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in"
1
CHEMISTRY
STRUCTURALIDENTIFICATION&POC-1
STRUCTURAL IDENTIFICATION :
(1) Calculation of Degree of Unsaturation (DU):-
It is the hydrogen deficiency index (HDI) or Double Bond Equivalence (DBE)
) O DU (
CH C H C H
3 2 3
=

H 2

H 2
CH
3
C CH or CH
2
= C = CH
2
or
That means Deficieny of 2His equivalent to 1 DU
(i) 1DU = Presence of 1 Double Bond or Presence of 1 Ring closure
(ii) 2DU= Presence of 2 Double bond or 1 Triple bond or two ring closure or 1 double bond + 1 ring closure.
G.F. D.U.
(i) C
x
H
y
(x + 1) |
.
|

\
|
2
y
(ii) C
x
H
y
O
z
(x + 1) |
.
|

\
| +
2
o y
(iii) C
x
H
y
X
s
(x + 1) |
.
|

\
| +
2
s y
(iv) C
x
H
y
N
w
(x + 1) |
.
|

\
|
2
w y
(v) C
x
H
y
O
z
X
s
N
w
(x + 1) |
.
|

\
| +
2
w s y
2. Monochlorination:-
When an alkane or a cycloalkane is treated with halogen (Cl
2
, Br
2
, F
2
, I
2
), a photochemical reaction takes
place and a C Hbond cleaves and a C Cl bond is formed. So, one H-atom is substituted by one halogen
atom. This is known as monohalogenation reaction.
Ex.1 CH
4

v h / Cl
2
CH
3
Cl + HCl Ex.2 CH
3
CH
3

Sunlight / Cl
2
CH
3
CH
2
Cl + HCl
Ex.3

v h / Cl
2
Cl

+ HCl Ex.4

v h / Cl
2
+ HCl
Ex.5

v h / Cl
2
Cl

+ HCl
Application : If a molecule has more than one type of H-atom, then on monochlorination, it forms a mixture
of monochloroisomers. All these isomers are position isomers.
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2
CHEMISTRY
Conclusion : Hence, it can be concluded that the total number of position isomers (structural) of monochloro
compounds is equal to the number of different types of H-atoms present in the reactant. The different type of
H-atoms are also known as non-identical Hydrogens or non-equivalent Hydrogens or chemically different
Hydrogens.
Ex.6 CH
3
CH
2
CH
3

nation Monochlori
2 (structural)
Ex.7 CH
3
CH
2
CH
2
CH
3

nation Monochlori
2 (structural)
Ex.8 CH
3
CH
2
CH
2
CH
2
CH
3

nation Monochlori
3 (structural)
Ex.9

nation Monochlori
4 (structural)
Ex.10
CH
3

nation Monochlori
5 (structural)
Remark : In aromatic hydrocarbons, the hydrogen atoms of the side-chain are chlorinated but H-atoms of
benzene ring are stable. In pure benzene, no monochlorination occurs.
Ex.11

CH
3

v h / Cl
2

CH Cl
2
3. Catalytic Hydrogenation of C = C; C C
(i) Alkenes, Alkynes, polyenes or polyynes can be hydrogenated by using catalysts Ni/Pt/Pdat roomtemperature.
(ii) All C Ct bonds(C = C, C C) are hydrogenated. The reaction cant be stopped at any intermediate stage.
(iii) Aromatic t bonds which are stable at room temperature but can be hydrogenated at high temperature.
(iv) It can be concluded that the hydrogenation product of an alkene or alkyne or any unsaturated compound is
always a saturated compound.
(v) The number of moles of H
2
consumed by 1 mole of compound is equal to the number of t bonds presents.
(vi) All positional isomers of alkenes or alkynes (duetomultiple bond) always givesameproduct onhydrogenation.
(vii) During catalytic hydrogenation no rearrangement in carbon skeleton takes place.
General reaction :
R CH = CH R + H
2

Ni
R CH
2
CH
2
R
R C C R + 2H
2

Pd / Pt / Ni
R CH
2
CH
2
R
) isolated Not (
R CH CH R =

2
H
R CH
2
CH
2
R
CH
2
= CH CH
2
CH
3

Ni / H
2
CH
3
CH
2
CH
2
CH
3

Ni / H 3
2

CH = CH
2
e temperatur room
Ni / H
2

CH CH
3 2
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3
CHEMISTRY
H /Ni
(100 150C)
2

CH CH
3 2
A

Ni / H
2
[Reaction cannot be stopped at any intermediate stage]
Ex.12
Ni / H 2
2
(X)

v h / Cl
2
+
Cl
Ex.13
CH
3

Ni / H
2
CH
3

v h / Cl
2
5 Monochloro product (structural)
Ex.14
CH
3

Ni / H
2
CH
3

v h / Cl
2
5 Monochloro product (structural)
4. Ozonolysis:
(i) It tells about position of unsaturation.
(ii) Alkene and polyalkene on ozonolysis undergo oxidative cleavage.
(iii) (a) The reagent of reductive ozonolysis is
(i) O
3
(ozone) (ii) Zn and H
2
Oor Zn and CH
3
COOHor (CH
3
)
2
S
(b) The reagent of oxidative ozonolysis is O
3
and H
2
O
2
.
(iv) The products are carbonyl compounds (aldehydes or ketones). This type of ozonolysis is known as reductive
ozonolysis.
(v) Ozonolysis does not interfere with other functional groups.
General Reaction :
R CH = CH R
O H / Zn ) 2 (
O ) 1 (
2
3

R CH = O + O = CH R + ZnO + H
2
O
Ex.15 CH
2
= CH
2
O H / Zn ) 2 (
O ) 1 (
2
3

CH
2
= O + CH
2
= O
Ex.16 CH
3
CH
2
CH = CH
2
O H / Zn ) 2 (
O ) 1 (
2
3

CH
3
CH
2
CH = O + O = CH
2
Ex.17 CH
2
= CH CH
2
CH = CH CH
3
O H / Zn ) 2 (
O ) 1 (
2
3

CH
2
= O + O = CH CH
2
CH = O + O = CH CH
3
Ex.18
O H / Zn ) 2 (
O ) 1 (
2
3

OHC CH
2
CHO(Propandial)
Applications:

The process is used to determine the position of C = C in a molecule.

If the products are rejoined, the position of C = C can be determined in the reactant molecule. All C = C (except
aromatic ones) undergo oxidative cleavage under normal conditions.

At higher temperature, the aromatic double bonds can also undergo ozonolysis.
"manishkumarphysics.in"
4
CHEMISTRY
Ex.19
Zn
3
O
O = CH CH
2
C
O
CH
2
HC = O + O = CH
2
Ex.20
Zn
) ( O
3

A
Ex.21
CH = CH CH
3

Zn / O
e temperatur low
3

CH = O
+ O = CH CH
3
Ex.22
CH = CH
O /H Zn
2
3
O

C
6
H
5
CH = O
POC-I :
Introduction
The main objective of an organic chemist is the determination of the structure of a new organic compound
which has been obtained in pure state either from a natural source or synthesised in the laboratory.
-
In order to establish the correct structure of an organic compound, it is necessary to detect element and
functional group present in the organic compound.
Detection of elements (Qualitative Analysis) :-
-
Most of the organic compounds contain 2 to 5 different elements
-
The principal elements present are carbon, hydrogen and oxygen.
-
Less commonly present elements are nitrogen, sulphur and halogens.
-
In feworganic compounds , phosphorus and metal may also be present
-
The order of abundance of these elements in organic compounds is given below:-
Carbon Always present
Hydrogen Nearly always present
Oxygen

Generally present
Nitrogen, halogen, sulphur Less commonly present
Phosphorus and metal

Rarely present
-
Detection of nitrogen, sulphur and halogens are tested in an organic compounds by lassaignes test.
-
The organic compound (N,Sor halogen) is fused with sodiummetal as to convert these elements in ionisable
inorganic substance i.e. nitrogen into sodium cyanide, sulphur into sodium sulphide and halogens into
sodium halides.
-
These cyanide, sulphide or halide ions can be confirmed in the aqueous solution by usual test. The
aqueous solution (fused sodium extract) is called lassaignes filterate.
"manishkumarphysics.in"
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CHEMISTRY
4.1 Identification of Elements in Organic Compounds
2. Sulphur
3. Halogens
4. Phosphorus
5. Nitrogen
and
Sulphur
Remark
The appearance of green or
prussian blue colour confirms
the persence of nitrogen.
Formati on of a whi te ppt.
indicates presence of sulphur
Appearance of purpl e
col ourati on conf i rms the
presence of sulphur
A white ppt. soluble in NH
4
OH
solution indicates chlorine.
A dull yellowppt. partly soluble
in NH
4
OH solution indicates
bromine.
,A yellow ppt. completely in-
soluble in NH
4
OHsolution indi-
cates iodine
A white ppt. of magnesium
pyrophosphate indicates
phosphorus
Blood red colouration confirms
presence of both nitrogen &
sulphur
Element
1. Nitrogen
Lassaignes test
Na + C + N NaCN
FeSO
4
+ 6NaCN Na
4
[Fe(CN)
6
] + Na
2
SO
4
3Na
4
[Fe(CN)
6
] + 4FeCl
3
Fe
4
[Fe(CN)
6
]
3
+ 12NaCl
(a) Oxidation test
3KNO
3
3KNO
2
+ 3[O]
Na
2
CO
3
+ S + 3[O] Na
2
SO
4
+ CO
2
BaCl
2
(aq) + Na
2
SO
4
(aq) BaSO
4
+ + 2NaCl(aq)
(b) Lassaignes test
2Na + S Na
2
S
Na
2
S + Na
2
[Fe(CN)
5
NO] Na
4
[Fe(CN)
5
NO.S]
Lassaignes test
X + Na NaX
NaX +AgNO
3
NaNO
3
+Ag X +
H
3
PO
4
+ Magnesia mixture MgP
2
O
7
+ H
2
O
2MgNH
4
PO
4
Mg
2
P
2
O
7
+ + 2NH
3
+ H
2
O
Lassaignes test
Na + C + N + S NaSCN
3
FeCl
Fe(SCN)
3
Test / Reaction
"manishkumarphysics.in"
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CHEMISTRY
F
u
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(
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C
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2
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|
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"manishkumarphysics.in"
7
CHEMISTRY
F
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p
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"manishkumarphysics.in"
8
CHEMISTRY
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"manishkumarphysics.in"
9
CHEMISTRY
MISCELLANEOUS SOLVED PROBLEMS (MSPS)
1. Identify X, Y & Z with the help of following reactions.
(X)
) n Hydrocarbo
Saturated (
) H C (
18 9

u h / Cl
2
Single monochloro structural product
(Y) (C
8
H
18
)

u h / Cl
2
Single monochloro structural product
(Z)
) n Hydrocarbo
Saturated (
) H C (
14 7

u h / Cl
2
Two monochloro structural productss
Ans. C, D.
Sol. X = or Y =
3 3
3 3
3 3
CH CH
| |
CH C C CH
| |
CH CH
Z = ,
2. X(C
8
H
10
) (Aromatic)

v h / Cl
2
Twomonochloro (structural)
Y(C
8
H
10
) (Aromatic)

v h / Cl
2
One monochloro (structural)
Ans.
(X) (Y)
3. An organic hydrocarbon on oxidative ozonolysis produces oxalic acid and butanedioic acid. Its structure is
(A) (B) (C) (D*)
Ans. (D)
"manishkumarphysics.in"
10
CHEMISTRY
Sol.
Oxidation
O
3

4. An optically active acyclic compounds X (molecular formula C
5
H
9
Br) give following reactions
The incorrect statements about 'X' are:
(A*) It has two stereoisomers (B*) It gives an achiral product (Y) on ozonolysis
(C*) It has two asymmetric carbon atoms (D) It has four stereoisomers and all are optically active
Ans. (A,B,C)
Sol.

3
O
(X)

2
H
5. A set of reagents (1 to 8) are successively reacted with the following compound
1. NaHCO
3
2. 2, 4, DNP 3. Na metal
4. AgNO
3
+ NH
4
OH 5. Fehlings solution 6. Cu
2
Cl
2
+ NH
4
OH
7. Br
2
/ H
2
O 8. NaNO
2
+ HCl
The reagents which give positive test with the given compound are :
(A) 1, 2, 3, 4, 5 (B) 3, 4, 5, 6, 8 (C) 1, 2, 3, 4, 8 (D*) All reagents except 1 and 8
Ans. (D)
Sol. There is no COOHgroup or NH
2
group.
Regents 1 and 8 will fail to give test.
6. Compounds I and II can be distinguished by using reagent.
(I) (II)
4-Amino-2-methylbut-3-en-2-ol 4Amino2,2-dimethylbut- 3-yn-1-ol.
(A) NaNO
2
/ HCl (B) Br
2
/ H
2
O
(C*) HCl / ZnCl
2
(anhydrous) (D) Cu
2
Cl
2
/ NH
4
OH
Ans. (C)
Sol.
(I) gives immediately turbidity by Lucas reagent and (II) does not give turbidity appriciably.