MODELLING FOR

REACTION KINETICS
 Unlike unit process dealing with separation
such as distillation columns or phase change
such as condensers, it is difficult to
generalize reaction kinetics, and virtually
useless to create general procedure for unit
operations as is done in previous chapters.

 The reason of course is that almost every

reaction is unique, characterized by a specific
reaction model, involving one or more
phases, and invariably taking place in one of
a great variety of reactor configurations.
GENERAL MODELING SCHEME FOR
REACTION KINETICS
 Ingeneral, reactants flow together in a reactor
environment where reaction rates are formed as
a function of temperature and other variables.
These rates will partially eliminates the original
components and form new components. Let us
consider a simple reaction
A +B R C+D
Where R- Reaction rate (mol/min). In this case
R = Rate of disappearance of A = rate
disappearance of B = Rate of appearance of C =
Rate of appearance of C = Rate of appearance of
D
If the stochiometry is given by
A + 2B R C+ D
Then Rate of disappearance of A is R.
Rate of disappearance of B is 2R since 2 moles of
B reacts with each moles of A.
 The reaction rates α reactant composition, thus the
composition can be regarded as the “potential ”
creating the reaction flow rates. In turn these
reaction flow rates are included in the component
balances together with physical flow rates that are
solved for the compositions.
 Therefore equation describing a reaction situation
are divided in to two groups.
 The component mass balances that are solved for the
compositions and kinetic rate equations that define the
reaction rates. Temperature
Compositions

I/P Component mass Kinetic Rate

&O/P balances Equations

Reaction Rates Reaction Rates

MODEL FOR LIQUID PHASE
ISO THERMAL CSTR
 CSTR(Continuous Stirred Tank Reactor) is the
most common system used in industry. Let us
consider the reactions
A+B C+D
C+B k k -2 3
E
A+ E k- 3
F
The reactant A & B are to produce the product
E which in turn produces the by product F by
further reaction with A. We consider the
reaction as isothermal liquid
k 1
phase reaction.
k2

k-1
Therefore reaction rate is given by
R1 = (k1CACB - k-1CCCD )* V
R1 = k1(CACB – CCCD / K1)*V (1)
similarly
R2 = k2(CCCB – CE / K2)*V (2)
R3 = k3(CACE – CF / K3)*V (3)
Where V - Reaction mixture volume (ft3)
Ci - moles of i/ ft3
ki - ft3 /(min.mole)
R - Reaction rate (mole/min)
Ki - Equilibrium constant (ki /k-i)
It is the ration between the forward rate constant to reverse rate
constant
 Unfortunately many CSTR involve
simultaneous evaporation where equilibrium
relationships are expressed in terms of liquid
and vapour mole fractions Xi and Yi.

 It is sometimes convenient in such a

simulation to unify the units by expressing
the reaction equation in terms of mole
fractions instead of composition units.
Conversion of rate equation in terms of mole
Fraction
R = k1CACB * V ------(i)
The units are :
Moles/min =
(ft3 /(min.mole))*(moles A/ ft3)*(moles B/ ft3)* ft3

R = k1XAXB * (M/V)* M ------(ii)

 where XA ;XB - mole fraction of A &B and term M/V is the
molar density of the reaction mixture; If the fluctuations in
this term resulting from changes in composition are small it
can be combined with reaction rate constant.
Then equation (ii) becomes
R = k1*XA *XB * M ------(iii)
Unit consistency is verified. Applying this transformation
in to equation (1) (2) &(3)
R1 = k1* M (XAXB – XCXD / K1)---------(4)
R2 = k2 * M (XCXB – XE / K2)-------------(5)
R3 = k3 *M (XAXE – XF / K3)------------(6)

This diagram shows the CSTR With input flow rate

Fi (mole/min)and output flow rate Fo( mole/min)
 Now the underlying assumption for a CSTR is that
the outlet flow has the same temperature and the
composition as the reactor contents.
The component mole-balance equation is given by
Component Abalance

--------(7)
Component B balance

----(8)
Component C balance

----(9)
Component D balance

----(10)

Component E balance

----(11)
Component F balance

----(12)
The sum of these component balance will give total mole
balance

----(13)

For this modelling of isothermal CSTR

The unknown variables : M,XA,XB,XC,XD,XE,XF,R1,R2 ,R3
No.of unknowns : 10;
No.of equations : 10;
Known Variable : Fi; Fo; T
Therefore information flow diagram is given by
Fi ,Fo

M,XA,XB,XC,XD,XE,XF

T & A(exponential factor)

R1, R2, R3 R1 = k1* M (XAXB – XCXD / K1)

R2 = k2 * M (XCXB – XE / K2)
R3 = k3(CACE – CF / K3)*V
MODEL FOR LIQUID PHASE
ADIABATIC CSTR
 In Isothermal CSTR modelling , The temperature
of the reaction mixture is constant So rate
constant is constant through-out the reaction.
 If the reactor is operating in adiabatic condition,
Temperature is not a constant, it varies with as
the reaction proceeds. So temperature of the
reaction mixture is estimated by energy balance
for the CSTR.

--(14)

--(15)
Fi ,Fo

M,XA,XB,XC,XD,XE,XF

R1 = k1* M (XAXB – XCXD / K1)

R2 = k2 * M (XCXB – XE / K2) Fi ,Fo,M

R1, R2, R3 R3 = k3(CACE – CF / K3)*V
Modelling For Radical
Kinetics
 Reaction models discussed on previous
section is reasonably straight forward that do
not involve Radical kinetics.
 The majority of reaction models are large and
complex which contains radical mechanisms
requiring appropriate treatment with in the
model.
 When these radical relationship expressed
mathematically give rise to system of
differential equations so stiff that a numerical
solution is virtually impossible by normal
methods.
 Let us consider the non-elementary reaction
which takes place in single phase
environment
A + 2B C
 If it is elementary reaction , the reaction rate
is given by its stoichiometric relationship,
that is
R = k ( CACB2 - CC/KE )*V-----(1)
Since it is a non-elementary reaction rate
relationship which is given in (1) is not
adequate. More precise relationship is
obtained by radical mechanism.
Elementary Reduction of Radical mechanism:
 Since there are three molecules involved in
primary section ,that is A and 2B , an
intermediate step is postulated based on bi-
molecular collision theory, that is
k
A+B 1
e
k k
e+B C
-1
2

Where e-intermediatek species. The reaction rate for

-2

each step is given by

R1 = (k1CACB - k-1Ce )* V

R2 = (k1CeCB - k-1CC)* V
Assumptions:
 Each step in the non-elementary reaction is
elementary reaction.
 Unit batch volume reaction mixture.
 The composition level of the intermediate e
is so small as to be virtually un-detectable.
So rate equation are rewritten by
R1 = k1(CACB – Ce / K1)----(2)
R2 = k2 (Ce CB – CC/K2)----------(3)
Component A & e balance is given by
Component A Balance

-----(4)
Component e balance
-------(5)
Substituting R1 & R2 from eqn 2 &3 in 4 & 5
We get

----(6)

---(7)
 Now the stiffness ratio between these two
differential equation is the ratio between the
negative feed back term, that is

Stiffness Ratio = = --(8)

 In order for component e have very low

concentration, either k2 is very large (i.e k2 >>k1)
Or (K1 is very small) for both cases lead to very
large stiffness ratio. This leads to very small
integration step (i.e) and excessive running for
simulation. So we resort to ‘steady state theory
Steady state theory
 Steady state theory implies that composition of
intermediate components are static during
reaction cycle. Since the intermediate
composition is so small there is no significant
accumulation of this component.

 There fore the rate of formation of intermediate

is practically identical to the rate of destruction;
that is, the rates are in equilibrium or steady
state. Therefore (dCe/dt ) = 0 Substituting in
equation (5) it becomes
R1 - R2 = 0;
R1 = R2
 -------(9)
Rearranging this equation which gives

-----(10)

------(11)

Substitute Ce from equation 10 in equation (2)

We get
 ----(12)

This equation (12) reduces to

These equation is further reduces in terms of

-----(13)
 By Knowing the value of k1 k2 K1 K2 the
composition of e has been eliminated by using
equation (11).
The procedure for the determination of constants
in radical Kinetics :
i] Equilibrium constant KE : This is obtained by
allowing the reaction mixture to come to
equilibrium , at which R =0
(i.e)
ii] Primary co-efficient (k’)
If only component C is placed in the
environment (i.e =0) and by sampling
procedures the rate of C is determined , then
extrapolation, the initial reaction rate is
determined. Since A and B’s initial concentration
is zero , this rate is given by

this is used to calculate k’.

iii] If the procedure (ii) is repeated for initial

mixture
A& B, then the rate will be
From this equation the ko is estimated.
Modelling For Reaction kinetics

Modelling For Heterogeneous

Kinetics
 Modelling and simulation to a reaction system
involving three phases( solid, liquid and gas) are
in great interest.

 Let us consider a high pressure auto-clave

containing an agitated liquid and gas phase and
consists of hydrogenating an organic
compound(A) to produce by product B and to
the final product (C).
The stochiometry of the reaction is given by
 A + H2 B
B + H2 C

Pressure

Temperature
 This reaction occurs on the surface a metal
catalyst in the form of loose particles, the reactant
diffusing from the liquid phase to the catalyst
surface reacting and returning to the liquid phase.
The three phases are enclosed in the autoclave.

 The reaction is exothermic (Assumption), which

will cause a significant rise in temperature and
pressure during the course of the reaction

 During the batch reaction a degree of control over

the internal temperature can be achieved by series
of cooling coils contacting the liquid phase.
 Several set of test data are available, consisting
of temperature and pressure transients for
different starting and operating conditions.
 As part of a process improvement program, it is
necessary to develop a model that matches the
available data. The model will then be used to
explore improvements in productivity and process
design.
 Because of the nature of the reaction, a
significant exchange of material balance between
the liquid and vapour phases occurs as the
reaction proceeds with simultaneous division of
energy.
 However , all phases will have the same temperature
since the agitation has sufficient violence to maintain
equilibrium.

Estimation of the reaction rate for Heterogeneous

catalytic reaction :
 The first step in assembling the model is to
develop the reaction rate equations. Since the
catalyst is involved a simple stoichiometric
relationship is in-adequate to describe the reaction.
 For this langmuir isotherm relationship are used to
relate the reaction rate to process variables.
 Langmuir Isotherm theory postulates that a unit
volume of catalyst that contains a number(S) of
active sites on the surface of the catalyst particles.

 The reactants, contained in a solvent, diffuse to the

catalyst surface ,react or become attached to the
active sites, and in a high energy state, react with
each other. The products then diffuse back to fluid
surrounding the catalyst. Each step can be
characterized as follows:
step 1: A + σ A σ;A reacts with free active site

Step2: G + σ G σ ;G reacts with free active site

step 3: A σ + G σ B + σ ;A &G reacts on active

site
Step4 : B + σ B σ; B reacts with free active site
Step 5: B σ + G σ C + σ; B &G reacts on active
site
Step 6 : C + σ C σ C reacts with free active site
 To develop the rate equation based on mechanism
, it is necessary to visualize the unit volume of
catalyst with the total number active sites S as
 S = σ + A σ +G σ +B σ +C σ --------(1)

 It is implied here that the solvent is inert and does

not occupy any active sites on the catalyst.
Symbolizing A,B,C and G as the liquid mole
fractions of the reacting species and the reaction
rate is stated as
Step 1: -------(2)

Step :2 -----------(3)

Step 3: ------------(4)

Step 4: ------------(5)

Step 5: ------------(6)
Step 6 : ----------(7)

In this equations ki - rate constant ;

Ki = equilibrium rate constant ; Note that step 3 and
step 5 are irreversible.
Steady state theory for the determination rate
limiting step :
Rate limiting step is specified for each of the two
primary reactions :
 Rate limiting step is specified for each of the
primary reaction A B and B C. The
other steps are in equilibrium.
The kinetic mechanism is given by
1. The rate limitation for the first reaction is the
resistance to the diffusion of the species A
migrating to the catalyst surface. This is
symbolized by step in reaction sequence.
-----(8)
 2. The rate limitation for the second step is given by
(i.e) surface reaction (step 5)

-------(9)

3. Remaining steps are in equilibrium which isleading to

---------(10)
-----------(11)
-----------(12)
 Since for the first reaction the diffusion step is rate
limiting, a further approximations made by
neglecting A . Substituting this in total site
equation & equation for RA which gives

------(13)
There fore -------(14)
Substituting equation (13) in (14) and (9)

-(15)

-(16)
Component Balance
Component A
-----(17)
Component B
----(18)

Component C
-----(19)
Component E ------(20)
Total mole balance is given by summing up
equation (17) (18) (19) &(20)
----(21)

Total energy balance is given by

It is rewritten in terms of temperature

----(22)
K