Lecture 8

Reaction mechanism and kinetic study

Reaction mechanism and rate equations

For irreversible gas phase reaction A ( g ) → B ( g ) , global rate for catalyst particles is

expressed in terms of temperature and concentration of A in bulk gas stream which can
be measured or specified directly. Global rates of catalytic reactions are usually
expressed per unit mass of catalyst.

Power law model

For homogeneous reaction, power law form of rate equation is used where rate is
function of concentration and rate is determined by fitting data to the equation. The
exponents on the concentration is the apparent order of the reaction and ‘k’ is the kinetic
constant or reaction rate constant which is independent of concentration and depends on
temperature.

For reactions A+B → C+D

dC
γa =
− a =kC αA C Bβ
dt

Here α is the order with respect to A and β is the order with respect to B

This power law approach can also be used for solid catalytic reactions. This analysis is
simple. The major disadvantage of this method is that it ignores all the factors associated
with adsorption and reaction mechanism on surface of solid catalyst. Hence, power law
kinetics fails to adequately describe any solid catalytic process and the rate equation
derived from mechanistic model is more preferred. Power law kinetics is preferred as a
mode of obtaining preliminary value of rate parameters for solid catalyzed reactions.

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Langmuir-Hinshelwood –Hougen-Watson(LHHW) model

The rate equation derived from mechanistic model that simulates the actual surface
phenomenon during the process is preferred for reactions involving solid catalysts. The
Langmuir-Hinshelwood–Hougen-Watson(LHHW) approach is one of the most
commonly used way of deriving rate expressions for fluid solid catalytic reactions. The
advantages of this method are that :

(1) Rate derived by this method takes into account the adsorption-desorption process
occurring over the surface along with the surface reaction.
(2) Rate equation derived can be extrapolated more accurately to concentrations lying
beyond the experimentally measured values.
During this method of derivation of rate expression, all the physical transport steps like
mass transfer from bulk phase to catalyst surface or diffusion of reactants from pore
mouth to interior pore (intraparticle diffusion) are excluded. Thus, it is assumed that the
external and internal mass transport processes are very rapid relative to the chemical
rate process occurring on or within the catalyst particle. The chemical rate depends on :
(1) chemisorption steps
(2) surface reaction steps
(3) desorption steps

This simple kinetic model assumes isothermal condition about and within catalyst that is
temperature gradient is zero.
In LHHW model development, the rate equation is first derived in terms of surface
concentration of adsorbed species and vacant sites. Then, these surface concentrations are
related to the fluid or bulk concentration that is directly measurable.
For the reaction A + B  C + D

Let ra = rates of adsorption ( g mol/s.gm of

catalyst)

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rs = rates of surface reaction ( g mol/s.gm of catalyst)

rd =rates of desorption ( g mol/s.gm of catalyst)

C AS = concentration of adsorbed A on surface ( g mol/gm of catalyst)

C BS = concentration of adsorbed B on surface (gmol/gm of catalyst)

C cs = concentration of adsorbed C on surface (g mol/gm of catalyst)

C DS = concentration of adsorbed D on surface (g moles/gm of catalyst)

CO = total concentration of active sites on surface (g mol/gm of catalyst)

CV = concentration of vacant sites on surface (g mol/gm of catalyst)

C A = concentration of A in bulk gas phase (g mol/cm3)

Similarly C B , CC , C D are the concentrations of B,C,D in the bulk gas phase,

respectively.

Let the reaction follows the mechanism given below ;

(1) A + S  A.S --- Adsorption of reactant A on surface vacant site S

(2) B + S  B.S --- Adsorption reactant B on surface vacant site S
(3) A.S + B.S  C.S + D.S --- Surface reaction between adsorbed A and B
(4) C.S  C + S --- Desorption of product C from surface creating a vacant
site
(5) D.S  D + S ---Desorption of product D from surface creating a vacant
site

Among the various steps described, the slowest step controls the overall rate of reaction
and the other remaining steps are assumed to be at near equilibrium conditions. This
approach greatly simplifies the overall rate expression, reducing the number of rate
constants and equilibrium constants to be determined from experimental data. Further

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each step in this method is assumed to be elementary and the number of sites is conserved
in each step.

Therefore, the controlling step can be either of the following:

(1) Surface reaction

(2) Adsorption
(3) Desorption

Now total concentration of active sites on surface, CO , will be the summation

concentrations of all sites on which either reactants or products are adsorbed and the
concentration of vacant sites.

∴ CO = CV + C AS + C BS + CCS + C DS

Where, CV is the concentration of vacant sites.

Case 1 : Rate is surface reaction controlling

The surface reaction is the slowest step and is the rate controlling. According to the
mechanism, surface reaction occurs between adsorbed A and adsorbed B producing
adsorbed C & adsorbed D.

AS + BS  CS + DS

The rate of surface reaction is given as

=rS k S C AS C BS − k S' CCS C DS k s = rate constant for forward surface reaction

k S' = rate constant for reverse surface reaction

 k S' 
= k S C AS C BS − CCS C DS 
 kS 

 1  kS
= k S C AS C BS − CCS C DS   KS = (1)
 KS  k S'

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Now, since all the other steps are considered to be in equilibrium, therefore concentration
of adsorbed species can be obtained as follows.

For adsorption steps and desorption steps :

C AS CCS
From step (1) KA = From step (4) K C =
C A.CV CC .CV

C BS C DS
From step (2) KB = From step (5) K D =
C B .CV C D .CV

K A , K B , K C , K D are adsorption equilibrium constants.

Then, the adsorbed phase concentrations can be written as

C AS = K AC ACV CCS = K C CC CV

C BS = K B C B CV C DS = K D C D CV

Substituting all these value in equation (1)

 1   K 
rS =k S C AS C BS − CCS C DS  =k S  K AC ACV . K B C B CV − C CC CV . K D C D CV 
 KS   KS 

 K K 
=or, rs k S  K A K B C AC B CV2 − C D CC C D CV2 
 KS 

 KC K D 
=or rS k S K A K B C AC B − CC C D  CV2 (2)
 KS K AKB 

Now , CO = C AS + C BS + CCS + C DS + CV

CO = K AC ACV + K B C B CV + K C CC CV + K D C D CV + CV

=CV [1 + K AC A + K B C B + K C CC + K D C D ]

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CO
CV = (3)
1 + K AC A + K B C B + K C C C + K D C D

For the reaction A+B  C+D , at equilibrium , the overall equilibrium constant is
CC C D
K= .
C AC B

All concentrations correspond to the equilibrium conditions in gas phase.

( C / K C CV )( C DS / K DCV )
K = CS =
CCS C DS K A K B CV2
.
( C AS / K ACV )( C BS / K BCV ) C AS C BS K C K D CV2

KAKB CCS C DS
Or , K = .K  KS = (4)
KC K D S C AS C BS

Substituting (3) &(4) in equation (2),

 1  CO2
=rS k S K A K B  C AC B − CC C D 
  ( 1 + K AC A + K B C B + K C C C + K D C D )
2
K

1
C AC B − CC C D
rS = k S K A K B C
2 K (5)
( 1 + K AC A + K B C B + K C C C + K D C D )
O 2

The above rate expression can also be derived in terms of bulk partial pressure.

Case 2: Rate is adsorption control

(a) Adsorption of A controlling

Let adsorption of A be the slowest step so that adsorption of B, surface reaction and
desorption of C are at equilibrium.

Adsorption of A is given as

A + S  AS

=
Rate of adsorption ra ka C ACV − kd C AS

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 k 
=ra ka C ACV − d C AS 
 ka 

 1  ka
=
Or, ra ka C ACV − C AS  KA = (adsorption equilibrium constant for A)
 KA  kd

 1 C AS 
=ra ka CV C A −  (6)
 K A CV 

Now as other steps are in equilibrium :

CCS C DS
KS =
C AS C BS

C BS C C
KB = K C = CS K D = DS
C B CV CC CV C D CV

C BS = K B C B CV CCS = K C CC CV C DS = K D C D CV

Then ,

CCS C DS K C CC CV . K D C D CV K C K D CC C D CV
C AS = = =
K S C BS K S K B C B CV KS KB CB

Substituting value in equation (6)

 1 K C K D CC C D CV 
=ra ka CV C A − 
 K ACV K S K B CB 

 K C K D CC C D 
=ra ka CV C A − 
 K S K A K B CB 

 1 CC C D 
=ra ka CV C A −  (7)
 K CB 

KS KAKB
K= = Overall equilibrium constant.
KC K D

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Now C 0 =CV + C AS + C BS + CCS + C DS

K C K D CC C D CV
=
CV + . + K B C B CV + K C CC CV + K D C D CV
KS KB CB

 K K K C C  
=CV 1 + C D A  C D  + K B C B + K C CC + K D C D 
 K S K A K B  CB  

 K C C 
=CV 1 + A C D + K B C B + K C CC + K D C D 
 K CB 

CO KS KAKB
CV = K =
K A CC C D KC K D
1+ + K B C B + K C CC + K D C D
K CB

Substituting value of CV in equation (7)

C C 
CA −  C D 
ra = ka C 0  KC B  (8)
K C C
1 + A C D + K B C B + K C CC + K D C D
KC B

For a given catalyst C 0 is constant.

Similarly expression when desorption of product is the rate controlling step can be
derived. For desorption of C controlling the whole reaction, the rate expression can be
derived as

C C 
C AC B −  C D 
rd = kd C 0 K  K 
1 + K AC A + K B C B + K C KC AC B + K D C D

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Eley Rideal model

Apart from power law and Langmuir-Hinshelwood models, other kinetic models are also
used to fit the data. EleyRideal model depicts the reaction mechanism in which one
reactant species (say A) is adsorbed while the second reactant species (say B) is not
adsorbed on the catalyst surface. The reaction then occurs when the passing gas
molecules of B in gas phase directly reacts with the adsorbed species A. The schematic
representation is shown in Fig. 1.

Fig. 1. Eley Rideal mechanism for reaction of adsorbed A with gas phase B producing product AB

(1) A + S  AS
(2) AS + B (g) → P

Assuming that step 2, the reaction between adsorbed A and gas phase B is irreversible
and the rate determining step, then the rate of reaction can be written as

r = k CAs CB (9)

The concentration of adsorbed A can be given as CAS = K A CA CV

Now , CO = CAS + CV = K A CA CV + CV = CV (1 + K A CA )

CO
CV =
1 + K A CA

K A C A CO
CAS =
1 + K A CA

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Substituting value of CAS in equation (9)

kCO K A CA CB
=r k=
CAS CB
1 + K A CA

If the products are chemisorbed then the reaction may become reversible as shown below.


AS + B(g) 
k

 PS
k b

PS → P + S

Then the rate expression can be written as

=r k CAs CB − k b CPs

The concentration of adsorbed product is CPS = K P CP CV

CO = CAS + CPs + CV = K A CA CV + K p CP CV + CV = CV (1 + K A CA + K P CP )

CO
CV =
1 + K A CA + K P CP

K A C A CO
=CAS K=
A CA CV
1 + K A CA + K P CP

K P C P CO
=CPS K=
P CP CV
1 + K A CA + K P CP

Substituting CAS and CPS in rate expression,

 1  k
=
r k CAs CB − k b C=
Ps k  CASCB − CPS  =
K
 K  kb

 K A C A CO 1 K P C P CO 
r k  CB − 
 (1 + K A CA + K P CP ) K (1 + K A CA + K P CP ) 

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 KP 
 K A CA CB − CP 
r = kCO  
K
1 + K A CA + K P CP

Estimation of model parameters

The various parameters in the kinetic models such as rate constants, reaction orders, and
equilibrium constants are derived by fitting the experimental data. The optimal values of
the parameters in the rate equation of a heterogeneous reaction are determined
traditionally by using gradient or direct search methods. For success of this method, a
very good initial estimate of the parameters is required. This proves to be difficult in most
cases. If the initial estimates are far from the global optima, then it is likely that the
gradient or direct search method will not converge at all or will converge to local optima.
Recently genetic algorithm (GA) is increasingly applied in estimation of kinetic
parameters. The major advantage of this method is that it is not dependent on the initial
estimate of the parameters. GA performs a multi-directional search.

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