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For JEE- Main & Advanced
 REACTION MECHANISM

INTRODUCTION
Application of chemical kinetics in organic chemistry
Chemical Kinetics deals with the speed of a reaction and its mechanism, the stepwise changes in which reactants
undergo in there conversion of product.
RATE OF CHEMICAL REACTION
The rate of change of concentration with time of different chemical species taking part in a chemical reaction is
known as rate of reaction of that species.
mol/lit.
Rate = = = mol lit–1 time–1 = mol dm–3 time–1
sec.

Rate is always defined in such a manner so that it is always a positive quantity.

For a reaction
R  P
Total change in concentration Δc Δ[R] Δ[P]
Rate = = =– =
Total time taken Δt Δt Δt

[P]

Conc.

[R]

Time

Relation Between the Rate of Reactions of Different Species Taking Part in a Chemical Reaction
We very well know that the rate of reaction of all the species taking part in a chemical reaction are not equal as
evident from their stochiometric coefficients. The following example will make it clear
Ex. N2 + 3H2  2NH3
–d[N 2 ]
rate of reacton of N2 =
dt
–d[H 2 ]
rate of reaction of H2 =
dt
d[NH3 ]
rate of reaction of NH3 =
dt
• From above we can have the following relation between the rate of reactions of different species
–d[N 2 ] –1 d[H 2 ] 1 d[NH3 ]
= =
dt 3 dt 2 dt
The value of above expressions is also written as rate of the given reaction.

1
 REACTION MECHANISM

Elementary Reactions
These reactions take place in single step without formation of any intermediate

Transition State
(T.S.)

Energy
Reaction coordinates

An elementary reaction the sum of stoichiometric coefficients is equal to order of the reactions.

Complex Reactions
Reaction which proceed in more than one steps. or having some mechanism. Complex reaction takes places in a
sequence of a number of elementary reactions.

T.S.-I
T.S.-II
Energy

intermediate

Reaction coordinates

For complex reactions order is to be experimentally calculated

Order of complex reaction can be zero fractions whole no, even negative w.r.t. some species.

MOLECULARITY
The number of molecules that react in an elementary step is the molecularity of the elementary reaction. Molecularity
is defined only for the elementary reactions which is equal to no of molecules which make transition state or
activated complex because of collisions in proper orientation and with sufficient energy. No elementary reactions
involving more than three molecules are known, because of very low probability of near-simultaneous collision of
more than three molecules.
The rate law for the elementary reaction
aA + bB  products rate = k[A]a[B]b, where a + b = 1, 2 or 3.
The mechanism of any complex reaction is always written in terms of elementary steps, so molecularity of each of
these steps will be defined but net molecularity of complex reaction has no meaning.
Comparison between molecularity and order of reaction

Sr. No. Molecularity of Reaction Order of Reaction

It is defined as the no. of molecules of It is defined as the sum of the power of
1
reactant taking part in particular step. concentration terms that appear in the law.
It is always a whole number.
2 It may be zero, fractional or integer.
It is can neither be zero nor fractional.
It is derived from slowest step in the
3 It is derived from rate expression.
mechanism of reaction.
4 It is theoretical value. It is experimental value.

3
CHEMISTRY FOR JEE MAIN & ADVANCED

1. Rate determining step

The slowest step of the mechanism known as rate determining step of the reaction.Order of reaction or rate law of
reaction is calculated with the help of mechanism of the reaction and generally using rate determine step (R.D.S).
An organic reaction can be represented as
solvent
Reactant (substrate) + Reagent  Product

Homolytic bond dissociation

Ex. A–B  Aº + Bº
Hetrolytic bond dissociation
Ex. A–B  A + B
2. Types of Reagents
A reagent generates three type of attacking species. Which are nucleophile, electrophile and radical.
(a) Electrophiles (b) Nucleophiles (c) Radicals
(a) Electrophiles : Electrophiles are electron deficient species.
    
Ex. H Cl , Br , NO2 , CH3 (positively charged species), PCl5, SO2, SO3 BH3(species with vacant orbital at central
atom, carbenes) etc.

(b) Nucleophiles : It is the electron rich species having atleast one unshared pair of electron. It can be neutral
or negativetely charged it is always a lewis base.
– – – –
Ex. CN , OH , Br , I , NH3 , H2O etc.
(c) Radicals : It is electron deficient species with seven electrons around an atom.
Ex. CH3 C2H5, C2H5O, CH3COO, X etc.

3. Nucleophilicity
The tendency to give e– pair to an electron deficient carbon atom is defined as nucleophilicity.

Leaving group Ability/Nucleofugality

(a) Order of leaving ability of halide ion

> > >

(b) Other good leaving groups are

24
CHEMISTRY FOR JEE MAIN & ADVANCED

Exercise # 1 [Single Correct Choice Type Questions]

1. Consider the chemical reaction,

2A (g)  B(g) + 3C(g)
The rate of this reaction can be expressed in terms of time derivatives of conc. of A(g) , B(g) or C(g). Identify the
correct relationship amongst rate expressions :
d [A] d [B] d [C] 1 d [A] d [B] 1 d [C]
(A) Rate = – = = (B) Rate = = =
dt dt dt 2 dt dt 3 dt
1 d [A] d [B] 1 d [C] 1 d [A] d [B] 1 d [C]
(C) Rate = – = = (D) Rate = =– =–
2 dt dt 3 dt 2 dt dt 3 dt

K
2. The differential rate law equation for the elementary reaction A + 2B  3C, is :
d [A] d [B] d [C] d [A] 1 d [B] 1 d [C]
(A) – =– = = k [A] [B]2 (B) – =– = = k [A]2 [B]
dt dt dt dt 2 dt 3 dt
d [A] 1 d [B] 1 d [C]
(C) – =– = = k [A] [B]2 (D) None of these
dt 2 dt 3 dt

3. The minimum energy for molecules to enter into chemical reaction is called.
(A) Kinetic energy (B) Potential energy
(C) Threshold energy (D) Activation energy
4. For an elementary process 2X + Y  Z + W, the molecularity is :
(A) 2 (B) 1 (C) 3 (D) Unpredictable

5. What is the order of a reaction which has a rate expression rate = k [A]3/2[B]–1 ?
(A) 3/2 (B) 1/2 (C) 0 (D) None of these

6. Following mechanism has been proposed for a reaction.

2A + B  D + E
Step -1 A + B  C + D – (slow)
Step -2 A + C  E – (fast)
The rate law expression for the reaction is :
(A) rate = K[A]2 [B] (B) rate = K [A] [B]
(C) rate = K [A]2 (D) rate = K[A][C]

7. Activation energy of a reaction is :

(A) The energy released during the reaction
(B) The energy evolved when activated complex is formed
(C) Minimum amount of energy needed to overcome the potential barrier of reaction
(D) The energy needed to form one mole of the product.

8. Catalyst increases the rate of reaction because :

(A) it decreases H (B) it increases H
(C) it decreases activation energy (D) it increases activation energy
9. Which of the following is not a Nucleophile ?
(A) AICI3 (B) (CH3)2 NH (C) C2H5OH (D) H2O

10. Which one of the following has maximum nucleophilicity ?

(A) CH3 S  (B) (C) Et3N (D)

28
 REACTION MECHANISM

Exercise # 2 Part # I [Multiple Correct Choice Type Questions]

1. Observe the following reaction and tick correct option (s)

r1 ................. (I)


CH3 – I + r2 ................. (II)

 

(A) r1 < r2
(B) Transition state in reaction (I) is less stable then transition state in reaction (II)
(C) Substrate of both the reactions are equally reactive to a particular nucleophile
(D) r1 and r2 both are directly proportional to the concentration of nucleophile CH3ONa

2. (X) (Y). Identify X & Y :

(A) X = CH3  CH  CH2 – C  CCH3 (B) Y = CH3  CH2  CH – C  CCH3

| |
O  CH3 OCH3

(C) Y = CH 3  CH  CH 2  C  CCH 3 (D) X =

|
O  CH 3

H O PCl 5
3. 2 product mixture  
AgNO 3

Fractional
No of product ‘m’ (Total isomers)    No. of Fractions ‘n’ .
distillation
(A) Value of m & n are 4,2 respectively.
(B) Product mixture, and all fractions are optically active.
(C) Value of m & n are 4,4 respectively.
(D) Reaction of product mixture with PCl5 is SN2 mechanism.
4. Which of the following reactions represent the major product.

CH CH O –
3 2 3 2 CH CH O –
(A)     (B)    
DMSO DMF

H O
(C) 2 (D)

37
 REACTION MECHANISM

Exercise # 3 Part # I [Matrix Match Type Questions]

1. Match the column I with column II.

Column-I (reaction) Column-II (Mechanism)
CH 3 OH CH3 Cl
C C
(A) Ph + SOCl2 Ph H (p) SN1
(+) H (+)

CH3 OH Cl
CH3
(B) C + SOCl2 Pyridine C (q) SN2
Ph
(+) H H 5C 6
(–)
H

–
(C) (r) SNi
CH3

CH3 OH Cl
CH3
(D) C +HCl  C (s) E2
H5C6 (+) H C 6H 5 H
(±)
2. Match the column I with column II.
Column-I Column-II
(Substrate) (Relative rate of solvolysis in 50%
aqueous ethanol at 45°C)
(A) Cl (p) 7700
(B) Cl (q) 1

H3C
(C) (r) 91
H3C Cl

(D) Ph Cl (s) 1,30,000

Part # II [Comprehension Type Questions]

Comprehension # 1

Nucleophilic substitution reactions generally expressed as

Nu– + R — L  R— Nu + L–

Where Nu–  Nucleophile ; R—L  substrate ; L  leaving group
The best leaving groups are those that become the most stable ions after they depart. Since most leaving groups
leave as a negative ion, the best leaving groups are those ions that stabilize a negative charge most effectively.
A good leaving group should be
(A) electron-withdrawing to polarize the carbon
(B) stable once it has left (not a strong base)
(C) polarisable- to maintain partial bonding with the carbon in the transition state (both SN1 and SN2). This
bonding helps to stabilise the transition state and reduces the activation energy.

47
CHEMISTRY FOR JEE MAIN & ADVANCED

Exercise # 4 [Subjective Type Questions]

1. In each of the following pairs of species which species is better leaving group :
(a) OH and H2O (b) OH and F

(c) Br and F (d) and

2. Label each of the following solvent as Protic or Aprotic

(a) Tetrahydrofuran (b) Acetonitrile (c) Acetic acid (d) Acetone
(e) DMSO (f) Formamide (g) Cyclohexane (h) Ammonia

3. Which of the following are non-polar solvent ?

(a) DMS (b) CCl4 (c) CHCl3 (d) Acetone
(e) Ethyl alcohol (f) Dimethylacetamide (g) Benzene (h) Tetrahydrofuran

4. Which of the followings are electrophile ?

–
(a) CN (b) H+ (c) Br+ (d) AlCl3

(e) BH3 (f) (g) NH3 (h)

5. Which of the followings are nucleophille ?

(a) HS– (b) BF3 (c) C2 H5 – OH 
(d) (CH3)3 N (e) :CH2

6. Arrange the given species in decreasing order of their nucleophilicity :

(a) H2O

(b)

7. Which compound in the following couples will react faster in SN1 reaction and why ?
(a) 1-Bromopentane or 2-Bromopentane (b) 1-Bromo-2-methylbutane or 2-Bromo-2-methylbutane.

8. What effect do you expect due to following changes in SN1 reaction of (CH3)3CBr with CH3OH ?
(a) The concentration of (CH3)3CBr is doubled and that of CH3OH is halved.
(b) The concentration of both (CH3)3CBr and CH3OH are tripled.

9.  A + B

A and B are two structural isomeric products of this reaction. Identify each. Which is predominant ?

50
 REACTION MECHANISM

Exercise # 5 Part # I [Previous Year Questions] [AIEEE/JEE-MAIN]

1. For the reaction A + 2B  C, rate is given by R = [A] [B]2 then the order of the reaction is :
[AIEEE- 2002]
(A) 3 (B) 6 (C) 5 (D) 7
2. The differential rate law for the reaction H2 + I2  2HI is : [AIEEE- 2002]
dH2  d[I ] d[HI] dH2  d[I2 ] 1 d[HI]
(A)   2  (B)  
dt dt dt dt dt 2 dt
1 dH2  1 d[I2 ] d[HI] dH2  d[I ] d[HI]
(C)   (D)  2  2 2  
2 dt 2 dt dt dt dt dt

3. Following reaction (CH3)3CBr + H2O  (CH3)3COH + HBr

is an example of : [AIEEE-2002]
(A) Elimination reaction (B) Free radical substitution
(C) Nucleophilic substitution (D) Electrophilic substitution
4. During dehydration of alcohols to alkenes by heating with concentrated H2SO4, the initation step is[AIEEE-2003]
(A) Protonation of alcohol molecule (B) Formation of carbocation
(C) Elimination of water (D) Formation of an ester
5. Rate of the reaction is fastest when Z is : [AIEEE-2004]

O O
R––C + Nu R––C +Z
Z Nu
(A) Cl (B) OCOCH3 (C) OC2H5 (D) NH2
6. Among the following compound which can be dehydrated very easily is ? [AIEEE-2004]
H3C H3C

(A) (B)
OH H3C OH

CH3
OH

(C) (D)
H3C CH3 H3C CH3
OH

7. Tertiary alkyl halides are practically inert to substitution by SN2 mechanism because of [AIEEE-2005]
(A) steric hindrance (B) inductive effect (C) instability (D) insolubility

8. Elimination of HBr from 2-bromobutane result in the formation of [AIEEE-2005]

(A) Predominantly 2-butyne
(B) Predominantly 1-butene
(C) Predominantly 2-butene
(D) Equimolar mixture of 1 and 2-butene

9. 2-Methylbutane on reacting with bromine in the presence of sunlight gives mainly ? [AIEEE-2005]
(A) 1-Bromo-3-methylbutane
(B) 1-Bromo-2-methylbutane
(C) 2-Bromo-3-methylbutane
(D) 2-Bromo-2-methylbutane

55
 REACTION MECHANISM

MOCK TEST

SECTION - I : STRAIGHT OBJECTIVE TYPE

COCH2COH3
NaOH
1. Br   P
D H
Which of the following statement is correct
O
COCH2COH3
(A) P = (B) P = C CH3
OH
O
H D D H

O O

(C) P = CH3 (D) P =

H DO H D

Br

NaOH
2.   Product, Product is
OH

OH

(A) (B)
O
OH

(C) (D)
O
OH

(i) CH3O
3. CH3 – CH2SH (ii) ethylene oxide
Product, Product is :
(A) CH3 – CH2 – S – CH2 – CH2 – OH

(B) CH3  CH 2 O
(C) CH3 – CH2 – O – CH2 – CH2 – OH

(D)

59
 11th Class Modules Chapter Details

Physics Chemistry Mathematics

5 5 5
Modules Modules Modules

PHYSICS CHEMISTRY MATHEMATICS

Module-1 Module-1(PC) Module-1

1. Physical World and Units 1. Mole Concept 1. Basic Maths and Logarithm
& Dimensions 2. Atomic Structure 2. Quadratic Equation
2. Basic Maths & Vector 3. Chemical Bonding 3. Sequence and Series
3. Kinematics 4. Gaseous State
Module-2
Module-2 Module-2(PC) 1. Trigonometric Ratio and
1. Thermodynamics Identities
1. Newton’s Law of Motion 2. Trigonometric Equation
& Friction 2. Thermochemistry
3. Chemical Equilibrium 3. Properties & Solution
2. Work, Energy & Power of Triangle
4. Ionic Equilibrium
Module-3 Module-3
Module-3(IC)
1. Centre of Mass & Collisions 1. Periodic Table & Its Properties 1. Permutation & Combination
2. Rotational Motion 2. Redox Reaction & Equivalent 2. Binomial Theorum
3. Gravitation Concepts 3. Complex Number
3. Hydrogen & Its Components
Module-4 4. S-Block Module-4
1. Straight Line
1. Mechanical Properties 2. Circle
of Matter Module-4(OC)
1. Nomenclature of 3. Conic Section
2. Thermal Properties of Matter (Parabola,Ellipse & Hyperbola)
Organic Compounds
Module-5 2. Isomerism
3. General Organic Chemistry Module-5
1. Simple Harmonic Motion 1. Mathematical Induction
2. Wave Motion Module-5(OC) 2. Mathematical Reasoning
3. Measurement Error 1. Reaction Mechanism 3. Statistics
& Experiment 2. Hydrocarbon
3. Aromatic Hydrocarbon
4. Environmental Chemistry

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 12th Class Modules Chapter Details

Physics Chemistry Mathematics

5 5 5
Modules Modules Modules

PHYSICS CHEMISTRY MATHEMATICS

Module-1 Module-1(PC) Module-1

1. Solid State 1. Sets & Relation
1. Electrostatics
2. Solutions and 2. Function
2. Capacitance
Colligative Properties 3. Inverse Trigonometric Function
3. Electro Chemistry 4. Probability
Module-2
1. Current Electricity Module-2(PC) Module-2
2. Magnetic Effect of Current 1. Chemical Kinetics and
and Magnetism Nuclear Chemistry 1. Limit
2. Surface Chemistry 2. Continuity
Module-3 3. Differentiability
Module-3(IC) 4. Method of Differentiation
1. Electromagnetic Induction
2. Alternating Current 1. Metallurgy
2. P- Block Module-3
Module-4 3. Transition Elements 1. Indefinite Integration
(d & f block) 2. Definite Integration
1. Geometrical Optics 4. Co-ordination Compound 3. Area Under the Curve
2. Wave Optics 5. Salt Analysis & Qualitative
Analysis Module-4
Module-5
Module-4(OC) 1. Application of Derivative
1. Modern Physics
1. Alkyl Halides & Aryl Halides 2. Matrix
2. Nuclear Physics
2. Alcohol, Phenol & Ether 3. Determinant
3. Solids & Semiconductor
Devices 3. Carbonyl Compound
Module-5
4. Electromagnetic Waves
5. Principle of Communication Module-5(OC) 1. Differential Equation
1. Carboxylic Acid & Their 2. Vector & 3-Dimensional
Derivatives
2. Biomolecules & Polymers
3. Chemistry in Everyday Life

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