ALCOHOL

Total number of Questions in Alcohol are :–

(i) In chapter Examples ........................ 12
(ii) Solved Examples ............................ 30

Total no. of questions ........................ 42

1. INTRODUCTION NOTE : Refer to chapter 'Alkenes' for mechanism
of above reaction.
(a) These are the organic compounds in which
2.2.2 Oxymercuration – demercuration–
–OH group is directly attached with carbon.
(b) These are hydroxy derivatives of alkanes and Alkenes react with mercuric acetate in the
mono alkyl derivatives of water. presence of water to give hydroxymercurial
(c) Their general formula is C nH2n+1OH or compounds, which on reduction yield alcohols.
CnH2n+2O. (Markovnikov addition)
(d) The hybridisation state of carbon is sp3. >C = C< + H2O + Hg (OAc)2 
(e) Geometry is tetra hedral.
Mercuric acetate
(f) In these compounds C-O bond length is 1.42 Å.
(g) These are of following types, depending upon I I Na B H4
I I
C  C    C  C 
the no. of OH groups. I I I I
(i) Monohydric alcohol:- OH Hg O Ac OH H
Contains one –OH group only, eg.C2H5OH Alcohol
(ii) Dihydric alcohol :- NOTE : Refer to chapter 'Alkenes' for mechanism
Contains two –OH groups. eg. glycol of above reaction.
(iii) Trihydric alcohol:- 2.2.3 Hydroboration – Oxidation :
Contains three –OH groups eg. glycerol
(iv) Polyhydric alcohol :- (Anti–Markownikov orientation)
Contains more than three - OH groups. eg,
sorbitol, manitol. 1
(h) Alcohol shows chain, position & functional >C = C< + (BH3)2  B
2
group isomerism. If chiral carbon atom is
present, they shows optical isomerism. Alkene Diborane Tri alkyl borane
H2O 2 I I
2. METHODS OF PREPARATION    C  C  + B(OH)
 3
OH I I
2.1 From Alkyl halides:- H OH
NOTE : Refer to chapter 'Alkenes' for mechanism
Alkyl halides reacts with aq. KOH/aq. AgOH or
of above reaction.
H2O and forms alcohol.
2.3 By Reduction of Carbonyl compounds :-
R–CH2 – X + K – OH (aq.)  R–CH2OH + KX
LiAlH / NaC H OH
R R  C  H + 2H  4 25
 R–CH2OH
| ||
R  CH  X + AgOH (aq.) O 1º alcohol
R LiAlH / NaC H OH
| R  C  R + 2H  4 25
 R  CH R
 R  CH  OH + AgX || |
O OH
R R
| | 2º alcohol
R  C  X + H – OH  R  C  OH + HX Note :
| |
R R (i) We cannot obtain 3º alcohol from this method
2.2 From Alkenes :- (ii) If we use NaH as reductant then the process
2.2.1 Hydration – Alkenes are catalytically hydrated is called as 'Darzen's process'.
by dilute mineral acid solution. 2.4 By Reduction of Acid & its derivatives :-
dil H2 SO 4
CH2 = CH2 + H2O    CH3CH2OH
R  C  OH + 4H LiAlH
 4
 RCH2OH
||
dil H2 SO 4 O
R – CH = CH2 + H2O   
R  CH  CH3
| R  C  X + 4H LiAlH
 4
 R CH2OH + HX
OH ||
O
 LiAlH4 Note : -
R– C – OR' + 4H    RCH2OH + R'OH
|| In this reaction if we take ethyl amine then main
O product will be ethanol while if we take methyl
amine, then main product will be dimethyl ether.
RCOOCOR + 8H LiAlH
 4
 2 RCH2OH + H2O

Important Note :- Acid amide does not form Methods of Preparation of Alcohol
alcohol on reduction. It forms primary amine.
2.5 From Grignard reagent : Ex.1 Which of the following reaction is called as
'Bouveault-Blanc reduction' -
2.5.1 With oxygen : –
(A) Reduction of acyl halide through
Grignard reagent forms alcohol of same no. of
Na/C2H5OH
carbon atoms as in Grignard reagent.
(B) Reduction of ester through Na/C2H5OH
2R – Mg – X + O2 2R – O – Mg–X (C) Reduction of anhydride through
Na/C2H5OH
2HOH
  2ROH + 2 Mg(X)OH (D) Reduction of carbonyl compounds through
2.5.2 With ethylene oxide : Na/C2H5OH
(Ans.D)
 Sol. Reduction of carbonyl compounds through
Na/C2H5OH is called as Bouveault–Blanc
reduction.

R–CH2–CH2–O–Mg–X Ex.2 Acid derivative which does not give alcohol

H2O on reduction:-
 R–CH2-CH2OH+ Mg(X)OH
Alcohol with two carbon more (A) R  C  X (B) R  C  NH2
than Grignard reagent || ||
O O
2.5.3 With carbonyl compounds :

 
R  Mg  X + (C) R  C  OR' (D)
||
O

H H
| | (Ans. B)
  R'C  R H2O
 R' C  R Sol. Acid amide forms primary amine on reduction.
| |
O  Mg  X OH
Ex. 3 In which of the following reaction alcohol is
Note : not formed-
(i) If R' = H , Product will be 1º alcohol.
H 
(ii) If R' = R, Product will be 2º alcohol. (A) R – CH = CH2 + H2O  
High pr .
(iii) If carbonyl compound is ketone, product will
be 3º alcohol. (B) R – COCl + 2H2 LiAlH
 4

(iv) It is the best method for preparation of
alcohol because we can prepare every type (C) (R – CO)2 O + 4 H2 LiAlH
 4

of alcohols.
H 
2.6 From Primary amines :- (D) R – CH2 – CH3 + H2O  
High pr .
HCl
R – NH2 + HNO2   R – OH + N2 + H2O. (Ans. D)
But it is not a good method for preparation of Sol. Alkanes are paraffins. They do not form
alcohol because a number of byproducts are alcohol on hydrolysis.
formed in this reaction like
alkyl chloride, alkyl nitrite, alkene and ether.
3. PHYSICAL PROPERTIES 4. CHEMICAL PROPERTIES
(a) Alcohols are colourless with specific smell Chemical reactions of alcohols are classified in
liquid. They are soluble is water due to H- the following three types :-
bonding. These are partially soluble in
4.1 Reaction of H atom of –OH group of Alcohols
organic solvents.
(b) They are liquid in nature up to 12-carbon. 4.2 Reaction of OH group of Alcohols
(c) Melting point and Boiling point 4.3 General reaction of Alcohols.
1 4.1 Reaction of H atom of –OH group of
 molecular mass 
No. of branches Alcohols:-
(d) Boiling point of alcohols are higher than
equivalent ethers. It is due to H-bonding. These are the reactions in which alcohol shows
acidic character.
(e) Alcohols are poisonous in nature also.
Poisonous character increase with increment 4.1.1 Reaction with Na :-
in molecular weight or branching. Ethanol is
2R–O –H + Na –––––– 2R – O – Na + H2 
exception, which is non-poisonous in nature.
It is most useful organic solvent. The acidic order of alcohols is
(f) Methanol causes blindness. MeOH > 1º > 2º > 3º
(g) Isopropyl alcohol is called as rubbing alcohol. 4.1.2 Esterification / Reaction with carboxylic
(h) Cholestrol is also an example of complex acid :-
alcohol which is called notorious alcohol
because it causes heart attack.
(i) Viscous nature of alcohol is directly
conc.H SO 4
proportional to H-bonding or number of -OH    2   R–C–O–R + H2O
groups. That is why we can say alcohol is ||
O
less viscous than glycerol & manitol is more
ester
viscous than glycerol.
Mechanism :-
(j) Ethanol is liquid while glucose is solid. It is
H2SO4 ––––– H+ + HSO 4
due to more H-bonding in glucose.
..

Physical properties of Alcohol RCO..

 H + H+ –––  
H O

2
||
O
Ex.4 Which one of the following alcohol has
highest boiling point - 
R  C  ROH
 R  O  C  R    R  C  OR
 H
(A) Methanol (B) Ethanol || | || ||
(C) Propanol (D) Isopropanol O H O O
(Ans.C) Note :- The above reaction is laboratory method of
Sol. Boiling point  molecular weight ester preparation.
4.1.3 Reaction with Acid derivatives :-
1

No. of branches Conc.H2 SO 4
R–O–H + X  C  R   
||
Ex.5 Dimethyl ether and ethanol have same O
molecular weight but boiling point of ethanol
R  O  C  R + HX
is greater than dimethyl ether, cause of this ||
is that dimethyl ether -
R  O  H  R  C  O  C  RO
(A) Having less no. of branches || ||
(B) Arrangement of hydrogen is different O O
(C) Due to hydrogen bonding in alcohol Conc.H SO
2 
 4
(D) None of these (Ans.3) R C  O R
||
Sol. Due to hydrogen bonding in alcohol boiling O
point of alcohol is high.
4.1.4 Reaction with Ketene :- 4.2.6 Reaction with HNO3 : –

  
R  O  H + CH2 = C R–OH + HNO 3  + H2O
||
O
(conc.) alkyl nitrate
   CH3  C  O  R
|| (soluble ester)
O
Mechanism :-
(enol form) (keto form)
4.1.5 Reaction with Isocyanic Acid :- HNO3  H+ + NO 3

  
R O H + H – N = C  
|| R – O – H + H+  R  O  H  
H2O
 R
O |
H

H – N = C  O  R  H – NH – C  O  R
|| R + NO 3 
|
OH O
amino ester (urethane) alkyl nitrate
4.1.6 Reaction with ethylene oxide :-
4.2.7 Reaction with H2SO4 :-
R – O- – H+ +  

(i)

ROH
 
H2 O
0 ºC
 
1,2-dialkoxy ethane  2H2O

4.1.7 Reaction with Diazomethane :- diethyl sulphate

R – O – H + CH2 N2  R – O – CH3
(ether) O
||
4.2 Reaction of – OH group of Alcohols :- (ii) C2H5OH + H  O  S  OH
||
O
4.2.1 Reaction with dry HX (Grove's Process) :–
O
R–OH + HX  R – X + H2O 20  35 º ||
  C H – O  S  OH
room temp 2 5
4.2.2 Reaction with PCl5 :– ||
O
R– OH + PCl 5  R – Cl + POCl3 + HCl
stable upto
4.2.3 Reaction with PCl3 : –
(80-100ºC)
3R – OH + PCl3  3R – Cl + H3PO 3
(iii) CH3 – CH2 – OH + H2SO 4
4.2.4 Reaction with SOCl2 (Darzen reaction): –
(excess)
R–OH +SOCl2 Pyridene
  R – Cl +SO2 + HCl
4.2.5 Reaction with ammonia : – ..
140 º C
 CH3 – CH2 – O
  ..
– CH2 – CH3
anhy. ZnCl2
R – OH+ NH3  
300  C
 RNH + H O
2 2
 Mechanism :- (v) For both (1º and 2º alcohol) we can use
common oxidising agent also, like chromic
H2SO 4  H+ + HSO4¯
acid in dilute H2SO 4. Colour of this solution
 : + H+  CH –CH 
CH3 – CH2 – O  
3 2  O –H is orange and it turns into green colour due
| |
H H to Cr+3.
(vi) Reacting species of solution is HCrO4¯.


CH3 – CH2 – OH
   CH3– C H2
acidic KMnO
   
4

(protonated ether)

[o ]
..


CH3  CH2  O CH2  CH3
..
160 º C
(iv) CH3 – CH2 –OH + H2SO4   CH2= CH2
(excess) acidic K Cr O
   
2 2 7

Mechanism :-
H2SO4  H+ + HSO4– [o ]



CH3 –CH2 – – H + H+  CH3 – CH2– –H

H CrO  dil. HNO

2  4  
3


  H
 CH – CH2  
H2O 3  CH2 = CH2
Note :-
In the above reaction excess of ethanol is present
so, intermediate carbocation satisfies itself by
(ketone of lesser carbon)
elimination.
4.3.3 Catalytic Oxidation / Dehydrogenation :-
4.3 General reaction of Alcohols :-
4.3.1 Reduction :-
RedP
R – O – H + 2 HI   R – H Cu
/ ZnO

150  C
300 º
4.3.2 Oxidation :
(i) Primary alcohol initially forms aldehyde on
oxidation and on further oxidation forms 1º alcohol aldehyde
respective acid.
(ii) Secondary alcohol initially forms respective
ketone on oxidation which on further oxidation Cu
/ ZnO

forms acid of less carbon. Oxidation of ketone 300 º
is slightly difficult than aldehyde due to
stability so, we use strong oxidising agent
for oxidation. secondary alcohol ketone
(iii) Tertiary alcohols are resistant to oxidation in
normal conditions but on taking strongest
oxidising agent like chromic acid in dilute
Cu
/ ZnO

nitric acid then they form less carbon ketone. 300 º
(iv) For oxidation of 1º alcohol, acidic KMnO4 is
used as oxidant while for 2º alcohol acidic
K2Cr2O7 (more strong than KMnO4) is used. tert. alcohol alkene
(Note : – This is dehydration process.)
4.3.4 Oxidation through Fenton's Reagent :– Sol. H2SO 4 is a strong acid and the corboxylic
Higher and branched alcohols are converted into acid behaves as base in presence of
diols through Fentons reagent. (FeSO4 + H2O2) H2SO 4. The mechanism of the reaction
is Fenton's reagent. also proves it.
 H
Fe+2 + H2O 2  Fe+3 + O H + O Ex.8 2-methyl 2-propanol with Fenton's reagent
gives -
CH3 CH3
| | • (A) 1,2-methyl propene -1
•
CH3–C–CH2–H + OH  CH3–C–CH2 + H2O
| | (B) 2-methyl propene -2
OH OH
(C) 2,5-dimethyl hexanediol-2,5
CH3 CH3
| • | (D) 2,2,3,3 - tetramethyl butane
•
CH3–C–CH2 + CH2–C–CH3 (Ans.C)
| |
OH OH Sol. Fenton's reagent proceeds the reaction by
Free radical mechanism to give 2,5-dimethyl
hexanediol.
           
5. INDUSTRIAL PRODUCTION OF ALCOHOL
2,5-dimethyl hexandiol-2,5
4.3.5 Self Condensation : - 5.1 Preparation of methanol : -
When alcohol is heated with sodium ethoxide Methanol is also called as carbinol or wood spirit.
then by self condensation they convert into higher
alcohol. 5.1.1 From Water Gas :-

RCH2–CH2–OH + H– –CH2–OH Al2O 3

[CO + H2] + H2   CH3OH (90 %)
ZnO / CrO 3
200  300º
 R–CH –CH – –CH2–OH
2 2
higher alcohol 5.1.2 From Methane : -
Note : – CH4 gives methanol on partial oxidation in Cu
The above reaction is called as 'Guerbet's tube.
Reaction'.
1
CH4 + O  Cu tube
 CH3OH (90%)
2 2 200º C

Chemical Reactions of Alcohol 5.1.3 By destructive distillation of wood : -

When wood is heated in absence of air in iron
Ex.6 Reactivity order of alcohols towards Na will
be - retorts at 400ºC then following products are
(A) 3º > 2º > 1º > MeOH formed.
(B) MeOH > 1º > 2º > 3º (i) Wood Gases : - These are mixture of natural
(C) 2º > 1º > 3º > MeOH gases like CH4, N2, H2 , CO2, SO 2 etc.
(D) 1º = 2º = 3º = MeOH (Ans. B) (ii) Pyroligneous acid : - It is also called as
Sol. In the above reaction O–H bond breaks and
pyro acid. It is brownish sticky liquid.
acidic character appears. The acidic strength
of the alcohol isMeOH > 1º > 2º > 3º (iii) Wood tar : - Blackish viscous liquid used in
formation of road and also preservation of
Ex.7 In the esterification of alcohol by
carboxylic acid, proton is given by – wood. It is used in formation of deodrant.
(A) Alcohol (B) Conc. H2SO 4 (iv) Wood coke : - It is used as a fuel.
(C) Acid carboxylic (D) None of these
(Ans.B)
5.1.4 By Pyroligneous Acid : -
It contains acetic acid ( 8-10%) acetone
(.5 - 2%), methanol (2 - 5%) and remaining water.
(i) Removal of Acetic acid : - Acetic acid is
separated by adding base Ca(OH)2. It forms
calcium acetate with acetic acid.
(ii) Removal of Acetone : - We can remove
acetone by fractional distillation because
boiling point of acetone is 56ºC and boiling
point of methanol is 65º C.
(iii) Removal of water : - W e can remove
impurities of water by using anhydrous
calcium chloride or anhydrous magnesium
chloride or anhydrous CuSO4. These forms
additional crystal salt with methanol.
anhy. CaCl2 + CH3OH  CaCl2 • 4CH3OH
(ii) Yeast is unicellular living parasite plant.
(iii) Enzymes : - Nitrogenous high molecular
weight complex compound which converts
complex organic compound in simple organic
compound without taking part in reactions
are called enzymes. They are also called as
biocatalyst. They are made of protein.
(iv) They are sensitiv e to temperature,
concentration and pH.
(v) Temperature at which enzymes are maximum
efficient is called optimum temperature. For
yeast enzyme it is 20 – 35º C.
(vi) Temperature at which enzymes are
destroyed, is called thermal death point

anhy. MgCl2 + CH3OH  MgCl2 • 6CH3OH
anhy. CuSO4 + CH3OH  CuSO4 • 2CH3OH
we get pure methanol on steam distillation
or
(TDP) > 60º. At low temperature they
becomes inactive.
(vii) They always work in dilute solution. They
cannot work in conc. solution.

we can use oxalic acid to separate water (viii) Their working pH range is 6.5 - 7.5 ( slightly
impurities. acidic slightly basic).

O=C–O–H H–O–CH3 (ix) Boric acid and mercuric salt are inhibitors.
| +  (x) Food of yeast cell is ammonium phosphate
O=C–O–H H–O–CH3
or ammonium sulphate.
oxalic acid methyl
5.2.3 Preparation of ethanol from sugar : -
methanol oxalate(solid)
(i) Molasses : - Waste product in sugar industry
we get pure methanol on alkaline hydrolysis
is called molasses. It is a mixture of sugar
O=C–O–CH3 H–O–Na
(30%) and invert sugar (32-40%).
| +
O=C–O–CH3 H–O–Na (ii) Invert sugar : - Combine form of glucose
and fructose is called as invert sugar.
 2CH3OH +
C12H22O 11 + H2O
5.2 Preparation of Ethanol : -
yeast cell
5.2.1 From Ethene : -  
 C6H12O 6 + C6H12O 6
invertase enzyme
By hydration with dil. H2SO 4
glucose fructose
CH2 =CH2 + H - OH  dil

. H2SO 4
 CH3 –CH2 – OH
5.2.2 General Definitions : -
C6H12O6 C2H5OH + CO2 + H2O
(i) Fermentation : - In presence of microbes like
yeast break down of complex organic Note : Glucose and fructose are functional
compounds into simple compounds is called
isomers.
fermentation. It is an exothermic process.
The term 'Fermentation' was proposed by
Lebeig.
5.2.4 Preparation of ethanol from starch :-
Industrial Production of Alcohol
(i) Starch solution is technically called 'Mesh'
(ii) Crushed germinated barley solution is called
Ex.9 When methane is passed in copper tube at
'Malt'.
200ºC with air, it gives -
2(C6H10O5)n + nH2O (A) Methanol (B) Ethanol
starch (C) Acetylene (D) Ethene
diastase
  nC12H22O111
(Ans.A)
maltose (wort) Sol. This is the industrial method of preparation of
methanol in which 90% yield is given
C12H22O 11 + H2O maltose
 2C6H12O 6
Ex.10 Acetic acid is removed from pyroligneous acid
maltose glucose
by the passing it in -
(monosaccharide)
(A) Al (OH)3 solution
2C6H12O6  zymase
 (B) Ba (OH)2 solution
(C) Ca (OH)2 solution
C2H5OH + CO2 + H2O + energy
(D) Ethanol (Ans.C)
(iii) From both of the methods conc. of ethanol Sol. Ca(OH)2 react with acetic acid to give
achieved is 10-12% which is called 'Wash'. calcium acetate which on treatment with dil
(iv) Distillation of wash is done in special acid gives acetic acid.
apparatus 'Coffee's still', which is based on (CH3COO)2 Ca + H2SO 4
counter current method. From this distillation  CaSO4 + 2CH3COOH
yield of alcohol is 90%, which is called Raw
Ex.11 Crushed germinated barley solution is called-
spirit.
(A) Mesh (B) Malt
Raw spirit Fractional

distillation
 (C) Wort (D) Wash
95.5% C2H5OH + 4.5% H2O (Ans.B)
(rectified spirit) Sol. Malt is the germinated barley solution rich in
diastase enzyme and used to convert starch
(v) Further purification is done in the following
(Mesh) into maltose (wort). 10-12% ethanol
ways : - solution is known as 'wash'
95.5% C2H5OH + 4.5% H2O
6. DIFFERENCE BETWEEN PRIMARY,
C6H6 + H2O + C2H5OH + Remaining C6H6 SECONDARY & TERTIARY ALCOHOLS
(64ºC) (78.5 ºC) + CH3CHO
(99.7%) (68ºC) 6.1 By Oxidation Reaction :-
C2H5OH + Ca metal Primary alcohol gives aldehyde on oxidation,
(99.7%) secondary alcohol gives ketone and tertiary
2  3 days alcohols are resistant to oxidation.
  C2H5OH + Ca(OH)2
(100%) 6.2 By Catalytical Oxidation / Dehydrogenation :
C2H5OH + anhy. CuSO4 Primary alcohol gives aldehyde on oxidation,
(99.7%) white secondary alcohol gives ketone and tertiary gives

 C2H5OH + CuSO4 • 5H2O alkene ( dehydration takes place in this condition
to tertiary alcohols.)
(100%)
6.3 Lucas Test :- 6.5 Difference between Methanol and Ethanol :-
A mixture of (anhydrous ZnCl2 + Conc. H2SO 4) Methanol Ethanol
is called as Lucas Reagent.
1. When CH3OH is heated 1. Ethanol does not
(i) 3º alcohol gives white ppt. with lucas reagent
on Cu coil it gives give formalin like
in 2-3 seconds only.
formalin like smell. smell.
(ii) 2º alcohol takes 9 - 10 minutes.
2. When CH3OH is heated 2. No such odour is
(iii) 1º alcohol does not gives white ppt. at room with salicylic acid in given by ethanol
temperature.
H2SO 4 (conc.) then
6.4 Victor Meyer Test : - methyl salicylate is
This test is also known as RBW ( Red, Blue, formed which has odour
White) test. like winter green oil
Re d P / I2 AgNO 3. It does not give 3. It gives haloform
(a) R – CH2 –OH
   R–CH2–I 
2

 AgI haloform or Iodoform test.
R - CH2 - NO2 + HNO 2
nitrate
Difference Between Alcohols

 Ex.12 Which one test is also known as RBW test-

(A) Lucas test
nitrolic acid
(B) Victor Meyer test
NaOH (C) Carbilamine test
 red solution
 
(D) Mullican-Barker test (Ans.B)
(b) R2 – CH –OH Re

d P / I2
 R2 – CH–I
Sol. In victor - Meyer test, 1º alcohol give Red
ppt, 2º alcohol Blue ppt and 3º alcohol no
AgNO
ppt, therefore according to colour of ppt this
2
  
is also known as RBW test.

nitrosoderivative NaOH (blue ppt.)

Pseudonitrile

(c) R3 – C –OHRe

d P / I2
 R3 – C– I  AgNO
 2


R3–C–NO2 HNO
 2
 no. reaction.
 ALCOHOL
GMP GR
3 5HX or PX or PX
(1)    RX
H2 O or KI +H 3PO 4 or SOCl2 or SO 2 Cl2
(1) Alkene  
Re d P / HI
aq. NaOH or aq. KOH
  (2)    RH
(2) RX
or aq. K 2 CO 3 or moist Ag2 O NH3
(3)    1º , 2º , 3º amines
dil. H2SO 4
(3) R - O - R  
 2H S
(4) 
 R - SH Thiol
dil. H2SO 4 ThO 2
(4) RCOOR  

RCOOH Na
(5)   RONa
HNO 2
(5) 1º amine   CH MgX
(6) 3
  CH4
Exception - Methyl amine gives
R' OR
CH3-O-CH3 or ether ald.R'CHO
(7) 
 C Acetal
NaH dry HCl
(6) Aldehyde or ketone  
Darzon reduction H OR
(1º alc.) (2º alc.) R-OH
Na / EtOH R' OR
(7) Acid or  

Bouveault Blanc reduction Ketone R'COR '
(8)     
 C Ketal
Acid derivative dry HCl

R MgX R' OR
(8) HCHO or Ald.or ketone  
R'COZ
H2 O (9)  R'COOR ester (Z = OH,Cl, OCOCH3)
 
(1º alc) (2ºalc) (3º alc.)
O
(10) H
2 SO 4
 ROSO2OH (Alkyl hydrogen sulphate)
2
(9) RMgX 
 
H2O (11) HNO
 3
 RONO2 (Alkyl nitrate)
CH2  CH2 (12) PhSO
 2 Cl
 RSO2Ph (Alkyl benzene sulphonate)
O
(10) CH3MgBr  

 (13)  CH  CH
 H3C - CH (OR)2 Acetal
H3 O

Fermentation (14)  CH
 2N2
 R - O - CH3 Ether
(11) Sugar  

O
CH 2  CH 2
(15)       RO - CH2 - CH2 - OH
Alkoxyalkanol
(16)  CH
2  CO
 ROCOCH3 Ester
(17) Dehydration
 Alkene
Catalytic dehydrogenation
(18)    Aldehyde or ketone
0 0 0
1 or 2 alcohol , Cu or ZnO , 300 C
Formation of EtOH by fermention - Exception - 3º alc  Alkene
Crystallization
(1) Cane sugar
 Molasses (19) 1ºalc.  
[ O]
Aldehyde[
O]
Acid (same no. of C-atom)
Sucrose
[ O]
Invertase
  Invert sugar  zymase (20) 2ºalc.   Ketone [
O]


hydrolysis Fermentation [ O]
(21) 3ºalc.  

EtOH
O HCrO 4
Diastase
(2) Grain  Starch   Maltose (22) 1º or 2ºalc. 
 Aldehyde or ketone + Cr+3 (green)
( orange)
HOH

Maltase Zymase O, HCrO 

  Glucose   (23) 3º alc  
4
 No reaction (No. green colour)
hydrolysis Fermentation ( orange)

EtOH
 WASH - ABSOLUTE ALCOHOL

Wash [10-15% EtOH]

Distillation

Raw spirit [90% EtOH]

Fractional distillation

20-21ºC 78ºC

Mainly CH3 CHO Rectified spirit [95.5% EtOH] Fusel oil

Excess benzene Azeotropic distillation [Glycerol + CH3COCH3

65ºC + Higher alcohol]

C6H6 + C2H5OH + H2O

(74.1%) (18.5%) (7.4%) (Ternary mixture)

680C

C6H6 + EtOH
(80%) (20%) (Binary mixture)

78.30C

Absolute alcohol
[100% EtOH]
 SOLVED EXAMPLES
Ex.1 Which is not an alcohol – Ex.5 Which of the following compound does not
(A) CH2 = CH-CH2OH (B) CH2OH. CH2OH give an alcohol as the main product by the
(C) C6H5 CH2OH (D) C6H5OH reaction with HNO2-
Ans. (D) (A) Ethyl amine (B) n-Propylamine
Sol. In the given compounds C6H5OH is not an (C) Methyl amine (D)Isopropyl amine
alcohol. It is a phenol in which a –OH group
Ans. (C)
is attached to a benzene ring. Alcohols are
regarded as monoalkyl derivatives of water or Sol. Primary amines react with (NaNO2 + dil HCl)
hydroxy derivative of hydrocarbons. Rest of to give a mixture of products consisting of an
the alcohol shown above are primary alcohols. alcohol with same number of carbon atoms
as amine, an alkyl nitrite, an alkyl halide, an
Ex.2 Which of the following statements is false: alkene etc. However methyl amine does not
(A) A primary alcohol has CH2OH group give an alcohol as the main product by the
(B) A secondary alcohol has two carbon reaction with HNO2.
atoms
(C) A tertiary alcohol has a minimum of four Ex.6 W hich of the following is a method of
carbon atoms preparing a primary alcohol-
(D) A primary alcohol with a branched chain (A) Reduction of ketone
has a minimum of four carbon atoms. (B) Hydrolysis of the adduct obtained from a
Ans.(B) Grignard reagent and ethanal
Ex.3 Ethyl acetate on reaction with the following (C) Oxidative alkaline hydrolysis of adduct
reagents gives ethanol - obtained from an alkene and borane
(A) P + HI (B) Na/C2H5OH (D) Hydrolysis of adduct obtained from a G.R.
(C) LiAlH4 (D) All above and a ketone
Ans.(D) Ans. (C)
Sol. Ethyl alcohol is formed by the treatment of Sol. A primary alcohol can be obtained by
all the above reagents like P + HI / Na & oxidative alkaline hydrolysis of adduct
EtOH / LiAlH4 on ethyl acetate. The reduction obtained from an alkene and borane.
takes place as follows : H O2
(CH3CH2CH2)3B 2   CH3CH2CH2-OH
CH3COOC2H5 
2H
 CH3CHO + C2H5OH

OH
trialkyl borane propanol
ethyl ethanoate   +2H
CH3CH2OH Ex.7 Which of the following reductants is used in
ethanol Bouveault Blanc reduction-
(A) Zn + HCl (B) LiAlH4
Ex.4 C2H5 NH2 Tilden NH
 B  3  C  D
HCl
(C) Na + C2H5 OH (D) Ni + H2
reagent HNO 2
Ans. (C)
the product D is an-
Sol. The reductants used in Bouveault Blanc
(A) Alcohol (B) Ether
reduction are Na + C2H5OH. The reduction
(C) Alkyne (D) All above
takes place as follows
Ans. (A)
2H
Sol. In the above reaction the product D is CH3CO-OC2H5   CH CHO + C H OH
Na / C H OH
2 53 2 5
C2H5OH (Ethanol) The reaction takes place
as follows :
ethyl acetate  +2H
CH3CH2OH
Tilden reagent (NOCl)
C 2 H 5 NH 2   C 2 H 5 Cl ethanol
N2 , H2 O
The reduction of an ester with Na and
HNO / HCl
NH3  2   C H OH C 2H 5OH is known as Bouveault Blanc
   C2H5NH2 N2 HCl 2 5
reduction.
Ex.8 The correct order of solubility of 1º, 2º and 3º Sol. Ethanol on reaction with acetic anhydride
alcohol in water is- gives acetic ester and ethanoic acid both. It
(A) 3º > 2º > 1º (B) 1º > 2º > 3º is called esterification reaction. The reaction
takes place as follows :
(C) 3º > 1º > 2º (D) None of these
 HOC 2H5
CH3CO. O. COCH3 
Ans.(A)   CH3COOH
Sol. There is a great braching in 3º alcohol and it acetic anhydride aceticacid
causes a reduction in intermolecular forces + CH3COOC2H5
(H-bonding). Hence the solubility in water CH3COOH + C2H5OH  CH3COOC2H5 + H2O
increases in the order 3º > 2º > 1º as acetic acid ethanol ethyl acetate
H-bond with water is formed more easily.
Ex.12 HBr reacts fastest with-
Ex.9 Methanol can be distinguished from ethanol (A) 2-Methyl propan-2-ol
by- (B) Propan-1-ol
(A) Heating with I2 and alkali (C) Propan-2-ol
(B) Treating with schiff's reagent (D) 2-Methyl propan-1-ol
(C) Treating with CrO3 solution in dil. H2SO 4 Ans. (A)
(D) Treating with Lucas reagent Sol. HBr reacts fastest with 2-methyl propan-2-ol,
because it is a tertiary alcohol and the
Ans.(A)
reactivity of the alcohols is in the order
Sol. Methanol can be distinguished from ethanol t > s > p
by heating with I 2 and NaOH. Ethanol
The reaction takes place by SNI mechanism.
undergoes the reaction and forms a yellow
ppt. of CHI3.
 I2 I2
CH3CH2OH  
 CH CHO 
NaOH 3  
ethanol
NaOH 2-methyl propan-2-ol
CI3.CHO HCOONa
  CHI (iodoform)
3
Methanol does not undergo above reaction  Br 

H2O
Ex.10 In the reaction involving C - OH bond, the
order of reactivity is- 2-bromo-2-methyl propane
(A) 1º > 2º > 3º (B) 3º > 2º > 1º Ex.13 The name of the compound B in the following
(C) 2º > 3º > 1º (D) None of these sequence is-
Ans. (A) alc
PCl5
Sol. In reaction involing C-O bond, the reactivity CH3CHOHCH3   A KOH
 B
order is 3º > 2º > 1º alcohol. This is due to (A) Propene (B) Propane
+I effect of alkyl group which increases the (C) Propyne (D) Propanol
electron density of oxygen which is greatest Ans. (A)
in case of 3º alcohol. In case of reactivity Sol. The name of the compound B in the given
order is 1º > 2º > 3º, because electrons sequence is propene. The reaction takes
density is more in O-H bond and hydrogen place as follows :
tends to separate as proton. Cl
|
Ex.11 Ethanol on reaction with acetic anhydride PCl5
CH3CHOH.CH3  CH3–CH–CH3
gives-
isopropyl alcohol isopropyl chloride
(A) Acetic ester
alc KOH
(B) Formic ester   CH –CH = CH
KCl / H O
2 3 2
(C) Ethanoic acid
propene
(D) Acetic ester and Ethanoic acid both
Alc. KOH is used in elimination reaction for
Ans. (D)
dehydro halogenation of an alkyl halide.
Ex.14 Which of the following compound can give Ex.18 Identify Z in the following series
most stable carbonium ion during dehydration
with H2SO 4- C2H5OH PBr
 3 Alc. KOH
 X  
(A) (CH3)2CHCH2OH
(B) (CH3)3COH Y (i) H2 SO 4
  Z -
(C) CH3(CH2)2CH2OH (ii) H2O + Heat
(D) CH3CHOHCH2CH3 Ans. (B)
Sol. The stability of carbonium ions follows the (A) CH2 = CH2 (B) CH3CH2OH
order 3º > 2º > 1º. The tertiary butyl alcohol (C) CH3CH2OCH2CH3 (D) CH3OH
give teritary butyl carbonium ion, Ans. (B)
(CH3)3COH  (CH3)3C+ + OH¯
PBr3 alc. KOH
Sol. C2H5OH    CH3CH2Br  
Ex.15 When 3, 3-dimethyl -butanol -2 is heated with H2 SO 4
conc. H2SO 4, the main product formed is-
(A) 3, 3-Dimethyl butene -1 CH2 = CH2 H
2 SO 4
 CH3CH2OH
(B) 2, 3-Dimethyl butene -2 H2 O Heat
(C) 2, 3-Dimethyl butene -1
(D) Cis and Trans isomers of the product
Ex.19 Pyrolignious acid is the source of -
obtained in (3rd)
Ans. (B) (A) Wood gas + wood charcoal
CH3 (B) Woodtar + acetic acid
CH3 – C – CH – CH3Conc.H
2SO 4
 (C) Acetone + methanol + Aceticacid
Sol. CH3 OH H O
2 (D) Ethanol + acetone + acetic acid
3,3 - dimethyl butanol -2
CH3 Ans.(C)
+
CH3 – C – CH – CH3Rearangement Sol. Pyrolignious acid is the brown aqueous upper

CH3 layer of the liquid distillation and contains
about (i) 5% methanol (ii) 0.5% acetone (iii)
CH3
10% acetic acid and rest water, hence it is
CH3 – C = C – CH3 a source of acetone, methanol and acetic
CH3 acid.
2,3 - dimethyl butene -2
Ex.16 Which of the following yields 2-butene on Ex.20 [C2H5OH + CH2N2] leads to the product :
dehydration with conc. H2SO 4-
(A) 2-Methyl-2-butanol (A) Higher alcohol (B) Simple ether
(B) 2-Propanol (C) Lower alcohol (D) Mixed ether
(C) 2-Methyl-2-propanol
Ans. (D)
(D) Secondary butyl alcohol
Ans.(D)
Ex.21 Ethanol cannot be dried by anhydrous CaCl2
Conc.H SO
Sol. CH3CHOHCH2CH3   2 4
 due to the formation of the following solvated
-H2O
product-
CH3 – CH = CH – CH3
(A) CaCl2. 2C2H5OH
2-butene
(B) 2CaCl2. 3C2H5OH
(C) CaCl2. 4C2H5OH
Ex.17 forms
(D) CaCl2. C2H5OH Ans. (C)
on reaction with : Sol. Ethanol forms a solid derivative with metallic
(A) CH3 – CHO (B) salt in which alcohol molecule shows
solvation phenomena e.g. CaCl2. 4C2H5OH
That is why alcohols cannot be dried by
(C) CH3 – CH2 – CHO (D) anhydrous CaCl2.
Ans. (B)
Ex.22 The enzyems A, B and C in the reaction Ex.25 Which of the following is least reactive
sequence are- towards ZnCl2 and con. HCl mixture-
(A) 2-Butanol
A B
(C6H10O 5)n   C12H22O 11  C6H12O 6 (B) 1-Butanol
C (C) 2-Methyl 2-butanol
 C2H5OH
(D) All of the above Ans. (B)
(A) Invertase, Maltase, Zymase
Sol. The primary alcohol 1-butanol is least
(B) Diastase, Maltase, Zymase reactive towards Lucas reagent ZnCl 2 and
(C) Maltase, Zymase, Invertase Con.HCl. It gives a white turbidity in half
(D) Diastase, Zymase, Maltase an hour or above. This test is used for the
distinction between primary, secondary
Ans. (B)
and tertiary alcohols and konwn as Lucas
Sol. The enzymes A, B and C in the reaction test.
sequence are Diastase, Maltase and Zymase.
Diastase
Ex.26 Primary, secondary and tertiary alcohols are
(C6H10O5)n   C12H22O11 distinguished by-
starch maltose (A) Oxidation method
Zymase (B) Lucas test
 C6H12O6   C2H5OH
Maltase

CO 2 (C) Victor meyer test
glucose ethanol (D) All of the above
The production of ethanol by the above Ans. (D)
method is called fermentation of starchy Sol. Primary, secondary and tertiary alcohols are
materials. distinguished by all the above methods like
oxidation method, Lucas test & victor Meyer
Ex.23 Phenol and ethanol are distinguished by the test. Out of these the last method is the
reaction with- most effective method of distinguishing
(A) Red litmus (B) NaHCO3 alcohols.
(C) FeCl3 (D) NaOH
Ans. (C) Ex.27 C2H5OH P / I2
 A  
AgNO 2
 B  
HNO2
 C,
Sol. Phenol is weakly acidic in nature while Product [C] is-
alcohol is neutral. Phenol and ethanol are (A) Pseudonitrolic acid
distinguished by the reaction with FeCl 3. (B) Nitrolic acid
Phenol gives a green or red colour with FeCl3, (C) Nitro ethane
while ethanol does not give it (D) Ether
Ans. (B)
Ex.24 The Lucas test is used to determine the type of- Sol. The product 'C' is Nitrolic acid. The reaction
(A) Amines (B) Alcohols takes place as follows :
(C) Acids (D) Phenols C2H5OH P  AgNO 2
 C2H5I  
 I2
 C2H5NO2
Ans. (B)
A
Sol. T he Lucas reagent i s a sol ut i on of
NaOH
ZnCl 2 + HCl. It is used to determine the 
HNO 2
 CH3-C-NO2   Red colour
type of alcohols. On adding it, tertiary B ||
alcohols give an immediate white turbidity. N-OH
Secondary alcohols give turbidity in five (C) nitrolic acid
minutes and primary alcohols give turbidity The abov e reaction is used f or the
in half an hour or more. identification of primary alcohols by Victor
It is used to distinguish among various types Meyer's method
of alcohols.
Ex.28 Power alcohol contains- Sol. Absolute alcohol is obtained from rectified
(A) Rectified spirit + petrol spirit by azeotropic distillation. Some
(B) Petrol + benzene + spirit benzene is added to the rectified spirit and
then distilled. A three component mixt.
(C) Methanol + ethanol + benzene
containing ethanol (18.5%) benzene (74.1%)
(D) Methanol + benzene + petrol and water (7.4%) is obtained at 65ºC.
Ans. (B)
Sol. Power alcohol is a mixture of spirit, benzene
and petrol. This is used as a substitute for Ex.30 CH3– –CH3, is the anhydride of :
petrol in the automobile engines to generate
power, in the countries poorer in petroleum
(A) 1,2–Butane diol (B) 2,2–Butane diol
resources. A small amount of ether or
tetraline is also added. (C) 2,3–Butane diol (D) 1,1–Butane diol
Ans. (C)
Ex.29 Absolute alcohol is obtained from rectified
spirit by-
(A) Rectification
(B) Fractional distillation
(C) Azeotropic distillation
(D) Denaturation Ans. (C)