ALCOHOLS

 Alcohols syllabus
 Describe briefly the nomenclature, isomerism and classification of monohydric
alcohol.

Distinguish primary, secondary and tertiary alcohols by Victor Meyer's Method.

 Show the preparation of monohydric alcohols from Haloalkane, primary amines
and esters.
 Explain the industrial preparation alcohol from: oxo process, hydroboration-
oxidation of ethane & fermentation of sugar.
 Define absolute alcohol, power alcohol, denatured alcohol (methylated spirit),
rectified spirit; and alcoholic beverage.
 State physical properties monohydric alcohols.
 Explain chemical properties of monohydric alcohols with HX, PX3, PCl5, and
SOCl2. Action with reactive metals like Na, K and Li. Dehydration of alcohols.
Oxidation of primary, secondary and tertiary alcohol with mild oxidizing
agents like acidified KMnO4 or K2Cr2O7. Catalytic dehydrogenation of 10 and
20 alcohol and dehydration of 30 alcohol, Esterification reaction and test of
ethanol.
 ALCOHOLS
 Hydroxy derivatives of aliphatic hydrocarbons
 Classification of alcohol
Based on
a) Number of –OH group
Monohydric alcohol - one –OH
Dihydric alcohol - two - OH
Trihydric alcohol -three -OH
Polyhydric alcohol -more than three -OH
 B) type of carbon to which –OH group is bonded
 Primary alcohol(10) - -OH group is bonded with 10C
 Secondary alcohol (20) -OH group is bonded with 20 C
 Tertiary alcohol (30) - OH group is bonded with 30 C
NOMENCLTURE OF ALCOHOLS
Common system - Alkyl alcohol
IUPAC system - alkanol
-select the longest chain of carbon which includes carbon
having –OH group.
Number the carbon atoms of the chain from the end
which gives lowest number to the carbon having –OH
group.
-assign the position for all substituents and name the
compound accordingly.
Suffix for –OH is -ol
ISOMERISM
Alcohols exhibit chain isomerism , positional isomerism and
functional isomerism.
Alcoholic isomers of C4H10 O

2-methyl-1-propanol 2-methyl-2-propanol
 Ether isomers of C4H10O
Optical isomers of 2- butanol
 VICTOR MEYER’S METHOD To
DISTINGUISE 10, 20 AND 30 ALCOHOLS
In this method to distinguish 10, 20 And 30 alcohols ,
 the given alcohol is first converted into iodoalkane by heating
with phosphorus and iodine.
 The iodoalkane obtained is then treated with alc. Silver nitrite
which gives nitro alkane.
 The nitro alkane is the reacted with nitrous acid which is generated
in reaction mixture by using NaNO2 + HCl
 The resulted solution is made alkaline . (KOH or NaOH)
 If red coloured solution is resulted the alcohol is 10 alcohol,
Blue coloured solution …………………………20 alcohol
Colourless solution…………………………… ..30 alcohol
Preparation of alcohol
 From haloalkane
 a) by hydrolysis- haloalkane when is hydrolysed by
boiling with aq.KOH or aq. NaOH or moist silver oxide
give alcohol.
From esters
 a) by hydrolysis
 Esters on hydrolysis with dilute mineral acids or alkali give
the acid and alcohol from which it is formed.
 Acidic hydrolysis
 Alkaline hydrolysis
 On alkaline hydrolysis of ester , a mixture of salt of corresponding
acid and alcohol is formed.
RCOOR’ +NaOH(aq) RCOONa + R’OH
 b) by reduction of ester
 Esters on reduction with reducing agents such as H2/Ni,
LiAlH4, NaBH4 or Na-C2H5OH produce alcohols.

 CH3COOC2H5 LiAlH4 2 CH3CH2OH

 C) From primary amines
 Primary amine when reacts with nitrous acid ( NaNO2
+HCl) in cold gives alcohol.

CH3CH2NH2 + HNO2 (NaNO2+HCl ) CH3CH2OH+ N2

0-5 0C
 d) by hydration of alkene
 Direct hydration – when alkenes are treated with
water under high pressure in presence of acid
catalyst H3PO4, direct hydration takes place
resulting alcohol.
 Indirect hydration
 Alkene when is passed into conc. H2SO4 forms alkyl
hydrogen sulphate as addition product which on hydrolysis
gives alcohol.

 Addition in unsymmetrical alkenes takes place according

to Makonikov’s rule.
MANUFACTURE OF ALCOHOL
 Oxo process
 In this process alkene is first converted into aldehyde by
reacting with a mixture of hydrogen and carbon monoxide
in presence of octa carbonyl dicobalt catalyst. Then the
aldehyde is reduced to primary alcohol by reduction with
H2 in presence of Ni/Pt/Pd catalyst.
 [Co(CO)4]2 H2/Ni
CH2 = CH2 + H2 +CO CH3CH2CHO CH3CH2CH2OH
 By hydroboration-oxidation of alkenes
When an alkene is reacted with diborane followed by
treatment with water in presence of alkaline hydrogen
peroxide, alcohol is formed.
 H2O2/OH-
 6CH2 =CH2 + (BH3)2 2(CH3-CH2)3B 6 CH3CH2OH
+2H3BO3
 In this method water is added against Markonikov’s rule. Diborane
required in this reaction is prepared in situ reacting sodium
borohydride with BF3.
 H2O2/OH-
 6CH3CH =CH2 + (BH3)2 2(CH3-CH2-CH2)3B 6 CH3CH2CH2OH
+2H3BO3
 FERMENTATION OF CARBOHYDRATES
 It is a process of breaking down of complex organic
molecules into simpler compounds by the action of
enzymes, the biocatalysts, produced by micro organisms
such as yeast.

 Ethanol can be manufactured by fermentation of sugars

and starchy food materials.
From sugar
 Molasses is the mother liquor obtained on crystallisation of
sugar from sugarcane juice. It is rich in sugar( sucrose,
glucose, fructose) and is used for fermentation process.
 In this process to the solution of molasses yeast is added
which produces enzymes like invertase, zymase etc.
 The reactions involved in this process are:
Invertase
 C12H22O11+ H2O C6H12O6+ C6H12O6
Sucrose glucose fructose
zymase
 C6H12O6 2 C2H5OH + 2CO2
 Glucose/fructose ethanol
 The fermented liquor obtained is called wash and contains
15-18% alcohol. The wash is then subjected to fractional
distillation . 93-95% ethanol obtained is called rectified
spirit.
 PHYSICAL PROPERTIES OF ALCOHOLS
 Lower members- colourless volatile liquids having
characteristic alcoholic smell and burning taste.
Higher members – colourless, tasteless and waxy solid
 Alcohols have higher boiling point than corresponding
alkanes and alkyl halides as alcohols can form
intermolecular hydrogen bonding and exist as associated
molecules.
 Lower alcohols are soluble in water as they can form
hydrogen bond with water molecules. Solubility of alcohol
decreases with increase in hydrocarbon chain which is
non-polar part.
 CHEMICAL PROPERTIES
Reactions involving breaking of O – H bond
 Acidic nature ( reaction with active metals)
 When alcohol reacts with active metals like Na , K
breaking of O-H bond takes place and H of alcohol
is replaced by the metal to form metal alkoxide.
The reaction shows that alcohol is acidic in nature.
ROH + Na RONa + ½ H2
C2H5OH + Na C2H5ONa + ½ H2
sod. ethoxide
 Reaction with potassium

C2H5OH + K C2H5OK + ½ H2
potassium ethoxide
Reaction with Lithium
C2H5OH + Li C2H5OLi + ½ H2
Lithium ethoxide
 Esterification ( reaction with carboxylic acid)
 Alcohol when reacts with carboxylic acid in presence of
conc. H2SO4 it gives ester. The reaction is called
esterification reaction. Here, conc.H2SO4 is used as
dehydrating agent. If conc. H2SO4 is not used , water can
hydrolyse ester back to acid and alcohol.
Reaction with acid halides and anhydrides
-results esters
 Reactions involving breacking of C-OH bond
 Reaction with halogen acids
 Alcohol when reacts with halogen acid, haloalkane
is formed.
 Reaction with phosphorus halides
 Alcohol when reacts with phosphorus halides ,haloalkanes
are formed.
 Reaction with thionyl chloride
 When alcohol reacts with thionyl chloride in
presence of pyridine, chloroalkane is formed.
Reactions involving both alkyl and
hydroxyl group
Oxidation
 Alcohols can be oxidised using acidified K2Cr2O7 or
Na2Cr2O7 or acidified KMnO4 etc.
 Primary alcohol easily gets oxidised to aldehyde and then
into carboxylic acid having same number of carbon atom
as in the alcohol used.
secondary alcohol gets oxidised to ketone with
same number of carbon. Ketones are oxidised
only on drastic condition to give acids containing
lesser number of carbon.
 Tertiary alcohols resist oxidation as they do not have
Hydrogen atom on carbon bonded with –OH group.
 Dehydration
 Alcohols, when heated with conc. H2SO4 at 170 0c or when
vapour of alcohol is passed over heated alumina at 350 0C ,
undergo dehydration resulting alkene.
 Catalytic dehydrogenation
 When alcohol vapours are passed over copper heated at
300 0C dehydrogenation takes place .
 Primary alcohol on dehydrogenation gives aldehyde.
 Secondary alcohol on dehydrogenation gives ketone.
 Tertiary alcohols are dehydrated to alkenes.
Test for alcohols
i) Esterification test
ii) Alcohols react with carboxylic acid to form ester with
fruity smell. The reaction is esterification reaction.
 ii) Iodoform test – Alcohols having CH3-CH(OH) group
give positive iodoform test.
 Alcohols having this group when is warmed with iodine
solution and aq.NaOH or Na2CO3 solution, gives pale
yellow precipitate of iodoform with hospital smell.
 This test is also given by aldehydes and ketones having
O
CH3-C- Group.
 How would you convert
 1. ethanol to i) methanol ii) Propanol
 2. convert 1-propanol to 2- propanol and vice versa
 3.How would you distinguish
a) ethanol from methanol?
b) n-butyl alcohol from sec.butyl alcohol?
4. What happens when 2-methyl-2-propanol is passed over heated
Cu at 300 0C?
 1. CH3CH2OH CH3CH2Cl CH3CH2CN

CH3CH2CH2NH2 CH3CH2CH2OH

2. CH3CH2OH CH3COOH CH4 CH3Br

CH3OH
3. CH3CH2CH2OH CH3CH=CH2 CH3CH(Br) CH3

CH3CH(OH) CH3
CH3CH(OH) CH3 CH3CH=CH2 CH3CH2CH2Br

CH CH CH OH
 1. CH3CH2OH PCl5 CH3CH2Cl alc KCN CH3CH2CN LiAlH4

CH3CH2CH2NH2 HNO2 CH3CH2CH2OH

2. CH3CH2OH CH3COOH
KMnO4/H NaOH+CaO CH4 P+Br2 CH3Br
aq.NaOH CH3OH

3. CH3CH2CH2OH H2SO4,170 CH3CH=CH2 HBr CH3CH(Br) CH3

aq.KOH CH3CH(OH) CH3

CH3CH(OH) CH3 H2SO4,170 CH3CH=CH2 HBr, peroxide CH3CH2CH2Br

aq KOH CH3CH2CH2OH
 Uses of alcohols
TYPES OF ALCOHOLS
Rectified spirit
The ethanol obtained after the fractional distillation of fermented
liquid containing upto 95% ethanol is called rectified spirit. It is
used for industrial purposes thus is called industrial alcohol.
Absolute alcohol
The alcohol obtained from rectified spirit by distillation of it with
calculated amount of quick lime, CaO, metallic Ca or calcium
carbide is absolute alcohol. It contains 99.5 to 100% ethanol.
Power alcohol
The mixture of ethanol and petrol in the ratio 20:80 along with
benzene or ether as co-solvent is called power alcohol. Power
alcohol is taken as the alternative source of energy in non
petroleum countries to solve crisis of gasoline(petrol).
 Denatured alcohol( methylated spirit)
Alcohol is an excellent solvent and is important for chemical
industries ,so is made cheaper. To prevent misuse of cheaper alcohol
for drinking purposes, the alcohol is made unfit for drinking by
adding some poisonous substances like pyridine, acetone etc,. Such
type of alcohol which is made unfit for drinking purpose by adding
poisonous substances is called denatured alcohol or methylated
alcohol.
 Alcoholic bevarage
l iquors used for drinking purposes containing ethanol, water,
flavouring and colouring substances are called alcoholic beverages.
These contains different percentage of ethanol.
Alcoholic beverages are of two types:

1. Distilled beverages
the liquor obtained after the distillation of fermented liquor
having high percentage of alcohol ( % or more) is called distilled
beverage. Eg. Whisky, brandy, rum gin etc.
2. Undistilled beverages
the liquor obtained by fermentation of fruits containing low
percentage of alcohol are called undistilled beverages. Eg. Wines,
beer, cider etc.
 1. Write down the isomeric alcohols of C3H8O with their IUPAC
names.
i) Explain Victor Meyer’s method to distinguish them.
Ii) Which one of these isomers give iodoform test? Write the
reaction involved.
Iii) how would you convert one isomer into another?
Iv) Arrange these isomers in the order of increasing boiling point.
 2. How would you prepare the followings using ethanol
i) ethene ii) ethyl ethanoate iii) ethane iv) ethanoic acid