Chemistry: l , For BCE,BME

# Introduction, Marks Distributions & Books .

# The whole course of chemistry, carries 150 marks .
80 marks = for final theory examination
20 marks = for internal assessment exam
# 100 marks = total marks, for the theory course of Chemistry
30 marks = for final practical examination
20 marks = for internal assessment exam
# 50 marks = total marks, for the practical course of Chemistry
Books of chemistry for BE :---
1.) A text book of engineering chemistry:---- by Ram kr.Sharma ,Bishnu
panthi, Yam Nath Gotame
2.) Chemistry for Engineering ( Bachelor in engg.):----- by dr. Bhushan
Shakya, Dinesh Saha
3.) Any Engg. chemistry books, & from web., pdf., you tube, Google etc.
# Chemistry Teachers: N.J.Dangi, B. Kaphley, YR Sahu & AK Chaudhary
• Let us start the course from # Unit: 10 , Reaction Mechanism in
Organic reaction. Generally this topic carries 10 marks ( 5+ 5) in the
final theory examination.
 Chemistry : l, Unit: 10
• Reaction Mechanism in Organic reactions:---
• What is reaction Mechanism ?
• The detailed step by step description of a chemical reaction is called
reaction mechanism.
• Substrate + Reagent-----‐--->Intermediate---------→Product

• # Substrate: the reactant molecule which is attacked by any reagent

• # Reagent: the attacking species (eg. electrophile, nucleophile ,free
radicals etc.)
 Let us suppose an example of reaction:---

A-B + C --------------> B-C + A / A-C + B

reactants products

A-B :- breakage of existing bond between A & B takes place

B-C/ or, A-C :- formation of new bonds between A&C / B&C takes place
# Therefore to study reaction Mechanism we should know the bond
breaking concept at first.
# Breakage of Covalent bonds :---
1) Homolytic bond fission ( Homolysis or, symmetrical cleavage):-
2) Heterolytic bond fission (Heterolysis or, unsymmetrical cleavage):-
 Bond fission( breakage of covalent bond):-
1. Homolytic bond fission:--------
Ex. A••B ----------> A• + B•
Free radicals
Cl • • Cl--------------> Cl• + Cl•
Free radicals
2. Heterolytic bond fission:---------
Ex. B •• X --------------> B+ + ••X -
Cation anion
H 3 C •• X ----------------> H 3 C+ + ••X -
Carbocation anion
 Carbocation & Carbanion
# Carbocation (carbonium ion):-
• CH 3 + (methyl Carbocation), R-CH 2 + (Primary Carbocation) ,
R 2 CH + (secondary Carbocation), R 3 C + (tertiary Carbocation)
• Relative stability:-- CH 3+ < 1 ° < 2° < 3°
# Carbanion:---
• CH 3 - (methyl Carbanion) , RCH 2 – (primary Carbanion) ,
R 2 CH – (secondary Carbanion), R 3 C – (tertiary Carbanion)
• Relative stability:-- CH 3 - > 1° > 2° > 3°
 # Attacking Reagents :----------
( Electrophiles & (Nucleophiles) :-----
1) Eectrophiles(E+):------
# Elecrophiles are electron loving species.
• Electrophiles are electron deficient species which can accept a pair
of electrons.
• They are +vely charged or neutral species, and can attack on
electron rich centre. They are lewis acids.
# Ex. H+ , H3O+ , SO 3H+ , R 3 C + , R 2 CH + , NO 2 + ,Br + , l+ etc.
# Neutral Electrophiles:-- AlCl 3, B Cl 3 ,BF 3 , FeCl 3 etc.
2) # Nucleophiles (Nu - ) :-----
• 2.)Nucleophiles:- # Nucleophiles are Nucleus Loving species.
• They are electron rich species which can donate a pair of electrons.
• They are negatively charged or neutral species, and can attack
electron deficient centre .
• Ex. OH - , CN - , Cl - , Br -, I - , CH 3 - , RCH 2 - , OCH 3 - etc.
• Neutral Nucleophiles:------ H 2 O , NH 3, R-O-R , RNH 2 etc.

• # Rate of reaction:--- the change in concentration of reactant or

product per unit time is known as rate of reaction.
 # Types of Organic reactions:------
1.) Addition reaction
2.) Substitution reaction
3.) Elimination reaction
4.) Rearrangement reaction
5.) Redox reaction etc.
#1) Substitution reaction:-----
The substitution reaction are of following types :-----
1)Nucleophilic substitution rxn( SN1&SN2) #2)Electrophilic #3)Free
radical
1.) Substitution Reaction:- The substitution reaction or, displacement
reactions are those reactions in which atoms or group of atoms attached
to a carbon atom in a substrate molecule is replaced by another atoms or
group of atoms.
The substitution reaction can takes place through different attacking
species ( nucleophile, electrophile or free radical ).Thus , the substitution
reactions may be following types,
1.Nucleophilic Substitution Reactions:- eg SN1 & SN2 reactions
2.Electrophilic Substitution Reactions & 3. Free Radical Substitution
Reactions.
Among these 3 types of substitution reactions You have to study only SN1
& SN2 (nucleophilic substitution reactions)
 Nucleophilic Substitution Reaction (S N )
# When the substitution reaction involves the attack by a Nucleophile,
the reaction is referred to as Nucleophilic substitution reaction. These
reaction are denoted by S N . Where S=substitution & N=Nucleophile
Ex. The hydrolysis of alkyl halide by aqueous NaOH is an example of
Nucleophilic substitution reaction.
R-X + OH - ------------> R-OH + X –
Alkyl halide Nucleophile alcohol leaving group
-R=alkyl group, X= halide group (eg. Cl,Br,I etc.),

Alkyl halides are very reactive compound & they undergo

substitution, elimination and reduction reaction.
 Reactivity of alkyl halide, and their
classification:-
# Inductive effect (I) has great influence on reactivity of alkyl halide. Due to –
Inductive(-I) effect of halogen, the carbon attached to halogen acquires a partial +ve
charge and the halogen acquires partial-ve charge. Therefore a Nucleophile(Nu - )
can readily attack on +ve centre.
#Configuration:- the 3D arrangement of atoms or groups in a molecule.
# Classification of alkyl halide:-
Alkyl halide are classified as primary (1°), secondary (2°), & tertiary(3°) depending
upon whether the X atom is attached to primary, secondary or tertiary carbon atoms.
CH 3 X, RCH 2 X : primary alkyl halide, R 2 CHX = secondary alkyl halide, R 3 C =
tertiary alkyl halide ,# where –R is alkyl group
Types of Nucleophilic Substitution reactions :-
# The Nucleophilic substitution reactions are divided into two classes:--
1.) S N 2 : --- ( Bimolecular Nucleophilic Substitution reactions)
2.) S N 1 :--- (Unimolecular Nucleophilic substitution reactions)
# 1.) S N 2 :--- Definition & example, :-
When the rate of a Nucleophilic substitution depends on the
concentration of both substrate & Nucleophile, the reaction is of
second order & is represented as S N 2 .
i.e. The rate of SN2 is directly proportional to concentration of
substrate and nucleophile.
1.) S N 2 reaction : definition & example

Rate ∝ [ substrate] [ nucleophile]

Example:--- Hydrolysis of primary alkyl halide by aqueous NaOH .
aqueous NaOH
CH 3 Br + OH - --------------> CH3 OH + ••Br –
Methyl bromide nucleophile Methyl alcohol Leaving group

# Mechanism of S N 2 reaction:--- Let us consider the hydrolysis of primary

alkyl halide ( eg methyl bromide ) by aqueous NaOH.
S N 2 reaction is one step reaction . The Nucleophile, ( i.e. OH - obtained
from aq. NaOH) attacks the substrate carbon of primary (1°) alkyl halide to
give short lived transition state ( T. S. ) , which is unstable and undergoes
decomposition to form alcohol.
Mechanism ( contd.)
 SN2 reaction ( summary):-----
# It is 1 step Mechanism, & 2 nd order reaction.
• Rate depends on the concentration of alkyl halide & Nucleophile.
• It is bimolecular, second order reaction.
• Rate depends on the structure of alkyl halide
i.e. CH 3 X > 1° > 2° > 3°
• Reaction is favoured by strong base ( strong Nucleophile) ,& less
polar solvent.
Factors affecting on Reactivity of SN2 rxn:---
1) Nature of Nucleophile: The stronger the Nucleophile greater will
be the rate of reaction.
H 2 O < ROH < OH - < RO - < I - < CN –
2) Structure of alkyl halide: ---
CH 3 X > 1° > 2° > 3°
Backside attack of Nucleophile on primary (1°) alkyl halide is easier.
Therefore for primary alkyl halide SN2 reaction is favoured.
Backside attack is quite difficult on tertiary alkyl halide.
Therefore for tertiary alkyl halide SN1 reaction favours.
Factors affecting SN2 reaction (contd.)
For secondary (2°) alkyl halide: backside attack of Nucleophile is not
easier as in 1° alkyl halide, so ,if backside attack possible favours SN2
reaction. And if backside attack is not possible favours SN1 reaction.
3) Nature of leaving group:---
For both SN2 and SN1 rxn the ease of elimination of leaving group is
as follows :- I - > Br - > Cl - > F -
4) Nature of Solvent:---- polarity of Solvent is important in case of
formation of the Carbocation. There is no formation of Carbocation in
SN2 reaction. So SN2 reaction favours less polar Solvent .
Energy profile diagram for S N 2 rxn
Questions:-
• 2077Chaitra #1.) What is meant by SN reaction?Explain the
mechanism for for nucleophilic substitution reaction that proceeds
with an inversion of configuration.Why does inversion product
predominates more than retention product in SN1? ( 1+3+1)
• #2.) What do you mean by elimination reaction?Write the
mechanism for dehydrohalogenation of bromoethane in alc.KOH.
Show your acquaintance to Saytzeff’s rule. (1+2+2)
 SN1 reaction:--- definition & example
# When the rate of a Nucleophilic substitution reaction depends only
on the concentration of alkyl halide (substrate),the reaction is of first
order, unimolecular & is represented as SN1.
Rate ∝ [ Substrate ] # Where , [Substrate] = concentration of -
- substrate ( i.e.Alkylhalide)
Ex. The hydrolysis of tertiary (3°) alkyl halide (i.e.3° Butyl bromide) by
aqueous NaOH.
( CH 3 ) 3 C-Br + OH - ------------------->(CH 3 ) 3 C-OH + ••Br -
3° butyl bromide nucleophile aqueous NaOH 3°butyl alcohol leaving group
Racemic mixture:---
# Racemic mixture :- The mixture of equimolar amount of
enantiomers is called racemic mixture.
# In other words, A mixture having an equal amount of d (+) or l (-)
isomers is called racemic mixture, or dl mixture.
# d(+)isomer: the isomer which rotates the plane polarized light slightly
towards right( i.e.clockwise), And , l(-)isomer:- the isomer which
rotates plane polarized light slightly towards left( i.e.anticlockwise)
# Stereochemistry of SN1 reaction:--- A mixture of products formed
i.e. Inversion of configuration & retention of configuration ,where
inversion of configuration is predominated. Therefore partial racemic
mixture is formed.
SN1 reaction (summary)
• SN1 consists two (2) steps mechanisms. # the rate of reaction
depends on the concentration of alkyl halide only.
• It is unimolecular, first order reaction. # the rate of reaction depends
upon the structure of alkyl halide , 3° > 2° > 1° > CH 3 X
• The reaction is favoured by polar Solvent.
# Reactivity of SN1 reaction ( Factors affecting SN1 ):---
1)Nature of Nucleophile 2) Structure of alkyl halide
3) Nature of leaving group 4)Nature of Solvent
Factors affecting SN1 (ReactivityofSN1)rxn:-
1.) Nature of Nucleophile:--- Nucleophile does not involve in the rate
determining step, therefore nature of Nucleophile does not affect the
rate of SN1 reaction.
2.) Structure of alkyl halide:--- The relative Reactivity of alkyl halide
follows the following order:---
3° > 2° > 1° > CH 3 X
# the Reactivity of SN1 reaction depends on the stability of
Carbocation. The greater the stability of Carbocation intermediate the
faster the SN1 reaction. The relative stability of Carbocation is,
3 ° > 2° > 1° > CH3 +
Factors affecting SN1 rxn (continued)
3.) Nature of Solvent:--- For SN1 reaction polarity of the Solvent is
important in the ease of formation of Carbocation.
Therefore, greater the polarity of solvent, greater will be the rate of
SN1 reaction
4.) Nature of leaving group:--- For both SN1 & SN2 rxns the ease of
elimination of leaving group is, I - > Br - > Cl - > F
# thus the order of Reactivity of alkyl halide is , RI > RBr > RCl > RF
Factors affecting(factors governing) both SN1
and SN2 reactions:-
Q.Give the factors affecting for both SN1 and SN2 reactions.(2+2)
1) Nature of Nucleophile:---
For SN2 rxn:---already described so write yourself--
For SN1 rxn:---
2) Structure of alkyl halide:
For SN2 rxn :---
For SN1 rxn :---
3) Nature of leaving group:-- For both SN2 &SN1 rxn:---
4) Nature of Solvent:-- For SN2 rxn :--- For SN1 rxn :---
 Questions :-
2073,bhadra Q.no.15) Write the mechanism of the reaction of tertiary
alkyl halide with , a) Aqueous NaOH , b) Alcoholic KOH (2.5+2.5)
2072,Bhadra & 2076,Bhadra Q.no.15) What is meant by SN reaction?
Explain the mechanism of the reaction between tertiary alkyl halide
and aqueous NaOH. (1+4)
2073,Chaitra Q.no.15) Why does SN1 reaction give both tetention &
inversion isomers but SN2 gives only inversion isomer? Write the
mechanism for the reaction between Bromoethane & aq.NaOH.(2+3)
#Q.no.15) Explain the SN2 rxn mechanism with reference to hydrolysis
of alkyl halide.what type of solvent favours this type of of path?How
can you say that carbocation is not formed during SN2 reaction?
 Elimination reactions:--definition & example
# Elimination reaction( beta elimination):--- Elimination reactions are
those, which involve the removal of atoms or group of atoms from two
adjacent carbon atoms in the substrate molecule to form a multiple
bond.
• In these reactions, two sigma bonds are lost & a new pi bond is
formed. Saturated compound becomes unsaturated.
• Ex. Dehydrohalogenation of alkyl halide with alcoholic alkali (i. e.
alcoholic KOH) is an example of elimination reaction.
R – CH 2 - CH 2 Br + KOH ---------------> R - CH = CH 2 + KBr + H 2 O
alkyl halide base alcohol alkene
Elimination Reactions ( continued ) :-
# There are 3 fundamental events in elimination reactions.
1.) Removal of a proton (H + ) from beta carbon
2.) Formation of the carbon –carbon double bond ( i.e. , saturated
compound becomes unsaturated )
3.) Breaking of the bonds to leaving group ( i.e., loss of leaving
group(e.g. commonly halide group )
# Depending upon the relative timing of these events, different
mechanisms are possible,
1.) E2 rxn:- bimolecular elimination reaction
2.) E1 rxn:-unimolecular elimination reaction
Elimination reaction( contd.):-
# The beta or,1,2, elimination reaction may be also called as follows,
-> or, trans elimination reaction
-> or, alpha beta elimination reaction
-> or, 1,2 elimination reaction
->or, beta elimination reaction or, dehydrohalogenation
Types of elimination rxn #1) E 2 :- ( Bimolecular elimination reaction )
# 2) E 1 :- ( Unimolecular elimination reaction)
1.) E2 rxn:- When the rate of elimination reaction depends upon the
concentration of the substrate and base ( i.e. alcoholic KOH ), the reaction
is of second order, bimolecular & is represented as E2.
E 2 rxn:-
Mechanism
of E2:-
E2(continued.):-condition at T.S.
• Carbon -Hydrogen bond & Carbon-Halogen bond are partly broken.
• Carbon-Carbon double bond is partly formed.
• Eliminating group H and Br are trans to each other.
# E2(summary):- E2 consists 1 step Mechanism. Rate of E2 depends
on the concentration of both alkyl halide and base. Rate of E2 favours
strong base.
• It is Bimolecular, second order rxn. Rate of E2 depends on the
structure of alkyl halide, i e 3° > 2° > 1°
(Because more highly branched alkene increases its stability. )
Reactivity of E 2 (Factors affecting E2):---
1) Nature of Base:--- E2 rxn rate depends upon the concentration &
nature of base. Stronger the base pulls a proton away from the alkyl
halide (substrate) faster. Therefore E2 rxn is favoured by stronger base.
Stronger the base greater will be the rate of E2 reaction.
2) Structure of the alkyl halide ( substrate):--- The order of reactivity
according to the structure of alkyl halide is as follows:---3° > 2° > 1°
This is so ,because more highly branched alkene increases its stability,
according to Saytzeff’s rule. More stable the alkene, the faster it is
formed.
Reactivity of E2(contd.)
3) Nature of Solvent:--- E2 rxn is 1 step reaction, & proceed without
formation of Carbocation so polarity of solvent have very little effect on
rxn rate. Therefore E2 favours less polar solvent.
4) Nature of leaving group:--- Better leaving group increases rate of
E2 & E1 rxns, therefore order of Reactivity of alkyl halide is as follows:
I - > Br - > Cl - > F –
# E2 vs SN2 :--- In E2 OH – abstracts a proton(H + ) from alkyl halide
but, in SN2 OH – attack(shares its electron) Carbon of alkyl halide.
Energy profile diagram:--- same as of SN2
#2)E 1 :-- Unimolecular elimination reaction:-
E1 rxn:--- when the rate of elimination reaction depends only on the
concentration of the substrate, the reaction is of first order & is
represented as E1.
i. e. , rate ∝ [ substrate]
Ex.Dehydrohalogenation of tertiary alkyl halide(3° butylbromide) by
alcoholic KOH.
E1 (continued):summary, &,Reactivity:
# E1 is 2 steps process, first order rxn, rearrangement can takes place to
form more stable Carbocation, eliminate a proton from beta carbon to
form alkene.
# Reactivity of E1: --- Reactivity of E1 reaction is determined by the
rate of formation of the Carbocation & it’s stability. The important
factors that affect the E1 rxn rate are as following
#1) Nature of base:--- E1 rxn rate is not affected by the concentration
or nature of the base. Because the base does not involve in the rate
determining step.
Reactivity of E1(Factors affecting E1)contd.
2) Structure of substrate (alkyl halide):--In E1 rxn, the rate is
determined by the rate of formation of Carbocation and it’s stability.
Therefore E1 rxn rate follows the order, 3° > 2° > 1°
3) Nature of Solvent:--- There is formation of Carbocation intermedite
in E1 reaction, therefore E1 reaction is favoured by high polar Solvent.
# 4) Nature of leaving group:-- Generally better leaving group
enhances elimination reaction. Therefore for both E1 and E2 reaction
the ease of elimination of the leaving group is,
I - > Br - > Cl - > F -
Saytzeff’s rule:-
# If the dehydrohalogenation of alkyl halide can produce more than
one alkenes,then according to Saytzeff’s rule “ the major product is the
most highly substituted alkene”
[Highly substituted alkene:- The greater number of alkyl groups
attached to doubly bonded carbon atoms.]
The order of stability of alkene is as following,
R 2 C = CR 2 > R 2 C = CHR > R 2 C = CH 2 , RHC = CHR > RHC = CH 2
>H 2C=CH 2
---------------------→ decreasing order of stability of alkene--------------------------------------→

[the more stable the alkene , the faster it is formed]

 Factors affecting (governing) bothE2 and E1:--
# 1) Nature of base:- already described so write yourself.
For E1 rxn:-
For E2 rxn:-
# 2) Structure of alkyl halide ( substrate):
For E1 rxn:-
For E2 rxn:’
# 3)Nature of leaving group:--- For both E1 & E2 reaction:
# 4) Nature of Solvent:- For E1: -
For E2:-
Difference between E1&E2:
Energy profile diagm.E1
 # Questions :-
2076 Bhadra ,1.) Write the mechanism of dehydrohalogenation of
tertiary alkyl halide with a suitable example. Write your aquintance
with Saytzeff’s rule. ( 3+2)
2072 Ashwin ,2.) What are elimination reactions ? Write the
mechanism of E2 reaction taking an example. Show your acquaintance
to Saytzeff’s rule. ( 1+2+2)
2073 Chaitra , 3.) What are the differences between E1 & E2 reactions?
Explain the reaction mechanism for the reaction of primary alkyl halide
with alcoholic NaOH. (2+3)
2075 Chaitra , 4.) Explain the mechanism of E1 reaction with a
suitable example. Write the differences between E1 & E2 reaction
mechanism. ( 3+2)