Notes for Class XII

Alcohols and Phenol

Prepared By
Prof. Dr. Bhawani Chand Thakuri
[email protected]
 Alcohols and Phenols
Alcohols
When hydrogen atom of any alkane is replaced by –OH functional
group, alcohol is formed. Alcohol can generally be represented by (R-
OH) where R- is any alkyl group
-H
R H R OH
+ OH Alcohol
Alkane

-H
eg. H3C H H 3C OH
+ OH
Methane Methanol

Classification of Alcohols (Monohydric alcohol)

Alcohols are classified as:
1. Primary alcohol (1O Alcohols)
2. Secondary alcohols (2O Alcohols)
3. Tertiary alcohols (3O Alcohols)
1. Primary alcohol(1O Alcohols)
If –OH group is attached to 10 carbon, that alcohol is called 10 alcohol
or when primary hydrogen from primary carbon is replaced by –OH
group, primary alcohol is formed.
2. Secondary alcohols (2O Alcohols)
If –OH group is attached to 20 carbon, that alcohol is called 20 alcohol
or when secondary hydrogen from secondary carbon is replaced by –
OH group, secondary alcohol is formed.
3. Tertiary alcohols (3O Alcohols)
If –OH group is attached to 30 carbon, that alcohol is called 30 alcohol
or when tertiary hydrogen from tertiary carbon is replaced by –OH
group, tertiary alcohol is formed.
H H H OH H H OH H
10 10 20 30
H C C OH H C C C H H C C C H

H H H H H H CH 3 H

10 Alcohol 20 Alcohol 30 Alcohol

(Ethanol) (Propan-2-ol) (2-methylpropan-2-ol)
 H H H H H H H H
0 0
1 0 1 10 20 10 3O 10
H C C H
1
H C C C H H C C C H
H H H H H H 10
H
HCH
0
2 carbons are 1 carbons 0
1carbon is 2 carbon H
0
1carbon is 3 carbon

Hydrocarbons showing Primary, Secondary and tertiary

carbons and hydrogens attached with primary, secondary and
tertiary carbons are called primary, secondary and tertiary
hydrogens.
Alcohols may be also classified as:
(i) Monohydric alcohols (containing one – OH group)
(ii) Dihydric alcohols (containing two – OH groups)
(iii) Trihydric alcohols (containing three -OH groups)
(iv) Polyhydric alcohols (containing more than two or three –OH groups )
H H OH OH OH OH OH

H C C OH H C C H H C C C H

H H H H H H H
Monohydric alcohol Dihydric alcohol Trihydric alcohol
(Ethanol) (Ethan-1,2-diol) (Propan-1,2,3-triol)

OH OH H OH OH

H C C C C C H

H H H H H

Polyhydric alcohol
(Pentan 1,2,4,5-tetraol)
Isomerism in alcohols:
Compounds having the same molecular formula but different
structural formula and chemical properties are called isomers
(Structural isomers) and the phenomenon is known as
isomerism. Alcohols exhibit only following three types of
structural isomerism.
1. Chain isomerism
Alcohols having same molecular formula but differ only in the
length of the carbon chain and properties are called chain
isomers and phenomenon is known as chain isomerism
H
H C H
H H H H H H H H
H C C C C C OH H C C C C OH
H H H H H H H H H
Pentan-1-ol 3-methylbutane-1-ol
Both are chain isomers to each other
2. Positional isomerism
Alcohol having the same molecular formula, same carbon chain
length but differ only in the position of the –OH group in the
carbon chain are called positional isomers and phenomenon is
known as positional isomerism.
H H H H H H H OH H H
H C C C C C OH H C C C C C H
H H H H H H H H H H
Pentan-1-ol Pentan-3-ol
Both are positional isomers to each other
3. Functional isomerism
Alcohols are isomeric with ether. So alcohols can be functional
isomers to each other.
H H H H
H C C OH H C O C H
H H H H
Ethanol Dimethyl ether
Both are chain isomers to each other
General methods for the preparation of Monohydric alcohols
Alcohols can generally be prepared by the following methods
1.Byhydrolysis of alkyl halides
When the alkyl halides are hydrolyzed in the presence of aqueous
NaOH or KOH, alcohols are prepared.
H2O
R X + NaOH R OH + NaX
Alkyl halide Alcohol

Cl OH
eg. H3 C CH 2 H2O
+ NaOH H3 C +
CH 2 NaCl
Ethyl chloride Ethyl alcohol
(Chloroethane) (Ethanol)

Br OH
eg. H3 C C H2O
CH 3 + NaOH H3 C C CH 3 + NaBr
H H
2-bromopropane Propan-2-ol
By acid catalyzed hydration:
Alkenes react with water in the presence of acid as catalyst to form
alcohols. In case of unsymmetrical alkenes, the addition reaction
takes place in accordance with Markovnikov’s rule
H H H H
H+ R C C OH
R C C H + H2O
H H
Alkene
Alcohol

H H H H
H+ H C C OH
H C C H + H2O
H H
Ethene
Ethanol

H H H H OH H
H+ H C C C H
H C C C H + H2O
H H H
H Propene
Propan-2-ol
3.From Grignard reagents
Alkyl magnesium chloride is known as Grignard reagent.
RMgX

Grignard ragent
 RMgX R- + MgX+
Grignard ragent

CH 3MgBr CH 3 - + MgX+
Methyl magnesium bromide
(Grignard reagent)

Aldehydes and ketones (Carbonyl compounds) react with

Grignard reagent in the presence of dry ether followed by
hydrolysis give primary (10 ), secondary (20 ) and tertiary (30 )
alcohols depending upon the type of aldehydes and ketones
used.
The first step of the reaction is the nucleophilic
addition of Grignard reagent to the carbonyl group to form an
adduct. Hydrolysis of the adduct yields an alcohol.
 1. Formaldehyde or methanal react with any Grignard
reagent, always give primary (10)alcohols

H H
+
C O + H3C MgBr H3C C O -
+ MgBr
H H
Methanal Methylmagnesium bromide
Grignard reagent

H H
Br H OH +
- MgBr
Mg H3C C OH H3 C C O
OH
+
H H
Bromomagnesium hydroxide
Ethanol Addition product(Adduct)
(10 Alcohol)
 2. Aldehydes other than methanal of formaldehyde react with
any Grignard reagent, always give secondary (20)alcohols

O -
O
R C + R MgBr +
R C R + MgBr
H Alkylmagnesium bromide
H
Aldehyde other than Grignard reagent
Methanal
+
OH O- MgBr
Br H OH
Mg + R C R R C R
OH
H H
Bromomagnesium hydroxide
(20 Alcohol) Addition product(Adduct)
Mechanism

O -
O
H3C C + H3C MgBr +
H3C C CH3 + MgBr
H Methylmagnesium bromide
H
Ethanal (Grignard reagent)

+
OH O- MgBr
Br H OH
Mg + H3C C CH3 H3C C CH3
OH
H H
Bromomagnesium hydroxide
Propan-2-ol Addition product(Adduct)
(20 Alcohol)
 3. Any ketones when react with any Grignard reagent , always
give tertiary (30 ) alcohols

Mechanism

O-
O
+
R C R + R MgX R C R + MgX

Alkylmagnesium halide R
Ketone
(Grignard reagent)

+
OH O- MgBr
X H OH
Mg + R C R R C R
OH
R R
Halomagnesium hydroxide
(30 Alcohol) Addition product(Adduct)
Mechanism
-
O O
+
H3C C CH3 + H3C MgBr H3C C CH3 + MgBr
CH3
Propnone Methylmagnesium bromide
(Grignard reagent)

OH +
O- MgBr
Br H OH
+ H3C C CH3 H3C C CH3
Mg
OH
CH3 CH3
Bromomagnesium hydroxide
2-methylpropan-2-ol
Addition product(Adduct)
( 3 0 Alcohol)
From primary amines
When primary amines are treated with nitrous acid. Alcohols are
formed. Nitrous acid is formed by the reaction of NaNO2 and
HCl. In this reaction nitrogen gas is also liberated.
R + HNO2 NaNO2 + HCl
NH 2 R OH + N2 + H2O
0
Primary amine Nirtous acid 0-5 C Alcohol
H
H
Eg. H C N H + HNO2 NaNO2 + HCl
0
H C OH + N2 + H2O
H H 0-5 C
H
Amino methane Methanol
(Methyl amine)
HONO
H 3C NH2 H3C OH + N2 + H 2O
OH N O Methanol
Methyl amine
From Hydrolysis of Ester
Alcohols can also be prepared by the hydrolysis of ester in the
presence of aq. Acidic or basic medium
O O
+
H
R C OR + H-0H R C OH + R OH
Ester Water Hil. HCl carboxylic acid Alcohol

O O
+
H dil. acid
H3C C OCH2CH3 + H-0H H3C C OH + CH3CH2 OH
Ethylethanoate Water Ethanoic acid Ethanol
(Ethyl acetate)
O O
+ H2O R OH
R C OR NaOH R C ONa +
Ethylethanoate Water Sodium ethanoate Alcohol
(Ethyl acetate)
 Industrial preparation of Alcohol
1. Fermentation of carbohydrates(sugar)
Fermentation is the slow decomposition of complex or higher
organic compound into simpler compounds by the action of
enzymes. The carbohydrates used for the fermentation are
sucrose, glucose ,fructose, molasses and sugar containing fruits
and starchy materials like wheat, rice, maize, barley, potato etc.
Fermentation is the old traditional method for the commercial
manufacture of ethyl alcohol.
enzyme used is the unicellular plant material which contains
enzymes like invertase, diastase, maltase, zymase etc.
1. From fermentation of sugar
Molasses is the big source of sucrose, glucose, fructose. Etc.
Molasses is the dark brown colored mother liquor obtained
after the crystallization of cane sugar in the sugar industries.
 Sucrose obtained from molasses when hydrolyzed in the
presence of enzyme ‘invertase’ give glucose or fructose. Glucose
or fructose then comes in contact with enzyme ‘zymase’ convert
into ethyl alcohol along with the evolution of CO2 gas.
Reaction:
Invertase
C12H22O11 + H2O C6H12O6 + C6H12O6
Sucrose (from molasses) Glucose Froctose
Zymase
C6H12O6 2C2H5OH + 2CO2
Glucose or Fructose Ethyl alcohol

The fermented liquor from the above process is called ‘wash’.

This wash contains 12-15% ethyl alcohol which can be obtained
in pure form by distillation process.
2. From fermentation of Starch
Starchy raw material used for the fermentation process are
rice, wheat, maize, barley, potato etc.
The raw materials are first thoroughly cocked or boiled with
water to release starch which is called ‘Mesh’. The mesh is then
mixed with yeast (Enzyme) and kept for about 7-10 days or
more.
Diastase
Starch + nH2O nC12H22O11
Sucrose
Invertase or Maltase
C12H22O11 + H2O C6H12O6 + C6H12O6
Sucrose (from molasses) Glucose Froctose

C6H12O6 Zymase 2C2H5OH + 2CO2

Glucose or Fructose Ethyl alcohol
This fermented liquor is called ‘wash’ this wash contains 12-15
% ethyl alcohol is obtained impure form by distillation
Favorable condition for fermentation:
 Yeast, a type of single-celled fungus, provides the enzymes needed
for fermentation.
 Little amount of ammonium sulphate or ammonium phosphate is
added as nutrient of yeast.
 If the yeast cells become too cold, fermentation happens very
slowly, or may not happen at all.
 If the yeast cells become too hot, their enzymes
become denatured and fermentation stops.
 sugars dissolved in water, and mixed with yeast
 an air lock to allow carbon dioxide out, while stopping air getting in
 warm temperature, 25-35°C
 The yeast dies when the ethanol concentration reaches about 15 %
 If air is present, the oxygen causes the ethanol to oxidize to
ethanoic acid, so the drink tastes of vinegar.
Oxo process:
This is also the industrial process for manufacturing of alcohol above ethanol.
In this process alkenes are treated with (CO+H2) the presence of cobalt carbonyl
catalyst (octacarbonyl dicobalt) to get aldehyde. This aldehyde on reduction in
the presence of Ni/H2 or Pt/H2 catalyst Catalytic hydrohenation) gives alcohol.

Co CO4 2 Ni/H2
H2C CH2 + CO +H2 CH3CH2CHO CH3CH2CH2OH
Ethene Propanal Propan-1-ol

Hydroboration-oxidation of ethene
Alkenes react with diborane (B2H6) or (BH3)2 undergo hydroboration to give
alkyl borane which on oxidation in the presence of H2O2 gives alcohol
Ether
H2C 1
CH2 + H-BH2 or /2 (BH3)2 CH3CH2
Hydroboration
Ethene Borane BH2
Ethylborane

H2O2/OH -
B(OH)3 + CH3CH2OH Oxdn
Boric acid Ethanol
Properties of alcohols (Monohydric alcohols)
1. Physical properties
 Lower alcohols are colorless liquid with characteristic smell and burning
taste while higher alcohols are colorless waxy solids.
 Lower alcohols are soluble in water due to presence of intermolecular
hydrogen bonding.
 solubility decreases with increase in the carbon chain or molecular
masses. This is due to the difference in the sizes of the alcohol and water
H
molecules. H
R O H O H O R

Intermolecular
Hydrogen bond
 The boiling points of the alcohols are much higher than those of other
hydrocarbons having comparable molecular weight. It is because of
intermolecular hydrogen bonding formation.
H

R O H O R

Intermolecular Hydrogen bonding among

alcohol molecules
 Boiling points of alcohols decreases with increase of branching.
OH OH
CH3-CH2-CH2-CH2-OH CH3-CH2-CH-CH3 CH3-CH-CH3
Butan-1-ol CH3
Butan-2-ol
0 2-methylpropan-2-ol
( B.Pt.=118 c) ( B.Pt. = 1080c) 0
( B.Pt. = 80 c)

 Chemical Properties of alcohols (Monohydric alcohols)

(1) Reaction with metals (Acidic nature of alcohols)
The reaction between highly electropositive metals like Na, K, Li etc. Involves in
the presence of ether, breaking of the bond between -O-H takes place and metal
alkoxide and H2 gas released showing the acidic nature of alcohols.

- +
General. 2R-OH + 2Na 2R-O Na + H2
Alcohol Sodium alkoxide
- +
Eg. 2CH3CH2OH + 2Na 2CH3CH2O Na + H2
Ethyl Alcohol Sodium ethoxide
(Ethanol)
(2)Esterification:
Alcohols react with carboxylic acid in the presence of few
drops of conc. H2SO4 to give esters. This reaction is called
esterification reaction. Conc. H2SO4 acts as dehydrating agent.
Conc. H2SO4
RCOOH + HO R RCOOR + H2O
Carboxylic acid Alcohol Ester

Conc. H2SO4
CH3COOH + HO CH2CH3 CH3COOCH3CH3 + H2O
Acetic acid Ethyl alcohol Ethyl acetate
(Ethanoic acid) (Ethanol) (Ethyl ethanoate)

This test is laboratory test for ethyl alcohol.

The order of acidic strength of alcohols is given as:
Primary alcohol Secondary alcohol Tertiary alcohols
H HO HO
H3C C OH H3C C CH3 H3C C CH3
H H H3C

(10 Alcohol) (20 Alcohol) (30 Alcohol)

Decerasing order of acidity of alcohols
(3) Reaction with halogen acid (Basic nature of alcohol)
In this reaction –OH group is replaced by halogen atom.
R OH + H X R X + H2O
Alcohol Halogen acid Alkyl halide

CH3CH2-OH + H Cl CH3CH2-Cl + H2O

Ethyl alcohol Hydrochloric acid Ethyl chloride
(Ethanol)
(4) Reaction with Phosphorous halide (PX3,PX5)
Alcohols are easily converted to alkyl halide when react with
phosphorous halides
R OH + PCl5 R Cl + POCl3 + HCl
Alcohol Phosphorus Alkyl Chloride Phosphoryl chloride
pentachloride
H3C CH2-OH + PCl5 H3C CH2-Cl + POCl3 + HCl
Ethyl alcohol Ethyl chloride Phosphoryl chloride
The order of basic strength of alcohols is given as:
Primary alcohol Secondary alcohol Tertiary alcohols
(5) Reaction with PX3
Alcohols also react with phosphorous trihalide to give alkyl
halide.
3CH3CH2-OH + PCl3 3CH3CH2-Cl + H3PO3
Ethyl alcohol Ethyl chloride Phosphorous acid
(Ethanol)

(6)Reaction with Thionyl chloride (SOCl2)

Alcohols react with thionyl chloride to give alkyl halides.

R OH + SOCl2 R Cl + SO2 + HCl

Alcohol Thionyl chloride Alkyl halide

CH3CH2-OH + SOCl2 CH3CH2-Cl + SO2 + HCl

Ethyl alcohol Ethyl chloride
(Ethanol)
(7) Reaction with H2SO4 :
Ethyl alcohol reacts with conc. H2SO4 to give different products
at different temperatures.
(1)At 1000C:
Ethyl alcohol reacts with conc. H2SO4 at 1000C to give ethyl
hydrogen sulphate.
CH3CH2-OH + HHSO4 CH3CH2HSO4 + H2O
Ethyl alcohol (Conc. H2SO4) 1000C Ethyl hydrogen sulphate
(Ethanol)

(1)At 1400C:
Ethyl alcohol reacts with conc. H2SO4 at 1400C to give ethyl
diethyl ether (Ethoxy ethane).

CH3CH2-OH + HO CH2CH3 (Conc. H2SO4) CH3CH2-O CH2CH3 + H2O

Ethyl alcohol 1400C Diethyl ether
Ethyl alcohol
(Ethanol) (Ethanol) (Ethoxy ethane)
(1)At 1700C:
Ethyl alcohol reacts with conc. H2SO4 at 1700C to give ethene.
H OH H H
Conc. H2SO4
H C C H H C C H + H2 O
1700C
H H
Ethanol Ethene

(8) Oxidation of 10,20 and30 alcohols by oxidizing agents:

Alcohols can easily be oxidized into aldehydes and ketones in
the presence of any oxidizing agents like acidic or alkaline
K2Cr2O7, KMNO4 etc.
(i) 10 Alcohol:
+ [O]
R-CH2-OH + [O] KMNO4/H R-CHO R-COOH
Ethyl alcohol Aldehyde Carboxylic acid
(Ethanol)
+ [O]
CH3CH2-OH + [O] KMNO4/H CH3CHO CH3COOH
Ethyl alcohol Ethanal Ethanoic acid
(Ethanol) (Acetaldehyde) (Acetic acid)
(ii) 20 Alcohol:
20 alcohols are oxidized into ketone with the same no of
carbon atoms. The ketones are further oxidized into carboxylic
acid with one carbon less than original ketones.
OH O
+ 4[O]
[O] KMNO4/H R C RCOOH + CO2 + H2O
R CH R + R
-H2O
0 Ketone
2 Alcohol

OH O
+
KMNO/H H C 4[O]
H3C CH CH3 + [O] 3 C CH3 CH3COOH + CO2 + H2O
-H2O
Propanone Ethanoic acid
Propan-2-ol
0 (Acetic acid)
( 2 alcohol)

(iii) 30 Alcohol:
30 alcohols are not oxidized in ordinary condition because in
30 alcohols carbon containing –OH has no hydrogen atom.
(9) Reduction of alcohols (Catalytic dehydrogenation &
dehydration)
When alcohol vapors are passed through the red hot copper tube at
3000 C, Different class of alcohols give different products.
(i) 10 Alcohol: 10 or primary alcohols are dehydrogenated into
aldehydes.
Cu
R-CH2-OH R-CHO + H2
0
10alcohol
300 C Aldehyde
Cu
CH3-CH2-OH
0
CH3-CHO + H2
Ethyl alcohol 300 C
Ethanal
(Ethanol)

(ii) 20 Alcohol: 20 or secondary alcohols are dehydrogenated into

ketones. OH O
Cu R
R CH R
0
C R + H2
0 300 C
2 Alcohol Ketone
OH O
Cu
H3 C CH CH3 H3C C CH3 + H2
0
Propan-2-ol 300 C Propanone
0
(2 alcohol)
(iii) 30 Alcohol:
30 or tertiary alcohols are dehydrated into alkenes in the presence of Cu
catalyst at 3000C.
OH H
Cu
H3C C C H H3C C CH2 + H2O
0
300 C
CH3 H CH3
2-methylpropan-2-ol 2-methylpropene
(30 alcohol)

Distinction between 1020 and 30 alcohols by Victor Meyer’s Method

There are several methods for distinguishing 1020 and 30 alcohols but
most important method is Victor Meyer’s Method.
(i) Oxidation method
(ii) Catalytic dehydrogenation
(iii) Victor Meyer’s Method etc.
(iv) Lucas Test
Victor Meyer’s Method:
Victor Meyer’s Method is most important and widely used
method for distinguishing 10, 20 and 30 alcohols. In this method
the given alcohol is first treated with phosphorous and iodine
solution (P+I2) to give iodo alkane which is then treated with
silver nitrite(AgNO2) to give nitro alkane. The nitro alkane is
then treated with nitrous acid (HNO2) and the resulting solution
is finally made alkaline by NaOH or KOH. Following results are
obtained.
(i) Primary alcohol gives red colour
(ii) Secondary alcohol gives blue colour
(iii) Tertiary alcohol gives no any colour

Table for distinguishing 10, 20 and 30 alcohols is given in next slide

Table for distinguishing 10, 20 and 30 alcohols
0 0 0
Primary (1 ) Alcohol Secondary (2 ) Alcohol Tertiary (3 ) Alcohol

R-CH2-OH OH OH
R C R R C R
P+I2 H R
P+I2 P+I2
I I
R-CH2-I R C R R C R
H R
Iodoalkane
Iodoalkane Iodoalkane
AgNO2
AgNO2 AgNO2
NO2 NO2
R-CH2-NO2 R C R R C R
Nitroalkane H R
Nitroalkane Nitroalkane
HNO2
HNO2 HNO2
(NaNO2+ HCl)
(NaNO2+ HCl) (NaNO2+ HCl)
NO2
R-C-NO2
R C R No Reaction
N OH
N O
Nitrolic acid
Psecudonitrole Iodoalkane
KOH
KOH KOH

Red colour Blue colour No colour

Example
Ethanol Propan-2-ol 2-methylpropan-2-ol
0 0 0
Primary (1 ) Alcohol Secondary (2 ) Alcohol Tertiary (3 ) Alcohol
OH OH
CH3-CH2-OH
H3C C CH3 H3C C CH3
P+I2 H CH3
P+I2 P+I2
I I
CH3-CH2-I H3C C CH3 H3C C CH3
H CH3
Iodoethane
2-Iodopropane 2-iodo-2-methylpropane
AgNO2
AgNO2 AgNO2
NO2 NO2
CH3-CH2-NO2 H3C C CH3 H3C C CH3
H CH3
Nitroethane 2-nitropropane
2-methyl-2-nitropropane
HNO2
HNO2 HNO2
(NaNO2+ HCl)
(NaNO2+ HCl) (NaNO2+ HCl)
NO2
CH3-C-NO2
H3C C CH3 No Reaction
N OH
N O
Nitrolic acid
Psecudonitrole
KOH KOH
KOH

Red colour Blue colour No colour

 Lucas Test
In This test the unknown alcohol is treated with the Lucas reagent (HCl + ZnCl2) .
This is the reaction of alcohol with HCl in the presence of dilute HCl.
The time taken for the reaction to occur is important to know the class of
alcohols. The occurrence of reaction can be observed by the appearance of
white turbidity or cloudness.
(i) For 10 alcohol, reaction occurs only after heating.
(ii) For 20 alcohol, reaction occurs within five minutes.
(iii) For 30 alcohol, reaction occurs immediately.
Table: 0
0 0 Tertiary (3 ) Alcohol
Primary (1 ) Alcohol Secondary (2 ) Alcohol

OH OH
R-CH2-OH + HCl
R C R + HCl R C R + HCl
ZnCl2 H R
ZnCl2 ZnCl2
Cl Cl
R-CH2-Cl R C R R C R
Chloroalkane H R
Chloroalkane Chloroalkane
(Reaction occurs only
after heating) (Reaction occurs (Reaction occurs
within five minutes) immediately)
Test for ethyl alcohol:
(i) Esterification Test (Already Studied)
(ii) Iodoform test
(Iodoform Test)
When ethanol is treated with iodine solution in the presence of NaOH or
KOH gives iodoform on gentle heating on water bath.
NaOH
CH3-CH2-OH + I2 CHI3 + HCOO-Na+
Ethanol Iodoform Sodiumformate (Salt)
Detail Rxn:
[O] 3I2 NaOH
CH3-CH2-OH CH3 CHO CI3 CHO CHI3 + HCOO-Na+
Ethanol Ethanal Tri-iodoethanal
Iodoform Sodiumformate
(Acetaldehyde) (Tri-iodoacetaldehyde)
(Salt)
Procedure: Ethanol solution is taken in a test tube and iodine solution is added till
it becomes brown colouration. NaOH solution is added drop wise till the
brown color is just disappeared. Now the above mixture is warmed gently on
water bath. Pale yellow crystals of iodoform are obtained which indicates the
presence of ethanol.
Alcohol Industry( Different types of Ethanol in Industry)
Ethyl alcohol is one of the important industrial raw material and
this ethyl alcohol is marketed or sold in the market in different
names and grades.
(i) Rectified spirit: Ethyl alcohol obtained by the distillation of
fermented liquor. Rectified spirit is 95% ethyl alcohol. Or 95%
pure ethyl alcohol is called rectified spirit. This percentage of
ethanol is made for industrial purposes.
(ii) Absolute alcohol: Ethyl alcohol of 100% purity is called absolute
alcohol. It can also be prepared by further distillation of rectified
spirit.
(iii) Methylated spirit or denaturated alcohol : Ethyl alcohol is made
available for industrial purposes only after making it unfit for
drinking purposes by mixing large quantities of ethyl alcohol with
little poisonous substances like methyl alcohol, pyridine, acetone
etc, The mixing of other chemicals in very small amount do not
effect the industrial purposes.
Alcoholic beverages :
The various liquors used for drinking purposes are made from
ethyl alcohol. These liquors are called alcoholic beverages.
Alcoholic beverages are of two types.
(i) Undistilled beverages
(ii) Distilled beverages
Undistilled alcoholic beverages:
The undistilled alcoholic beverages are prepared by the
fermentation of Juices of the fruits like apple juices, grapes juices,
banana juices etc. This undistilled beverage contains low
percentage of ethyl alcohol. Beers and various kinds of wines
belong to this categories.
Distilled alcoholic beverages:
The distilled beverages are made by the distillation of fermented
liquors and contains higher percentage of ethyl alcohol. Such
beverages includes Whiskies, Brandies, Rums, Vodkas Gins etc.
Uses of Alcohols
 Lower members of alcohols are used as solvent for paints and other
organic compounds.
 Alcohols are also used as preservative for biological specimens and
other decaying materials.
 Ethyl alcohol is used as important industrial raw material.
 Lower members of alcohols are also antiseptics, disinfectants and
also germicides.
 Ethyl alcohol is Used as an ingredient in alcoholic beverages E.g.
whiskies. Rum, brandies, wine, beer etc.
 Used to produce methylated spirit (meth) Methylated spirit is
ethanol mixed with small amounts of methanol and other
poisonous chemicals for making it unfit for consumption.
 Used as a fuel. Ethanol burns cleanly to form carbon dioxide and
water.

………………End (Monohydric alcohols)………………

Dihydric Alcohols:
Alcohols containing two –OH functional groups are called dihydric
alcohols. They are called diols in IUPAC and glycols in common system.
OH OH OH H OH OH H H OH

H C C H H C C C H H C C C C H
H H H H
H H H H H
Dihydric alcohol Dihydric alcohol Dihydric alcohol
(Ethan-1,2-diol or ethylene glycol) (Propan-1,3-diol) (Butan-1,4-diol)
Ethan-1,2-diol:
Ethan-1,2-diol or ethylene glycol is prepared by following methods
(i) By hydroxylation of ethene:
When ethene is treated with the cold dilute solution of alkaline KMnO4 ,
Ethane-1,2-diol is prepared.
CH2 - CH2 OH
+ [O] KMnO4/OH
CH2 CH2 OH
Ethene Ethane-1,2-diol
By hydrolysis of ethylene chlorohydrin:
CH2 CH2 OH H-OH CH2 OH
CH2
+ HOCl + HCl
CH2 Cl NaHCO3 CH2 OH
Ethene Ethylene chlorohydrin Ethan-1,2-diol
By hydrolysis of epoxy ethane:
CH2 CH2
H-OH CH2 OH
1
CH2
+ O2 O
2 CH2
Dil HCl OH
Ethene CH2
Ethan-1,2-diol
Epoxy ethane
Uses of Ethan-1,2-diol:
(i) Ethan-1,2-diol or ethylene glycol is used as antifreeze for automobile
radiator and as coolant in aircraft engine.
(ii) It is used as starting material in the manufacture of nitroglycol which is
an explosive.
(iii) It is used as an anesthetic and also used as solvent in printing inks and
stamp pad inks.
Trihydric alcohols
Alcohols containing three hydroxyl groups in their molecules are
called trihydric alcohols. In IUPAC the are called triols
Propan-1,2,3-triol (Glycerol)
Glyceron or propan-1,2,3-triol is an important examples of
trihydric alcohols.
HO OH OH
H2C CH CH2
Propan-1,2,3-triol (Glycerol)

Industrial preparation of glycerol

From oils and fat
Oils and fats are the triesters of glycerol with long chain fatty
acids mainly palmitic acid(C15H31COOH), stearic
acid(C17H35COOH), oleic acid (C17H33COOH), linoleic
acid(C17H31COOH) etc. These triesters are also called
triglycerides.
During the manufacture of soaps, oils and fats are heated with
strong solution of NaOH or KOH. This is alkaline hydrolysis of
triglycerides called saponification. After the completion of the
saponification process, the triglycerides are converted into
glycerol and soap which is the sodium or potassium salts of long
chain fatty acids.
CH2OOC-R NaOH CH2 OH

-- +
CHOOC-R NaOH CH OH + 3RCOO Na
Boil Sodium salt of long chain Fatty acid
CH2OOC-R NaOH CH2 OH (Soap)
Glycerol
Oil or Fat (Triglyceride)
The soap is prepared by the adding NaCl solution. The syrupy
liquid left after the separation of soap is called spent lye. Glycerol
is manufactured from spent lye.
From Propene or (Propylene)
Glycerol is also prepared synthetically from propene as follows.
CH3 CH2 Cl CH2 OH CH2 OH CH2 OH
Cl2 Na2CO3 HOCl
CH CH CH CH Cl CH OH + NaCl
0 0 -NaCl
500 C 150 C (-NaCl) NaOH(aq.)
CH2 CH2 CH2 CH2 OH CH2 OH
Propene Allyl chloride Allyl alcohol 2-chloropropane--1,3-diol Glycerol
(3-chloroethene) Propen-1-ol

Uses of Propan-1,2,3-triol (Glycerol)

(i) Glycerol is hygroscopic in nature which absorbs moisture so it is
used as shaving cream, moistening cream, hand lotion etc.
(ii) It is used in bakery product as sweetening agent.
(iii) It is used in manufacturing explosive like glyceryl trinitrate.
(iv) It is used as lubricant for small machinery parts like watch parts etc.
(v) It is used as solvent for non-drying printing inks, stamp pad inks etc.
 H O
H C H C C

Phenyl Benzyl Benzal Benzo

Why cresol is less acidic than phenol?

OH OH

CH3
Phenol Cresol
 Phenol
Phenols are hydroxy derivatives of aromatic hydrocarbons. In
phenol hydroxy group (-OH) is directly attached to an aromatic
ring. The general formula of phenol is;
Ar-OH
Where Ar- is aryl group. Phenols are classified as mono-, di- , and
trihydric phenols according to the numbers of –OH groups
attached to aromatic ring.
OH OH OH OH

OH OH

OH
Hydroxy benzene Napthol 1,2-dihydroxy benzene 1,2,3-tridihydroxy benzene
(Phenol) Monohydric (Catechol) (Pyrogallol)
Monohydric Dihydric Trihydric phenol
But The aromatic compound in which –OH is not
directly attached to aromatic rings are not phenol, they
are aromatic alcohols.

CH2OH CH2CH2OH

Phenylmethanol Phenylethanol
(Benzyl alcohol)
Preparation of Phenol
Phenol can be prepared by the following methods.
(i) From chlorobenzene (Dow’s process)
Phenol is prepared in large scale by heating chlorobenzene with
dil. NaOH solution at 3500C under a pressure of 300 atm. In
the presence of copper catalyst. Sodium phenoxide is formed
which on acidification gives phenol.
Cl - +
O Na
3500C, 300 atm
+ NaOH + NaCl
Cu
Sodium phenoxide
Sodium phenoxide
O-Na+ OH

+ HCl + NaCl

Sodium phenoxide
Phenol
From benzene sulphonic acid
Sodium salt of sulphonic acid on fusion with sodium hydroxide at
3000C gives sodium phenoxide which on acidification give
Phenol.
O-Na+
SO3Na
Fuse
+ 2NaOH + Na2SO3 + H2O

Sodium benzene sulphonate Sodium phenoxide

(Benzene sulphonic acid)
O-Na+ OH

+ HCl + NaCl

Sodium phenoxide Phenol

From Diazonium salt: (Laboratory preparation)
Phenol is prepared in the laboratory by warming an aqueous
solution of benzene diazonium chloride which is obtained by
diazotization of aniline.
+
NH2 N NCl- OH
NaNO2 + HCl H2O
+ + + N2 + HCl
0
0-5 C
Aniline Benzene diazonium chloride Phenol

Properties of Phenol
Physical properties of Phenol
1. Phenol is colorless crystalline solid and deliquescent . However,
it turns into pink/reddish colour due to slow oxidation with air.
2. Its boiling point is 1820C and melting point is 410C
3. It is slightly soluble in water forming reddish pink colour
solution but it is easily soluble in organic solvents like alcohols
and ether. The limited solubility is due to presence of polar –OH
group (Hydrophilic) which forms hydrogen bond with water and
the benzene ring remains hydrophobic (water repealing nature)
Intermolecular
Hydrogen bonding with water

OH H O H OH

3. The boiling point of phenol is high it is because of the

intermolecular hydrogen bondings between phenol molecules.
Intermolecular
Hydrogen bonding
O H O H O H
Chemical Properties:
Acidic Nature of Phenol:
Phenol is acidic in nature. It gives H2 gas with active metals and
neutralizes alkalies to give salt and water, and turns also blue
litmus paper to red. Although the phenol is stronger acid than
alcohol and water but weaker than carboxylic acids. They are
unable to decompose carbonates or bicarbonates.
Reaction with metals:
Phenol reacts with the alkali metals like sodium and potassium to
form salt and hydrogen gas is liberated.
O H O - Na +

2 + 2Na 2 + H2

Phenol Sodium phenoxide

(2) Reaction with alkalies
Phenol reacts with alkalies like sodium or potassium hydroxide
to form salt and water.
O H O - Na +

+ NaOH + H2O

Phenol Sodium phenoxide

(3) Phenol does not react with sodium carbonates and bicarbonates.
O H

+ Na2CO3 No Reaction

Phenol
Phenol exist as resonance hybrid of following contributing
structures where as alcohols do not do this. +
.. .. .. .. .. ..
:O H + O H +O H +O H :O H :O H

Phenol
(a) (b) (c) (II)
(I) (Resonance hybrid)

Contributing structures or delocalizing structures

Resonance in Phenol
During the resonance in phenol, the oxygen atom acquires a partial
negative positive charge. It weakens the O-H bond and release of
proton becomes easier.
.. .. .. .. .. ..
:O :O :O
..
O
..

..

O O

Phenoxide ion
(a) (b) (c) (II)
(I) (Resonance Hybrid)

Contributing structures or delocalizing structures

Resonance in Phenoxide ion
From the above resonance, phenoxide ion is more stabilized by
resonance than phenol, there is no charge separation in
contributing structures. During the ionization of phenol,
equilibrium is very much in favours of phenoxide ion(forward
reaction favoured), and concentration of H+ increases in aq.
Solution which increases the acidic strength of phenol and
becomes more acidic
..
than alcohols.
..
: OH :O

(aq.)
+ H+(aq.)

Phenol Phenoxide ion

On the other hand, in case of alcohols neither alcohols nor alkoxide

ions are stabilized by resonance and they behaves as weaker acids
than phenol.
.. (aq.)
R .OH
. R O- + H+ (aq.) No resonance
(Alcohol) (Alkoxide ion)
Due to the positive inductive effect of alkyl group in alcohol,
electron density increases around oxygen and hydrogen is more
strongly attached to oxygen and can’t be released in aqueous
solution. But in phenol oxygen becomes fractional positive charge
due to resonance and electron density around oxygen decreases and
bond between oxygen and hydrogen becomes weaken and H+ can
be broken easily and concentration of protons H+ in aqueous
solution increases and acidic strength increases. So due to above
evidences, phenols are more acidic than alcohols.
+ ..
R O
.. H H+ Can't be broken easily

+ ..
..

O H

H+Can be broken easily

Effect of substituent on the acidic strength of phenol.
The acidic strength of the phenol is effected considerably by the
presence of the substituent in the ring. In general, The electron
withdrawing group ( i.e. –NO2,-CHO, -X etc) increases the acidic
strength by stabilizing the phenoxide ion by the dispersal of –ve
charge. Easy to release

.. H2O .. +
.O. H .O. + H3O

G G
G = electron withdrawing group Stabilized

The electron releasing group ( i.e. –R,-NH2, -OH etc) decreases

the acidic strength by destabilizing the phenoxide ion by
intensifying the –ve charge.
Difficult to release

.. H2O .. +
.O. H .O. + H3O

G G = electron releasing group G destabilized

2. Reaction with phosphorous halides
 With phosphorous pentachloride:
When phenol is treated with PCl5, it gives little amount of
chlorobenzene because the major product triphenyl phosphate is
produced by the reaction between byproduct POCl3 and phenol.
OH Cl

+ PCl5 + POCl3 + HCl

Phenol Chlorobenzene
OH

+ POCl3 (C6H5O)3P=O
Triphenyl Phosphate

Phenol
 Reaction with PCl3
OH Cl

+ PCl3 3 + H3PO3
3
Phosphorous acid

Phenol Chlorobenzene

3. Reaction with ammonia:

Phenol reacts with ammonia at 3000C in the presence of anhydrous
ZnCl2 to give aniline.
OH NH2

3000C
+ NH3 + H2O
An. ZnCl2

Phenol Aniline
4. Reaction with Zinc dust :
When phenol is refluxed or distilled with zinc dust, it is reduced
to benzene. OH

Distilled/reflux
+ Zn + ZnO

Phenol Benzene

5. Reaction with benzene diazonium chloride:( Lab.Test)

When phenol is condensed with benzene diazonium chloride in
slightly alkaline medium, it gives a dye or colored compound
called azodye, This reaction is called coupling reaction

Alkaline medium
+ -
N N Cl + H OH N N OH +
0 0
0 -10 C
H2O
Benzene diazonium chloride Phenol p-hydroxy azobenzene
(Yellow Dye)
6. Reaction with phthalic anhydride:
Phenol on condensation with phthalic anhydride in the presence of
conc. H2SO4 to give phenolphthalein which is an important
indicator used in acid base titration. Conc. H2SO4 is used as a
dehydrating agent.
Phthalic anhydride

O O
C C

O O

C Conc. H2SO4 C + H2O

H O
H

OH OH
OH OH Phenolphthalein
Phenols
7. Acylation reaction ( Reaction with acid chloride and anhydride)
Phenol undergoes acylation reaction on reacting with acid
chlorides in the presence of pyridine and with acid anhydride in
the presence of H2SO4 or CH3COONa to give ester esters in both
O
cases. OH O CH C 3
O Pyridine
+ Cl C CH3 + HCl
Acetyl chloride
Phenol Phenyl acetate(ester)
O
OH O C CH3
O
H3C C H2SO4 or
+ O + CH3COOH
H3C C CH3COONa

Phenol O Phenyl acetate(ester)

Acetic anhydride
8. Kolbe Reaction (Carboxylation reaction):
When sodium phenoxide is heated with CO2 at 1400C under 4-7
atm pressure, sodium salicylate is obtained which on acidification
gives salicylic acid. This reaction is known as Kolbe reaction. –
COOH group is introduced in this reaction, so this reaction is also
called carboxylation reaction.
OH O- Na+

+ NaOH + H2O

Phenol Sodium Phenoxide

O- Na+ OH OH
COO-Na+ COOH
0
140 C dil HCl
+ CO2
4-7 atm

Sodium Phenoxide Sodium Salicylate Salicylic acid

 This salicylic acid is raw material to prepare very important
medicine 2-acetoxy benzoic acid (Aspirin). This medicine is
well known analgesics as well as antipyretic. This is prepared
when salicylic acid reacts with acetic anhydride in the presence
of conc. H2SO4
O

O O C CH3
OH
CH3 C
Conc H2SO4 COOH
O
COOH
+ CH3COOH
+ CH3 C

O Acitic acid
2-acetoxybenzoic acid
Acetic anhydride (Aspirin)
Salicylic acid
9. Reimer-Tiemann’s reaction:
When phenol is refluxed with chloroform (CHCl3) and NaOH at
600C followed by hydrolysis, it gives o-hydroxybenzaldehyde and
p-hydroxybenzaldehyde. Both isomers can be separated from by
steam distillation. This reaction is known as reimer-Tiemann
reaction. ONa OH

CHO CHO
+
H /H2O
OH

NaOH o-hydroxybenzaldehyde
+ CHCl3
ONa OH
600C

Phenol H+/H2O

CHO CHO
p-hydroxybenzaldehyde
Electrophilic Substitution reaction:
Phenol due to the presence of electron releasing -OH group is
ortho and para directing or ring activator. During the electrophilic
substitution reaction, the incoming electrophile always comes to
ortho and para position rather than meta position. Some ring
substituting reactions are given as below.
(i) Halogenation(Bromination)
Phenol reacts with halogens to give poly halogen substituted
compounds. For example phenol react with bromine to give
2,4,6-tribromophenol (o,p-tribromophenol.)
OH OH

Br Br

+ 3Br2 (Aq.) + 3HBr

Br
Phenol 0,p-tribromophenol
(2,4.6-tribromophenol)
 If phenol react with bromine in the presence of less polar compounds
like CS2, CCl4 at low temp. give the mixture of 0-bromophenol and p-
bromophenol.
OH OH OH

Br
CS2
+ Br2 (Aq.) + + HBr
0
0-5 C

Br
Phenol
0-bromophenol p-bromophenol

(ii) Nitration Reaction:

Phenol reacts with conc. Nitric acid in the presence of conc. H2SO4 to
give 2,4,6-trinitrophenol(o,p-trinitrophenol).
OH OH

O2N NO2
H2SO4
+ 3HO-NO2 + 3H2O
Conc.
NO2
Phenol 0,p-trinitrophenol
 But with dilute nitric acid at low temperature about 20-300C, a
mixture of ortho and para nitrophenol is obtained.
OH
OH OH

NO2
+ HO-NO2 + + H2O
Dilute

NO2
Phenol
0-nitrophenol p-nitrophenol
(iii) Sulphonation Reaction:
OH
SO3H
OH 200C
o-hydroxybenzenesulphonic acid
(2- hydroxybenzenesulphonic acid)
+ HO-SO3H OH
Conc
1000C
p-hydroxybenzenesulphonic acid
Phenol
(4- hydroxybenzenesulphonic acid)
SO3H
(iv) Alkylation reaction ( Friedel Craft’s alkylation)
Phenol react with alkyl halide in the presence of anhydrous AlCl3
to give ortho-alkyl phenol and para-alkyl phenol.
OH OH OH
H R
AlCl3
+ R Cl +
Alkyl chloride
H o-alkyl phenol R p-alkyl phenol
Phenol

OH OH
OH
H
AlCl3 CH3
+ CH3 Cl + + HCl
Methy chloride
H CH3 p-methyl phenol(p-cresol)
Phenol o-methyl phenol(o-cresol)
 Reaction with ferric chloride( Lab. Test of Phenol)
Phenol reacts with ferric chloride solution to form water soluble
violet-coloured iron hexaphenoxide ion complex. This is the
laboratory test of phenol.
3- +
3 C6H5OH + FeCl3 Fe(OC6H5)6 3H+ + 3HCl

Phenol Ironhexaphenoxide ion

Violet colour
Uses of Phenol
(i) For the manufacture of phenol formaldehyde plastic or bakelite.
(ii) As a raw material to prepare salicylic acid and aspirin (medicine).
(iii) For making phenolphthalein and explosive like picric acid.
(iv) It is used for the preparation of antiseptic, disinfectants,
weedicides, insecticides, germicides & also for photographic
developer(ortho and para amino phenol.
.