Lecture 2

Kinetic:
Include: Reaction rate, order of reaction, temperature dependence of the
reaction. The industrial chemical reaction can be divided in the following
groups:
1) According the type of chemical process (introduce of energy for
the reaction)
-Thermal process-Electrochemical process-Biochemical Process
The thermal processes are the widely used
2) Classification according the system.
a- Homogenous
b- Heterogenous
3) Classification according of method of working.
a- Isothermal (at constant temperature)
b- Adiabatic (without heat change with the surrounding if the
reaction vessel is able to absorb or supply the heat of
reaction.if not (temperature change with time)
c- Non isothermal not adiabatic
4) Classification according the type of reaction.
a- Simple reaction, irreversible (forward reaction)
A

R
R
A

b- Complicated reaction
I- Simultaneous reaction
A

k1

A
k2

The yield of R is reduced by the simultaneous side reaction S

S
R
A

II- Consecutive reaction

A
k 1
B

k2

C B undergoes a consecutive reaction to unwanted C

C
1

A
B

Lecture 2

III- Complicated consecutive reaction

A B

k1

A R

k2

A S

T etc .
Ex :Chlorination of Benzene
k3

C6 H 6 Cl
2
C6 H 5Cl Cl
2
C6 H 4Cl 2 Cl
2

C6 H5Cl

HCl

C6 H4Cl 2 HCl
C6 H3Cl 3 HCl

IV- Reversible reaction (forward and backward reaction)

S

k1

B
A k 2

A
B

A
B

5- Classification according the reactor type

Stoichiometry and Reaction Rate

Stoichiometry and Limiting Species
Reaction Rate

aA bB

cC

dD

For homogeneous reactions, it is defined as the number of

molecules disappeared or produced per unit time per unit
volume. [mol/s.dm3]
Its definition depends on a reactor flow condition. For a
constant volume batch reactor:
rA

d N A /V
1 dN A

V dt
dt

dC A
dt

Select one species, usually the limiting species as the basis

of calculation
rA rB rC rD

a
b
c
d

Lecture 2

Reaction Rate Constant & Rate Laws

How the rate of a reaction is determined?
aA bB

cC

dD

Temperature
Concentration of reacting species
rA k A (T )f n (C A ,C B ,...)

Rate law f n (C A ,C B ,...)

Specific reaction rate (constant):
k A (T ) Ae

k A (T )
E

RT

Under a specific temperature, kA can be taken as a constant

Reaction Order
The Reaction Order
rA k AC AC B

The reaction order of A is .

The reaction order of B is .
The overall reaction order is +
Zero order reaction rA k A
First order reaction rA k AC A
Second order reaction rA k AC A2
Third order reaction rA k AC A3

Elementary Reactions
For the reaction in which the reaction orders of each species is identical
with the stoichiometric coefficient, i.e.
2NO O
2
CO Cl
2

2NO 2
COCl 2

is elementary
is not elemetary

Molecularity:
The no. of species involved in the rate limiting step of the reaction
unimolecular, bi, tri, etc.
CH3
CH3EX:
NaOH CH 3 C CH
3
Br
OH

CH
3 C CH
3 NaBr

The rate law is determined from experimental observation

rTBB kC TBB

Lecture 2

The reaction is irreversible, homogenous, liquid phase, first order and

nonelementary

Reversible Reaction
The gas phase reaction
k1

C 12 H 10 H 2
2C 6 H 6 k 2
(Benzene )

(diphenyle )

elementary and reversible

k1 and k2 will be defined with respect to Benzene (B)

rB formed k 1C B2 or rB formed k 1C B2
rB reverse k 2C DC H 2

The net rate of formation of B

rB rB ,net rB ,formed rB ,reverse
rB k 1C B2 k 2C D C H 2

k
k 1 C B2 2 C DC H 2
k1

C DC H 2
k
k 1 C B2
where K eq 1 (equilibrium cons tan t )

K eq
k2

Nonelementary Reaction
H 2 Br2
2HBr is nonelementary with rate low

The reaction rHBr

1/ 2
k 1C H 2C Br
2

k 2C HBr Br2

and the reaction, CH 3CHO CH 4 CO

At T=500oC is 3/2 order with respect to CH3CHO

3/ 2
rCH 3CHO kC CH
3CHO

In many gas solid catalyzed reaction is preferable to take the partial

pressure.
C 6 H 5CH (CH 2 )
C 6 H 6 C 3H 6
C

i.e.
rC

k PC PB PP / k P
1 k C PC k B PB

rC as a function of conversion, replace Pi with conc. Using the ideal gas

law

PC C C RT
rA B (rA )

Where
-rA=per unit volume
rA = per unit weight of catalyst
B = bulk density of catalyst
4

Lecture 2

K- dependence on T (Arrhenius equation)

k T Ae

RT

Where
A: Pre exponential factor or frequency factor
E: Activation energy, j/mol or cal/mol
E is the minimum energy which must be passed reacting molecules
before the reaction will occur and it's determined by carrying out the
reaction at different temperature
Ln k Ln A
rA

E 1

R T

dC A
dt

E
React.

E
dC A
A .e RT .C A .C B
dt

E
P

Ln A

E
R

Ln k

1/T

Effect of Pressure on Reaction Rate

The effect of P on r is negligible or small for liquid reactions, because
liquids are not compressible, then no conc. Change with P. For gas
reaction. The concentration is a function of P, so r is depended on P. this
is varied according the order of reaction.
A

For first order

R
dC
rA A k C C A
dt
dP
A k P PA ,
PA partial pressure
dt
n
P
because C A A A
V
RT
n
d A
V k C P , where k C k gives dPA k P
P
P A
RT A
dt
RT
dt

Lecture 2
PA PA o .e

Integration:

bt

RT

, because k f .e

RT

PA Pt .y A
y A mole fraction
resulted: Pt y A Pt . y Ao .e

bt

RT

r is independent on the pressure, for first order reaction for 0.5order:

dC A
k C C A0.5
dt
dPA
k P PA0.5
dt

rA
and

Integration:

1
PA0.5 . y A0.5 Pt 0.5 . y A0.5 k P .t
2
because : PA Pt .y A and PA o Pt .y Ao
yA

y Ao

0.5

2k P t

Pt y Ao 0.5

Its recognized from the equation that for a given intial concentration of A
(reactor input) and a given t, yA/yAo increase with increasing the total
pressure, while the conversion will be decreased with Pt for 0.5 order.
For 2nd order reaction
dC A
k C C A2
dt
dPA
k P PA2
dt

rA
and

Integration gives P P k P t
A
Ao
In case of pure reactant yA=1 followed
1
1
k Pt
Pt y A Pt