CHEM344 Part II 201402

Chemical Kinetics
 Introduction
 Definition
Chemical kinetics is concerned with the rate of chemical reactions,
and the mechanism by which they proceed.
 Chemical Reaction
A process including breaking of bonds or formation of bonds
or both.
Types of reactions
1. Homogeneous:- reaction takes place in one phase (e.g. two miscible
liquids)
Alcoh +H2O  one phase
2. Heterogeneous:- reaction takes place in two or more phases (e.g. two
immiscible liquids)
Benzen +H2O  not one phase
 Factors Affecting Reaction Rate
1. Concentration
2. Temperature
3. Catalysts
4. Nature of reactants "Strength of bond" (gas, liquid, solid) or ( ions,
molecules)
NaOH + RCOOR\  RCOONa + R\OH
Electrolyte Fatty acid Electrolyte

OH- = RCOO- in charge

OH- < RCOO- in size
Ch arge
Note Charge Density 
Volume
So OH- > RCOO- in reaction

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CHEM344 Part II 201402

 The Rate of Chemical Reaction

The rate of chemical reaction (its velocity or speed) is the No. of
moles transferred from reactant to product in unit time
e.g. for reaction Conc. dx x
dt [B]
(mol/L)

AB
d[B]
r= increase of product B
dt dc c
dt [A]
d[A]
r =- decrease of reactant A Time (S)
dt

Has +ve slope Has -ve slope

(concentration increases) (concentration decreases)
dx dc
Rate    Unit is mol L-1 S-1
dt dt
Measure the product
Measure the reactant
concentration at
concentration at
various times
 Note various times
The rate of reaction may have different numerical values according
to the way it is measured
For example
N2  3H2  2NH3
1mol  3mol  2mol
So rate of consumption (disappearance) of H 2 is 3 times rate of
consumption of N2
-d[H2] -d[N2]
 3*
dt dt
And rate of formation (appearance) of NH 3 is 2 times rate of
consumption of N2
d[NH3] -d[N2] -d[H2 ] 3 d[NH3]
2*  *
dt dt dt 2 dt

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CHEM344 Part II 201402
 Order of Reaction
Summation of power of concentration of reactants in rate equation
A  B  Product
r  [A] 1st Order
r  [A]2 2nd Order
r  [A][B] 2nd Order
Rate Equation
r  k[A]O [B]O
r  k[ ]n
Where
r is rate of reaction
[ ] is concentration of reactants
n is order of reaction
k is specific rate constant of reaction
:the rate of reaction when the concentration is unity

 General Case
A  B  C  ....  x  y  z  ....
r[A] [B ]  [C ]
So the rate is th order in A, th order in B, th order in C and so on
And the total order n is
n        ....

 Important notes
1. In some reactions we can’t determine the order of reaction due to
its complexity
e.g. H2  Br2  2HBr
The rate equation will be
d [HBr ] k [H2 ][Br2 ]1 / 2

dt 1  k `[ HBr ]
[Br ] 2

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CHEM344 Part II 201402

2. We should not deduce the order of reaction from its stoichiometry

(molecularity) but by experiment
e.g. in simple reaction
H2  I2  2HI 2nd order
In complex reaction
H2  Br2  2HBr Undefined

3. The order of reaction may be not a whole number, it may be zero

or non-integer (fractional order)

 The Rate-Constant (k)

It is called the specific rate constant at constant temperature (its
value depends on temperature)
Its units depends on the order of reaction
For 1st order
r mol L1 S-1
unit of k    S -1

C mol L1
For 2nd order
r mol L1 S-1
unit of k  2   mol 1
L S-1
C mol L
2 2

For 3rd order

r mol L1 S-1
unit of k  3   mol 2
L2 S-1
C mol 3 L3
 Generally
unit of k  mol 1 n
Ln 1 time -1

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CHEM344 Part II 201402

 1st Order Reaction

A  P k
Initial concentration at time =0 a 0
Concentration at time =t a-x x
Concentration at time =∞ 0 a
-1
 The concentration of A will be (a-x) mol L after time (t), and the amount
of A decomposed or amount of B formed after same time is (x) mol L -1.

d [P ]  d [A]
r    k [A]
dt dt
dx
  k (a  x )
dt
x t
dx
   kdt
0
(a  x ) 0

 ln(a  x )0  k t 0
x t

 (ln(a  x )  lna )  kt
a
ln  kt
a x

Kinetic Equation for

1st Order Reaction

ln(a  x )  lna  kt

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CHEM344 Part II 201402
 Graphical Representation
ln a
a ln(a-x)
ln
a-x

slope = k
slope = -k

time time

 Half Life Period (time) t1/2

The time at which half of material of reactants is consumed and half
of product is produced
A  P
Initial concentration at time =0 a 0
Concentration at time =t a-x x
Concentration at time =∞ 0 a
Concentration at time = t1/2 ½a ½a
a
ln  kt
a x
1 a
t  ln
k a x
1 a
t  ln
k a  a2
1
2

1
t  ln2
k
1
2

0.693
t 
k
1
2
t1/2 is independent on initial
OR
concentration
ln 2
t 
k
1
2

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CHEM344 Part II 201402

Examples
1- 1st order reaction with k=5 x 10 -2 min-1 what is the t90%
Solution
a 1st order reaction
ln k t
a -x k=5 x 10-2 min-1
At t90% x = 90 a=100
t90% = ?? min
100
ln =5 * 10-2min-1 *t
100-90

t  46 min

2- 1st order reaction with t1/2 = 5 min, calculate the time required to 75% of
reaction to occur
Solution
1st order reaction
At t1/2 x = 50 a=100
At t75% x = 75 a=100 t1/2 = 5 min
t75% = ?? min
50 ≡ 5 min
75 ≡ t min

5 * 75
t   7.5 min
50

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CHEM344 Part II 201402
3- The reaction SO2Cl2  SO2  Cl2 is 1st order gas reaction with k=2.2 x 10-5 S-1
at 320 C. What % of SO2Cl2 decomposed on heating at 320 C for 90 min ?

Solution
a 1st order reaction
ln k t
a -x k=2.2 x 10-5 S-1
% of SO2Cl2 decomposed = x a=100
t = 90 min
a
ln  2.2  10 -5 S 1  5400S = 90 * 60 = 5400 Sec
a -x
100
 1.126
decomposed x
100-x
% decomposed = x =?? a=100

100  1.126 *100  1.126x  1.126x  112.6  100  12.6

 % decomposed = 11.2 %

4- The 1st order reaction is 30% complete in 35 min, what is the value of the
rate constant in S-1 ?, what % of reactant will remain after 5 hours ?
Solution
a 1st order reaction
ln k t
a -x
k=?? S-1
x  30 a =100
t = 35 min=2100 S
100
ln  k *2100 S complete  x
100-30 % complete = x=30 a=100
 k  1.69 * 10 4 1
S
t = 5 hours= 18000 Sec

a remain  a-x
ln  1.69 * 10 S
4 1
* 18000 S % remain =a-x =?? a=100
a -x

100 a -x
 20.95   0.0477
a -x 100

 %remain  a  x  4.77%

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CHEM344 Part II 201402
5- In a certain 1st order reaction half of the material is decomposed in 1000 S,
how long will it be until only 0.1 is left?
Solution
0.693 1st order reaction
t   1000S
k
1
2
t1/2 =1000 S
 k  6.93 * 10 4 S 1
a-x  0.1*100=10 left  a-x
 x  90 % left = a-x  100 =0.1 *100
a a =100
ln k t
a -x
100
ln  6.93 * 104 t
100-90
t  3322 .63S
 Pseudo-1st Order Reaction
The reaction which satisfy the 1st order reactions, but actually more
than one molecule is involved in chemical reaction (one with low
concentration while the others with very high concentration)
A  B  C  Pr
at time =0 1 100 100 0
at time =t 0.5 99.5 99.5 0.5
dx
  k [A][B ][C ]  k [A]
dt k   k [B ][C ]
So 1st order equation Constan
Constant t
 Examples
1-The hydrolysis reaction of ester in acidic (or basic) solution
RCOOR \  H   H2O  RCOOH  R \OH  H2O
dx
  k [RCOOR \ ][H  ][H 2O ]
dt
Since the acid is present in large excess, and water is the solvent, so the
amount used in reaction is negligible in comparison with the total i.e may
be regarded as constant
dx
  k [RCOOR \ ]
dt

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CHEM344 Part II 201402
2-The Inversion of Sucrose
C 12H22O11  H2O 
H
C 6H12O6  C 6H12O6


Sucrose Glucose Fructose

 The rate depends only on the concentration of sugar due to water
(solvent) and hydrogen ion (catalyst) remain constant
 Due to the mixture of glucose and fructose (products) are levo-
rotatory, so the reaction can be followed by measuring  with the
polarimeter t

   

Gl & Fr Suc Gl & Fr Suc

a tx
tax
0 : angle of rotation at time zero
 : angle of rotation at 
t : angle of rotation at time t
 From the 1st order equation
a
ln k t
a -x
  
 ln 0 k t
t   
Ex: In the inversion of sucrose in presence of an acid, the following
polarimeter reading is obtained
t (min) 0 30 40 150 630 
 46.75 41.00 30.73 22.00 -10 -18.75
Determine the rate constant and half life period
   0 = 46.75
ln 0 k t
t     = -18.75
46.75  18.75 at  = 41 t = 30 min
ln  k *30  k  3.1 *103 min1
41  18.75 at  = 22 t = 150 min
46.75  18.75
ln  k *150  k  3.1 *103 min1
22  18.75
0.693
t1   226.3min
2
3.1 * 103 min 1

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CHEM344 Part II 201402

 2nd Order Reaction

 One reactant
2A  P
Rate  k [A]2
 Two reactants
A  B  P
Rate  k [A][B ]

 Case 1 two reactants where [A]0 = [B]0

A  B  Pr k
at time =0 a a 0
at time =t a-x a-x x
 The concentration of A and B will be (a-x) mol L-1 after time (t), and the
amount of A and B decomposed or amount of product formed after same
time is (x) mol L-1.
dx
  k (a  x ) 2
dt
x t
dx
   kdt
0 (a  x ) 2
0
x
 1 
   kt
 a  x 0
1 1
  kt
a x a

Kinetic Equation for

2nd Order Reaction
[A]0 = [B]0

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CHEM344 Part II 201402
 Graphical Representation

 Unit of k
r mol L1 time -1
unit of k    mol 1
L time -1
C2 mol 2 L2
 Half Life Period (time) t1/2
x
 kt
a (a  x )
a
2
 kt1 / 2
a (a  2) a

1
t  t1/2 is dependent on initial
ak
1
2
concentration

Examples
1- A second order reaction involving reactants initial present in 0.1 mole/L, and
found to be 20% complete in 40 minutes. Calculate
a) The rate constant b) Period of half life
c) How long will it take for the reaction to be 20% completed if a = 0.02
Solution 2nd order reaction
x
a)  kt a=0.1 mol/L
a (a  x )
a  100  0.1 t = 40 min= 2400 Sec
x  20  ?? complete x
x =(20/100) * 0.1 = 0.02 mole/L
% complete = x=20 a=100

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CHEM344 Part II 201402
0.02molL1
 k * 2400s
0.1molL1 (0.1  0.02)molL1
 k  1.04 * 10 3 L mol -1S 1

1 1
b) t1 / 2    9600 S
ak 0.1 * 1.04 * 10 -3

c)
x =0.2 * 0.02 = 4 * 10-3 mole/L
4 * 103
 1.04  103 t
0.02(0.02  4 * 10 )
3

t = 12019 S

2- A 2nd order reaction in which [A]0 = [B]0 is 20% completed in 500 S. How
long does it take for 50% completion.
Solution
x 2nd order reaction
 kt
a (a  x )
t = 500 S
x  20 a=100 complete  x
20 % complete = x=20 a =100
 k * 500
100(100  20)
 k  5 * 106 S 1
1 1
t1/2    2000 S
ak 100 * 5 * 10-6

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CHEM344 Part II 201402
 Case 2 [A]0  [B]0

A  B 
k
Pr
at time =0 a b 0
at time =t a-x b-x x
 The concentration of A will be (a-x) mol L-1 and that of B will be (b-x) mol
L-1 after time (t), and the amount of A and B decomposed or amount of
product formed after same time is (x) mol L -1.
dx
  k (a  x )(b  x )
dt
x t
dx
0 (a  x )(b  x )  k 0 dt
And by integration

Kinetic Equation for

2nd Order Reaction
[A]0  [B]0
 Graphical Representation b(a-x)
ln
a(b-x)

slope = k(a-b)

time
 Half Life Period (time) t1/2
In that case we can’t get an equation for t1/2, but we can get it from
the kinetic equation using x= half of the smallest concentration of
the reactants.
A  B  Pr
1 2
0.5 0.5 0.5
 In this case for simplicity we can use the idea of pseudo-1st order

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CHEM344 Part II 201402
Examples
1- The 2nd order rate constant for an alkaline hydrolysis of ethylformate at 30
C is 4.53 L mol-1 S-1, calculate the half life of the reaction if
a) The reactants are both present at 0.01 mol/L
b) The con. of one of the reactants is doubled and the other is cut in half
Solution
1 1 2nd order reaction
a) t1 / 2    22.075 S
k = 4.53 L mol-1 S-1
ak 0.01 * 4.53
a=0.01 mol/L
1 b (a  x )
b) ln  kt
(a  b ) a (b  x )
a=0.02 mol/L
1 0.005(0.02  0.0025 ) b=0.005 mol/L
ln  4.53 * t
(0.02  0.005) 0.02(0.005  0.0025 ) x= ½ * 0.005 (the smallest)
= 0.0025 mol/L
t1 / 2  8.235 S
2- The alkaline hydrolysis of ethylacetate is 2nd order reaction, for which the
rate constant at 25 C is 6.49 L mol-1 S-1, calculate the t1/2 if
a) The initial concentration of ester and base are each 0.0125 mol/L
b) The [ester]0 is 0.0125 mol/L and [base]0 is 0.025 mol/L
2nd order reaction
Solution k = 6.49 L mol-1 S-1
1 1
a) t1 / 2    12.326 S a=0.0125 mol/L
ak 0.0125 * 6.49

1 b (a  x ) a=0.0125 mol/L
b) ln  kt
(a  b ) a (b  x ) b=0.025 mol/L
x= ½ * 0.0125 (the smallest)
= 6.25*10-3 mol/L
1 0.025(0.0125  6.25 * 10 3 )
ln  6.49 * t
(0.0125  0.025) 0.0125 (0.025  6.25 * 10 3 )

t1 / 2  4.998 S

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CHEM344 Part II 201402

 3rd Order Reaction

 That can be one reactant, two reactants or three reactants
3A  P Rate  k [A]3
A  2B  P Rate  k [A][B ]2
A  B  C  P Rate  k [A][B ][C ]
 If all the initial con. of reactants are equal
Rate  k (a  x )3
 In case of two reactants
A  2B  P
Rate  k (a  x )(b  x )2
If b=2a
Rate  k (a  x )(2a  2x )2
Rate  4k (a  x )3
 Generally

3A 
k
Pr
at time =0 a 0
at time =t a-x x
 The concentration of reactants (a) mol L -1 will be (a-x) mol L-1 after time
(t), and the amount of reactants decomposed or amount of product formed
after same time is (x) mol L -1.
dx
  k (a  x ) 3
dt
x t
dx
   kdt
0 (a  x ) 3
0
x
 1 
 2 
 kt
 2(a  x )  0
1 1
   kt
2(a  x ) 2
2a 2

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CHEM344 Part II 201402
1 1
   2kt
(a  x )2 a2
OR Kinetic Equation for
3rd Order Reaction
same initial conc.
 Graphical Representation

 Unit of k
r mol L1 time -1
unit of k  3   mol 2
L2 time -1
C mol 3 L3
 Half Life Period (Time) t1/2
Note at t = t1/2 x = a/2

1
t1 / 2 
ka n 1

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CHEM344 Part II 201402

 Determination of the Order of Reaction

1. Integration Method (Try and Error Method)
Determine by analysis the amount of reactant decomposed with
interval times
t (S)
x (mol/L)
a) Numerically :
The concentration and time data are substituted into the various kinetic
equation for the deferent order reaction (1st, 2nd, 3rd,…) to get (k). The
equation giving the most constant value for (k) over a range of time intervals
is the equation corresponding to order of reaction
b) Graphically :
That by plotting the concentration and time data
i ) If plot of ln (a/a-x) # t gives straight line so the reaction is 1st order
ii) If plot of x/(a-x) # t gives straight line so the reaction is 2nd order
iii) and so on
2. Half Life Method
 For 1st order
0.693
t  Independent on initial concentration
k
1
2

 For nth order

1
t1 / 2  Inversely proportional to a with power n-1
a n 1

log(t1 / 2 )  const  (n  1)log(a )

 By making an experiment at two different initial conc. and

determining the t1/2 at each concentration

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CHEM344 Part II 201402
 If t1/2 unchanged so it is 1st order reaction
 If t1/2 changed so it is not 1st order reaction and we can using the
following equation
Conc.
n 1
(t1 / 2 )1  a2 

 

(t1 / 2 )2  a1 
By taking log and rearranging
log[(t1 / 2 )1 /(t1 / 2 )2 ]
n 1 t1/2 time
log[a2 / a1 ]

Example
The half life of reaction AP at deferent concentrations are found to be
Conc. (mol/L) 0.01 0.03 0.05
t1/2 (S) 200 67 40
Determine the order of reaction and the specific rate constant and t 90% for
1st conc
Solution
Since t1/2 depends on Conc. so it is not 1st order reaction
log[(t1 / 2 )1 /(t1 / 2 )2 ] log[200 / 40]
n 1 1 2 2nd order
log[a2 / a1 ] log[0.05 / 0.01]
1 1 1
t 12  k  k   0.5 Lmol 1S 1
ak at 12 0.01 * 200
At t1/2 x = 50 a=100
At t90% x = 90 a=100
50 ≡ 200 S
90 ≡ t min
200 * 90
t   360 S
50
Note
If n= 1.07 so n≈1
If n= 1.95 so n≈ 2

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CHEM344 Part II 201402
3. Deferential Method (Initial rate method)
 The rate of reaction (γ) related to the conc. (C) of reactants by
  kC n log V
log   logk  n logC
 Plotting log γ # log C gives a straight line slope = n
with slope = n (order of reaction) and
intercept = log k log k
log C

o The rate of reaction (γ) can be measured by at various initial

concentrations (initial rate) , the –ve slope at beginning of each
reaction is the rate
Conc.
a1

a2

a3

time
4. Isolation Method
 Using this method when the rate of reaction depends on more than
one Conc.
A  B  C  ...  products
 By converting the reaction into pseudo order reaction that is if one
of reactants kept with small concentration (isolated), while the
others in large excess (act as solvents)
 The order of reaction can be determined by any methods described
above with respect to the isolated reactant
 If CB , CC >> CA So order of reaction is respect to A is 
 If CA , CC >> CB So order of reaction is respect to B is 
 If CA , CB >> CC So order of reaction is respect to C is 
 So the total order is
n        ...

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CHEM344 Part II 201402

 Effect of Temperature on Reaction Rate

 The rates of reaction depends on temperature
 Arrhenius derived equation describing the variation of rate constant with
temperature using the idea of activation
 Activation energy: that reactant molecules must acquire before they can
form the activated complex
 Minimum amount of energy to overcome transition state,
independent on temperature or concentration
 i.e.
Activated complex
Reactant   Product
Transition State
Activated
E complex
Energy
k  Ae RT
E
Where A is frequency factor
E is activation energy
R
R is gas constant
P
T is absolute temperature

Rxn Cord.

 Taking log
E
ln k  ln A 
RT
E
log k  log A 
2.303RT

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CHEM344 Part II 201402

 For a reaction at equilibrium

k

A  B 
1
C +D
k2

At equilibrium γf= γb
k1 [A]a [B]b
K 
k2 [C]c [D]d
 The E is the activation energy of forward
reaction (γf), and it is the difference in energy
between transition state and reactant
 The E\ is the activation energy of backward
reaction (γb), and it is the difference in energy
between transition state and product
 Note that the heat of reaction (H = E – E\)
 If H=+ve so the reaction is endothermic, if H=-ve so it is exothermic
 It is found that
d ln K H

dT RT 2
d ln(k / k \ ) E  E \

dT RT 2
d ln k d ln k \ E E\
  
dT dT RT 2
RT 2
d ln k E

dT RT 2
 By integration
E
 d ln k   RT 2
dT
E
ln k   Const .
RT

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CHEM344 Part II 201402

 The activation energy can be get

experimentally, by performing a T 298 303 ---
certain reaction at different k
temperature to get their rate constant 1/T
 Plotting ln k # 1/T gives a straight ln k
line with slope equal (-E/R)
 If we consider the integration constant ln A
be ln A (Const. = ln A)
ln k
 i.e.
E
ln k   ln A
RT
E slope = -E/R
 k  Ae RT

1/T
Where A is pre-exponential (frequency) factor
 Using limited integration
k2 T2
E
 d ln k 
k1
T RT 2 dT
1

k2  E  1 1 
ln    
k1 R T2 T1 
k E 1 1
ln 2    
k1 R T1 T2 

Arrhenius Equation of
Activation energy

Page 23 of 39
CHEM344 Part II 201402
Examples
1- The rate of a reaction at 30 C is twice that at 20 C. Calculate the energy
of activation

Solution
Arrhenius Equation
k E T T 
ln 2   2 1  T1 = 20+273 = 293 K
k1 R  T1T2 
K2 = 2 k1 T2 = 30+273 = 303 K
 k2/ k1 = 2 R = 8.314 J mol -1 K-1
E  303  293 
ln 2    K2 = 2 k1
8.314  303 * 293 
E = ??
 E  51.162 kJmol 1

2- A reaction has activation energy of 80 kJ/mol. Calculate the ratio of its

rates at 40 C and 50 C.

Solution
Arrhenius Equation
k E T T 
ln 2   2 1  T1 = 40+273 = 313 K
k1 R  T1T2 
k 80 * 1000  323  313  T2 = 50+273 = 323 K
ln 2   
k1 8.314  323 * 313  R = 8.314 J mol -1 K-1
k K2 / k1 = ??
 2  2.6
k1

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CHEM344 Part II 201402

3- At 378 C the half life period for the 1st order thermal decomposition of
ethylene oxide is 363 min, and the energy of activation of the reaction is
218 kJ/mol. From these data estimate the time required for ethylene oxide
to be 75 % decomposed at 450 C.
Solution
0.693 1st order reaction
t   21780 S
k t1/2 =363 min
1
2

 k1  3.18 * 10 5 S 1 = 21780 S

k2 E T2 T1  decomposed x

ln   
k1 R  T1T2  % decomposed = x=75 a=100
k2 218 * 1000  723  651  Arrhenius Equation
ln   
3.18 * 10 5 8.314  723 * 651  T1 = 378+273 = 651 K
 k2  1.76 * 10 3
T2 = 450+273 = 723 K

a R = 8.314 J mol -1 K-1

ln k t
a -x t = ??
100
ln  1.76 * 103 *t
100-75

t  787.66 S

OR t  13.13 min

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CHEM344 Part II 201402

 Physical Significance of Arrhenius Equation

 At the same temperature all molecules has the same kinetic energy,
but differ in velocity depends on mass.
3 1
 KE  kT  mv2
2 2
 At high temperature, the ratio of molecules that overcome energy
barrier is high so the reaction is fast
 The barrier energy is called the activation energy
 At heating average energy increases that moves the peak to the RHS
ni E
  const * exp( i )
nt RT
 Only fraction of molecules under the dashed curves have the
sufficient energy to react, and so this No increases by increasing
temperature

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CHEM344 Part II 201402

 Theory of Reaction Rate

 There are two theories called Collision and Transition State theories
 Collision Theory (Frequency Factor)
 The collision theory depends on
 For any reaction to tack place, Molecules must be collide
 Using Arrhenius concept of activation energy, not all collision leads to
reaction but only molecules which acquire sufficient energy to over-
come the activation barrier can react
 In collision theory it is considered that two particles A and B will
collide if their nuclei get closer than a certain distance.
 The area around a molecule A in which it can collide with an
approaching B molecule is called the cross section of the reaction and
is, the area corresponding to a circle whose radius is the sum of the
radii of both reacting molecules(σ A + σB)
 The volume swept per unit time by moving A molecule is
 (A  B )2 * C
Where C is the relative velocity of AB molecule
 The No of B molecules colloid with one A molecules per unit time is
nB
 (A  B ) * C * 2

V
 The total No. of collision per unit time is
nB nA
 (A  B )2 * C * *
V V
 The relative velocity is
8kT
C

Where μ is reduced mass
 The total No. of collision per unit time is called Z (collision frequency)
 So the rate of reaction is
Ei /RT
  Ze   k[A][B]

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CHEM344 Part II 201402
 For bimolecular gas reaction it is found that the kcalc  kobs
kobs (determined experimentally)
kcalc (calculated from above equation)
 In more complicated reactions and in solution reactions it is found that
the kcalc >> kobs
 That can be explained on the basis that the theory considers that each
collision will give reaction (that is incorrect)
 For example, for a certain reaction it may be 10 collisions can lead to only
1 reaction, that is to say kcalc = 10 kobs
 The correct equation can be
E
k  pZe RT

Where p is the probability factor (steric factor)

is the No. of collision which leads to reaction
for above example p = 1/10 (its maximum is unity)
 This theory has two disadvantage
 There is no relation between p and the structure or properties of
molecule
 In some reactions it is found that kobs >> kcalc

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CHEM344 Part II 201402

 Transition State Theory

 The transition state theory depends on
 The bond breaking and bond forming must occur simultaneously
 For example, the reaction between H 2 & I2 can be showed graphically
as follows
H2  I2  2HI
H H
H H H H

I I I I I I
 The intermediate product with the partial formed bonds is known as the
transition state or the activated complex
 This theory focus attention on the activated complex or the transition
state which corresponds to the top of the potential energy barrier
 For the reaction X#
Energy

k

A  B 
1

 X # k2
 P A+B
k 1

 The k-2 is very small so can be neglected P

 The decomposition of X# into products is
Rxn Cord.
slow step so it is the rate determining step (RDS)
  k2[X# ]
 The steady state approximation state that the concentration of the
activated complex [X#] is constant during the reaction
d[X# ]
i.e. 0
dt
 By application of the steady state approximation
 The rate of formation of X# is
 k1 [A][B]
 The rate of disappearance of X# is

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CHEM344 Part II 201402

 k1 [X# ]  k2[X# ]

 k1  k2  [X# ]
d[X# ]
  k1 [A][B]  k1  k2  [X# ]  0
dt
 k1 [A][B]  k1  k2  [X# ]
 The concentration of the activated complex can be
k1
[X# ]  [A][B]
k
1
 k2 
 And the rate of reaction is
k1k2
  k2 [X# ]  [A][B]
k 1
 k2 
 k2<<k-1 so
k1k2
 [A][B]  k2K[A][B]
k1
  k\ [A][B] 2nd order reaction
Where K is equilibrium constant
 Do the same for the 1st order reaction

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CHEM344 Part II 201402

 Unimolecular reaction
1. In case of decomposition of a gas A, the reaction seems to be 1 st order
reaction, while to reach the activated complex it must be colloid A+A and
will be 2nd order reaction
2. Lindeman theory
 In a container full with A, the inter-molecular collisions are continually
producing molecules with higher energy
k

A+ A  1
 A# + A
 then A# 
k2
Prod
k 1

 The activation process consists of transfer of translational kinetic

energy from one molecule to vibrational of the other molecule, so
increase the amplitude of vibration on a certain bond causes
dissociation giving product
 Appling the steady state approximation (the appearance of the
activated molecule is almost zero)
d[A# ]
= k1 [A] 2 - k-1 [A# ][A] - k2 [A# ]  0
dt
k1 [A] 2 = k-1 [A# ][A] + k2 [A# ]
k1 [A] 2
 [A ] = #
k-1 [A] + k2
k2 k1 [A] 2
 = k2 [A ] = #
k-1 [A] + k2
 At very high pressure [A] is very large so k-1 [A]  k2
 So we can neglect k2
k2 k1 [A] 2
V =  k[A] 1st order reaction
k-1 [A]
k2 k1
Where k=
k-1
 At very low pressure [A] is very small and so k-1 [A]  k2
 So we can neglect k-1[A]
k2 k1 [A] 2
V =  k1 [A] 2 2nd order reaction
k2

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CHEM344 Part II 201402

 Chain reactions
 It is found empirically that the rate equation of the H 2 and Br2 reaction is
complex while that in case of the H 2 and I2 is simpler
H2 + Br2  2HBr
1/2
d HBr  k H2 Br2 
=
dt 1 + HBr  /k  Br2 
H2 + I2  2HI
d HI 
= k H2 I2 
dt
 That can be explained by the chain reaction that is the reaction can be
follow in 5 steps, in which the Br and H radicals are formed that are called
the chain carrier
1) Br2  k1
2Br  Initiation Step

2) Br   H2  k2
HBr + H 
Propagation Steps
3) H   Br2  k3
HBr + Br 
4) H   HBr  k4
H2  Br  Inhibition Step
5) Br   Br  k5
Br2 Termination Step
 The step 1 is called the initiation step, steps 2 & 3 are called propagation
steps, step 4 is the inhibition step which explains the inhibition of HBr,
and finally step 5 the termination step.
 By applying the steady state approximation, that is the rate of appearance
of chain carriers are almost zero
d Br   2
= k1 Br2   k2 Br   H2   k3 H   Br2   k4 H   HBr   k5 Br    0
dt

d H  
= k2 Br   H2   k3 H   Br2   k4 H   HBr   0
dt
 Adding to equations
2
k1 Br2   k5 Br  

Page 32 of 39
CHEM344 Part II 201402
1/ 2
k  1/ 2
Br    1 

Br2 
 k5 
 And from that and last equation
k2  k1 k5 
1/ 2 1/ 2

H   
H2 Br2 
k3 Br2   k4 HBr 
 The rate equation of the HBr is
d HBr 
= k2 Br   H2   k3 H   Br2   k4 H   HBr 
dt
 Substituting for [H  ], and [Br  ] and rearrangement so
d HBr  2k2  k1 k5  H2 Br2 
1/2 1/2

=
dt 1 + k4 HBr  / k3 Br2 
 And that is similar to the empirical one
1/2
d HBr  k H2 Br2 
=
dt 1 + HBr  /k  Br2 
 In case of the I2 reaction it is not chain reaction because the activation
energy is very high so it will be Proceeds by molecular reactions

 Explosive reactions (Branched Chain reactions)

 For a reaction between H2 and O2 giving water with ordinary rate (steady
reaction) at 550 C and 2 mmHg pressure.
 If the pressure gradually increases the rate increases and at certain
critical pressure (~50 mmHg) explosion occur
 The critical pressure depends on the size and shape of the container
 If the reaction is initially maintained at 200 mmHg, the reaction will be
steady reaction, if the pressure gradually decreases it will be explode at
about 100 mmHg
 The 1st figure show the relation between the rate and the pressure so it
describes the regions in which steady or explosion reactions occur
 In the 2nd figure show the relation between the pressure and the
temperature of the reaction, so it will describe the regions of steady and
explosion reactions and the limits between them

Page 33 of 39
CHEM344 Part II 201402

3 rd E

Explosion Reaction
xplos
Rate

n
ion lim

tio
it

Pressure
ac
Steady Reaction

Re
n
Steady Reaction tio

dy
ac
Re

ea
it
im
nl

St
s io n
o io
os
p l
nd Ex pl
Ex
2
X 1st Explosion limit
Explosion Reaction

Pressure 460 600 Temp.

Figure 1 Figure 2

 It shows that the reaction will be in steady one below 460 C and at any
pressure, and will explode above 600 C and at any pressure
 The 1st and 2nd explosion limits known as lower and upper explosion limits
which are must be known for any gas reaction (that is important in
industry)
 The 3rd explosion limit found only at very high pressures
 The explosion reactions can be caused by two reasons
1. In exothermic reaction can be caused by thermal explosion
2. in other systems can be caused by the branched chain reaction, in
which in the propagation steps gives with the product a chain carrier
so a branched chain occur
 To describe the kinetics of branched chain reactions suppose the following
reaction
nA  k1
R Initiation Step
R  A k2
 P + R Propagation Step
R k3
destruction Termination Step
 Applying the steady state approximation
d R  n
= k1 A   k2 R A   k2 R A   k3 R   0
dt
n
k1 A   k2 R A  1     k3 R   0
n
k1 A   k2 R A  1     k3 R 
n
k1 A 
 
R =
k2 A  1     k3

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CHEM344 Part II 201402
 For the destruction step with rate constant k3 , the destruction of the
chain carrier can be occur by two methods
1. By walls of the container that is destruction of the chain carrier when
collide with walls, and the rate constant will be kw
2. By bulk of the gas that is the normal destruction of any two collision
of chain carriers, and the rate constant will be k g
 So
k3  kw + kg
n
k1 A 
 
R =
k2 A  1     kw + kg
 From the last equation it is obvious that
1. When  >> 1 so there is a –ve term and if it will be greater enough to
equal the +ve term so the dominator will be zero, i.e. the concentration
of chain carrier is  and explosion occur
2. When  = 1 so it will be a normal chain reaction in which
n
k1 A  rate of production
 
R = 
kw + kg rate of destruction
 Also from the above equation we can explain why the 1 st explosion limit only
depends on the size and shape of the container
1. That is, if a reaction in an explosion area (X) at the figure 1, if the
pressure decreases the chain carriers will reach to the walls to be
destructed (1st explosion limit), and that is depends on the size and
shape of container
2. But if we increases the pressure the chain carriers will be destructed
in bulk (2nd explosion limit), and that is depend on the material
 For the H2 and O2 reaction the propagation steps are
O + H2 
k
OH + H
H + O2 
k
OH + O
 Note that all OH, O, and H are a chain carriers which causes the branched
chain reaction

Page 35 of 39
CHEM344 Part II 201402

 Reactions in Solution
 Reactions between ions
1. Influence of Solvent
 According to the transition state theory
kT - G # /RT
k= e
h
 In case of reaction between ions the electrostatic interaction is the most
important contribution to the free energy G
G #  Gn.e.l
#
 Ge.l#
 To get the electrostatic free energy the simplest treatment is used
 The charged ions are considered to be conducting spheres, and the solvent
has a continuous and fixed dielectric constant
 Consider that the ions initially at infinite distance, and in the activated
state, they are considered to be intact by a distance d AB
 The force arising between the tow ions at a distance x can be
ZA ZB e 2
F=
x 2
Where ZAe and ZBe are the electronic charges of ions
 is the dielectric constant of solvent
ZAe

dAB

activated state

ZBe
initial state

 And the work must be done to move them a distance dx is

ZAZB e 2
dW = - dx
x 2

The –ve sign due to the x decreases

Page 36 of 39
CHEM344 Part II 201402
 By integration with the reaction limits
dAB
ZAZB e 2
W= - dx

x 2

ZAZBe 2
W=
dAB
 Note that the work will be +ve if the two ions are similar signs and will be –
ve otherwise
 This work is equal to the free energy change due to the electrostatic
contribution or
ZA ZB e 2 NA
G = #
e.l
dAB (per molecule)

 And so
kT - Gn.e.l
#
/RT -ZA ZB e 2 / dAB kT
k= e e
h
kT Gn.e.l #
ZAZB e 2
Lnk = Ln - -
h RT dAB kT
ZAZB e 2
Lnk = Lnk0 -
dAB kT
Where k0 is the rate constant of reaction on a medium of  dielectric
constant
 The above equation indicates that the logarithm of rate constant vary
linearly with the reciprocal of the dielectric constant of the medium (1/)
Lnk

Dioxan ZAZBe2
0 10 ------ 90 100 Slpoe=
edABkT
=4
Water
100 90 ------ 10 0
 = 71

1/
Page 37 of 39
CHEM344 Part II 201402

 That if a reaction occur in a series of mixed solvents of varying  and

plotting Lnk # (1/) a straight line obtained in a good agreement, but a
deviation will occur at very low dielectric constant
ZAZBe 2
 From the curve the slope is equal to in which all are known except
dAB kT
the dAB so this method can be used in determination of the d AB

1. Influence of Ionic Strength

 That is the effect of neutral salt on rates of reaction in solution
 For a reaction
K
A+ B X #  k1
Prod
a# X #  
K=  #
aAaB A B   A B
 
X #  = K A B  A B
#
 The rate of the reaction is
 A B
V = k1 X  = k1K A B 
 #

#
 
V = k0 A B  A B
#
 And the rate constant of the reaction will be
V  
k= = k0 A B
A B  #
Logk = Logk0  Log  A  Log  A  Log  #
Log   -0.5Z 2 I

Page 38 of 39
CHEM344 Part II 201402
 So for a reaction
K
A ZA + B ZB X #ZA+ ZB
Log  A  -0.5ZA2 I
Log  B  -0.5ZB2 I
Log  #  -0.5  ZA  ZB 
2
I


Logk = Logk0 - 0.5 I Z + Z  Z A  Z B 
2
A B
2 2

Logk = Logk0 + ZA ZB I
 This is a linear relationship, that if we plot Logk # square root of ionic
strength it will gives a straight line but the slope of the line depends on
the signs of the reactants, so there are 3 cases
1. When ZAZB is +ve (similar charges) so the slope will be +ve and
acceleration will occur with increasing ionic strength of medium
2. When ZAZB is -ve (different charges) so the slope will be -ve and
retardation will occur with increasing ionic strength of medium
3. When ZAZB is zero (one of reactants is neutral) so the slope will be
zero and there is no any effect on the rate constant with increasing
ionic strength of medium
 Note also that in case of the divalent Ln k ZAZB=+2
k0
reactants the acceleration (retardation) ZAZB=+1
is larger than that of the univalent
reactants
 In some cases ion-pair formed which can ZAZB=0
0
causes reduction of the true ionic strength
and also changes in the electrostatic
interaction between reactants and that ZAZB=-1
will cause deactivation of the reaction
ZAZB=-2

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