ELECTROPHILIC AROMATIC Br PHYSICS

WALLAH
+ Cl
N2
SUBSTITUTION
I

CH2Cl

1. H
2. H 2 NO 2, H 3

4
nCl
3. N
NO2

AlBr3, FeBr3
NO 3

l5 , S
a
(Ni)

, H2

Br2

SbC
Cl2

3
I2
O
o

HN
CH

r
SO 4
Fe, H 5°C

3,
2O

O ,0

eCl
,H

+
CH2OH H

I2
Cl NH2

2
l3 , F

Cl
3 PO

Cl
3
NO

-
CH

Cu
4 H

AlC
2O
SO
4
Zn ,H
Cl Cl H2
CH
, H SO 4
2O
2 2
NO 3
H O+ 1. H l ) , HCl
, SnC 2
3
COOH ( Z n CH3
1. CH3I, AlCl3 2. Fe CH3I
2. K2Cr2O7, H2O AlCl3
n-PrC
l (n-P
+ SO 3 C rBr)
. H S O 4
d , 3 50 ° Et A l C
– + 1 2 e CO l
ONa , 3 . fus Cl 3 (FeBr )
aOH ./ ∆ or 3
2. N n c (E
Al tC
co

1.
S O4 Cl O)

Et
4
SO 2O

2.
/H 2

t-Bu
H 3PO 4
3

CO
Zn
2 3
H SO
ol

Cl
(H
Cl2C=O (limited)
r
xan

OH
o O

,A
g)
, BF 3
anh.AlCl3
lohe

lC
,H
3

or t-
BF

l3
Cl
SO3H
Cyc

or A
BuC
lCl 3
l

O
 Purification of Organic Compounds Chromatography
Methods of purification Latest technique

Sublimation
Distillation
To purify To separate In
Sublimation Chromatography Stationary Chromatography Mobile
compound is used mix
phase there are phase
Solids Liquid or gas Differential extraction
Solid is converted directly into vapour without undergoing liquid state. 2 phases
Crystallisation eg: Purification of iodine, Camphor, Naphthalene, ammonium chloride etc. Pure solvent
Chromatography
Solid/liq. or
mix. of solvents
or
To test purity gases

Crystallisation: Distillation :
of compound

Types of chromatography
It is based on the difference in the solubilities of the compound & the impurities
in a suitable solvent.
Principle : Based on difference in b.p. of components of mixture.
The impure compound is dissolved in a solvent in which it is sparingly soluble at Also used to separate : Volatile liquids from nonvolatile impurities
room temperature but appreciably soluble at higher temperature.
If the compound is highly soluble in one solvent and very little soluble
in another solvent, crystallisation can be satisfactorily carried out in
1) Adsorption Chromatography:
a mixture of these solvents.
eq: Purification of sugar, purification of potash alum etc.
a) Column Chromatography
Based on the fact that different components of a mixture have
different degrees of adsorption on adsorbent (silica gel or alumina)

Types of distillation:
Involves separation of a mixture over a
Stationary phase - solid column of adsorbent (stationary phase)
Moblle phase - liquid/gas Column packed in a glass tube.
Chromatography
Component of the mixture which is more
2 Types soluble in stationary phase is adsorbed first
Thin layer than the component which is less soluble in
Chromatography stationary phase.
(TLC)
Simple distillation : Fractional distillation: Vacuum distillation Steam Distillation The most readily adsorbed substances are
(distillation under reduced pressure)
To separate liquids which have sufficient difference in b.p To separate liquids which have small difference in b.p.
eg: To separate different fractions of crude oil This method is used to purify liquids having very high boiling points
• To separate substances which are steam volatile retained near the top and others come down to
eg: chloroform (334K) & aniline (457K) in petroleum industry. but they decompose at or below their boiling points. and are immiscible with water.
eg: Aniline, Nitrobenzene, o- nitro phenol.
various distances in the column
eq: Glycerol is separated from spent - lye in soap industry.

b) Thin layer chromatography (TLC)

Differential Extraction Retardation factor:-

Principle:- express degree of adsorption of each Component of mixture.

Involves separation of substances of a

mixture over thin layer of an adsorbent distance moved by component
coated on glass plate.
The components of the mixture move up of mixture from base line
along with the eluent to different distances Rf =
When an organic The organic solvent & aq:
depending on their degree of adsorption distance moved by solvent
compound is present solvent should be The org. solvent is and separation takes place.
Based on difference (mobile phase) from base line.
in an aqueous medium, immiscible with each later removed by
in solubility
it is separated by other so that they distillation or
of organic shaking it with evaporation to
e
form 2 distinct layers
compounds in an organic solvent in which can be get back org.
different solvents. which it is more separated by comp.
soluble than in water. separatory funnel.

2) Partition chromatography:
Example : NaHCO3 NaHCO3
No reaction Based on continuous differential partitioning of components of a mixture between
stationary & mobile phase. Also known as liquid paper chromatography
Stationary phase - liquid
x+y organic : solvent x organic : solvent NaHCO3
i.e. Mobile phase – liquid
• A special quality paper known as chromatography paper is used.
eg: cellulose paper
water y water
• Chromatography paper contains water trapped in it, which works as Stationary
phase.
• Moving phase is a solvent or a mixture of solvents in which spotted chromatography paper is
suspended.

Q. A mixture of camphor and benzoic acid can be separated by: Q. The best method for the separation of naphthalene and benzoic acid from their mixture is:
(a) Chromatography
• The solvent rises up the paper by capillary action and flows over the spot. The paper selectively
(a) Sublimation retains different components according to their differing partition in the two phases.
(b) Extraction with a solvent (b) Crystallisation
The paper strip so developed is called Chromatogram
(c) Chemical method (c) Distillation
(d) Fractional distillation (d) Solvent extraction

Q.In steam distillation, the sum of the vapour pressure of the Q. A liquid compound can be purified by steam distillation only if it is
volatile compound and that of water is: (b) Steam volatile, miscible with water
(c) Not steam volatile, immiscible with water
Q. Paper chromatography is an example of : Q. The most suitable method of separation of 1 : 1 mixture of ortho & para-nitrophenols is
(a) Equal to atmospheric pressure
(b) Less than atmospheric pressure (d) Steam volatile, immiscible with water (a) Partition chromatography (a)Steam distillation
(c) More than atmospheric pressure (b) Thin layer chromatography (b)Sublimation
(d) Exactly half of the atmospheric pressure (c) Column chromatography (c)Chromatography
(d) Adsorption chromatography (d)Crystallisation
 PHYSICS
WALLAH
Qualitative Analysis of Organic Compound Quantitative Analysis
01 Detection of C & H 2a Detection of Halogen:-
Δ C + 2CuO → 2Cu + CO2
01 Liebig’s method % of carbon =
12 Mco
× ×100
2

O. C. + CuO Lassaigne extract + AgNO3 → ppt 44 Moc

2H + CuO → Cu + H2O 12
Ag+ + Cl– → AgCl 2
(While ppt soluble in NH4OH.)
Ca(OH)2 + CO2 → CaCO3 ↓ + H2O Carbon CO2 44 Hydrogen H2O 18 2 M H2O
White turbidity Ag+ + Br– → AgBr % of hydrogen = × × 100
(Light yellow ppt
18 Moc
CuSO4 + 5H2O → CuSO4 . 5H2O sparingly soluble in NH4OH.)
Blue Ag+ + I– → AgI
(yellow ppt-insoluble in NH4OH)

Detection of N, S,P & X 02 Detection of Nitrogen 2b 02 Estimation of Nitrogen

Fuse with sodium Lassaigne extract + FeSO4 (Freshly prepared) (2a) Duma’s method (2b) Kjeldahl method
O.C. Sodium fusion extract +drops of conc. H2SO4 gives blue color
boil with distilled water (Lassaigne extract)
P1V1 760 × VSTP VSTP 28 NaOH, Δ
FeSO4 + conc. H2SO4 → Fe2(SO4)3 = %(N) = × × 100 O.C + H2SO4
Δ
(NH4)2SO4 NH3
Na + X → NaX Na + C + N → NaCN T1 273 22400 moc
Na + C + N → NaCN 1.4 × N × Vml
2Na + S → Na2S Na + C + N + S → NaSCN
Volume of nitrogen collected = V1 mL ,Temperature = T1 K 2NH4 + H2SO4 (NH4)2SO4 % of N =
6CN + Fe → [Fe(CN)6]
– 2+ 4–
MOC
p1= Atmospheric pressure – Aqueous tension Kjeldahl' s method is not used for
3[Fe(CN6)] 4–
+ 4Fe → Fe4[Fe(CN)6]3
3+

[Iron (III) hexacyanoferrate (II)] Nitro

2d Detection of Phosphorous
Prussian blue
Azo compounds

03 Estimation of X, S, P
O.C. + Na2O2 gives H3PO4 which gives yellow ppt
with ammonium molybdate
2c Detection of Sulphur
Carius method
Mx × WAgX× 100 32 × wBaSO4 × 100
H3PO4 + 12(NH4)2.MoO4 + 21HNO3 %X= % S= 31 × wAPM × 100 62 × wMg2P2O7 × 100
Lassaigne extract + Sodium nitroprusside gives violet color MAg × WOC 233 × WOC %P= %P=
Ammonium 1877 × WOC 222 × WOC
molybdate S–2 + [Fe(CN)5 NO]–2 → [Fe(CN)5 NOS]–4
(NH4)3PO4 . 12MoO3 + 21NH4NO3 + 12H2O violet

Ammonium phospho
If both N & S are present: Na + C + N + S → NaSCN
- molybdate (yellow) Q. During estimation of nitrogen present in an organic compound by Kjeldahl's method,
(APM) the ammonia evolved from 0.5 g of the compound in Kjeldahl's estimation of nitrogen
Lassaigne extract + ferric chloride gives blood red color
- neutralized 10 mL of 1MH2SO4. The percentage of nitrogen in the compound is :
SCN + Fe3+ → [Fe(SCN)]2+
PW1673
(a) 56% (c) 50%
(b) 45% (d) 40%

Q. On complete combustion, 0.246 g of an O.C gave 0.198 g of carbon Q. In Dumas' method for estimation of nitrogen, 0.3g of an organic compound Q. In Carius method of estimation of halogen, 0.15 g
dioxide & 0.1014 g of water. Determine % composition of carbon & gave 50mL of nitrogen collected at 300 K temperature and 715 mm pressure. of an organic compound gave 0.12 g of AgBr. What
hydrogen in the compound. Calculate the percentage composition of nitrogen in the compound. (Aqueous is the percentage of bromine in the compound?
tension at 300 K=15 mm)
(a) 4.58,21.95 (c) 45.8, 21.95 (c) 6.25% (a) 68.08% (c) 42.1%
(a) 17.5%
(b) 21.95,4.58 (d) 2.195,45.8 (b) 28% (b) 45% (d) 50%
(d) 31%

Q. Which of the following compounds will be suitable for Kjeldahl's method for nitrogen estimation?

(a) (b) (c)

(d)
 PHYSICS
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CONSTITUTIONAL ISOMERISM CONSTITUTIONAL ISOMERISM

[STRUCTURAL]

CHAIN [SKELETAL] PROTOTROPIC TAUTOMERISM

ISOMERISM [PROTOTROPY]
OH H X Y=Z, X=Y Z H
OH
OH POSITION ISOMERISM
[REGIOISOMERISM] O OH
O H
O
O O FUNCTIONAL ISOMERISM keto enol
O

METAMERISM O–H
Pair of functional isomers: O
H 2C N
• Alcohols and ethers (CnH2n+2 O) H3C–N
• Aldehydes and ketones (CnH2nO) Nitroso form oxime
• Carboxylic acids and esters (CnH2nO2) Q. The number of structural isomers possible from
• 1°, 2° & 3° amines (CnH2n+3 N) the molecular formula is
(a) 4 (b) 5 (c) 2 (d) 3 O +
OH
+
∑n (v - 2) Q. Identify the compound that exhibits tautomerism R2CH N R 2C N
DBE = + 1 = sum of no. of π bonds + rings (a) 2-Pentanone (b) Phenol
2 O O
in the molecule
(c) 2-Butene (d) Lactic acid Nitro form Aci form

(n is no of atoms of particular element & ν is corre- Q. The number of structural isomers for C6H14 is
sponding valency in given molecule). (a) 3 (b) 4 (c) 5 (d) 6
 PHYSICS
WALLAH
STEREOISOMERISM
STEREOISOMERISM

CONFIGURATIONAL ISOMERISM CONFORMATIONAL ISOMERISM

OPTICAL ISOMERISM
CONFORMER
[(+)/d dextrorotatory (–)/l levorotatory]

DIASTEREOMER ENANTIOMER RING CONFORMATIONS ROTAMER ATROPISOMER

chirality centre axial chirality:

COOH COOH H3C CH3
(asymmetric atom):
H OH H OH C2
Br Br boat* eclipsed
HO H H OH H
H H
COOH COOH H H H
Cl F F Cl NO2 O2N
HO2C CO2H
(R, R) (R, S) (S) (R) CH3
meso- twist* HO2C NO2 O2N CO2H
H CH3
staggered
COOH COOH (gauche)
H H
HO H H HO
GEOMETRIC ISOMERISM EPIMER chair* H Sa = M Ra = P
H OH HO H
HCH3 (conformational enantiomers )
COOH COOH
CHO CHO allylic strain:
(S,S) (R,R) CH3 eclipsed
H OH H OH R H H
ABSOLUTE RELATIVE axial chirality: H
HO H HO H
stereochemistry stereochemistry R* R R*
H OH HO H C2 HO Cl Cl OH CH3
E/Z-ISOMER cis/trans-ISOMER H H
H OH H OH staggered
H3C CH3 H3C CH3 (anti)
Cl Br Cl Cl Cl Cl CH2OH CH2OH H H
(R,S,R,R) (R,S,S,R) (Ra = P) (Sa = M)
CH3
H F H H H H
(Z)-zuammen cis- cis- H CH3
Cl H OH
Cl F Cl H HOOH H eclipsed
HO O O H H Q. Out of the following, the alkene that
H Br H Cl H Cl H3C exhibits optical isomerism is:
HO HO
(E)-enigegen trans- trans- OH OH OH OH Q. Which of the following does not show (1) 2-methyl-2-pentene
CH3 (2) 3-methyl-2-pentene
D-Glucose D-Galactose geometrical isomerism? H3C H (3) 4-methyl-1-pentene
(1) 1, 2-dichloro-1-pentene staggered
(2) 1, 3-dichloro-2-pentene (gauche) (4) 3-methyl-1-pentene
OH OH H H
(3) 1, 1-dichloro-1-pentene
ANOMER O O (4) 1, 4-dichloro-2-pentene H
HO HO
OH
HO HO H3C CH3
glycosides, hemiacetals, sugars OH OH
α β
OH
H eclipsed
H H
α-D-Glucose β-D-Glucose H
Q. With respect to the conformers of ethane, which of the
following statements is true?
(1) Both bond angles and bond length remains same
(2) Bond angle remains same but bond length changes
(3) Bond angle changes but bond length remains
(4) Both bond angle and bond length change