3 Chemical Kinetics

Welcome to
Chemical Kinetics and

Nuclear Chemistry
Extent of a Speed of a
Feasibility of
Chemistry is always chemical chemical
a reaction
concerned with change. reaction reaction
Chemical Equilibrium
By means of a
chemical reaction
Thermodynamics Chemical Kinetics
Chemical Kinetics
It deals with the Along with feasibility

rate of a chemical and extent, it is
reaction and the equally important to
know the rate and the
mechanism by
factors controlling the
which it proceeds. rate of a chemical
reaction.
Chemical
Kinetics
Thermodynamics vs Chemical Kinetics
Thermodynamics tells only about

the feasibility of a reaction.
However, chemical kinetics

tells about the speed
with which it proceeds.
Rate of a Chemical Reaction
Some reactions are rapid

Some reactions proceed with moderate Speed
Inversion of cane sugar
C12H22O11 + H2O C6H12O6 + C6H12O6

Sucrose Glucose Fructose
Decomposition of hydrogen peroxide
2H2O2 2H2O + O2
Some reactions are very slow

Rate can be expressed as
The rate of change

of concentration,
The rate of decrease in
with time, of different
concentration (disappearance)
chemical species
of reactants
taking part in a chemical
reaction.
The rate of increase in

Known as rate of reaction concentration (appearance)
w.r.t. that species of products
For a gaseous reaction at

constant temperature,
Concentration ∝ Partial pressure

of species
Rate is expressed as the rate

of change in partial pressure
of a reactant or a product.
Types of Rate
Types of rates
Average Instantaneous
rate rate
Average Rate of Reaction
For the reaction,
R P
Total change in concentration

Average
rate
= Total time taken
Cfinal ⎻ Cinitial
= tfinal ⎻ tinitial
ΔC
=
Δt
R P
Rate of disappearance of reactant (R)

[R]initial = Initial concentration
of reactant at tinitial Decrease in concentration of R
[R]final = Final concentration
Average
rate
=
Time taken
of reactant at tfinal
[R]final < [R]initial
[R]final ⎻ [R]initial
Average
rate
= tfinal ⎻ tinitial
R P
Rate of appearance of product (P)
[P]initial = Initial concentration Average Increase in concentration of P

of product at tinitial rate = Time taken
[P]final = Final concentration
of product at tfinal
[R]final < [R]initial Average [P]final ⎻ [P]initial
rate = tfinal ⎻ tinitial
As we know,
During a
reaction
The concentration The concentration

of the reactant of the product
decreases. increases.
[R]f < [R]i [P]f > [P]i

For reactant R,
Average [R]final ⎻ [R]initial Δ[R]

The rate is defined in
rate = tfinal ⎻ tinitial = ⎻
Δt
a manner so that
It is always a For product P,

positive quantity
Average [P]final ⎻ [P]initial Δ[P]
rate = tfinal ⎻ tinitial = +
Δt
R P
1 mol of R 1 mol of P
Rate of
disappearance of R
= Rate of
appearance of P
Average rate of Δ[R] Δ[P]

reaction, ravg
= −
Δt
= +
Δt
Average Rate of Reaction (Graph)
[R]0
[R1]
Concentration of R vs time ravg
Concentration
– {[R2] − [R1]}
of reactants
Δ[R]
Rate = =− Δ[R]
(t2 − t1) Δt
[R2]
Δt
t1 t2
Time
(P)
ravg
Concentration of P vs time
Concentration
[P2]
of products
+ {[P2] − [P1]} Δ[P]
Rate = = +
(t2 − t1) Δt Δ[P]
[P1]
Δt
t1 t2
Time
[R]0
On a concentration vs time graph,the
average rate of reaction is the slope
Concentration
[R1]
of reactants
ravg
Δ[R] of a secant joining two points,
[R2]
Δt
which defines concentration at
different instants on the curve.
t1 t2
Time
Instantaneous Rate of Reaction
For the reaction,
R P
The rate of a reaction
at a particular instant
ΔC dC
RInstantaneous = lim
Δt 0 Δt
= dt
Instantaneous Rate of Reaction
R P
Δ[R] Δ[P]
ravg = − =+
Δt Δt
Instantaneous rate of Instantaneous rate of

disappearance of R appearance of P
d[R] d[P]
RInstantaneous = –
dt
RInstantaneous = +
dt
Instantaneous Rate of Reaction (Graph)
Product
The instantaneous rate of reaction
Molar Concentration, [J]
a) Tangent, can be determined by drawing a

d[P] tangent at time t on the
rinst = = slope
dt concentration vs time curve.
b) Tangent,
d[R]
rinst = – = – slope For negative slopes, the sign is
dt
changed when reporting the rate.
Reactant Hence, all reaction rates are
positive.
Time, t
Instantaneous vs Average Rate of Reaction (Graph)
[R]0
C1 Δ[R] (C2 − C1)

ravg = − =−
Concentration Δt (t2 − t1)
C2 − d[R]
rinst = = − Slope
dt
t1 t2 t
Time
Relation between Rates
of Different Species
Involved in a Reaction
Rate of Reaction
Example N2 (g) + 3H2 (g) 2NH3 (g)
d[N2]
These all are
Rate of reaction
w.r.t. N2
= –
dt
correct rate
expressions.
Rate of reaction d[H2]
w.r.t. H2
= –
dt
Rate of reaction d[NH3]

However, they
are not equal w.r.t. NH3 = +
dt
Rate of Reaction
N2 (g) + 3H2 (g) 2NH3 (g)
1 Rate of
Rate of
consumption of N2
= 3 consumption of H2
1 mol N2 reacts
with 3 mol H2 to 1 Rate of
produce 2 mol NH3. = 2 formation of NH3
By convention, the rate of a reaction is

expressed as the overall rate of
reaction by dividing
the individual rates with their
stoichiometric coefficients.
N2 (g)
+ 3H2 (g) 2NH3 (g)
Rate of reaction
Overall rate d[N2]
d[N2] of reaction
= –
dt
w.r.t. N2 = –
dt
d[H2]
1 d[H2]
w.r.t. H2 = –
dt = –
3 dt
d[NH3]
w.r.t. NH3 = +
dt
1 d[NH3]
= +
2 dt
aA bB cC dD
+ +
Average rate 1 Δ[A] 1 Δ[B] Instantaneous d[A] 1 d[B]

of reaction, = – = – rate of = – 1 = –
a Δt b Δt a dt b dt
ravg reaction, rinst
Δ[C] + 1 d[C] + 1 d[D]

= + 1 = + 1 Δ[D] = =
c Δt d Δt c dt d dt
Important
The value of the rate of

reaction is independent on the
stoichiometric coefficients of
substances involved in a reaction.
However, the rate w.r.t. any

species is dependent of
its stoichiometric coefficient.
Unit of Rate of a Chemical Reaction
We know,
Unit of ΔC mol/L
1 L = 1 dm3 = 10-3 m3 = 103 cm3 Unit of
rate
= = s
Unit of Δt
ΔC
Rate =
Δt
= mol L−1 s−1
Where,
ΔC: Change in concentration
of any species
Δt: Time change corresponding = mol dm−3 s−1
to the concentration change
Note!
For a gaseous reaction at a constant
temperature, rate is expressed as
dp
rinst = dt
Where,
p: Partial pressure of the
component
Unit of rate equation = atm s−1

Factors Affecting Rate of a Chemical Reaction
1 Effect of concentration
Effect of nature of
2
reactant and product
Kinetic studies help us
determine the speed of
a reaction and describe 3 Effect of Pressure
the conditions that can
alter the reaction rate.
Effect of temperature 4
5 Effect of catalyst
Effect of Concentration
The rate of reaction is often

found to be proportional to the
concentrations of the reactants
raised to a power.
Rate Law or Rate Expression
Simple rate laws can

be obtained by starting
Instantaneous with pure reactants.
rate
For these reactions,
It is an equation that expresses

the rate of reaction as a
function of the concentration
Rate ∝ (concentration)order
of all the species present in the
overall chemical equation for
the reaction at some time.
Rate = k (concentration)order
Rate Law or Rate Expression
Rate of reaction ∝ [A]x [B]y

aA + bB cC + dD
Rate of reaction = k [A]x [B]y …(1)

k: Proportionality constant (rate
constant)
x and y: May or may not be equal to Where a, b, c, and d are stoichiometric
stoichiometric coefficients coefficients of reactants and products
(a and b) of reactants
Rate Law
Rate of reaction = k [A]x [B]y …(1)

It is the expression in which the
reaction rate is given in terms of the
Eq. 1 can also be written as molar concentration of reactants.
d[A]
⎻ dt = k [A]x [B]y
With each term raised to some power
Which may or may not be the same

Differential as the stoichiometric coefficient
rate equation of the reacting species
Rate Law
It can only be established Reactant Product

by experiments.
It may differ for the same reaction Rate = kk [Reactant]order

under different conditions.
Rate Constant
Rate = k[Reactant]order
It is the rate of reaction when the Rate

concentration of reactant is unity. k = [Reactant]n
It is also known as the

specific reaction rate Where n is the order of the reaction
Rate Constant
The rate constant (k) Unit of

mol L−1
depends only on concentration
temperature and not
on concentration.
Unit of rate (Concentration)1 time−1

Rate dC
k= Rate =
[Reactant]n dt
Unit of k mol1−n Ln−1 s−1

Order of a Reaction
Experimentally,
aA + bB + cC Products
R ∝ [A]p [B]q [C]r
The power to which

the concentration of a
species is raised in a Where,
rate law is the order p: Order of reaction w.r.t. A
of the reaction with q: Order of reaction w.r.t. B
respect to that species. r: Order of reaction w.r.t. C
Order of a Reaction
R ∝ [A]p [B]q [C]r
Rate ∝ [A]p [B]q [C]r
Thus p, q, and r indicate

how sensitive the rate is
Order of a Reaction: to change in concentration
It is the sum of powers of A, B, and C, respectively.
of the concentration of
the reactants in the rate
law of a chemical
reaction. Sum of the
(p + q + r)
exponents
Remember!
Rate ∝ [A]p [B]q [C]r
‘p’ may or may not be equal to ‘a’.
‘q’ may or may not be equal to ‘b’.
‘r’ may or may not be equal to ‘c’.

Characteristics of Order of a Reaction
The order of a reaction can be

1 zero or any whole number.
It can be a
2 fractional number.
It can even be negative with

3 respect to a particular reactant.
Overall order can

never be negative.
Order of a Reaction
Example:
2N2O5 (g) 4NO2 (g) + O2 (g)
Rate law = k [N2O5]1
Overall
order
= 1
Order of a Reaction
Example:
5Br− (aq) + BrO−3 (aq) + 6H+ (aq) 3Br2 (l) + 3H2O (l)
Rate law = k [Br− ] [BrO3− ] [H+]2
Overall
order
= 1+1+2 = 4
Order of a Reaction
A balanced equation does not The reaction involves

necessarily give us a true picture only a single step.
of how the reaction takes place.
For an elementary reaction,
Rarely, a reaction gets The sum of

Order of the
completed in one step. stoichiometric = reaction
coefficients
Remember!
For the elementary reaction,
H2 (g) + I2 (g) 2HI (g)
Rate = k [H2] [I2]
Overall
order
= 2
Remember!
For a complex reaction,
The reaction Steps involved:

involves more
than one step. 2NO ⇌ N2O2 Step 1
N2O2 + H2 N2O + H2O Step 2

The order is experimentally
calculated.
N2O + H2 N2 + H2O Step 3
For example:
2NO + 2H2 N2 + 2H2O Rate = k [NO]2 [H2]

Methods to Analyse Rate of a Reaction
1 Initial rate method
Integrated rate
2
law method
3 Graphical method
Unit method 4
Initial Rate Method
aA + bB + cC Products [R]0 rinitial

It is instantaneous rate
at the start of the
The method involves reaction (t = 0).
finding the initial rate
rinst
Concentration
of reactant R
of the reaction
d[R]
dt
By taking known
concentrations of
different reactants.
t
Time
Initial Rate Method
Involves comparison
of different initial
rates of a reaction
By varying the
Rate = k [A]p [B]q [C]r
concentration of one
of the reactants
The concentration of A is
While other reactants changed, by keeping the
are kept constant concentrations of B and C
same as before.
Initial Rate Method
Two different initial concentrations [A0]1 p

r1
of A, [A0]1, and [A0]2 are taken.
r2
=
[A0]2
The initial rates of the
reaction are determined as,
r1 = k′ [A0]1p The value of ‘p’ can be

calculated by measuring the
values of r1, r2, [A0]1, and [A0]2.
r2 = k′ [A0]2p
Following the same method, q
and r can also be calculated.
k′ = k [B]q [C]r
Methods to Analyse Rate of a Reaction
The rate law tells about

the rate of the reaction
dependency on the
concentration of reactant(s).
But it does not tell how the

concentration changes with time
Integrated Rate Law Method
This method, quantitatively,

gives the concentration of
reactant(s) as a function of time.
The form of the integrated rate

equation depends on the order of
reaction.
Zero-order
reaction
Integrated First-order
rate law for reaction
Second-order
reaction
Zero-Order Reaction
For a general reaction For a zero-order

reaction
Where,
A Product(s) n : Order = 0
k : Rate
constant
[A] : Concentration of
According to the rate law, reactant A
Rate of
reaction
= k [A]n
Rate = k
Plot of Rate vs Time
For a zero-
Rate = k [A]0 order reaction
Rate = k[A]n
Zero-order
d[A]
− = k[A]0
Rate
dt
d[A]
⎻ = k
Concentration dt
Zero-Order Reaction
Rate = k [A]0
When Concentration
of A = [A]0
time = 0
⎻ d[A] = k dt
Initial
concentration
Integrating both sides from time (t) = 0 to t
[A]t t
⎻∫ d[A] = ∫
k dt
When Concentration
= [A]t
0 time = t of A
[A]o
Zero-Order Reaction
[A]t t
⎻∫ d[A] = k dt ∫
[A]0 0
[A]t t
Integrated rate { ⎻ [A] }
[A]0
= k{ [t] }
0
law of zero-order
[A]0 ⎻ [A]t = kt
Plot of Concentration of Reactant vs Time
[A]t = [A]0 − kt
… (1)
[A]0
Zero-order
Slope = -k
[A]
t
Rate Constant for Zero-Order Reaction
Unit of k = mol1−n Ln−1 s−1
[A]0 − [A]t
k =
t
Unit of k Concentration1 time−1
So, Unit of k mol L−1 s−1

Time of Reaction Completion (tC)
At this time, the reactants
are consumed [A]0 − [A]t
completely. k =
t
So, at tc,
[A]tc = 0
[A]0 − 0
k =
tc
Zero-order
[A]
[A]0
tc =
k
t tC
Half-Life Period (t1/2)
When the concentration At

of reactants becomes half
of its initial concentration t = t1/2
[A]o
[A]t =
It means that the reaction 2
is half-completed.
[A]0 − [A]t Putting concentration value at t1/2 in eq. (1),

k= … (1)
t
[A]o ⎻ {[A]o/2}
t1/2 = k
[A]o
t1/2 =
2k
t1/2 ∝ [A]0
Plot of t1/2 vs Concentration
t1/2 ∝ [A]o
Zero-order
t1/2
Concentration
Examples of Zero-Order Reaction
Pt
i 2NH3 (g) N2 (g) + 3H2 (g)
Generally,
the decomposition of Au
gases on metal surfaces ii 2HI (g) H2 (g) + I2 (g)
at high concentration
follows zero-order Ni
iii 2PH3 (g) 2P (g) + 3H2 (g)
kinetics.
hν
iv H2 (g) + Cl2 (g) 2HCl (g)
Zero-Order Reaction
In a zero-order reaction equal concentration

of reactants get consumed in equal time.
t1/2 A0 t1/2
A0 0
2
tc
Example
t = 10 s t=5s t = 2.5 s
[R] 100 90 85 82.5
Zero-Order Reaction
Generally, in a zero-order reaction, Replace k by nk in all the previous formulas.
nA Product Rate = nk
Rate = k [A]o [A]0 ⎻ [A]t = nkt
d[A]
⎻ = k tc =
[A]0
n dt nk
First-Order Reaction
Rate = k [A]n
For a general reaction,
For a first-order
Where,
A Product reaction,
n : Order = 1
According to the rate law, k : Rate constant
reactant A
Rate (R) = k [A]n
Rate = k [A]
Plot of Rate vs Time
R = k [A] Rate = k [A]n
R = k [A]
First-order
Rate
d[A]
⎻ = k [A]
dt
Concentration
A Products
d[A]
⎻ dt
= k [A]
Time = 0 a 0
d(a − x)
⎻ = k (a − x)
dt
Time = ‘t’ a–x x
x t
dx
∫ a−x
0
= k
∫ dx
0
dx
dt
= k (a − x)
Integrating both sides,
As ‘a’ is a constant value, a

ln
a−x = kt
dx
a−x
= k dt
a
2.303 log
a−x = kt
The integrated rate law of first-order reaction
a 1 [A]0
ln
a−x
= kt … (1)
t
ln = k
[A]
[A]0 2.303 [A]0

ln = kt
… (2) t
log
[A]
= k
[A]
2.303 [A]0
log k
t [A] =
kt
log[A]0 − log[A] = 2.303
kt
log [A] = log[A]0 −
2.303
Plot of log [A] vs Time
kt
log[A] = log[A]0 −
2.303
First-order
log [A]
t
[A]0 Multiplying eq. (2) by -1,

ln = kt … (2)
[A] [A]0
— ln = — kt
[A]
[A]
ln
[A]0
= — kt
Eliminating natural log from both the

sides,
[A] ⎻ = [A]0 e—kt … (3)

Plot of [A] vs Time
[A] = [A]0 e−kt
First-order
[A]
t
Half-Life Period for First-Order Reaction
Putting the value of x in eq. (1),
a
ln = kt …(1)
a−x a
ln
a−
a = kt1/2
Reaction will be 2
half-completed.
1
t1/2 = ln2
At
x = a k
t = t1/2 2
0.693
t1/2 ⎻ = k
Plot of t1/2 vs Concentration
0.693
t1/2 =
k
First-order
Does not depend
on the concentration
t1/2
of reactants
Concentration
Average Life for First-Order Reaction
There is another Average life

important parameter (tav)
1
tav = k
k: Rate constant of a reaction

Time of Completion of Reaction
Putting the value of [A] in eq. (3),
From the first-order rate expression,
0 = [A]o e −kt
[A] = [A]o e−kt …(3)
e −kt = 0
At completion,
It will happen when,
The reactant concentration
will be zero. So, [A] = 0
tc = ထ
Unit of Rate Constant (k)
Rate = k [Conc.]
Unit of rate mole L−1 sec−1
Unit of conc. mole L−1
Unit of k sec−1
Note!
Generally, for a first-order reaction,
nA Product
Rate = k [A]
d[A]
⎻ n dt
= k [A]
Note!
In the first-order reaction, an

equal percentage of reactants
get consumed in equal time.
Example
t = 5 sec
[R] 100 90
t = 5 sec
t = 5 sec
72.9 81
Examples
1 Decomposition of H2O2 takes place.
MnO2
2H2O2 (aq) 2H2O (l) + O2 (g)
All radioactive decays are

2
always first-order kinetics.
226Ra
88
222Rn
86
+ 4
2He
Second-Order Reaction
For a second-
For a general reaction, order reaction
Where,
n : Order = 2
A+A Product(s) k : Rate constant
reactant A
According to the rate law,
Rate = k [A]n
Rate = k [A]2
A + A Products
Rate = k [A]2
a a 0
(a – x) (a – x) x
Rate
(conc.)2
Rate = k [A]2
dx
dt
= k (a − x)2
1 1
−
(a − x) a = kt
x
dx
∫ (a − x)
0
2 = ∫ kdt or
1 1 1
1
x
[A][A]
−−
[A]0 = kt
(a − x)
= kt
0
1 1
[A]
−
[A]0
= kt
1 At
[A]
Second order
t = t1/2
1
[A]0
t
[A]0
[A]t =
2
Putting the concentration value at t1/2 in eq. (1),
1 2 1
t1/2 = k [A]0 − [A]0
1 1 1
k= … (1)
t [A]t − [A]0 1
t1/2 = k[A]0
1
t1/2 ∝ [A]0
1
t1/2 ∝ [A]0
t1/2
1
(conc.)
Unit of Rate Constant (k)
Rate = k [Concentration]n Unit of k: mol1−n Ln−1 s−1
Unit of For zero

mol L−1 s−1
mol L−1 order (n = 0)
concentration
For first
s−1
Unit of rate mol L−1 s−1 order (n = 1)
For second
mol−1 L1 s−1
Unit of k mol1−n Ln−1 s−1 order (n = 2)
Pseudo Order Reactions
The order of a reaction is

sometimes altered by conditions.
Depending upon the
conditions, a second-order
reaction can behave as a
first-order reaction.
A reaction whose order is different
from the actual order due to excess
concentration of one of the reactants
is known as pseudo order reaction.
Pseudo First-Order Reaction
For a second-order reaction,

If the concentration of one reactant,
A + B Product(s)
A, is taken in excess,
The change in concentration of A

Rate = k [A][B]
is negligible during the reaction.
So, it can be considered

as constant.
Now, the reaction rate

depends on the concentration
of the other reactant (B) only.
The reaction becomes

a first-order reaction.
Rate = k [A] [B]
The reactions that are actually of

A + B Product(s) second (or higher) order but
behave as first-order reactions
Rate = k′ [B]
Pseudo first-order reactions
Where k′ = k[A]
Examples of Pseudo First Order Reaction
Hydrolysis of Ethyl Acetate
0.01 mol of ethyl H+

CH3COOC2H5 + H2O CH3COOH + C2H5OH
acetate + 10 mol H2O
t=0 0.01 10 0 0
t=t 0.01-x 10-x x x

CH3COOC2H5 + H2O CH3COOH + C2H5OH
Rate = k [CH3COOC2H5] [H2O] Rate = k′[CH3COOC2H5]
As the change of [H2O] during the reaction is

negligible (≈ 0.01 mol out of 10 mol consumed),
Pseudo first-order reaction
k [H2O] = Constant = k′
C12H22O11 + H2O C6H12O6 + C6H12O6
Water
(excess)
Rate = k [sucrose] [water]
Rate = k′ [sucrose]
Rate vs Concentration of Reactant(s)
For nth order reaction
Zero-order First-order
Rate = k [A]n
Rate
Rate
Concentration Concentration
Second-order Second-order
Rate
Rate
Concentration (Concentration)2
Concentration of Reactant(s) vs Time (For Zero-Order)
[A] = [A]0 − kt
[A]0
[A]
[A]0
k
Time
Concentration of Reactant(s) vs Time (For First-Order)
[A] = [A]0 e−kt
kt
[A]
log[A] = log[A0] −
2.303
Time
[A]0
[A]
log [A]
log
Time Time
Concentration of Reactant(s) vs Time (For Second-Order)
1 1
= kt +
[A] [A]0
Slope = k
[A]
1
1 —---------------
[A]0
Time
t1/2 vs Concentration of Reactant(s)
[A]0 0.693 1
t1/2 = t1/2 = t1/2 =
2k k k[A]0
Zero-order First-order Second-order

t1/2
t1/2
t1/2
Concentration Concentration 1/Concentration
Unit Method
For an nth order reaction, we know that, Unit of k: mol1−n Ln−1 s−1
Rate
k= For zero
[Concentration]n mol L−1 s−1
order (n = 0)
Unit of k = mol1 − n Ln − 1 s−1 For first

s−1
order (n = 1)
In this method, the order

of a reaction can be
For second
determined by observing mol−1 L1 s−1
order (n = 2)
the unit of the rate constant.
Half-Life Method
For a general nth order reaction,
For a reaction, half-life A Product(s)

can be determined at
two different initial
concentrations and We know,
related to the order of
1
the reaction. t1/2 ∝
[A]n0 − 1
Half-Life Method
For the reaction,
At a different initial concentration [A]0,
A Product (s)
Initial
concentration = [A]0′
of A
Initial
If, concentration = [A]0
of A
New half-life,
1 1
So, t1/2 ∝ …(1) ′
t1/2 ∝ …(2)
[A]n − 1
0
[A] ′n − 1
0
Half-Life Method
1 1
t1/2 ∝ ′ ∝
t1/2
…(1) …(2)
[A]n0 − 1 [A]′0n − 1
On dividing eq. (1) by eq. (2), we get,
n−1
1 t1/2 [A] 0′
−
′
[A] t1/2
= [A] 0
…(3)
‘n’ can be calculated by

′ , [A]0, and [A]0′
measuring t1/2, t1/2
values.
Pressure measurement
Volume measurement
In the following
methods, only
Titration method the first-order
reaction kinetics is
Methods to considered.
monitor the Optical rotation method
progress of a
reaction
Pressure Measurement
As we know,
n
PV = nRT
So, P = V
RT
n
V: Volume P ∝ V
n: Number of moles
P: Pressure
R: Gas constant
T: Temperature P ∝ Concentration
A (g) B (g)
+ C (g)
So, for the reactions
involving gaseous
reactants and products
Progress of a reaction involving
gaseous reactants/products
can be monitored by
Pressure is considered
to monitor the reaction
instead of concentration Measuring the total pressure at a
fixed volume and temperature
In terms of
concentration A B + C A (g) B (g) + C (g)
At time t, a−x x x
t=0 P0 0 0
t=t P0 − Pr Pr Pr
P0: Initial pressure

Pr: Pressure due to amount of
reactant consumed up to time ‘t’
The pressure measurement

can be done in two ways
(i) Partial pressure of the reactant
(ii) Total pressure of the reaction system

In terms of
concentration A B + C Total pressure
Pt
at time ‘t’
At time t, P0 − Pr Pr Pr
According to Dalton’s law,
Pt = (P0 − Pr) + Pr + Pr
Pt = P0 + Pr
Pr = Pt − P0
As, Concentration ∝ Pressure
a ∝ P0
a−x ∝ P0 − Pr
a P0
a−x
= …(1)
P0 − Pr
For the first-order reaction,
a [A]0
kt = ln
a−x
= ln
[A]
a P0
= …(1)
a−x P0 − Pr Substituting values from eq. (1) in
the first law expression,
P0 [PA]0
Pt = (P0 − Pr) + Pr + Pr
Pt = P0 + Pr
kt = ln
P0 − Pr = ln
[PA]
Substituting the value of Pr,

P0
kt = ln
2P0 − Pt
Volume Measurement
In terms of
concentration A B + C
At time = t; a − x x x A (s) B (l) + C (g)
At time = tထ; 0 a a
t=0 0
Monitoring the progress
of a reaction t=t Vt
t = tထ Vထ
By measuring
the volume of
the product Vt: The volume of C collected at time ‘t’
formed Vထ: The volume of C collected at the
end of the reaction
Volume Measurement
In terms of concentration First-order integrated rate law,
A B + C a
kt = ln a − x …(1)
At time t, a−x x x
At time tထ, 0 a a
a Volume of gas
(amount of solid ∝ collected at
taken initially) infinite time Vထ
Volume of gas
Amount of solid
decomposed (x)
∝ collected at any
time Vt
Volume Measurement
a a ∝ Vထ
kt = ln …(1)
a−x x ∝ Vt
a−x ∝ Vထ − Vt
Putting these values in eq. (1),
Vထ
kt = ln Vထ − Vt
Titration Method
Decomposition reaction
△
2H2O2 (l) 2H2O (l) + O2 (g)
By measuring the
volume of titrating The progress of a reactant is
agent, we can monitor monitored by titrating a fixed volume
the amount of reactant of H2O2 solution in a KMnO4
remaining or the amount solution in an acidic medium.
of product formed at
any time.
The volume of KMnO4 used
corresponds to the undecomposed
hydrogen peroxide.
Titration Method
The volume of
KMnO4 used Assuming it as a first-order reaction,
initially
V0 ∝ Initial concentration
of H2O2 (a)
Concentration of
Vt ∝ H2O2 at that instant
(a − x)
The volume of
KMnO4 used
after time ‘t’
Titration Method
The integrated rate law for a first-order reaction,
a
kt = ln
a−x
Applying eq. (1) in the rate law expression,
V0
kt = ln
Vt
Optical Rotation Method
It is used for optically active

samples. It is applicable if there is at
least one optically active species
involved in chemical reaction.
The optically active species

may be present in the
reactant or the product.
Inversion of Cane Sugar (Sucrose)
H+
C12H22O11 + H2O C6H12O6 + C6H12O6
(dextro–rotatory)
(dextro–rotatory) (laevo–rotatory)
+ 66.5°
+ 52.5° − 92°
(laevo–rotatory)
H+
C12H22O11 + H2O C6H12O6
+ C6H12O6
t=0 a 0 0
t=t a−x x x
t = tc 0 a a
Rotation at infinite Initial concentration
It is found that
time (r0 ⎻ r∞) ∝ of sucrose (a)
Rotation at any instant

of time (r0 ⎻ rt)
∝ Amount of sucrose
hydrolysed (x)
Where,
a: Initial concentration
x: Amount consumed
r0: Optical rotation at t = 0
rt: Optical rotation at t = t
r∞: Optical rotation at t = ∞
a−x ∝ (r0 − r∞) − (r0 − rt)
a−x ∝ rt − r∞
The integrated rate law for first-order reaction

a
kt = ln
a−x
r0 − r∞
kt = ln
rt − r∞
Molecularity of a Reaction
Elementary reaction:
aA bB Product
+
The number of reacting species
(atoms, ions, or molecules) taking Molecularity = (a + b)
part in an elementary reaction
1, 2, or 3
Which must collide Molecularity is simply the sum of

simultaneously in order to bring the stoichiometric coefficients
about a chemical reaction of the different reactants.
Molecularity of a Reaction
Elementary reactions involving

more than three molecules
Are not known
So, Molecularity ≤ 3
Comparison Between Order and Molecularity
Molecularity of reaction Order of reaction
It is defined as the It is defined as the

number of reactants sum of the power of
taking part in a concentration terms
1 chemical reaction. that appear in rate law.
NH4NO2 N2 + 2H2O NH4NO2 N2 + 2H2O
Molecularity = 1 Rate = k[NH4NO2]
Order = 1
It is always a whole
number. It can It may be zero,
2
neither be zero fractional, or integer.
nor be fractional.
Comparison Between Order and Molecularity
Molecularity of reaction Order of reaction
It is defined for
It is defined only for
3 elementary as well as
elementary reactions.
complex reactions.
It is an experimental
4 It is a theoretical value.
value.
Type of reactions
Elementary/Simple
Complex/Multi-step
/Single step
Elementary/Simple/Single Step Reaction
These reactions take

place in a single step For the elementary reaction,
Without the formation of

H2 (g)
+ I2 (g) 2HI (g)
any intermediate
Rate = k [H2] [I2]
Formed during the course

of a reaction, but not present
in the overall balanced equation
AB + C AC + B The state
Transition
state corresponding to
the highest P.E.
Energy of
products
P.E. Energy of +
reactants
+
Reaction coordinate
Elementary reaction:
Example
aA + bB Product
For these type of reactions
Order of a
Molecularity = reaction Rate = k[A]a[B]b
Stoichiometric Order with

coefficient of = respect to Molecularity/
any reactant that reactant Order = a+b
Complex Reaction
For the complex reaction,
2NO + 2H2 N2 + 2H2O
2NO ⇌ N2O2 Step 1
Reaction that proceeds in

more than two steps or N2O2 + H2 N2O + H2O Step 2
follows some mechanism
N2O + H2 N2 + H2O Step 3
Sequence of
steps that converts
reactants into products
Complex Reaction
Every step So, each step

As it consists
behaves as an has its own
of multiple
elementary molecularity
steps
reaction
Complex Reaction
A Intermediate P
Transition
states
P.E.
Intermediate
Reaction coordinate
Rate Determining Step (R.D.S.)
The rate of flow

Narrow of sand is Narrow
opening opening
decided only by
(R.D.S) the narrow (R.D.S)
opening.
Largest Large
opening opening
Similarly, the
Large rate of reaction Largest
opening is decided only opening
by the slowest
step.
Large
opening
Narrow
opening
(R.D.S)
The rate of flow Large

of sand is opening
decided only by
the narrow
opening.
The step of a
complex reaction
The order of any reaction (complex) that is the slowest
has to be always determined and on which, the
experimentally overall reaction
rate is dependent.
Effect of the Temperature on Rate of Reaction
The effect of Can be

Generally, for a chemical temperature mathematically Temperature
reaction with rise in on reaction expressed coefficient
temperature by 10°, rate using
the rate constant
is nearly doubled.
Temperature Coefficient
The ratio of the rate of reaction at two

10ºC
different temperatures differing by
Temperature kt + 10
coefficient (T.C.) = kt
≈ 2 to 3
Arrhenius Theory
For a reaction, the relationship between
temperature
and rate constant follows the equation
k Ae -Ea/RT
The temperature =
dependence of the rate of
a chemical reaction can be Where,
accurately explained by k : Rate constant
Arrhenius theory. A : Arrhenius factor or frequency factor or
pre-exponential factor
Ea: Activation energy (in J/mol)
R : Gas constant
T : Temperature of reaction (K)
Trying to Interpret Arrhenius Theory
Example
Elementary reaction
A2 + B2 2AB
According to Transition state theory,
The reaction can take place

1 only when a molecule of A2
and a molecule of B2 collide.
The collision leads to the

2
formation of an unstable state.
Transition state
It exists for a very short
Potential
energy
time and gradually a product

is formed from this.
Reaction coordinate
This is called Transition-state
complex/ Activated complex
Reaction and Transition State Complex
A B A B A B
+ +
A B A B A B
Transition state
Reactants complex/Activated Products
complex
Energy required to form

3
the activated complex
Activation energy
Plot of Potential Energy vs Reaction Coordinate
A B
A2 + B 2 2AB
Activated
complex A B
Endothermic
Activation
Potential energy
or exothermic energy (Ea)
The final enthalpy A B
of the reaction depends A B A 2 + B2 A B

upon the nature of
A B 2AB
reactants and products.
Reaction coordinate
Enthalpy Change During a Reaction
For exothermic
A+B C+D △H < 0
We know enthalpy reaction
change for a reaction
Activated
complex
△H = ΣHP − ΣHR
Potential energy
Ea
ΣHP = Summation of enthalpies of ∑HR

product(s) Reactants ΔH
ΣHR = Summation of enthalpies of ∑HP A+B
Products
reactant(s) C+D
Progress of the reaction
For endothermic
A+B C+D △H = ΣHP − ΣHR > 0
reaction
Activated
complex
Potential energy Ea
∑HP Products
ΔH C+D
∑HR
Reactants
A+B
Progress of the reaction
For a reversible
exothermic reaction
Ea E
Reactants ⇌ Products f ab
Enthalpy (H)
∑HR
Reactants
ΔH
Enthalpy change can
also be expressed in terms ∑HP
of activation energy, Products
Progress of reaction
(or reaction coordinate)
△H
= Eaf − Ea
b
Eaf = Activation energy of the forward reaction
Eab = Activation energy of the backward reaction
Remember!
Greater the height

of the energy barrier
E
Potential energy
∑HR Greater will be the

activation energy
∑HP
Reaction coordinate
Slower will be the
reaction rate
Activation Energy vs Threshold Energy
Threshold Activation
energy energy
Potential energy
Eaf Ea Threshold
b
The minimum energy

energy that the The extra energy Reactants (or enthalpy)
colliding required by a
reactant Products
reactant to
molecules participate in a
must possess reaction. Progress of reaction
for the chemical (or reaction coordinate)
reaction
to occur.
Energy of
ET = Ea + reactant molecule
Maxwell–Boltzmann Statistics and Arrhenius Theory
All molecules in the reacting

species do not have the
The distribution of kinetic energy may be
same kinetic energy.
described by plotting the fraction of
molecules (NE / NT) with a given kinetic
energy (E) versus kinetic energy.
It is difficult to predict the
behaviour of any one
molecule with precision.
Where,
NE is the number of molecules with
Statistics is used to predict energy, E
the behaviour of a large NT is the total number of molecules
number of molecules.
When temperature is raised Area under the

curve constant
The maxima of the curve moves
to the higher energy value
Fraction of
molecules
Most probable
Curve broadens out kinetic energy
Kinetic energy
Greater proportion of molecules
possess much higher energies
Increasing temperature T1
This area shows
fraction of
T2 additional
molecules
Fraction of
molecules
Increases the fraction of which react
molecules This area shows
at (T2)
the fraction
of molecules
that react at T1
Which collide with
energies greater than Ea
activation energy (Ea) Kinetic energy
k = A e─E
- Eaa/RT
/RT
By increasing the
temperature or
decreasing the
activation energy,
The fraction of molecules the rate of reaction
that have kinetic energy increases.
greater than Ea
Calculation of Activation Energy (Ea)
Calculation of
activation energy (Ea)
By measuring rate
Graphically constant (k) at two
different temperatures
Graphically
Arrhenius equation
-Ea/RT
k = Ae
Taking natural logarithm on both sides
ln k = ln [A e-Ea/RT ]
Ea
ln k = ln A - .…(1)
RT
Plotting ln k versus (1/T), can give a straight line
Ea 1
ln k = ln A - ×
R T
Plot of ln k vs 1/T
Ea 1
ln k = ln A - × …(1)
R T
Intercept = ln A
Straight line
Ea
Slope = -
R
Ea
ln k Slope = -
R
From the Ea can be

graph calculated
0 1
T
Rate Constant at Different Temperatures
At temperature T1, Arrhenius equation:
Ea
ln k1 = ln A - RT1
…(1)
k1: Rate constant at temperature T1
At temperature T2, Arrhenius equation:

Ea
ln k2 = ln A - RT2
…(2)
k2: Rate constant at temperature T2

Rate Constant at Different Temperatures
Subtracting eq (1) from eq (2)
Ea Ea
ln k2 - ln k1 = RT1
- RT2
Ea … (1)
ln k1 = ln A - k2 Ea 1 1
RT1 ln
k1
= R T1
─
T2
. . . (3)
Ea
ln k2 = ln A - … (2)
RT2
k2 Ea 1 1
log
k1
= 2.303R T1
─
T2
. . . (4)
Catalyst
Catalyst is a substance
that can alter the Types of catalyst
rate of reaction
Without undergoing any Positive catalyst Negative catalyst

permanent chemical change
Increases the Decreases the

This phenomenon rate of a reaction rate of a reaction
shown by a catalyst is
known as catalysis
Catalysis
Example
Thermal decomposition of
H2O2 is accelerated
Generally, by the term

“catalysed reaction”
By the presence of MnO2
The presence of a positive

catalyst is assumed 2H2O2 + MnO2 2H2O + O2 + MnO2
General Characteristics of Catalyst
A catalyst does not initiate Only a small amount of

1 any reaction; it simply 2 catalyst can catalyse a large
speeds up the reaction. amount of reactants.
A catalyst does not alter It does not alter the Gibbs

3 4
the position of equilibrium energy (ΔG) of a reaction
Catalyses spontaneous
It only reduces the time reactions but not non-
taken to reach the equilibrium
spontaneous reactions
Function of Catalysts
Different pathway
A catalyst provides
an alternate pathway
or reaction mechanism
Activation energy Activation energy

By reducing the activation decreases increases
energy between reactants and
products and hence, lowering
the potential energy barrier. Positive Negative
catalyst catalyst
(inhibitor)
Positive Catalyst
Reaction path
without catalyst
Reaction
path with Ea
Potential energy
catalyst without
Ea with catalyst catalyst
Reactants
Products
Reaction coordinate
Negative Catalyst
Ea in the
presence of
negative
Ea without catalyst
Potential energy
catalyst (inhibitor)
Reactant
Products
Reaction coordinate
Arrhenius Equation (With and Without Catalyst)
Without catalyst
k = Ae -Ea/RT … (1)
With catalyst
Potential
Ea
energy
Ea′
kcat = ′
Ae -Ea/RT … (2)
R
P
k: Rate constant without catalyst
Reaction coordinate
kcat: Rate constant with catalyst
Ea: Activation energy without catalyst
Ea′: Activation energy with catalyst
Comparing eq. (1) and eq. (2)
k = Ae-Ea/RT … (1)
kcat -Ea′/RT
′
= e
-Ea/RT
k
kcat = Ae-Ea/RT … (2) e
kcat (Ea - Ea′ )/RT

= e
k
We know,
Ea > Ea ′
Potential energy
′ Ea kcat
Ea (Ea ─ Ea′ )/RT
k
= e > 1
R
P
Reaction coordinate
kcat > k
Rate of catalysed Rate of uncatalysed

reaction
> reaction
Arrhenius Equation Variation With Ea and Temperature
k = Ae -Ea/RT
Rate of a catalysed and

an uncatalysed reaction
can be equal if
The temperature of the

uncatalysed reaction is more
than the catalysed reaction
Assuming the rate of reaction of

catalysed and the uncatalysed
k = Ae -Ea/RT1 … (1) reactions are equal
-Ea/RT1 -Ea′/RT2
′ e = e … (3)
kcat = Ae -Ea/RT2 … (2)
T1 : Temperature at which
uncatalysed reaction occurs
T2 : Temperature at which
catalysed reaction occur
-Ea/RT1 -Ea′/RT2
e = e … (3)
Though Arrhenius equation
is applicable under a wide
From eq. (3),
range of circumstances
Ea Ea′
T1
=
T2
A more advanced
theory was developed
Ea > Ea′
We get, With greater insights into the

energetic and mechanistic
aspects of reactions
T1 > T2
Collision Theory
The reactant molecules are

assumed to be hard spheres
Rate of reaction
A reaction occurs when molecules,

having sufficient energy, collide
with each other
Collision Activation Orientation
frequency energy factor
It is based on the kinetic
theory of gases
Collision Frequency
Collision frequency can be

The number of increased by increasing the
collisions per concentration and temperature
second per unit
volume
of the reaction
mixture is Both factors contribute towards
more number of collisions per
unit time per unit volume
Known as collision
frequency (Z)
Activation Energy
Not all collisions result

in product formation
E
a
Potential Energy
∑HR
A few reactant molecules

∑HP acquire activation energy
Reaction coordinate
Activation energy is
inversely related to
the rate of a reaction
Collision Theory
For a bimolecular elementary reaction
A + B Products
Rate = ZAB e -Ea/RT … (1)
ZAB: Collision frequency of reactants, A and B

e -Ea/RT : Fraction of molecules with energies
equal to or greater than Ea
Collision Theory
-Ea/RT
Rate = ZAB e … (1)
Rate expression predicts the value Not all collisions

of rate constant fairly accurately
lead to product
for simple atoms/molecules
formation i.e., only
few collisions are
effective.
For complex molecules, significant

deviations are observed
Collision Theory
The collisions in which molecules

collide with sufficient threshold
energy and proper orientation
So as to facilitate the breaking

of bonds between the reacting
species and the formation of
new bonds to form products
Effective Collision
How can we predict

if the collisions are
effective or not?
Conditions
Sufficient
kinetic energy
Proper orientation
Sufficient Kinetic Energy
The minimum amount of
energy
Potential energy
Ea ET
R
The colliding molecules
P
must possess to participate
in a chemical reaction Reaction coordinate
Energy of
Threshold
Threshold energy So, if colliding ≥ energy
molecule
Only the molecule that satisfies this condition can cross the energy barrier.
Proper Orientation
Energy alone does

not determine the
effectiveness of a collision
Conditions
Sufficient The reacting molecules

kinetic energy must collide in a
proper orientation to make
Proper orientation the collision effective.
Proper Orientation
Proper collision
Reactants Transition Product

state
A2 + B2 2AB
Proper Orientation
Improper collision
The proper orientation of No reaction

the reactant molecules leads
to bond formation
Transition No products
Reactants
state are formed
Whereas improper orientation
makes them simply bounce back
and no products are formed.
Effective Collision
To account for proper orientation Final expression of rate becomes
Rate = P ZAB e -Ea/RT
A factor “P” is introduced
Fraction of molecules
Orientation
Collision factor
frequency
with sufficient energy.
Probability or steric factor
Radioactivity
Spontaneous
disintegration of nuclei Radioactivity is independent
due to the emission of of external conditions like
radiations like 𝛂, β, 𝛾 is temperature, pressure etc. and
called radioactivity. physical state of substance.
Nuclei
phenomenon
Properties of α, β and γ Radiations
Property 𝛂-rays β-rays 𝜸-rays
4
2He (nucleus 0
Nature -1e EM radiation
of He atom)
Relatively low
Greater than Very high
Velocity (depends on
𝛂 - particles (3 ×108 m/sec)
the source)
Ionising Less than

Very high Very low
power 𝛂 - particles
Intermediate
Penetrating (much greater
Low Very high
power than
𝛂 - particles)
Group Displacement Law
When one 𝛂 emission takes place

from a nuclei, the newly formed
1
nuclei occupies two positions
left in the periodic table.
When one β emission takes place

from a nuclei, the newly formed
2
nuclei occupies one position
right in the periodic table.
Note
Exceptions are
possible in the group
displacement law
238 234 + 2He4

92U 90Th
f-Block element f-Block element

(Group-3) (Group-3)
Nuclear Stability
High stability of most nuclei of

stable elements is due to the
very strong nuclear forces that
operate within the nucleus (or at
nuclear distance, of the order of
10–15 m or fm)
Nuclear Stability
Last stable
nucleus
Number of neutrons
Stability belt
Number of protons (Z)

Nuclear Stability
Isotopes which lie in

band of stability (stability
belt) are found to be
stable (non-radioactive).
Nuclear Stability
Upto 20 > 20
Stable nuclei with n/p n/p ratio increases with Z in

ratio nearly 1 : 1 stable nuclei region
More number of neutrons

are required to reduce
repulsion between protons.
Nuclear Stability
For heavier isotopes, Unstable isotopes will

n/p ratio for stable try to be in the band of
isotopes may be as high stability after
as nearly 1.5. adjustment of their n/p
ratio.
Nuclear Stability
Case 1
If n/p ratio is high
If n/p ratio is high Stability will be gained

by losing β-particle.
1 1 + -1e0
On 1H
(β-particle)
Example
n 6
6 C12 (stable)
p = 6
n 8
6 C14 (radioactive)
p = 6
(High)
Example
14 14 + -1e0
6C 7N
n 8
6 C14 p = 6
n 7
7N
14
p = 7
Nuclear Stability
Case 2
01 𝛂-Particle Emission
If n/p ratio
02 Emission of Positron
If n/p ratio is low is low, it is
adjusted
by
03 K-shell Electron Capture
Nuclear Stability
1 By 𝛂-particle emission
Generally observed
in heavier isotopes
A A-4 + 2He4
ZX Z-2X′
238 234 + 2He4

92U 90Th
Nuclear Stability
A A + 1e0
ZY Z-1Y′
2 By emission of positron
22 22 + 1e0
11Na 10Ne
Generally observed
in lighter isotopes
1 1 + 1e0
1p 0n (From nucleus)
Nuclear Stability
Nucleus Electron
By K-shell electron
3
capture
X - Ray
In some radioisotopes
stability (usually for elements
with high Z) is gained by K-shell K - Shell L - Shell
electron capture by the nucleus.
A + -1e0 A
ZX′ Z-1X″
197 + -1e0 197
80Hg 79Au
K-shell
Mass Defect and Binding Energy
It is experimentally found
that atoms of every element Oxygen atom 8p, 8n, 8e‒
is slightly lighter in mass
than the sum of masses of
its constituent particles.
Observed mass
of O16 atom
≈ 15.99 amu
When protons and neutrons combine
to form nucleus, there is a mass loss
called mass defect. Mass sum of
An equivalent amount of energy is 8p, 8n, 8e‒ ≈ 16.13 amu
released which is called binding
energy.
E = Δm × c2
Where,
E is binding energy Higher the binding
Δm is mass defect energy per nucleon,
c is velocity of light (c = 3 × 108 ms-1) greater will be the
stability of nucleus.
1 amu = 931.5 MeV

B.E. per nucleon
Mass No. (A)

Binding Energy (B.E.)
Lighter nuclei may

B.E. per nucleon undergo fusion while
is found to be heavier nuclei may
maximum for mass undergo fission to get
number near 60. into stability zone under
appropriate conditions.
Types of Nuclear Reactions
01 Nuclear fission
Nuclear 0
reaction2
02 Nuclear fusion
Nuclear Fission
The heavier nuclei being

unstable have tendency to
split into medium nuclei.
This process is called fission.
Example
Various nuclei
92U
235 + 0n1 92U*
236
and neutron
Nuclear Fusion
Example
The lighter nuclei being

unstable have tendency to
2 + 1H3 4 + 0n1
fuse into a medium nucleus. 1H 2He
Hydrogen bomb is based on fusion.

This process is called fusion.
Very high temperature

is required
Rate of Radioactive Decay
All radioactive disintegrations follow 1st order kinetics.
A B + C
– dN
dt
= λN
Where, initial nuclei of A is N0

and at time t, remaining nuclei of A is N
–dN
is rate of decay/ Activity (A)
dt
λ is decay constant
Units Of Activity
Curie (Ci) = 3.7 × 1010 dps
Millicurie (mCi) = 3.7 × 107 dps
Microcurie (μCi) = 3.7 × 104 dps
Rutherford (1 Rd) = 1 × 106 dps
Where dps = disintegration per second

N0
Number
of nuclei
t
λ is independent of temperature
–dN –λt
N = λdt N = N0e
∫–dN
N = ∫ λdt
N0
1
λ = t
ln
N
–λt
N = N0e
Half Life of Radioactive Decay
t = t1/2; N = N0/2
1 N0 ln 2
λ = t1/2
ln
N0/2
= t1/2
ln 2 0.693
t1/2 = λ
= λ
Average Life of Radioactive Decay
∞
∫ dN.t 1
tavg = 0 = λ
N0
1
tavg = λ
= 1.44 t1/2
Carbon Dating
In living matter
existing in nature
Radioactive Stable
14 12
6C : 6C
C14 is used to determine age

of organic materials like 1 : 1012
animal fossil or wooden
logs.
In upper atmosphere
14 + 0 n1 14 + 1 p1
7N 6C
Carbon Dating
Ratio of radioactive carbon in

dead animals or trees decreases
with respect to time.
1 A0
t = λ
ln
A
A0 = Activity of fresh wood piece

A = Activity of old wood piece

3 Chemical Kinetics

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3 Chemical Kinetics

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Welcome to

Chemical Kinetics and

It deals with the Along with feasibility

Thermodynamics tells only about

However, chemical kinetics

Some reactions are rapid

Some reactions proceed with moderate Speed

Inversion of cane sugar

C12H22O11 + H2O C6H12O6 + C6H12O6

Decomposition of hydrogen peroxide

Some reactions are very slow

The rate of change

The rate of increase in

For a gaseous reaction at

Concentration ∝ Partial pressure

Rate is expressed as the rate

Total change in concentration

Rate of disappearance of reactant (R)

Rate of appearance of product (P)

[P]initial = Initial concentration Average Increase in concentration of P

The concentration The concentration

[R]f < [R]i [P]f > [P]i

Average [R]final ⎻ [R]initial Δ[R]

It is always a For product P,

Average rate of Δ[R] Δ[P]

For the reaction,

Instantaneous rate of Instantaneous rate of

a) Tangent, can be determined by drawing a

C1 Δ[R] (C2 − C1)

Example N2 (g) + 3H2 (g) 2NH3 (g)

Rate of reaction d[NH3]

N2 (g) + 3H2 (g) 2NH3 (g)

By convention, the rate of a reaction is

Average rate 1 Δ[A] 1 Δ[B] Instantaneous d[A] 1 d[B]

Δ[C] + 1 d[C] + 1 d[D]

The value of the rate of

However, the rate w.r.t. any

Unit of rate equation = atm s−1

The rate of reaction is often

Simple rate laws can

It is an equation that expresses

Rate of reaction ∝ [A]x [B]y

Rate of reaction = k [A]x [B]y …(1)

Rate of reaction = k [A]x [B]y …(1)

Which may or may not be the same

It can only be established Reactant Product

It may differ for the same reaction Rate = kk [Reactant]order

It is the rate of reaction when the Rate

It is also known as the

The rate constant (k) Unit of

Unit of rate (Concentration)1 time−1

Unit of k mol1−n Ln−1 s−1

R ∝ [A]p [B]q [C]r

The power to which

Rate ∝ [A]p [B]q [C]r

Thus p, q, and r indicate

Rate ∝ [A]p [B]q [C]r

‘p’ may or may not be equal to ‘a’.

‘q’ may or may not be equal to ‘b’.

‘r’ may or may not be equal to ‘c’.

The order of a reaction can be

It can even be negative with

Overall order can