Chemical Kinetics /
Analysis of rate equations
1
Chemical Kinetics  outcomes
Understand the significance of kinetics
Aware of concentration dependencies
Understand the difference elementary / nonelementary reactions
Calculate the order of reaction
Aware of temperature dependencies Arrhenius, activation energy
2
The Rate Equation / Stoichiometry
aA+ bB cC+ dD
dt
dN
V
r
A
A
1
=
rate of disappearance of A
dt
dN
V
r
C
C
1
=
rate of appearance of C
d
r
c
r
b
r
a
r
D C B A
= =
Relationship
between rates of
reaction
3
Concentration / Temp. dependency terms
.) ., ( temp conc f r =
,...)] , ( )][ ( [
B A A
C C f T k r =
Reaction rate
(constant)
Concentration
dependent terms
4
Concentrationdependent term
,...)] , ( [
B A A
C C f k r =
Almost without exception determined by experimental observation!!!
Most common expression:
o  o
D B A A
C C kC r .... =
Order of reaction:
A in order o
B in order 
order overall ... n = + + =  o
5
Elementary / Nonelementary Reactions
Elementary reactions iff stoichiometric coefficients are the same as the
individual reaction order of each species
Nonelementary reactions stoichiometry does not match the kinetics
D C B A + +
B A A
C kC r =
stoichiometric coeff:
1 = = = = d c b a
1 = = a o
B A A
C kC r
2
=
2 = o
1 = 
 o
B A A
C kC r =
1 = = b 
A sequence of elementary reactions
6
Elementary reactions / Molecularity
= the number of molecules involved in a reaction
refers ONLY to elementary reaction!!!
Elementary reactions
P X
P X 2
P Y X +
P X 3
P Y X +2
P Z Y X + +
Rate Law
X
kC
2
X
kC
Y X
C kC
3
X
kC
2
Y X
C kC
Z Y X
C C kC
Molecularity Comments
unimolecular
bimolecular
bimolecular
termolecular
termolecular
termolecular
X decomposes
X collides with X
X collides with Y
X+X+X collide
X+Y+Y collide
X+Y+Z collide
ty moleculari order =
7
Nonelementary reactions
Overall reaction:
) ( 2 ) ( 2 ) ( ) ( 4
2 2 2
g Br g O H g O g HBr + +
k
exp
Sequence of reactions proposed mechanism:
) ( ) ( ) (
2
g HOOBr g O g HBr +
) ( 2 ) ( ) ( g HOBr g HBr g HOOBr +
) ( ) ( ) ( ) (
2 2
g Br g O H g HBr g HOBr + +
) ( ) ( ) ( ) (
2 2
g Br g O H g HBr g HOBr + +
(1)
(2)
(3)
(4)
k
1
k
2
k
3
k
4
elementary
reactions
(bimolecular)
(slow)
(fast)
(fast)
(fast)
k
exp
=func(k
1
,k
2
,k
3
,k
4
)
k
exp
=k
1
8
Concentration / Temp. dependency terms
.) ., ( temp conc f r =
,...)] , ( )][ ( [
B A A
C C f T k r =
Reaction rate
(constant)
Concentration
dependent terms
9
Rate constant (k)
,...)] , ( [
B A A
C C f k r =
Dimensions vary with order of reaction (n) :
n
ion concentrat time
1 1
) ( ) (
Reaction order
(mol/m
3
)
C
A
(mol/m
3
)
(mol/m
3
)
(mol/m
3
.s)
(mol/m
3
.s)
(mol/m
3
.s)
r
A
Rate law
(mol/m
3
)/s
k r
A
=
A A
kC r =
2
A A
kC r =
1/s
(m
3
/mol)/s
zero
1
st
2
nd
k
10
Temperature dependency
Arrhenius Law
Arrhenius suggested the following relationship:
RT E
e k k
/
0
=
k
0
= frequency / preexponential factor
E = activation energy [J/mol] or [cal/mol]
R = gas constant = 8.314 J/mol.K=1.987 cal/mol.K
T = absolute temperature [K]
Activation energy (E) definitions:
Min energy that must be possessed by molecules to react
Nothing more than an empirical parameter (some suggestions!)
Average energy of (reacting molecules all molecules)
11
Temperature dependency
Activation energy
RT E
e k k
/
0
=
Activation energy (E) calculation:
data for same concentration different temperatures

.

\

=
T R
E
k k
1
ln ln
0

.

\

=
T R
E
k k
1
3 . 2
log log
0
or


.

\

=
2 1 1
2
1 1
ln
T T R
E
k
k
T
1
,T
2
ln, log


.

\

=
2 1 1
2
1 1
3 . 2
log
T T R
E
k
k
12
Activation energy calculation
example 1
First order reaction:
C B A +
Data:
k (1/s) 0.00043 0.00103 0.0018 0.00355 0.00717
T(K) 313 319 323 328 333


.

\

=
2 1 1
2
1 1
3 . 2
log
T T R
E
k
k
2 1
1 2
/ 1 / 1
) / log( ) 3 . 2 (
T T
k k R
E
=
00303 . 0 / 1 005 . 0
1 1
= = T k
00319 . 0 / 1 0005 . 0
2 2
= = T k
Hint: for
1 ) / log( 1 . 0
2 1 1 2
= = k k k k
mol kJ E / 120 =
13
0
0.5
1
1.5
2
2.5
3
3.5
4
0.00295 0.003 0.00305 0.0031 0.00315 0.0032 0.00325
1/T Vs log k
Log k
1/T
Activation energy calculation
example 2
To obtain pasteurised milk:
heating at 63C for 30 min
heating at 74C for 15 s
K T t 336 min 30
1 1
= =


.

\

= =
2 1 2
1
1
2
1 1
ln ln
T T R
E
t
t
k
k
Reaction rate is inversely
proportional with reaction time
K T t 347 min 25 . 0 sec 15
2 2
= = =

.

\

=
347
1
336
1
314 . 8 25 . 0
30
ln
E
mol J E / 422000 =
Find the activation energy of the process
14
Data on the tenebrionid beetle whose body mass is 3.3 g show that it can
push a 35g ball of dung at 6.5 cm/s at 27 C, 13 cm/s at 37 C, and 18 cm/s
at 40 C. How fast can it push dung at 41.5 C? [B. Heinrich. The Hot
Blooded Insects (Cambridge, Mass.: 1993).]
Activation energy calculation
example 3
15
The behavior of the beetle can be modeled by the Arrhenius equation.
The beetle's speed (k) increases exponentially with temperature.
Arrhenius equation:
To calculate how fast the beetle can push the ball determine:
the activation energy (E)
the Arrhenius coefficient (k
0
) of the beetle
Activation energy calculation
example 3
RT E
e k k
/
0
=
16
k1 = 6.5 T1 = 300 K
k2 = 13 T2 = 310 K
k3 = 18 T3 = 313 K
k4 = ? T4 = 314.5 K
ln(k) for T=314.5 is equal to ~2.95
This corresponds to a k4 value of 19.1 cm/s.
Activation energy calculation
example 3
Plot ln(k) vs. 1/T
Predict ln(k) for T=314.5 K
Rate (cm/s) Temp (K)
How would you solve the
problem analytically?
17
Analysis of rate equations  outcomes
Be able to use experimental data to get empirical rate equations
Necessity of a rate equation for design purposes
Able to analyse different types of reactions
Expand the analysis to multiple reactions
Chain reactions and their interpretation & analysis
18
Analysis of rate equations general
issues
dt
dN
V
r
i
i
1
=
The rate equation:
The form might be suggested by:
Theoretical considerations
Empirical curvefitting procedure
The value of equation constants experimental only!
2 stepprocedure:
Find concentration dependency at Temp=const.
Find temperature dependency of the rate constants
19
dt
dN
V
r
i
i
1
=
The rate equation:
Equipment used for getting the empirical data
batch reactor container that holds the reactants usually for
homogeneous reactions
flow reactor continuous flow in / flow out  usually for
heterogeneous reactions
Measurements:
concentration of a component
change in physical properties (conductivity, refractive index)
change in total pressure when V=constant.
change in volume when P=constant.
Analysis of rate equations general
issues (contd.)
20
dt
dN
V
r
i
i
1
=
The rate equation:
Procedures for analysing the kinetic data:
integral method:
guess a form of rate equation
integration & mathematical manipulation
predict the plot of C=f (time) as a straight line
plot the data and if good fit accept the equation
differential method:
find (1/V)(dN/dt) from the data
test the fit directly (no integration)
Analysis of rate equations general
issues (contd.)
21
0
0
A
A A
A
N
N N
X
=
Conversion of A:
Constant volume batch reactor
conversion
= the fraction of A
reacted away
0 0 0 0
0
1
/
/
1 1
A
A
A
A
A
A
A
A A
A
C
C
V N
V N
N
N
N
N N
X = = =
=
The volume of reaction mixture = constant
= constant density reaction system
dt
dC
r
A
A
=
22
Constant volume batch reactor
stoichiometric table
A
D
a
d
C
a
c
B
a
b
A + +
Species
B
C
D
) (inert I
0 A
N
0 B
N
0 C
N
0 D
N
) (
0
X N
A
0 I
N
) (
0
X N
a
b
A
) (
0
X N
a
c
A
) (
0
X N
a
d
A
) (
0 0
X N N N
A A A
=
) (
0 0
X N
a
b
N N
A B B
=
) (
0 0
X N
a
c
N N
A C C
+ =
) (
0 0
X N
a
d
N N
A A D
+ =
0 I I
N N =
) ( 1
0 0
X N
a
b
a
c
a
d
N N
A T T

.

\

+ + =
Initially
(mol)
Change
(mol)
Remaining
(mol)
0 T
N
23
A. Integral method
 irreversible, unimolecular, first order rxs. 
s Product A
A
A
A
kC
dt
dC
r = =
Test the firstorder rate equation form:
using concentration
using conversion
0
1
A
A
A
C
C
X =
0 A
A
A
C
dC
dX =
A
A A A
A
kC
dt
dX C
dt
dC
r = = =
0
0 A
A A
C
C
k
dt
dX
=
) 1 (
A
A
A
X k
dt
dX
r = =
24
A. Integral method
 irreversible, unimolecular, first order rxs. 
} }
=
t X
A
A
dt k
X
dX A
0 0
1
Separate & integrate:
} }
=
t C
C
A
A
dt k
C
dC A
A
0
0
kt
C
C
A
A
=
0
ln
using concentration
using conversion
kt X
A
= ) 1 ln(
A
A
kC
dt
dC
=
) 1 (
A
A
X k
dt
dX
=
25
A. Integral method
 irreversible, unimolecular, first order rxs. 
Plot the experimental data & the proposed equation line:

l
n
(
C
A
/
C
A
0
)
o
r
l
n
(
1

X
A
)
t
If the data fit Accept firstorder rate equation
k slope =
26
B1. Integral method
 irreversible, bimolecular, second order rxs. 
s Product B A +
r
A
=
dC
A
dt
=
dC
B
dt
= kC
A
C
B
Test the secondorder rate equation form:
using concentration
using conversion
0 A
A
A
C
dC
dX =
( )( )
A A B A A A
A A A
A
X C C X C C k
dt
dX C
dt
dC
r
0 0 0 0
0
= = =
0 0 A B
C C M =
) )( 1 (
2
0 0 A A A
A
A A
X M X kC
dt
dX
C r = =
A A A A
X C C C
0 0
=
A A B B
X C C C
0 0
=
27
( )( )
} }
=
t
A
X
A A
A
dt k C
X M X
dX A
0
0
0
1
Separate & integrate:
A
B
A B
A B
A
A
A
B
MC
C
C C
C C
X M
X M
X
X
ln ln
) 1 (
ln
1
1
ln
0
0
= =
t
t
A
B
C
C
ln
k C C slope
A B
) (
0 0
=
M
C
C
ercept int
A
B
ln ln
0
0
= =
k C C slope
A B
) (
0 0
=
0 0 B A
C C =
29
B2. Integral method
 irreversible, bimolecular, second order rxs. 
s Product A 2
2 2
0
2
) 1 (
A A A
A
A
X kC kC
dt
dC
r = = =
The secondorder rate equation form:
kt
X
X
C C C
A
A
A A A
=
=
1
1 1 1
0 0
t
A
C
1
k slope =
0
1
A
C
ercept int =
t
k C slope
A0
=
A
A
X
X
1
}
30
B3. Integral method
 irreversible, bimolecular, second order rxs. 
s Product B A +2
) 2 )( 1 (
2
0 A A A B A
A
A
X M X kC C kC
dt
dC
r = = =
The secondorder rate equation form:
kt
X
X
C C C
A
A
A A A
2
1
1 1 1
0 0
=
=
kt M C
X M
X M
C C
C C
A
A
A
A B
A B
) 2 (
) 1 (
2
ln ln
0
0
0
=
=
}
2 = M
2 = M
31