872/T)
= 14.023 + 2682/T
ln K = A + B / T

where
r = rate of reaction
k = pre-exponential factor
T = absolute temperature
To = reference temperature
n = temperature exponent
E = activation energy
R = gas law constant
C = Component concentration
m = Adsorption expression exponent
K
1
, K
2
, K
i
= Equilibrium constants
v = Concentration exponent
i, j = Component Index
A,B,C,D = Constants

Summary of Aspen Plus LHHW input:
Kinetic factor:
k = 7.44 e10
E = 90854000 J/kmol
driving force expression:
Term 1 CHCL3 exponent = 1 A = 0
Term 2 CHCL3 exponent = 1 A = -100
adsorption term
Adsorption expression exponent = 1
Term 1: =0
Term 2 HCl exponent = 1: A = 15.602 B = 1228
Term 3 CHCl
3
exponent = 1: A = 14.023 B = 2682