Prof.

Muhamad Umer Mangrio

Prof. larishankar Mathrani
c
CHEMISTRY-XI
CHAPTER NO.9

CHEMICAL KINETICS
9.1 CHEMICAL KINETICS:
Def:
The study of:
(i) Rate of chemical reaction.
(ii) Mechanism of reaction
Factors which cffect rate of chemical reaction is called chemical kineties.
(ii)
OR
The study of rate of reaction, mechanism of reaction and factors effecting then
rate of chemical reaction is called chemical kinetic.

9.2RATE OF REACTION (R.R):

Def:
Increase in molar concentration of products or deorasdimmolar concentration of
reactants per unit time is called rate ofreaction
i.c Rate of reaction is the ratio of change in eoucentratioih of product or reactant to change
in time.

In other words:
Rate of reactiom changenconc. of product or reactant
Change in time
Ax
e Ratcefreaction At
Unit:n's.I Units:-
Conc. is expressed in moles/dm°.
Time is expressed in seconds.
Rate of reaction is expressed in (moles/dm*)S" Sec.

Example:-A-B
Rate of appearance of product:-
It means conc. of product increase with time.
AB
R=
A
Rate of dis-appearance of Reactants:-
It means conc. of reactants decreases with time
R 44
Ar
9.2.1 RATE LAWAND RATE EXPRESSION:
Rate law:
Rate of reaction depends upon molar concentration of reactants.

Def: According to Rate law:

"Rate of reaction is directly proportional to the product of active masses ol
reactants".

Reaction (Ex):- TtA + yB3 product.

Conposed By Azhar Ali
Prof. harishankar Mathrani_ Prof, Muhamnad Umer Mangrio
According to def:
Rate of reaction a [AT [BP
R. R K [AI |B|
K is ealled rate constant.
Imcans Active mass means Conc: in moles \ dm

Cone: of reactants is 1 - moles \ dm' then above equation will be written as:

R.R K [1][l]
R.R= K
Here 'K is called specific rate constant because Cone: of reactants is specified.
lt (K) changes with change in temperature.
It (K) does not depend upon change in concentration of reactants.

9.2.2 ORDER OF REACTION AND ITS DETERMINATIONL

Order of Reaction:
Def:
Sun of all the exponents of concentration of reactants
etivemasses) expressed
in Rate law is called order of reaction.
Rate law and order of reaction are deiermihcd by experiments and not by
exponents in equation.

Orders of reactionar lassified as zero order, first order, second order. Third
Order etc.
Zero orderreäction does not depend upon concentration of reactants.
Such reattion occurs on surface of metal.
Such reaction occurs in presence of light (Radiation) i.e Photo chemical reaction
because they take place by absorbing light.
Example (i):-
H2+Cl2 No reaction in Dark.
H2 +Cl2 Sunlight 2HCI (Zero order Reaction)
Example (ii):-
A+B product.
R .R K [AT' [B]' Sum of exponents 1+1 2 :-2h order reaction.

Example (ii):-
2NO +O2 2NO2
R .R K [NOJ [O1 Sum of exponents 2+ 1 3 :-3 order reaction.

9.2.3 ELEMENTARY AND OVER ALL RATE CONSTANT AND ITS UNITS:=
Elementary reaction:-
The single step reaction is called as elementary reaction.

Complex reaction:-
Two or more steps reaction is called as complex reaction.

Rate determining step:

Slow step of reaction is called rate determining step of reaction. It is also called as

rate controlling step.

Cu 1 Azhar Ali
Praf. Harishankar Mathrani Prof. Muhammad mer Mangrin

Examplc:-
NO,+ CO-NO +CO
This reaction is based on 2- clementary steps and mechanism of this reaction
involves following two steps.
(i) NO2 + NO Ki NO;+ NO (Slow steps)
(ii) NO; + CO K2NO +CO2 (Fast steps)
Above mechanism gives us information that its kineties and moleculariy which
may be described below.
Ki and K2 are rate constant of elementary reactions and NO; is intermediate of the
reaction.
Step (i) is slow step there fore called as rate determining steps.
As 2-molcules are involved in slow step there fore it is also called bimolecular
reaction.
In rate determining step only NO2 is involved therefore rate o réaction is
independent of concentration of CO.
As for kinetic is concerned it is second ordefreatiowith respect to N0
With respect to CO it is zero orderteacton
The over all ratelawill belekptessed as.
Over all rate Ki[NO;F
Unit of Ratéconstant (K):-
-nitofrate constant (k) depends upon order of reaction.
AiS caleulated from rate law.
Example: Decomposition of N0;
2NO2 NO, NO
.. Rate of reaction K [NO,1
reaction mole/dm'.Sec = dm'.mole.Sec
. K =Kate
2NO mole/dm']
K M'. Sec'.(As M =Moles.dm
= Ms=dm'.molc")
Rate law and units of rate constant of various order of reactions

Zero Order Rate K Ms H2g+Cl2g) HC%g

1 Order Rate K A] NHNO2(aq) N2)+ 211,0,
Rate K [AJ |B]
2Pnd Order Ms2Hl(g) Hagp l20g)
Rate =K [A]-
Rate K [A]2 [B]
3rd Order Or M s 2NO +Clh 2NOC
Rate K [AJ |B]

Composed Bv Azhar Ali

Prof. Harishankar Mathrani_ Prof, Muhannmad Umer Man

9.2.4 FACTORS EFFECTING RATE OF REACTION (R.R):-

There are (5) factors which effect rate of reaction.
() Nature of reactant. (2) Concentration of reactants.
(3) Surlace arca. (4) Radiation (Light).
(5) Temperature.

(1) Nature of reactants:-

Rate of reaction depends upon.
(i) Structure of reactants.
(ii) Nature of bonding.
iii) Physical state.
ExampleC-
4Na +Op 2Na20 (very fast R.R)
4Fe+ 3O 2Fe03 (very slow R.R)
Examplc:-
2Na + 21H,O
2NaOH+H2 (very fasnR.RiG
(Na is highly electropositive)
Ca +2H0 Ca (OH)2+ H2 Moderate RR)
i) Rate of reaction of lonic
compounds isfaster thencoyalent
ii) Rate of reaction of highly compounds.
Example:
electnopositielementis faster.
Sodium is more electropositiveletementthan calcium hence rate of reaction of
sodium is faster than calcium,
U
(2)
Concentration af reactanu (Conc.)-
According to Laivof massaction (Rate Law)
Rafeot reaction is directly proportional to the product of active masses of
reactants
Example:- A +B AB

R.R a [A][B]
Or R.R=K [A][B]
If Conc: of "A" or "B" is doubled then R.R
will be twice.
If Conc: of "A" and "B" both is doubled
then R.R will be Four (4) times more.
This is because effective collision
increases
chances

2 A
B
4 1/2s4
1 x 1 2 x2 3 x 2
Efect of increase in concentration
of A and B on the rate of
reactio
(3) Surface Area (S.A):-
Rate of reaction is
directly proportional to the surlace area of reactants.
-

Surface area of proportional form reactant is more than

Chunk (Chip).
Cu d H Azhar Ali
Prof. Harishankar Mathrani Praf. Mulhammad Umer Mangri

Example:
Zn +Z1IC ZnCl + 11

(powder lorm) (Rapid R.R because of more S.A)

Zn + ZHCI ZnCl +H
(Slow R.R because of' less S.A)
(Chip)
4) Radiation (Light):-
Some of the reactions take place in the presence Radiation (Light). such reaction.

are called Photo chemical reactions.

1. R.R a Radiation (Absorbing of light).
Due to absorbing of light. bonds of reactants are broken and form new substances

(products) rapidly.
2HCI (Fast R.R)
Exanple: H +Clh Light (Radiation)
(Photon)
Dark
H2+ Cl 2HCL(Slo RR
Ex:- Photosynthesis (In Plants):-
(
6CO2 +61He0 Sunigh CoH1206 +602
UChloröphyll
Ex: Photography:
On exposing the plhoto'film in
film in light
light. reaction takes place rapidly.
0O
n (
(5)
(5) Temperature: (Temp:)
Rate of reaction is directly proportional to temperature.
i.e R.R a Temp.
By increasing temperature, collision between molecules increases.
Every collision does not lead to reaction.
Only those molecules would react to form product which have energy equal to or
greater than critical energy means Activation Energy.
Such collision is called Effeetive Collision.
It is observed that by increase of 10°C temp. Rate of reaction doubles.
T Ti+ 10°c
Ea

Greater fraction
of high energy
molecules

Tz

Kinetic Energy

Effcct of temperature on the number of molecules

having kinetie energy greater than Ea.

Compased Bv AzharAli 5
Prof. Harishankar Mathrani Prof. Muhammad Unner Mangri
9.3 COLLISION THEORY TRANSITION STATE AND
ACTIVATION ENERGY:
Chemical Reaction:
Def:
Reaction in whichexisting bonds are broken and new bonds are formed is called
chemical reaction.
Due 1o effective collision of
Tormed and thus chemical reaction molecules; bonds are broken and new bonds are
takes place.
Collision Thcory:-
According to Collision Theory:- Activated complex
Rate of reaction a No: of
B
effective collision of molecules of Transition state
unit time per A-A (Threshold point)
i.e R.R a Effective Ea
Collisions
All the collision does not
affect
bond breaking but some of them
help in bond breaking. Such A-B

collisions are called effective

collision.
A B

Effective collision (successfu

molecular collisions depcnds Reactiorn Progress

upon.
i. High
ii.
Kinetic Enereck-i) A A
Act vated complex
Propen Orientàtion of Colliding
otecules ransition state
(Threshaid point)
When reactants are mixed, then
molecules. A-A
Come close to each other. Ea
AB
Some of them are
repelled by
their electron cloud and do not
take
part in chemical reaction.
Where as some of them
possess
high K.E which overcome repulsive
force and convert Reaction Progress
into vibration
energy which helps in bond breaking Potential energy diagran
and formation of of (a) exotheruiic|
product. reaction (b) endothermic
reaction

AVERAGE INTERNAL ENERGY OF MOLECULES

Def:
(EVA):
The internal
of
Internal energy of molecules reaction
energy moleeules before they are nmixed is called
(Eva) Average

THRESHOLD ENERGY (ET):

Def:
The minimum amount of
energy at which there is effective collision of
moleeules which is essential for re:cting
completion of reaction is called Threshold Energy (:1)

Cunpeed B Azhar Ali

6
 Prof. MuhamnadUmer Mangrio
Prof. Harishankar Mathrani

ACTIVATION ENERGY (EA):

Def ol
Ihe amountof energy required in excess to average energy for complction
reaction i.e to reach Threshold Energy is called Activation Energy,
i.e Activation Energy= Threshold Energy Average Encrgy.

Ea = E T - Eva

E
1) Smaller "Ea" means greater no: of effectivecollision:
Reaction is fast Ea
|Ea
2) Greater "Ea" means less no: of effective collision:
Reaction is slow

3) Exothermic Reaction:-
level
In of exothermic reaction, in the start, the reaction, have higher energy
case
than product.
UL
4) Endothermic Reaction:- i o C

have low energy level

In case of endothermic Peaction, f
reaction, in the(startthe
reactants

than product

9.4 CATALYSIS:
Catalysis:o
chemical reaction without under going
Def THesubstance which alters the rate of
chemical nature is called catalyst.
permanent changes in its
chemical change i.e remains un-
(ii): The substance which itself does not under go
altered but increases or decreases the rate of chemical reaction is called catalyst.
Due to catalyst Maximum product is obtained in minimum time.

CATALYSIS:
Def: (i): The process involving the use of catalyst is called catalysis.
The chemical reaction in which catalyst is used is called catalysis.
(ii):

9.4.1 CHARACTERISTICS OF CATALYST:

effective collision
By of catalyst, Energy of Activation (Ea) decreases. hence
use

of molecules take place for chemical reaction.

in second step it is obtained
Catalyst takes part in first step of reaction and then
back (reproduced) in same (equal) amount.

Un-Catalyzed Bi-molecular Reaction:-

Slow
AB
A +B

Composed By Azhar Ali

 Prof. Mulhammad Umer Mangr
Prof. Iarishankar
Mathrani

Catalyzed Bi- molecular Reaction: involved two (2) steps.

Bi-molecular reaction
Catalyzed
fast.
Rate of reaction in
-

In first step catalyst is used and slow Rate of Reaction.

back with
-

In second step catalyst is re-produced

Ex
) First Siep: Fast
At Catalyst A-Catalyst
Uncatalyzed
pathway
ii) Second step:- Slow
A-Catalyst + B - Catalyzed
AB +Catalyst pathwayY
Catalyst can be separated after
of reaction and thus can be
completion Prpdúts
re-usedagain.

EFFECTOF CATALYST: |ReactatNKOGU

1ofcatalyzed
Show that the energy of activat
1. Positive Catalyst: reaction is lower than uncatalyzed reaction.
Increases Rate of reaction by
the energy of activation of catalyzcd
decreasing Energy of Activation means showsthatis lower than uncatalyzed reaction.
effective collision ofn molécules eaction
inereascs.

2. Negative Catalyst:
Decreases Rare of Reaction by increasing Energy of Activation mean effective
collisionofmolécules decreases.
- Posiuve catalyst is simply called as catalyst.
Negative catalyst is called retarding catalyst or inhibitor.
Example:- Fe
(1) N+3H2 2NH3 Positive catalyst.
(Power)

(2) 2SO2 +O2 V2Os 2S03 Positive catalyst.

(3) 2KCIO3 MnO2 2KCI + 30, Positive catalyst.

(4) CHCI,+ 0 , 2% Euhyl Alcohol coClh+ HCI Negative catalyst.

(5) H,O Glyeerin H2 +O2 Negativecatalyst.

94283) CATEGORIES OF CATALYTIC REACTION:

Catalytic reaction is divided (Categorized) in two (2) groups such as.
(a) Homogenous Catalysis
(b) Heterogencous Catalysis

These groups depend upon:

(i) Physical state of catalyst.
ii) Mode of Action of Catalyst.

Gmsdly Azhar Ali

 Prof. Haris/hankar Mathrani Prof. Muhammad mer Mangria

List of positive and negative catalyst of some industrially significant process

Chemical Process Catalyst Nature
Synthesis of NH; by Haber process
N2+ 3H2 Iron Powder Positive
2NH3
Synthesis of H2S04 by contact process
VO Positive
2S02+O2 2S0
Decomposition of Potassium Chlorate
2KCIO3 2KCI +302 MnO Positive
Oxidation of Chloroform
2% ethyl alcohol Negative
CHCl3+0, COCl + HCI
Decomposition of Hp02
Glycerin NegativC
H202 H2 +O2

9.4.2 (a)HOMOGENEOUS CATALYSIS:

The catalytic reaction in which both catalyst and reactants are in sanme phase
(aqueous phase) is called Homogencous Catalysis.

Kinds:-
There are (2) Kinds of homogenous Catalytic reatioin.
(i) Acid- Base Catalysis (Catalytiereaction)
(ii) Auto Catalysis

(i) Acid - Base Catalxsis

Organic.cáctions ake place ín presence ofH or OH ions as catalyst.
Reth atalyst and reaction are in same aqueous phase.
ExampiUGUD
ydrolysis of Ethyl acctate in presence of H2SO.

CHCOOC,H; +H2O-HSO4lar) CH:COOH+C2HOH

Catalyst
(ii) Auto Catalysis (Auto Catalytic Reaction):
The chemical Reaction, in which one of the products formed act as catalyst. is
called Auto catalytic reaction.
Initially Rate reaction is slow but as product is formed. Rate of reaction inereases.

Ex:- Red ox Titration between KMnO4 and oxalic acid:

In this reaction Mn" ions are formed from MnSO, act as auto catalyst
2KMnO+5HC2O +3H2SO 2Mn"S*0,+ K2SO, + 10C0 +811,0

9.4.3 (b) HETEROGENEOUS CATALYSIS:

The catalytic reactions in which both catalyst and reactants are not in same phase
are called heterogeneous catalysis (Catalytie reaction).
Example:-
i) Formation of SOg:
V2Os
2S02+O, 2S0

i) Formation of NH
Fe(s)
N2 + 3 2
2NH3

Copoed1By Azhar Ali 9

Prof. Ilarishankar Mathrani_ Prof. Muhammad Umer Mangrio

Solid caalyst absorbs reactant molecules on its surfacc as such Cnergy of

lctivation (Ea) decrease hence Rate of reaction increase. In other word cffcctive collision
of reacting molecules increases.

9.4.4 ENZYME CATALYSIS:

Enzyme is kind of proteins which act as Bio-chemical catalysts in living system.
In other word they are called as Bio-Catalysts.
They catalyze the reaction thousand times faster than in-organic catalysts.
They are also highly specific as compared to in-organic catalyst.
Each enzyme has specific shaped active site on its surface where molecules of
substance attach when come in close contact through proper orientation.
Bio-chemical catalysis is complex.

A+B+E ABE AB + E
A and B' are reactants.
E is enzyme.
ABE represent substrate - Enzyme intermediate in the Dransitlo state
"ABE" complex produces "AB" which has lower finergyr Activation (Ea) there
fore Rate of reaction is fast.
Example:
1) Digestion of food is catalyzed.bý nzme such as protease, Amylase, Lipasc etc.
They break down lafgersin earbohydrates. proteins, lipids into smaller size to be
absorbed by cellplármeuberof intestine.
Enzymesarelalso nsedas catályst in Industries

Digestion offood is catalyzed by enzyme such as protease, amylase. lipase ete.

They break down large size carbohydrates, proteins, Lipids into smaller size to be
absorbed by cellular membrane of Intestine.
Enzymes are also used as catalyst in Industries.

3) Fermentation of sugar cane:

Sugar cane nZyme zymase, invertase A

Obtained form yeast

Substratec
A B

Enzyme

Enzyme Activity
Produet
A B
Enzyme Enzyme
Transition
slate

Scheme showing enzyme kinetic for a

biochemical process

L . \ z h a r Ali
T0