BASIC PRINCIPLES OF CHEMICAL KINETICS

AB
d  A d  B 
rate  v   
dt dt
A  2 B  3C  D
d  D 1 d  C  d  A 1 d  B
  
dt 3 dt dt 2 dt

1 d[ J ]
v
 j dt

where j is the stoichiometric coefficient with minus sign for

reactants and plus sign for products
v  f ([ A][ B ].......) k is the kinetic rate constant
v  k[ A]a [ B ]b .... (always lower case)

a, b, … are not necessarily the stoichiometric coefficients

are not necessarily integers

The reaction order is the sum of the exponents of

concentration factors in an experimental rate law

a + b +…..

The reaction order is an experimental result

 BrO3  5 Br   6 H   3Br2  3H 2 O
d [ BrO3 ]
  k[ BrO3 ][ Br  ][ H  ] 2
dt

The reaction is first-order with respect to [BrO4-] and [Br-] and

second order with respect to [H+]. Overall, the reaction is fourth
order
Molecularity : number of molecules that react in a single step
(elementary step or elementary reaction).

For an elementary reaction reaction order = molecularity

but this is not true for reactions occurringin many steps.

A bimolecular elementary reactions has second order

kinetics, but a reaction showing second order kinetics
may be complex
 d [ A]
 k Zero order reaction
dt

d [ A]
  k[ A] First order reaction
dt

d [ A]
  k[ A]2
dt
Second order reaction
d [ A]
  k[ A][ B ]
dt
 Determination of order of reaction

a) The method of integration: the concentration of a

reactant or product is determined at various times

b) The differential method: the velocity is measured

at various values of the reactant concentration.
 Method of integration
First-order reactions
d [ A]
  k[ A]
dt
d [ A]
  kdt
[ A]
[ A] t
d [ A]
   k  dt
[ A ]0
[ A] t 0

ln
 A
 kt
 A 0
 A   A 0 exp(kt ) [ k ]  s 1
 A B

 A   B   A 0   B 
 B 0  0

 B   A 0   A   A 0 1  e  kt 
The half-time (or half-life), t1/2

[ A]o
[ A]o 
2

For a first order reaction t1/2 is independent of [A]0

[ A]0 2
 ln  kt1 2
[ A]0

ln 2 0.693
t1 2  
k k
 Use of physical properties in kinetic studies

The rate of a reaction can be determined by removing

samples at various times, quenching the reaction, and then
carrying out a chemical analysis. The method is quite
tedious and instrumental determinations have supplanted
direct analysis.

Consider a property which is linearly related to concentration,

as the absorbance or optical density,D

D  lc Lambert-Beer law

 A B
Dt   A  A   B  B 

For first-order kinetics

Dt   A  A 0 exp(kt )   B  A 0 1  exp(kt )

D0   A  A 0 The value of D at the start of the reaction

D   B  A 0 The value of D at the end of the reaction

Dt  D0 exp( kt )  D 1  exp( kt ) 

Dt  D  D0 exp(kt )  D exp( kt )
Dt  D
 exp( kt )
D t  D    D 0  D   exp(kt) D0  D
For any general reaction, which proceeds to completion,
the concentration of A, the limiting reagent at any time t
is given by

 A   A 0  Dt  D 
 D0  D 
 Second-order reactions

1) 2 A  B v  k  A
2

2) A  B  P v  k[ A][ B]
 d [ A]
1)   k[ A]2
dt
d [ A]
 2
 kdt
[ A]
 A d [ A] t
  k  dt
 A  0 [ A]2 0

1

1
 kt  A 0   A  k  A t 1 1
 A  A 0 or  A 0 [k ]  M s

1
 t1 2
k  A 0
If the reaction is studied by UV-vis spectroscopy

 A   A 0  Dt  D 
1 1
We can substitute whitin   kt
 D0  D   A  A 0

D0  D 1
  kt
 A 0  Dt  D   A 0
1   D0  D   1  D0  D  Dt  D 
 1    kt
 A 0   Dt  D    A 0 
 Dt  D 

D0  Dt
 k[ A]0 t
Dt  D We need to know [A]0 to calculate k
 d [ A]
2)   k  A B 
dt
[ B] [ B]0
ln  ln   [ B ]0  [ A]0  kt
[ A] [ A]0

Method of flooding or pseudo-order reactions

 B 0   A 0
k[ B ]0  k '
d [ A]
  k '[ A]
dt
 k '  s 1
In general

d [ A] BrO3  5 Br   6 H   3Br2  3H 2O
  k[ A]a [ B ]b [C ]c
dt
d [ BrO3 ]
[ B ]0  [ A]o   k[ BrO3 ][ Br  ][ H  ]2
dt
[C ]0  [ A]o [ Br  ]0  300[ BrO3 ]0
d [ A] [ H  ]0  1000[ BrO3 ]0
  koss [ A]a
dt d [ BrO3 ]
  k '[ BrO3 ]
koss  k  B  0  C  0
b c dt
k '  k[ Br  ][ H  ]2
 Zero-order reactions

A reaction rate cannot be independent of the concentration

of all the species involved, but can be independent of the
concentration of one reagent.

If this species is used in deficiency, the reaction results to be

pseudo zero-order

d [ A]
A B  P  A   B 
dt
 k[ B]
 d [ A]
  k'
dt

 A   A 0  k ' t

 k '  M s 1

 A 0  t1 2
2k '
 Differential methods (or initial rate) method)

The initial rates (i.e. the slope of the concentration-time curves)

are measured at various initial concentrations

1 d  A
v  k  A a  B  b C  c
v A dt
 B 0, C  0   A 0
v0  k '  A 0a
ln v0  ln k '  aln A 0
The slope of the double-logarithmic plot is the order with
respect to the substance whose concentration is being
varied
 Reversible reactions

k d  A
A 1

B   k1  A  k 1  B 
 dt
k 1

 A 0   B 0   A   B   A eq   B eq
At equilibrium
d  A
  k1  A eq  k 1  B  eq  0
dt
 B  eq k1
k1  A eq  k 1  B  eq  A eq

k 1
K
 B    A eq   B  eq   A
k1
  A eq   A eq   A
k 1
 k1  k 1 
  A eq   A
 k 1 

d  A  k1  k 1 
  k1  A  k 1   A eq  k 1  A
dt  k 1 

d  A

dt

  k1  k 1   A   A eq 
 A   A eq
ln   k1  k 1  t
 A 0   A eq
 Dt  Deq
ln   k1  k 1 t
D0  Deq
 
k
1
A B  C
k 1

d  A
  k1  A B   k 1  C 
dt

 B  0   A 0 k1  B   costante

 A   A eq
ln   koss t
 A 0   A eq

koss  k1  B   k 1
The influence of temperature on rate constants

Reaction rates are profoundly influenced by temperature

Temperature must always be controlled in kinetic studies

Rates of many reactions approximately double for each 10 °C

rise in temperature
Arrhenius developed his theory by comparing kinetic
observations with the known properties of equilibrium constants

d ln K r H van’t Hoff equation


dT RT 2

k1
K
k 1

k1
d ln
k 1 d ln k1 d ln k 1 r H
  
dT dT dT RT 2
d ln k1 H1 
 2

dT RT
d ln k 1 H 2 
 2

dT RT

Se   0 assunzione di Arrhenius

d ln k Ea
 2
dT RT
Arrhenius equation (empirical)

d ln k Ea

dT RT 2

Ea activation energy

Ea
ln k    ln A
RT
 E 
k  A exp  a 
 RT 
A constant of integration
Transition-state theory(Eyring, 1935)
A bimolecular reaction

A B 
 v  k  A B 
k
prodotti

can be represented

 ‡
A  B
 X  prodotti

Where X‡ is the activated complex, which corresponds to the

configuration of the system in the state of maximum energy
(the transition state).

The activated complex must be distinguished from an

intermediate, which represents a minimum on the
reaction profile.
The concentration of X‡ is assumed to be in equilibrium with
those of the reagents

X   K  A B
‡ ‡

From quantum-mechanical considerations

RT ‡ RT   G ‡ 
k K  exp  Equazione di Eyring
Nh Nh  RT 
Remembering that at p = constant

G  H  TS

RT ‡ RT   H ‡   S ‡ 
k K  exp  exp 
Nh Nh  RT   R 

ln(k/T)

1/T
 Consecutive reactions
A 
k1
B 
k2
C

d  A
  k1  A
dt

 A   A 0 exp(k1t )
d  B
 k1  A  k 2  B 
dt

d C 
 k2  B 1 k1
dt t max  ln
k1  k 2 k 2
Steady-state approximation
d  B
 k1  A  k 2  B 
dt
d  B k1  A
0  B ss 
dt k2
 A   B    C    A 0
d  A d  C 
 
dt dt
dC d  A
  k2  B
dt dt
 k1  A
 Consecutive reactions with elements of
reversibility
k1 k2
A B C D
k 1

d  A
  k1  A B   k 1  C 
dt
d C 
 k1  A B   k 1  C   k 2  C 
dt
d  D
 k2  C 
dt
 B  0   A 0
dC k1  A B    k 1  k 2   C 
0
 C   k1 A B 
dt
k 1  k 2

d  A d  D 
   k2  C 
dt dt
k1k 2  A B 

k 1  k 2

k1k 2  B 
d  A k1k 2  B  k obs 
  dt  k oss dt k 1  k 2
 A k1  k2
k 2  k 1
koss k 1  B  Step 1 is rate-determining

k 1  k 2
k1k 2  B 
koss  Step 2 is rate-determining
k 1
 Pre-equilibria
1 k k2

A B C  D
k 1

 B 0   A 0
d  D
 k 2  C   k 2 K  A B 
dt

 A   C    D   A 0
 A1  K  B    A 0   D
d  A
 1  K  B   d  D
dt dt
 d  A
 1  K  B  k2 K  A B
dt -3
6.0x10

d  A k 2 K  B 
-3
5.0x10

  dt
-3
4.0x10

 A 1  K  B -3
3.0x10

-1
kobs, s
-3
2.0x10

d  A
-3
1.0x10

  k obs dt
 A
0.0

0.0 -2
2.0x10 4.0x10
-2
6.0x10
-2 -2
8.0x10 1.0x10
-1

[L], M

k 2 K  B
k obs 
1  K  B If K  B   1 k oss  k 2 K  B 
kinetics are first-order with respect to [B]

If K  B   1 k oss  k 2

kinetics are zero-order with respect to [B]