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Chemistry Notes Created by

Waqar Ahmed Mirani

Chapter 09
Chemical Kinetics
The branch of chemistry , which discuss the rate of chemical the rate
of chemical reaction , the mechanism through which reaction proceeds and the
factors , which are affecting the rate of chemical reaction , is called chemical
kinetics .

(Rate of Chemical reaction)

The decrease in the conc: of the reactants per unit
time or increasing the conc: of products per unit time .
Or
The number of the moles of the reactants used per unit time or the
number of the moles of the product form per unit time .
Or
Rate of disapeearance of the reactants or rate of appearance of the
product .
Briefly , the rate of reaction is defined as : “The change in the conc: of the
reactant or products per unit time”.

Mathematically

Change∈conc : of reactant∨product
Rate of reaction=
Time taken∈that change
dx of R∨P dx
¿ =
dt dt
−3 −1
unit=mol . dm sec
(rate equation and Rate Constant)
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H 2 + I 2 ⟶ 2 HI

rate of reaction∝ [ H 2 ] [ I 2 ]

dx
=K [ H 2 ][ I 2 ] → rate equation∨rate law .
dt
dx
dt
K= → Constant∧expression iscalled rate constant expression
[ H 2] [I 2]
K is called rate constant which is defined as : “The ratio of rate of reaction to
the conc: of reactants .
mol . d m−3 . sec −1
K=
( mol . dm−3 ) ( mol . dm−3)
3 −1 −1 a
K=dm . mol . sec → Unit of K ¿ this equation .
c

(Specific rate Constant)

The rate constant in which conc: of the reactant is unity
, then rate of reaction is called specific rate constant .
H 2 + I 2 ⇌ 2 HI
Rate of reaction=K [ H 2 ] [ I 2 ] .

Rate of reaction
K=
[ H 2 ][ I 2 ]
dx
dt
Kspecific=
( 1 ) (1)
Kspecific=Rate of reaction.

(Characteristics of K)
K will remain constant at constant Temp: . It varies
directly with the temp: .
By changing the conc: of reactant , K will not change b/c by changing the
conc: of the reactant conc: rate of reaction will also change with same value .
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(Order of Reaction)
Molecularity :-
The number of the molecules taking part in a chemical
reaction is called molecularity , it is determined by observing the chemical
reaction .
The sum of all the exponents to the conc: in rate equation is called rate
of reaction .
It may also be defined as : “The number of reacting molecules whose conc:
alters in a chemical reaction” .
=>It’s important to note that order of reaction is experimentally determined
quantity and cannot be simply by looking at the reaction equation .
=>The sum of the exponents in the rate equation , may or maynot be the same
as in balanced chemical equation .
Rate of reaction provide variable information about the mechanism of the
reaction .
=>chemical reactions are classified as Zero , 1st , 2nd and 3rd order reaction .
=>The order of reaction is usually positive integers or zero , but it also may be
in fraction i-e , 1.2 , 2.5 etc or can have a negative value .

1)1st order of reaction :-

When a conc: of only one molecule alters .

1
Ex (1) N 2 O5 ⟶ 2 NO 2+ O2
2
Rate=K [ Reactant ]
Dx
=−k [ N 2 O 5 ]
dt

(2) Hydrolysis of bromomethane .

pseudo 1st order ( H2O is not considered ) .
CH3 CH3

CH3 C Br H2O -- CH3 C OH Br

CH3 CH3 CH3

dx / dt = K ( CH3 C Br )
CH3
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2)2nd order of reaction :-
The reaction in which conc: of two molecules
alters .
Ex (1) :- 2 CH 3 CHO →CH 4 +2 CO
Dx
=K [ CH 3 CHO ] 2
dt
(2) :- NO+O3 → NO 2 +O2
dx
=K [ NO ] [ O3 ]
dt
1 + 1 = 2

3)3rd order of reaction :-

The reaction , in which conc: of three molecules
alters .
2 NO+O2 ⟶2 NO2
Dx
=K ⌊ NO 2 ⌋ [ O2 ]
dt
2+1=3.

2 FeCl 3 +6 KI →2 Fe I 2 +2 KI + I 2
dx
=K [ FeCl 3 ] [ KI 2 ]
dt
1+2=3

The rate of equation suggests that the reaction takes place in more
than one step , and in slow step , only three molecules are taking part so it’s 3 rd
order reaction .

4)Order of reaction may be in fractions :-

CH 3 Cl 3+ Cl2 ⟶CCl 4 + HCl

( )
1
dx
=K [CH 3 Cl3 ] 1 2
dt
1 + 0.5 = 1.5 . order of reaction .

5)Zero order reaction :-

Reactions may be zero order reactions .
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=>the reactions , in which conc: of thee reactants doesn’t affect the rate of
chemical reaction .
=>The reaction occurs in the [presence of sunlight , so these reactions are
called photo m—chemical reactions .
=>When sunlight touches to the reactants , they provide the energy of
activations to the reactants and then reaction start .
Ex (1) :- Chlorination of Methane .
hv
CH4 + Cl2 ---- CH3Cl + HCL
(2) Formation of HCL .
hv
H2 + Cl2 ---- 2HCL .

(Factors affecting the rate of reactions)

1)nature of reactants :-
Rate of chemical reaction also depends upon nature
of reactants .
=>Reactions of first A element are faster than 2nd A element . The reason is the
atomic size of 1st A is greater than 2nd A . So , they are highly electronegative
due to greater size , they loose electron immediately .
=>The reactions of sodium are faster than Iron due to greater size of sodium
than iron . Reaction of ionic compounds are faster than covalent compounds .
Because in ionic compounds , ions are involved .

2)Surface area of reactant :-

This factor will affect the heterogenous
chemical reaction means elements are present in different physical states .
=>Greater the surface area of reactants , greater will be the touching area of
reactants . The greater will be collisions b/w reactants . faster will be rate of
reaction .

3)Temperature :-
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Temperature has an important effect on rate of chemical
reaction . Rate of reaction increases when temp: increases b/c (K.E0 increases
, the number of collision will increase , the rate of reaction will increase .
=>A/c to law of thumb , it is observed that by increasing the 100C of temp: the
rate of reaction become doubled because the number of molecules with
activation energy increases .

4)Conc: of Reactants :-
Generally , increasing the conc: of reactants leads
to a higher rate of reaction . This is because there are more reactant
molecules present , increasing the frequency of collision and thus the
likelihood of successful collision .

(Light or Radiations)
In chemistry , there are some chemical reactions in
which conc: of the reactants doesn’t affect the rate of chemical reacting . By
increasing or decreasing of the reactant , there’ll be increase on rate of
chemical reaction . Such reactions are called photochemical reactions when
sunlight touches the reactants , they provide the energy of activation to the
reactants , the reaction will stop .
Ex :- Chlorination of methane .
hv
CH4 + Cl2 ---- CH3Cl + HCl .

(Catalyst)
The substance which on addition alters the rate of
chemical reaction without taking part in a chemical reaction , without
undergoing into a physical or chemical change , without undergoing into
quantitative change , without appearing in a final product and highly specific in
their action is called catalyst .
=>There are two types of catalyst i.e. Positive and negative catalyst .
1)Positive catalyst :-
The catalyst which increase the rate of chemical
reaction by decreasing the energy of activation .
2)Negative catalyst :-
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The catalyst which decrease the rate of chemical
reaction are called negative catalyst . They contaminate with the reactants
and decrease the collision b/w reactants , so rate of reaction will decrease , so
, they are also called inhibitors .

On the basis of physical state , there are two types of catalysis i.e.
Homogenous and heterogenous catalysis .
1)Homogenous catalysis :-
The type of catalysis in which reactants and
catalyst are present in same physical state .
a)Acid – base catalysis :-
In organic chemistry , various chemical reactions
occurs in the presence of acid or base catalyst and are present in aqueous
phase .
Ex :- Hydrolysis of ester Is catalyzed by sulfuric acid .

CH 3 COOC 2 H 5 + H 2 O →CH 3 COOH +C 2 H 5 OH

b)Auto Catalysis :-
The reactions in which product of the reaction catalyze
the reaction catalyze the reaction . In starting , These reactions are slow when
after the formation of the product , reaction become fast .
Ex:- Redox reaction .
Redox titration between KMnO4 and oxalic acid Mn+2 ion of MnSO4 catalyzed
the reaction .

2 KMnO 4+ 5 H 2 C 2 O4 +3 H 2 SO 4 → 2 Mn SO 4 +10 CO 2+ 8 H 2 O+ K 2 SO 4

2)Heterogenous Catalysis :-
The reactions in which reactants and catalyst
are present in different physical state .
Ex:- Oxidation of sulfur dioxide .

2 SO 2 +O2−→ 2 SO 3

(Enzyme Catalyst)
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Enzymes are biological catalyst , They catalyze the
biochemical process occurring in the livings . They’re highly specific in their
action . They are active in minute quantities . They are very sensitive to their
action . They possess active center which touches the substrate which is not
their real substrates it will be destroyed .

(Collision Theory)
The copllision theory of chemical reactions was
primarily developed by Max Trautz and William Lewis in early 20th Century .
This theory provides an explanation for how chemical reactions occurs at
molecular level .
=>The collision theory state that : for a chemical reaction to occur reacting
particles (atoms , Molecules or ions) must collide with sufficient energy and
proper orientation . This means that not all collisions b/w particles result in a
chemical reaction ; only collision melting specific criteria lead to a successful
reactions .

(Energy of Activation)
According to collision theory , chemical reaction is a
result of collisions among the reactants . All the collisions are not effective it
is not necessary that all colliding molecules are convert into produt . Only
those molecules are converted into products which possess the energy of
activation .
=>During collision energy produced called ctivtion energy , substrate have their
own energy called average energy .
Average energy + activation energy = Threshold energy .
=>Energy of activation is not provided by outer source , it is produce during
collsions .
=>When energy of activation decrease , the reaction become fast . When
activation energy increases , the reaction become slow .