17 Alcohols General formula alcohols CnH2n+1OH

Naming Alcohols
OH
These have the ending -ol and if necessary the position
Butan-2-ol
number for the OH group is added between the name stem CH3 CH CH2 CH3
and the –ol 1 2 3 4

O
If the compound has an –OH group in addition to other H3C CH C 2-hydroxypropanoic acid
functional groups that need a suffix ending then the OH can be
named with the prefix hydroxy-): OH OH

HO CH2 CH2 OH Ethane-1,2-diol

If there are two or more -OH groups then di, tri are used. H2C OH
Add the ‘e’ on to the stem name though
propane-1,2,3-triol
HC OH

H2C OH

Bond angles in Alcohols

All the H-C-H bonds and C-
C-O are 109.5o (tetrahedral
shape), because there are 4
109.5O
bond pairs of electrons
repelling to a position of
minimum repulsion.
H The H-O- C bond is 104.5o (bent line
H shape), because there are 2 bond
O H pairs of electrons and 2 lone pairs
C 104.5O
C repelling to a position of minimum
H
repulsion. Lone pairs repel more than
H bond pairs so the bond angle is
H reduced.

Boiling points

The alcohols have relatively low volatility and δ- δ+ δ-

O H δ+
high boiling points due to their ability to form O H
hydrogen bond between alcohol molecules. H
C Hδ +
H H
C
H
H
Different types of alcohols
H

H H H O
H H H H H

H C C C H
H C C C O H H C C C H

H H H H O H H H
H C H
Propan-1-ol H
H
Primary Propan-2-ol
Secondary methylpropan-2-ol
Tertiary
Primary alcohols are alcohols Secondary alcohols are alcohols Tertiary alcohols are alcohols
where 1 carbon is attached to where 2 carbon are attached to where 3 carbon are attached to
the carbon adjoining the the carbon adjoining the oxygen the carbon adjoining the oxygen
oxygen

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1. Combustion of Alcohols
Alcohols combust with a clean flame CH3CH2OH + 3O2  2CO2 + 3H2O

2. Substitution reactions of Alcohols to form Halogenoalkanes

Various halogenating compounds can be used to substitute
the –OH group for a halogen
Reaction with phosphorous (V) halide
CH3CH2OH + PCl5  CH3CH2Cl + POCl3 + HCl
PCl5 / PCl3 / conc HCl / SOCl2 / mixture of NaCl +
H2SO4 can all be uses for substituting a Cl
This reaction with PCl5 (phosphorous(v)chloride)
can be used as a test for alcohols. You would
observe misty fumes of HCl produced.

For Br use KBr, 50% concentrated H2SO4

CH3CH2OH + HBr  CH3CH2Br + H2O to produce HBr

Reaction with phosphorous (III) iodide

The phosphorous (III) Iodide is produced in situ by
PI3 + 3 CH3CH2OH  3CH3CH2I + H3PO3 reacting red phosphorus and Iodine.

The reaction of KI and conc H2SO4 cant be used to produce HI because the sulphuric
acid with oxidise the hydrogen halides to other products

3. Reaction of Alcohols with Sodium Observations:

Sodium reacts with alcohols • effervescence, This reaction can be
• the mixture gets hot, used as a test for
2CH3CH2OH + 2Na  2CH3CH2O-Na+ + H2 • sodium dissolves, alcohols
• a white solid is produced.

Oxidation reactions of the alcohols

Potassium dichromate K2Cr2O7 is an oxidising agent that The exact reaction, however, depends on the type
causes alcohols to oxidise. of alcohol, i.e. whether it is primary, secondary, or
tertiary, and on the conditions.

Partial Oxidation of Primary Alcohols

H
O
An aldehyde’s name ends in –
Reaction: primary alcohol  aldehyde al
Reagent: potassium dichromate (VI) solution and dilute H C C It always has the C=O bond on
sulphuric acid. the first carbon of the chain
Conditions: (use a limited amount of dichromate) warm gently Ethanal
H
H so it does not need an extra
and distil out the aldehyde as it forms: number

H H
H H H O Observation: the orange
+ [O] H C C C + H2O dichromate ion (Cr2O72-)
H C C C O H reduces to the green Cr 3+
H H H ion
H H H
OH + [O] O + H2O

CH3CH2CH2OH + [O]  CH3CH2CHO + H2O

propan-1-ol
propanal
Write the oxidation equations in a simplified form using [O] which represents O from the oxidising agent

When writing the formulae of aldehydes in a condensed way write CHO and not COH e.g.CH3CH2CHO

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 Full Oxidation of Primary Alcohols
H H
O
Reaction: primary alcohol  carboxylic acid
Reagent: potassium dichromate(VI) solution and dilute H C C C
sulphuric acid
Conditions: use an excess of dichromate, and heat H H
O H
under reflux: (distill off product after the reaction
has finished) Propanoic acid

H H H H H O
+ 2 [O] H C C C + H2O Observation: the
H C C C O H
orange dichromate
H H H H H O H
ion (Cr2O72-)
OH + 2[O] OH reduces to the
+ H2O green Cr 3+ ion
O
CH3CH2CH2OH + 2[O]  CH3CH2COOH + H2O
propan-1-ol Propanoic acid

Oxidation of Secondary Alcohols

Ketones end in -one
H O H
Reaction: secondary alcohol  ketone When ketones have 5C’s
H C C C H
Reagent: potassium dichromate(VI) solution and or more in a chain then it
dilute sulphuric acid. H H
needs a number to show
Conditions: heat under reflux the position of the double
Propanone bond. E.g. pentan-2-one

H H H

H O H
H C C C H
+ [O] Observation: the
H C C C H + H2O orange dichromate
H O H ion (Cr2O72-) reduces
H H to the green Cr 3+ ion
H
propan-2-ol Propanone

There is no further oxidation of the ketone under these conditions.

Tertiary alcohols cannot be oxidised at all by potassium dichromate: This is because there is no hydrogen
atom bonded to the carbon with the OH group

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Distinguishing between Aldehydes and Ketones
The fact that aldehydes can be further oxidised to carboxylic acids whereas ketones cannot be further oxidised is the
chemical basis for two tests that are commoly used to distinguish between aldehydes and ketones

Tollen’s Reagent Fehling’s solution

Reagent: Tollen’s Reagent formed by mixing aqueous
ammonia and silver nitrate. The active
substance is the complex ion of [Ag(NH3)2]+ .
Conditions: heat gently
Reaction: aldehydes only are oxidised by Tollen’s
reagent into a carboxylic acid and the silver(I)
ions are reduced to silver atoms
Observation: with aldehydes, a silver mirror forms
coating the inside of the test tube.
Ketones result in no visible change
Reagent: Fehling’s Solution containing blue Cu 2+ ions.
Conditions: heat gently
Reaction: aldehydes only are oxidised by Fehling’s
solution into a carboxylic acid and the copper
ions are reduced to copper(I) oxide .
Observation: Aldehydes :Blue Cu 2+ ions in solution
change to a red precipitate of Cu2O. Ketones do
not react
CH3CHO + 2Cu2+ + 2H2O  CH3COOH + Cu2O + 4H+

CH3CHO + 2Ag+ + H2O  CH3COOH + 2Ag + 2H+

The presence of a carboxylic acid can be tested by addition of sodium carbonate. It will fizz and produce carbon
dioxide

Reaction of ethanol with iodine in presence of alkali

Reagents: Iodine and sodium hydroxide Only alcohols with a methyl group next to H H
Conditions: warm very gently the C-O -H bond will do this reaction. H C C H

The product tri-iodomethane CHI3 is a H OH

This reaction is called the Iodoform test
yellow crystalline precipitate with an
antiseptic smell

CH3CH(OH)CH3 + 4I2 + 6NaOH → CHI3 + CH3COONa + 5NaI +5H2O

CH3CH(OH)R + 4I2 + 6NaOH → CHI3 + RCOONa + 5NaI +5H2O

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Reaction of Alcohols with Dehydrating Agents

Reaction: Alcohol  Alkene

Dehydration Reaction: removal of a
water molecule from a molecule
Reagents: Concentrated Sulphuric or Phosphoric acids
Conditions: warm (under reflux)
Role of reagent: dehydrating agent/catalyst
Type of reaction: acid catalysed elimination
H
H
H H H
H C
H C C C O H H
C C
+ H2O
H H H
H H
propan-1-ol Propene

CH3CH2CH2OH  CH2=CHCH3 + H2O

H H
H C
Some 2o and 3o Butan-2-ol But-1-ene
alcohols can give H H H H C C C H
more than one
product, when the H C C C C H H
H H
double bond H H
forms between H H O H H H
different carbon C C
atoms H
H H
C C
Butan-2-ol can form both alkenes
although more but-2-ene would be But-2-ene
H H
formed
But-2-ene could also exist as E and Z
isomers

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Esterification
H H O H Esters have two parts
Carboxylic acids react with alcohols, in the to their names, eg
presence of a strong sulfuric acid catalyst, H C C C O C H methyl propanoate.
to form esters and water. H H H
H+ The bit ending in –anoate The bit ending in –yl comes from
Carboxylic Acid + Alcohol Ester + water comes from the carboxylic the alcohol that has formed it
acid and includes the C in and is next to the single bonded
the C=O bond. oxygen.

H H H O H H
O The reaction is reversible. The
H+ reaction is quite slow and needs
+ H C C O H H C C O C C H + H2O
H3C C heating under reflux, (often for
OH H H H H H several hours or days). Low yields
(50% ish) are achieved. An acid
CH3CO2H + CH3CH2OH CH3CO2CH2CH3 + H2O catalyst (H2SO4) is needed.
Ethanoic acid Ethanol Ethyl Ethanoate

Esterification with acyl chlorides

Change in functional group: alcohol ester This reaction for making esters is much better than
Reagent: alcohol using carboxylic acids as the reaction is much
Conditions: room temp. quicker and it is not a reversible reaction

RCOCl (l) + CH3CH2OH  RCO2CH2CH3 + HCl (g)

O H O H H

CH 3 C + CH3CH2OH  H C C O C C H + HCl
Cl H H H

Observation: Steamy white fumes of HCl

are given off

O
O C
 + HCl
OH + C O
Cl

phenol Benzoyl Phenyl

chloride benzoate

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Phenols
In a phenol the OH group is directly attached to the CH2OH
benzene ring.
OH
In a phenol the lone pair of electrons on the
oxygen is delocalised with the electron
charge cloud of the arene ring.
The delocalised bonding changes the
This is not a phenol, but is
reactivity of the OH group and the arene ring.
an alcohol because the
OH group is attached to an
alkyl group rather than the
Phenols are very weakly acidic. They are weaker acids than carboxylic acids. benzene ring.
Both phenols and carboxylic acids will react with sodium metal and sodium
hydroxide. Only carboxylic acids will react with sodium carbonate as a phenol
is not strong enough an acid to react.

-
OH + Na O Na+ + ½ H2

The sodium phenoxide

- compound is more soluble
OH + NaOH O Na+ + H2O
than the original phenol. So
the solid phenol dissolves on
sodium phenoxide addition of NaOH

Reaction with Bromine

Reagents: Br2
Conditions: room temp
OH Phenol does not need a FeBr3
OH
catalyst like benzene and
Br Br undergoes multiple
substitution whereas benzene
+ 3 Br2 + 3 HBr will only add one Br.

The product in this reaction is a

Br white solid
2,4,6 –tribromophenol

In phenol the lone pair of electrons on the oxygen (p- orbital) is

partially delocalised into the ring. The electron density increases
and the Br2 is more polarised

Phenols are used in the production of plastics,

antiseptics, disinfectants and resins for paints.

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Reaction of Phenol with Nitric acid
In comparison with benzene, phenol does not need the
concentrated sulphuric acid catalyst

With 4M HNO3 single substitution occurs (in comparison

to the conc HNO3 needed for benzene)
Reagent 4M HNO3
Conditions: room temp
OH
OH
with 4M
NO 2
OH HNO3
or

NO2
2 -nitrophenol 4 -nitrophenol

Reaction with diazonium ion

coupling of diazonium ion with a phenol under alkaline
conditions;
NaOH
+
N N + OH N N OH

4-hydroxyazobenzene
C6H5N2+ Cl− +C6H5OH  C6H5N2C6H4OH +HCl

Azo dyes are used for dyes, pigments and

colourings

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