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Reaction Engineering

Chemical Kinetics /
Analysis of rate equations
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Chemical Kinetics - outcomes
Understand the significance of kinetics
Aware of concentration dependencies
Understand the difference elementary / non-elementary reactions
Calculate the order of reaction
Aware of temperature dependencies Arrhenius, activation energy
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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
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Concentration / Temp. dependency terms
.) ., ( temp conc f r =
,...)] , ( )][ ( [
B A A
C C f T k r =
Reaction rate
(constant)
Concentration
dependent terms
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Concentration-dependent 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
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Elementary / Non-elementary Reactions
Elementary reactions iff stoichiometric coefficients are the same as the
individual reaction order of each species

Non-elementary 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
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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 =
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Non-elementary 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

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Concentration / Temp. dependency terms
.) ., ( temp conc f r =
,...)] , ( )][ ( [
B A A
C C f T k r =
Reaction rate
(constant)
Concentration
dependent terms
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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
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Temperature dependency
Arrhenius Law
Arrhenius suggested the following relationship:
RT E
e k k
/
0

=
k
0
= frequency / pre-exponential 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)

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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
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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
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Data on the tenebrionid beetle whose body mass is 3.3 g show that it can
push a 35-g 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
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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?
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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
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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 curve-fitting procedure
The value of equation constants experimental only!
2 step-procedure:
Find concentration dependency at Temp=const.
Find temperature dependency of the rate constants
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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.)
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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
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A. Integral method
- irreversible, unimolecular, first order rxs. -
s Product A
A
A
A
kC
dt
dC
r = =
Test the first-order 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 = =
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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
=
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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 first-order rate equation
k slope =
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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 second-order 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
= =

B1. Integral method


- irreversible, bimolecular, second order rxs. -
kt C C kt M C
A B A
) ( ) 1 (
0 0 0
= =
1 = M Condition:
0 0 B A
C C =
or
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Plot the experimental data & the proposed equation line:
B1. Integral method
- irreversible, bimolecular, second order rxs. -
A B
A B
A
A
C C
C C
or
X M
X M
0
0
ln
) 1 (
ln

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 =
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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 second-order 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
}
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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 second-order 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
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