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ISOMERISM
DEFINITION
Compounds having same molecular formula but differ in atleast one physical or chemical or biological properties
are called isomers and this phenomena is known as isomerism.

Types of Isomerism : (A) Structural isomerism (B) Stereo isomerism

(A) STRUCTURAL ISOMERISM
Structural isomerism is a form of isomerism in which molecules with the same molecular
formula have atoms bonded together in different orders.
TYPES OF STRUCTURAL ISOMERISM

CHAIN ISOMERISM METAMERISM

This type of isomerism is due to difference in the arrangement This type of isomerism occurs when the isomers differ with
of carbon atoms constituting the chain. respect to the nature of alkyl groups around the same
Key points : polyvalent functional group.
e.g. C4H10O :
Parent carbon chain or side chain should be different.
CH3 – O – CH2 – CH2 – CH3
e.g. C5H12 : CH3 – CH2 – CH2 – CH2 – CH3 n-propyl methylether
CH3 – CH2 – O – CH2 – CH3
n-pentane diethyl ether

CH3 RING-CHAIN ISOMERISM

H3C – CH – CH2 – CH3 , H3C – C – CH 3 In this type of isomerism, one isomer is open chain but
another is cyclic.
CH3 CH3
iso-pentane neo-pentane CH2
e.g. C3H6 : CH3 – CH = CH2 H2C–CH2
POSITIONAL ISOMERISM propene cyclopropane
It occurs when functional groups or multiple bonds or • For chain, positional and metamerism, functional group
substituents are in different positions on the same carbon must be same.
chain.
• Metamerism may also show chain and position
Key point : Parent carbon chain remain same and
isomerism but priority is given to metamerism.
substituent, multiple bond and functional group changes
its position.
TAUTOMERISM
CH3 This type of isomerism is due to spontaneous
CH 3 CH3 interconversion of two isomeric forms into each other with
CH3
different functional groups in dynamic equilibrium.
e.g. C6H4(CH3)2 : , , Conditions :
CH3 CH3
o-xylene m-xylene
O O
p-xylene
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(i) Presence of –C– or – N ® O

FUNCTIONAL ISOMERISM (ii) Presence of at least one a-H atom which is attached
It occurs when compounds have the same molecular formula to a saturated C-atom.
but different functional groups. e.g. Acetoacetic ester.
e.g. C3H9N : CH3– CH2 – CH2 – NH2, O OH
1-propanamine CH3–C–CH2COOC2H5 CH3–C=CHCOOC2H5
CH3 – CH2 – NH – CH3, keto form enol form
N-methylethanamine ENOL CONTENT ENHANCE BY:
CH3 * Acidity of a-H of keto form
CH3 – N – CH3, * Intra molecular H-Bonding in enol form
N, N-dimethylmethanamine * Resonance in enol form
* Aromatisation in enol form

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(B)STEREOISOMERISM
Compounds with the same molecular formula and structural formula but having difference in the spatial arrangement of
atoms or groups in 3D space are called stereoisomers and the phenomenon is called stereoisomerism.
TYPES OF STEREOISOMERISM

GEOMETRICAL ISOMERISM OPTICAL ISOMERISM

It is due to restricted rotation and is observed in following Compounds having similar molecular and structural formula
systems but differing in the stereo chemical formula and behaviour
towards plane polarised light are called optical isomers and
this phenomenon is called optical isomersim.
a a a
a a l Types of optical isomers
C=C C=N–OH N=N
b b , b , a b, (1) Optically active (2) Optically inactive
b b • dextrorotatory (d) • meso
• laevorotatory (l)
a
(Ring greater than 7
C l Condition :
member with double ,
bond) b Molecule should be asymmetric or chiral i.e.
CH3 symmetry element (POS & COS) should be absent.
l The carbon atom linked to four different groups is
l Cis-trans isomerism : The cis compound is the
called chiral carbon.
one with the same groups on the same side of the
bond, and the trans has the same groups on the l Fischer projection : An optical isomer can be
opposite sides. Both isomers have different physical represented by Fischer projection which is planar
and chemical properties. representation of three dimensional structure.
Fischer projection representation of lactic acid
H H H COOH
e.g. C=C C=C (2-hydroxypropanoic acid)
HOOC COOH HOOC H
cis trans COOH COOH
3 2 1
maleic acid fumaric acid
CH3 – CH – COOH : HO H H OH
OH CH3 CH3
l General physical properties of geometrical isomer
of but-2-ene
l Configuration of optical isomer :
(i) Stability trans > cis (a) Absolute configuration (R/S system)
(b) Relative configuration (D/L system)
(ii) Dipole moment cis > trans
l Determination of R/S configuration :
(iii) Boiling point cis > trans Rule-1 Assign the priority to the four groups
attached to the chiral carbon according
(iv) Melting point trans > cis
to priority rule.
Calculation of number of geometrical isomer Rule-2 If lowest priority 4 is bonded to vertical
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line then moving

Unsymmetrical 2n Clockwise
R
1 2 3
Symmetrical 2n–1 + 2 m–1 Anti clockwise
S
n
m= (If n is even)
2 Rule-3 If lowest priority 4 is bonded to
n +1 horizontal line then moving
m= (If n is odd)
2
Clockwise
1 2 3 S
* Where n = number of sites where GI is possible. Anti clockwise
R
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DETERMINATION OF D/L SYSTEM : l Diastereomers are stereoisomers which are not mirror
• Reference molecule glyceraldehyde images of each other. They have different physical
• It is used to assign configuration in carbohydrate, and chemical properties.
amino acid and similar compounds l Meso compounds are those compounds whose
Rule: Arrange parent carbon chain on the vertical line molecules are superimposable on their mirror images
• Placed most oxidised carbon on the top or nearest inspite of the presence of asymmetric carbon atom.
to top. l An equimolar mixture of the enantiomers (d & l) is
• On highest IUPAC numbered chiral carbon called racemic mixture. The process of converting
If OH group on RHS ® D d- or
If OH group on LHS ® L l- form of an optically active compound into racemic
form is called racemisation.
CHO CHO l The process by which dl mixture is separated into d
H OH HO H and l forms with the help of chiral reagents or chiral
HO H H OH catalyst is known as resolution.
H OH HO H l Compound containing chiral carbon may or may
H OH HO H not be optically active but show optical isomerism.
CH2–OH CH2–OH l For optical isomer chiral carbon is not the necessery
condition.
D–Glucose L–Glucose Calculation of number of optical isomers
l CIP SEQUENCE RULE :
The following rules are followed for deciding the Optically
The compound
precedence order of the atoms or groups :- active forms
(i) Highest priority is assigned to the atoms of
higher atomic number attached to Unsymmetrical 2
n
Zero
asymmetric carbon atom.
(ii) In case of isotopes, isotopes having higher
atomic mass is given priority. Symmetrical n

If n = even 2(n–1) 2 2 –1
(iii) If the first atom of a group attached to
asymmetric carbon atom is same then we
consider the atomic number of 2nd atom or Symmetrical
If n = odd 2(n–1) – 2(n–1)/2 2(n–1)/2
subsequent atoms in group.
(iv) If there is a double bond or triple bond, both
* Where n = no. of chiral carbon
atoms are considered to be duplicated or
triplicated. The different arrangement of atoms in space that results
l Non-superimposable mirror images are called from the carbon-carbon single bond free rotation by 0-
enantiomers which rotate the plane polarised light 360° are called conformations or conformational isomers
up to same extent but in opposite direction. or rotational isomers and this phenomenon is called
conformational isomerism.

CONFORMATIONAL ISOMERISM

Newmann projection : Here two carbon 4 3 2 1

l Conformations of butane : CH3 – CH2 – CH2 – CH3
atoms forming the s bond are represented one
by circle and other by centre of the circle. Circle CH3 CH3 CH3 CH3
represents rear side C and its centre represents CH3 H CH3 H H H
front side carbon. The C–H bonds of front
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carbon are depicted from the centre of the circle 60°

Rotation
60° 60°
Rotation Rotation
while C–H bond of the back carbon are drawn H H CH3
H H H H H H H
from the circumference of the circle. H H H
CH3
Fully eclipsed (less stable) Gauche (more stable) Partially Eclipsed form Anti Staggered-form
Ha Ha (most stable)
Ha Hb Hc
60°
l The order of stability of conformations of n-butane.

Hc Anti staggered>Gauche>Partially eclipsed>Fully eclipsed.

Hc Hb Hb Hc Hb
Ha l Relative stability of various conformation of cyclohexane is
Eclipsed form (least stable) Staggered form (most stable)
Chair > twist boat > boat > half chair

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REACTION MECHANISM
Electrophiles are electron deficient species. Relative electron withdrawing order (–I order)
eg. H , R , NO , X , PCl 3, PCl5
Å Å Å
2
Å Å Å Å
- N F3 > - N R 3 > - N H 3 > –NO2 > –CN > –COOH > –X
Å
( N H4 and H3 OÅ are not electrophile) > –OR > –OH > –CºCH > –NH2 > –C6H5 > –CH = CH2

Nucleophiles are electron rich species. Relative electron releasing order (+I order)
e.g. Cl, CH3, OH, RO, CN, NH3, ROH, CH2=CH2, CHºCH –NH > –O > –COO > 3° alkyl > 2° alkyl > 1° alkyl > –CH3

RELATIVE STABILITY ORDER ACIDIC STRENGTH µ Stability of conjugate base

(A) Stability of carbocation 1
Å Å Å Å
µ Ka µ
pK a
(i) > (Ph)3 C > (Ph)2 CH > Ph - CH2 > CH2 = CH - CH2
(i) H2O > CH º CH > NH3
Å Å Å Å Å Å (ii) CH º CH > CH2 = CH2 > CH3–CH3
(ii) (CH3 )3 C > (CH3 )2 C H > CH3 CH2 > C H3 > CH2 = C H > CH º C
(B) Stability of free radical OH

& > (Ph) CH& > PhCH& & (iii) R–SO3H > R–COOH > > R–OH
(Ph)3 C 2 2 > CH2 = CH - CH2 >

& > (CH ) CH

& > CH CH
& & (iv) HCOOH > CH3COOH > CH3CH2COOH
(CH3 )3 C 3 2 3 2 > CH3
(C) Stability of Carbanion OH
Q Q Q Q
(v) NO2 NO2
> HCOOH > C6H5COOH > CH3COOH
(Ph)3 C > (Ph)2 CH > Ph - CH2 > CH2 = CH - CH2 >
Q Q Q Q
NO2
CH3 > CH3 CH2 > (CH3 )2 C H > (CH3 )3 C (vi) CCl3COOH > CHCl2COOH > CH2ClCOOH
(vii)
1
BASIC STRENGTH µ Kb µ pK OH
b
(viii) C6H4 Phenol > m > p > o
• Basic strength of amine :-
CH3
In aqueous medium
R Þ –CH3 2° > 1° > 3° > NH3 OH
(ix) C6H4 p > o > m > Phenol
R Þ –CH2CH3 2° > 3° > 1° > NH3
NO2
In gaseous medium
R Þ –CH3 3° > 2° > 1° > NH3 OH OH OH OH
R Þ –CH2CH3 3° > 2° > 1° > NH3 NO2 NO2 NO2
(x) NO2 > > >
• Reactivity towards nucleophile (NAR)
(1) HCHO > CH3CHO > (CH3)2CO NO2 NO2
(2) CCl3CHO > CHCl2CHO > CH2ClCHO
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COOH
• Reactivity order towards acyl nucleophilic
(xi) C6H4 o > p > m > benzoic acid
substitution reaction NO2
Acid chloride > anhydride > ester > amide
COOH
• Order of electronic effect
Mesomeric > Hyperconjugation > Inductive effect (xii) C6H4 o > benzoic acid > m > p
CH3
• Stability of alkene µ no. of a-hydrogen
COOH
R 2 C=CR 2 > R 2 C=CHR > R 2 C=CH 2 > RCH=CHR > RCH=CHR
trans form cis form (xiii) C6H 4 o > m > benzoic acid > p
OCH3
RCH=CH2 > CH2=CH2
1 COOH
• Heat of hydrogenation µ (xiv) C6H4 o > m > p > benzoic acid
Stability of alkene Cl
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PRACTICAL ORGANIC CHEMISTRY

PURIFICATION METHODS LASSAIGNE'S METHOD
DISTILLATION TECHNIQUES (detection of elements)
Type :
Element Sodium Confirmed test
(A) SIMPLE DISTILLATION (B) FRACTIONAL extract
Conditions DISTILLATION Nitrogen N a + C + N
(i) When liquid sample has non (N a C N +FeS O 4 +N aO H )
When b.p. D bo il a nd co ol
volatile impurities
difference is 10K +Fe Cl 3 +co nc . H Cl ® Fe 4 [Fe(CN ) 6 ] 3
(ii) When boiling point difference N aC N
Examples Prussian blue colour
is 30 K or more.
(i) Crude oil in
Examples
(i) Mixture of chloroform petroleum
(BP = 334K) and Aniline industry
(BP = 457K) (ii) Acetone (329 K)
(ii) Mixture of Ether and Methyl (i) N a 2 S + N a 2[Fe(C N) 5 N O ]
alcohol (338K)
Sulphur 2Na + S s od ium n itro sop r usid e
(b.p. = 308K) &
Toluene (b.p. = 384K)
D ® N a 4 [Fe(C N ) 5N O S ]
a d eep v iolet colo ur
(iii) Hexane (342K) and N a2S
Toulene(384K)
A b lack p p t. (Pb S ¯)
(C) DISTILLATION UNDER REDUCED PRESSURE
(Vacuum distillation)
When liquid boils at higher temperature and it may
decompose before b.p. is attained. N aX + H N O 3 + AgN O 3
Halogen N a + X
Example (i) Concentration of sugar juice (i) W h ite pp t. so lub le in aq .
(ii) Recovery of glycerol from spent lye. D
N H 3 confirm s C l.
(iii) Glycerol N aX (ii) Yel low p pt. pa rtially solu ble
in a q. N H 3 co nfirm s B r.
(D) STEAM DISTILLATION (iii) Ye llo w pp t. insolu ble in aq .
When the substance is P = P 1 + P2 N H 3 con firm s I.
immiscible with water and Vapour Vapour Vapour
steam volatile. pressure pressure pressure
of of water
Example :
Organic Nitrogen N a +C +N +S A s in te st fo r nitrogen; instea d o f
(i) Aniline is separated liquid
from water and gre en o r b lu e co lou r, blo o d red
D co lou ratio n c onfirm s pre se nce
(ii) Turpentine oil (iii) Nitro Benzene sulphur
together N a CN S of N an d S bo th
(iv) Bromo Benzene (v) Naphthalene
S o d ium th io cy a na te
(vi) o-Nitrophenol (B lo od red c olo u r)

QUANTITATIVE ANALYSIS OF ORGANIC COMPOUNDS

Estimation of carbon and hydrogen ESTIMATION OF NITROGEN
- Leebig's method Duma's method : Kjeldahl's method :
The nitrogen containing organic In this method nitrogen containing
CxHy + O2 ¾¾® xCO2 + y/2 H2O
excess
compound yields nitrogen gas on compound is heated with conc. H2SO4 in
heating it with copper (II) oxide in presence of copper sulphate to convert
12 wt. of CO the presence of CO 2 gas. The
% of C = 44 ´ wt. of org. compd ´ 100
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2
nitrogen into ammonium sulphate which is
mixture of gases is collected over decomposed with excess of alkali to liberate
potassium hydroxide solution in
2 wt. of H2O ammonia. The ammonia evolved is
% of H = ´ ´ 100 which CO2 is absorbed and volume
18 wt. of org compd of nitrogen gas is determined. 1.4 ×volume of acid (ml)
Note : This method is suitable for ×normality of acid
æ Vol. of N2 ö % of N =
estimation if organic compound contains ç collected ÷ wt of organic compound
C and H only. In case if other elements 28 ç at N.T.P. ÷
% of N = ´ç ÷ ´ 100 Note : This method is simpler and more convenient
e.g., N, S, halogens are also present the 22400 ç Wt. of ÷ and is mainly used for finding out the percentage of
ç organic ÷
organic compound will also give their compound nitrogen in food stuffs, soil, fertilizers and various
è ø
oxides which is being absorbed in KOH agricultural products. This method cannot be used for
Note : This method can be used to
and will increase the percentage of carbon compound having nitro groups, azo group (–N = N–)
estimate nitrogen in all types of organic
and therefore following modification and nitrogen in the ring (pyridine, quinole etc.) Since
compounds nitrogen in these compounds is not quantitatively
should be made. converted in to ammonium sulphate.

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