Chemical Kinetics

The change in the number of moles / litre of any reactant or product per unit time is known as rate
of reaction.

The rate measured over a long time interval is called average rate and the rate measured for an
infinitesimally small time interval is called instantaneous rate.

Consider a reaction

A → B Average rate of reaction =

Instantaneous Rate

In general, for a reaction,

n1A + n2B → m1C + m2D

The instantaneous rate may be expressed as

rinst = dx/dt = 1/n1 x d[A]/dt = -1/n2 x d[B]/dt = 1/m1 x d[C]/dt = 1/m2 x d[D]/dt

([R] = concentration of reactant and [P] = concentration of product)

Rate at the time t = slope of tangent = tan(θ)

Reaction Life Time- It is defined as the time taken by a reaction to proceed to 98% of
completion. The half life period is defined as the time during which the concentration of a
reactant is reduced to one half of its initial value or the time in which half of the reaction is
completed.

Elementary and Complex reactions, Reaction Mechanism

An elementary reaction is a single step reaction with a single transition state and no
intermediates.

Elementary reactions add up to complex reactions; non-elementary reactions can be described

by multiple elementary reaction steps. A set of elementary reactions comprises a reaction
mechanism, which predicts the elementary steps involved in a complex reaction.

Reaction between Br- and H2O2 in acidic medium:

The overall reaction is 2Br- + H2O2 + 2H+ → Br2 + 2H2O The proposed mechanism is

Step 1: 2Br- + H2O2 + H+ → HOBr + H2O Slow

Step 2: HOBr + H+ + Br- → Br2 + H2O Fast

The molecularity of a reaction is the number of reactant species (molecules ions or atoms)
taking part in a single step of the reaction.(undergoing simultaneous collision) eg

PCl5 → PCl3 + Cl2 Unimolecular

2HI → H2 + I2 Bimolecular

2SO2 + O2 → 2SO3 Trimolecular

 Molecularity is a theoretical concept

 Molecularity cannot be zero, -ve, fractional, infinite and imaginary
 Molecularity cannot be greater than three because more than three molecules may
not mutually collide with each iother

Order of Reaction

The mathematical expression showing the dependence of rate on the concentration(s) of

reactant(s) is known as rate-law or rate-expression of the reaction and sum of the indices
(powers) of the concentration terms appearing in the rate law as observed experimentally is
called order of reaction.
aA + bB → Products is experimentally found to be as follows:

Rate α [A]m [B]n Rate = k [A]m [B]n

Then order w.r.t. A = m order w.r.t. B = n overall order = m + n

Eg Dissociation of N2O5. N2O5 → N2O4 + O2 Order = 1, Molecularity = 1

Dissociation of H2O2. H2O2 → H2O + 1/2O2 Order = 1, Molecularity = 1

Dissociation of HI, 2HI → H2 + I2 Order = 2, Molecularity = 2

Formation of NO2. 2NO + O2 → 2NO2 Order = 3, Moelcularity =3

Pseudo- Order Reactions

Reactions whose actual order is different from that expected using rate law expression are
called pseudo-order reactions; e.g.,

RCl + H2O → ROH + HCl

Expected rate law:

Rate = k[RCl] [H2O] Expected order = 1+1 =2

Actual rate law:

Rate = k'[RCl]; Actual order = 1

Water is taken in excess; therefore, its concentration may be taken constant. The reaction is,
therefore, pseudo first order. Similarly, the acid catalysed hydrolysis of ester, viz.,

RCOR' + H2O ↔ RCOOH + R'OH

follow first order kinetics:

Rate = k[RCOOR']

 Kinetic order is experimental

 Order may change with reaction conditions, it can have zero, fractional values as well.
Decomposition of ammonia on tungsten is zero order, on hot quartz it is first order
 Order may or may not be equal to molecularity, but in elementary reactions they are
generally equal

Consider the reaction, it is found that

2NO(g) + 2H2(g) → N2(g) + 2H2O (g)

Rate [NO]2 [H2]

mechanism proposed.
 1 NO + NO ⇌ N2O2 (fast and reversible)

2 N2O2 + H2 → N2O + H2O (slow) rate determining step

3 N2O + H2 → N2 + H2O (fast)

Rate of overall reaction = Rate of step II = k2 [N2O2] [H2]

First step

Rate reaction = k2×Kc× [NO]2 [H2] or Rate of reaction = k[NO]2 [H2]

Some typical linear plots for the reactions of different orders:

Integrated rate laws

Zero Order

A→P
−𝑑[𝐴]
= 𝑘0 [𝐴]0
𝑑𝑡

−𝑑(𝑎 − 𝑥)
= 𝑘0 (𝑎 − 𝑥)0
𝑑𝑡
‘a’ initial conc and ‘a-x’ conc at time t
 𝑑𝑥
= 𝑘0
𝑑𝑡
ie 𝑥 = 𝑘0 𝑡 [𝐴0 ] − [𝐴𝑡 ] = 𝑘0 𝑡
𝑎
Half life- 𝑡1⁄ =
2 2𝑘0

Rate = rate constant for zero order unit mol L-1 s-1

First Order Reaction

A→P
−𝑑[𝐴]
= 𝑘1 [𝐴]
𝑑𝑡
−𝑑(𝑎−𝑥)
= 𝑘1 (𝑎 − 𝑥)
𝑑𝑡

1 𝑎 2.303 𝑎
 𝑘1 = 𝑙𝑛 or 𝑘1 = 𝑙𝑜𝑔
𝑡 (𝑎−𝑥) 𝑡 (𝑎−𝑥)

1 [𝐴0 ] 2.303 [𝐴0 ]

𝑘1 = 𝑙𝑛 or 𝑘1 = 𝑙𝑜𝑔
𝑡 [𝐴] 𝑡 [𝐴]

 [𝐴] = [𝐴0 ]𝑒 −𝑘𝑡 [𝐴] = [𝐴0 ]10−2.303𝑘𝑡

𝑘1 𝑡
Graph log(𝑎 − 𝑥) = − + 𝑙𝑜𝑔𝑎
2,303

log(𝑎 − 𝑥) 𝑣𝑠 𝑡 graph is a straight line

0.693 0.4622
Half life 𝑡1/2 = quarter life 𝑡1/4 = Time required for
𝑘1 𝑘1
completion of any definite fraction of reaction is a constant.

Examples 1) decomposition of N2O5

N2O5  2 NO2 + ½ O2 total

Initial a 0 0 a
 t a-x 2x ½ x a + 3x/2

Initial pressure Pi α a Pressure at time t Pt α (a + 3x/2)

3pi
k = 2.303 log
5pi −2pt

2) Acid hydrolysis of ester – pseudo first order

HCl
CH3-COOC2H5 + H2O CH3-COOH + C2H5-OH
a y 0 0
a-x x x
Drawing equal volumes of reaction mixture titrated with standard
alkali at different intervals of time V- volume of alkali used
V0 α y Vt α x + y V∞ α a + y
𝑉∞ −𝑉0
k =2.303 log
V∞ −Vt

Inversion of cane sugar – pseudo first order

H+
C12H22O11 + H2O C6H12O6 + C6H12O6
a 0 0
a-x x x
Specific rotation of the mixture is measured at regular intervals
a α r0 - r∞ x α r0 – rt a-x = rt - r∞
𝑟0 −𝑟∞
k =2.303 log
rt −r∞

Second Order Reaction

2A → P
 −𝑑[𝐴]
= 𝑘2 [𝐴]2
𝑑𝑡
−𝑑(𝑎−𝑥)
= 𝑘2 (𝑎 − 𝑥)2
𝑑𝑡

1 1 1
 𝑘2 = ( (𝑎−𝑥) − 𝑎 )
𝑡

1 1
Graph
(𝑎−𝑥 )
= 𝑘2 𝑡 + 𝑎
1
𝑣𝑠 𝑡 graph is a straight line
(𝑎−𝑥)

1 1
Half life 𝑡1/2 = quarter life 𝑡1/4 = half life or fractional life
𝑎𝑘2 3𝑎𝑘2
is proportional to concentration

Different Reactants, different initial Concentraions

A+B→P
−𝑑[𝐴] −𝑑[𝐵]
= 𝑘2 [𝐴][𝐵]
𝑑𝑡 𝑑𝑡
−𝑑(𝑎−𝑥)
= 𝑘2 (𝑎 − 𝑥)(𝑏 − 𝑥)
𝑑𝑡

1 𝑏(𝑎−𝑥)
 𝑘2 = ln[ 𝑎(𝑏−𝑥)]
𝑡(𝑎−𝑏)
1 𝑎(𝑏−𝑥)
 𝑘2 = ln[ 𝑏(𝑎−𝑥)]
𝑡(𝑏−𝑎)

𝑏(𝑎−𝑥)
ln[ 𝑎(𝑏−𝑥) ] vs t graph is astraight line ( no intercept.
through origin)
Example- Saponification of ester, equal conc of ester and alkali
CH3-COOC2H5 + NaOH CH3-COONa + C2H5-OH
a a 0 0
 a-x a-x x x

Equal volumes of reaction mixture titrated against standard acid.

V0 α a Vt α a - x
1 𝑉0 −𝑉𝑡
k= [ ]
𝑡 𝑉0 𝑉𝑡

Third Order Reaction

3A → P
−𝑑[𝐴]
= 𝑘3 [𝐴]3
𝑑𝑡
−𝑑(𝑎−𝑥)
= 𝑘3 (𝑎 − 𝑥)3
𝑑𝑡

1 1 1
 𝑘3 = ( (𝑎−𝑥)2 − 𝑎2 )
𝑡

1 1
Graph = 𝑘2 𝑡 + 𝑎 2
(𝑎−𝑥)2

1
𝑣𝑠 𝑡 graph is a straight line
(𝑎−𝑥)2
3 7
Half life 𝑡1/2 = quarter life 𝑡1/4 = half life or fractional
𝑎2 𝑘3 9𝑎2 𝑘3
life is proportional to square of concnetration

First order auto catalysis

A  P
t=0 a b
t=0 a-x b+x
𝑟 = 𝑘 [𝐴][𝑃]
𝑑𝑥
= 𝑘(𝑎 − 𝑥 )(𝑏 − 𝑥)
𝑑𝑡
 1 𝑎(𝑏+𝑥)
 𝑘2 = ln[ 𝑏(𝑎−𝑥)]
𝑡(𝑎−𝑏)

Second order auto catalysis

HCl
Ester + H2O Acid + Alcohol
t=0 a b c
t=0 a-x b-x x x
𝑑𝑥
= 𝑘(𝑎 − 𝑥 )(𝑐 + 𝑥)
𝑑𝑡
1 𝑎(𝑐+𝑥)
 𝑘2 = ln[ 𝑐(𝑎−𝑥)]
𝑡(𝑎−𝑐 )

Unit of rate constant

nth order (mol L-1)1-n s-1

Third Order Reaction

3A → P
−𝑑[𝐴]
= 𝑘2 [𝐴]3
𝑑𝑡
−𝑑(𝑎−𝑥)
= 𝑘3 (𝑎 − 𝑥)3
𝑑𝑡

1 1 1
 𝑘3 = ( (𝑎−𝑥)2 − 𝑎2 )
2𝑡

1 1
Graph = 𝑘2 𝑡 + 𝑎 2
(𝑎−𝑥)2

1
𝑣𝑠 𝑡 graph is a straight line
(𝑎−𝑥)2
 3
Half life 𝑡1/2 =
𝑎2 𝑘3

Nth Order Reaction

nA → P
−𝑑[𝐴]
= 𝑘2 [𝐴]𝑛
𝑑𝑡
−𝑑(𝑎−𝑥)
= 𝑘3 (𝑎 − 𝑥)𝑛
𝑑𝑡

1 1 1
 𝑘𝑛 = ( (𝑎−𝑥)𝑛−1 − 𝑎𝑛−1 )
(𝑛−1)𝑡

1 1
Graph = (𝑛 − 1)𝑘𝑛 𝑡 + 𝑎𝑛−1𝑛
(𝑎−𝑥)𝑛−1

1
𝑣𝑠 𝑡 graph is a straight line
(𝑎−𝑥)𝑛−1

1 2𝑛−1 −1
Half life 𝑡1/2 =
(𝑛−1)𝑘𝑛 𝑎𝑛−1

1
𝑡1/2 𝛼
𝑎 𝑛−1

Temperature dependence of reaction rates- theories of reaction

rate
𝑘𝑇+10
Temperature coefficient = ≃ 2 𝑡𝑜 3
𝑘𝑇

Rate and temp coefficient

𝛥𝑇⁄
𝑅2 = 𝑅1 (𝑇𝐶 ) 10 TC is temperature coefficient

Increase in rate due to increase in effective collisions

Arrhenius Equation
Empirical, can be obtained fron Vant Hoff reaction isotherm
−𝐸𝑎⁄
𝑘 = 𝐴𝑒 𝑅𝑇

Ea Activation energy, the minimum relative kinetic energy required by the colliding
molecules to undergo reaction.
−𝐸𝑎⁄
𝑒 𝑅𝑇 exponential factor-fraction of molecules having energy equal to or greater than Ea

A pre-exponential factor or frequency factor –represents to frequency of molecular collisions

𝐸𝑎
𝑙𝑛 𝑘 = 𝑙𝑛 𝐴 −
𝑅𝑇
𝐸𝑎
𝑙𝑜𝑔 𝑘 = 𝑙𝑜𝑔 𝐴 −
2.303𝑅𝑇

−𝐸𝑎
log k vs 1/T graph is a straight line slope , intercept log A
2.303𝑅𝑇

𝑘1 𝐸𝑎 1 1
𝑙𝑜𝑔 = [ − ]
𝑘2 2.303𝑅 𝑇1 𝑇2