CHEMISTRY OF THE ALCOHOLS

ALCOHOLS
The alcohols are also called the alkanols. Their functional group
is the hydroxyl group (OH).
Monohydric alkanols (i.e. alkanol with one OH connected to a
saturated carbon) have general molecular formula CnH2n+1OH
which is the same with ethers.

R–H ROH
HOH ROH
Replacement of the two hydrogen atom in water with alkyl
groups gives ether
HOH ROH
The general way of representing the monohydric alknols is ROH
where R represents the alkyl group.
There are alkanol containing two, three or more hydroxyl groups
and they are regarded as dihydric, trihydric and polyhydric
alcohols respectively.

Monohydric alcohol can further be classified as primary (10),

secondary (20) and tertiary (30) alcohols depending on the nature
of the hydroxyl bearing carbon.
NOMENCLATURE
In the common system of naming alcohols, they are named as
alkyl group followed by the word alcohol in two separate words.
CH3OH CH 3CH2OH
CH3CH2 CH2 OH
Methyl alcohol ethyl alcohol
propyl alcohol
Sometimes it becomes necessary to indicate the classification of
the alcohol (di.e. 10, 20 or 30 alcohols). Examples are;

In the IUPAC system of naming, the alcohols are named as

alkanol following the under listed rules;
1. Select the longest continuous carbon chain bearing the
hydroxyl group. This is named as the parent chain.
2. Name the parent chain as a derivative of the corresponding
alkane by replacing the ending ‘e’ with the suffix –ol
3. Indicate the position of the functional group (-OH) on
the parent chain by numbering in such a way that gives the
lowest possible number to the OH bearing carbon
 4. Indicate the position of other functional groups within the
molecule.

METHODS OF PREPARATIONS
Several methods are available for the preparation of alcohols,
they include the under listed;
1. FROM ALKENES (HYDRATION OF ALKENE)
Acid catalysed hydration of alkene results to the
formation of alcohol and the addition also follows
 Markovnikov’s rule. The reaction is a reversible
reaction.
The mechanism is similar to hydrohalogenation reaction.

The mechanism of the reaction entails the following steps;

i. Protonation of the alkene to form the carbocation

intermediate

ii. Nucleophilic addition of water to the carbocation

An acid-base reaction occurs where the carbocation is the

 iii. Deprotonation of the oxonium to form alcohol the
proton catalyst

OR
Oxonium ion stabilizes by losing hydrogen ion

A wide range of catalyst and reaction condition can be used

depending on the class of alcohol to the prepared.

2. REDUCTION OF CARBONYL COMPOUNDS

. Aldehydes and ketones can be reduced by refluxing in
acidic medium with sodium borohydride (NaBH4)

Reduction of aldehydes gives rise to primary alcohol

while ketone gives secondary alcohol.

The reduction simply requires the addition of two hydrogen

atoms to the aldehydes and ketone molecules
 Reduction of carboxylic acid gives the corresponding
alcohol while ester give two separate alcohol corresponding to
the alcohol portion of the ester and a primary alcohol from the
carboxylate portion.
3. ADDITION OF GRIGNARD REAGENT TO
CARBONYL COMPOUNDS

Grignard reagents (RMgX) add to carbonyl compounds to

give alkoxymagnesium halide which is later hydrolyzed to
give the equivalent alcohol.

a. Addition to methanal gives a 10 alcohols

b. Addition to ethanol and other aldyhydes gives a 20 alcohols

 c. Addition to ketones gives a 30 alcohols

4. SUBSTITUTION REACTION FROM HALOALKANES

Primary alkyl halides react with aqueous sodium hydroxide
or potassium hydroxide to give primary alcohols. The
reaction can proceed through SN1 or SN2

5. HYDROLYSIS OF ESTERS
Alcohols can be prepared industrially by the hydrolysis of
esters with dilute sulfuric acid or alkali.

INDUSTRIAL PREPARATION OF ETHANOL

In the industries ethanol is produced by the fermentation using
the following steps;
1. Starchy food stuff are first grinded and pressure cooked to
extract the starch in them
2. The starch are treated with malt (malt is partially
germinated Beverly) at 500C – 600C for an hour. Malt
contains the enzyme diatase which converts the starch to
maltase.
 2(C6H10O5)n + H2O (C12H22O11)
Starch Maltose

3. Yeast is added at room temperature yeast contain two

enzymes namely
i. Maltase which converts maltose to glucose

C12H22O11 + nH2O 2(C6H12O6)

Maltose glucose

ii. Zymase which decompose glucose to carbondioxide

and ethanol
C6H12O6 2C2H5OH + 2CO2

PHYSICAL PROPERTIES
Properties of alcohols are principally affected by intermolecular
forces such as dipole – dipole interactions and hydrogen
bonding which are in turn modified by the hydrocarbon portion
of the molecule. Lower members of the group are volatile
colourless liquid at room temperature, with a characteristic small
and a burning taste. Generally, the physical properties can be
discussed under the following headline.
1. Boiling Point: The boiling points of alcohol are quite
higher than values predicted by their molecular weight. The
hydroxyl group allows the alcohol to associate through
hydrogen bonding which they form with one another and
with other compounds. The hydrogen bond requires large
amount of energy (heat) to overcome the attractive force.
And as such the boiling points of alcohol is usually higher
 than comparable hydrocarbon. For example, the boiling
point of ethanol is 78.30C compared to 690C for hexane and
34.60C for diethyl ether.
Also, boiling point within the family increases as the
alcohol members becomes larger. Furthermore, branched
isomers are more water soluble and volatile than their
straight chain counterparts.

2. Solubility: The solubility in alcohols is influenced by the

hydroxyl portion which is hydrophilic and the alkyl portion
which is hydrophobic. The hydrophilic portion promotes
solubility in water while the hydrophobic portion resists it.
Therefore, lower members (Cl – C3) are soluble in water
because the hydroxyl portion wins over the alkyl portion.
Butanol is moderately soluble because of a balance
between the two trends, while member with more than four
carbons are successively insoluble in water with increase in
molecular mass as the alkyl group increasingly wins over
the hydroxyl group.

3. Acidic/basic nature of alcohol: Alcohol can show both

basic and acidic properties at the O-H group like water.
Generally, alcohols are slightly weaker acids than water. As
acids they; react with strong bases such as sodium
hydroxide to form the alkoxide salt and water.
ROH + NaOH RONa + H2O
React with reactive metal/metal hydride such as sodium/hydride
to liberate hydrogen
 2ROH + 2Na 2RONa + H2
ROH + NaH RONa + 2H2
The lone pair of electron on the hydroxyl oxygen gives the
molecule weakly basic character. Therefore, in the presence of
strong acids such as sulphuric acid the alcohol is protonated.

CHEMICAL PROPERTIES
1. REACTION WITH REACTIVE METAL OR THEIR
METAL HYDRIDE
Alcohols react with very strong electropositive metals (K
and Na) to corresponding alkoxide suit and giving off
hydrogen gas.

2C3H7OH +2Na 2C3H7ONa + H2

The alkoxide formed are nucleophiles which react with
alkylhalide to form ethers in the Williamson etherification
reaction

The alkoxide can also readily dissolves in water give the original
alcohol and the hydroxide of the metal
C3H7ONa + H2O C3H7 OH + NaOH
2. DEHYDRATION OF MONOHYDRIC ALCOHOLS
(ELIMINATION REACTION)

Alkene can be prepared by heating alcohol in the presence of

concentrated tetraoxosulphate (VI) acid at 180 0C. The β
elimination reaction here involves the removal of a hydrogen
atom and a hydroxide from adjacent carbons. That is, reaction
removes the OH group from the alcohol carbon atom and a
hydrogen atom from an adjacent carbon atom in the same
molecule:

The overall reaction involves the removal of one molecule water

from alcohol by hot concentrated tetraoxosulphate (VI) as the
dehydration of ethanol. The mechanism proceeds in three steps;

1. In the first stage, the lone pair of electron on the oxygen

atom picks up a hydrogen atom from the sulphuric acid to
form a protonated alcohol

2. The second stage is the use of water from the protonated

alcohol to form a carbocation
 3. Finally is the elimination of a proton from the carbocation.

At lower temperatures (about 1400C) and in excess amount of

alcohol, nucleophilic substitution reaction occurs. Another
molecule of alcohol acts as nucleophile and attacks the
protonated alcohol (oxonium salt acting as an electrophile)
formed initially to give dialkyl ether (simple or symmetrical
ether). To get ethers primary alcohol are used. Here the etire
OH group of one alcohol molecule and only the hydrogen atom
of the OH group of the second alcohol molecule are removed.
The two ethyl groups attached to an oxygen atom form an ether
molecule.

Other dehydrating agents include phosphorus pentoxide (P 2O5),

iodine, Zine chloride, potassium hydroxide and phthalic
anhydride.

3. SUSTITUTION REACTION OF ALCOHOL

a. Haloalkanes formation from alcohol
 Haloalkanes can also be derived from alcohols by
substituting the - OH group from alcohols with halogen.
This can be achieved by several methods which includes;

i. By the action of halogen acids (HI, HBr, HCl).

ii. By the action of phosphorus halide (PX3 and PX5)
iii. By the action of thionyl chloride (SOCl2)

i. By the action of halogen acids (HI, HBr, HCl).

A very convenient way to convert an alcohol to the
corresponding haloalkane is by reacting it with halogen acids
(hydrogen halides). The reaction is a substitution reaction and
the ease with which alcohols reacts is 3 0 > 20 > 10 while for
haloalkane is HI > HBr > HCl. Reactions with tertiary alcohols
are faster and proceeds via the formation of a carbocation. Thus
possible rearrangement of the carbocation could occur to form a
more stable one. This could result to an alkyl group of the alkyl
halide being different from the starting alcohol
The reaction of alcohol with hydrogen iodide occurs readily to
form the corresponding iodoalkane. However, a catalyst is
required for reaction with hydrogen bromide and especially
hydrogen chloride. Alcohol reacts with hydrogen bromide in
the presence of a little quantity of sulphuric acid (H 2SO4) as
catalyst.
Also, chloroalkanes are formed by the reaction of alcohol with
hydrogen chloride in the presence of anhydrous ZnCl2. The
mixture of Zinc chloride and hydrochloric acid is called Lucas
reagent. The chloroalkane is formed as an insoluble oily layer in
the reaction mixture. Different classes of alcohol react
differently with Lucas reagent. And as such used to distinguish
the different classes of alcohols however, the test cannot be used
for alcohols that exceeds six carbon atoms While 3 0 alcohols
react readily at room temperature, 2 0 react at 600C While 10
under reflux condition. Thus the reaction is used to differentiate
between the three classes of alcohol.
Tertiary alcohols (30) react immediately with Lucas reagent to
form insoluble oils.

Secondary alcohols (20) react slowly with Lucas reagent to form

insoluble oils

Primary alcohols (10) give no visible reaction until reactants are

boiled under reflux
 ii. By the action of phosphorus halide (PX3 and PX5)
Haloalkanes can be formed from alcohols by reacting it with
phosphorus halides. The reaction is a nucleophilic substitution
reaction where the hydroxyl group of the alcohol is substituted
with the halide. Alcohols react with phosphorus trichloride
(PCl3) or phosphorus pentachloride (PCl5) when boiled under
reflux to produce chloroalkanes.

Bromo- and iodoalkanes can be prepared by reacting alcohols

with phosphorus tribromide (PBr3) or phosphorus triiodide (PI3).
In this case, the tribromide or phosphorus triiodide generated in-
situ by reacting alcohol with a mixture of bromine or iodine with
red hot phosphorus.

iii. By the action of thionyl chloride (SOCl2)

Thionyl chloride reacts with alcohol when boiled under reflux in
the presence of pyridine to give haloalkane. Pyridine is added in
order to absorb the hydrogen chloride gas generated. The
advantage of this method over the other methods were alcohol
are used is that the by-products are gases and as such the
haloalkane obtained in very pure form.
 b. Reaction with ammonia
Alcohols react with ammonia at 360 0C using alumina or
thoria as catalyst to form a mixture of primary, secondary
and tertiary amines.

CH3 CH2OH + NH3 CH3 CH2 NH2 + H2O

CH3 CH2 OH + CH3CH2 NH2 (CH 3 CH2)2 NH

+ H2O
CH3 CH2 OH + (CH3CH2) NH (CH3 CH2)3 N
+ H2O

4. ESTERIFICATION REACTION: The reaction of alcohols

with carboxylic acids in the presence of an inorganic acid
catalyst (dehydrating agent) to form esters is called
esterification reaction

The reaction is an equilibrium reaction, so in order to

increase the yield, are of the products must be removed as it
is formed

The mechanism for esterification takes place in following

steps.

1. Protonation of the carbonyl oxygen is protonated by the

acid catalyst, activating it toward a nucleophilic attack
bythe ethanol.
2. Nucleophilic attack on the carbonyl by the alcohol. A lone
pair of electrons from the oxygen atom of the alcohol
forms a bond with the carbonyl carbon, breaking its pi
bond with the other oxygen. The pi bond electrons move
up to the oxygen and neutralize its positive charge. This
results in an oxonium ion.

3. A proton transfer occurs from the oxonium ion to the OH

group, giving rise to an activated complex. This can be
divided into two further steps where the alcohol first
deprotonates the oxonium ion giving a tetrahedral
intermediate after which the OH group accepts the proton
from the alcohol. This step can be illustrated as:

4. A 1,2 elimination of water occurs, giving the protonated

ester. A lone pair of oxygen forms a pi bond with the
carbon, thereby expelling the water as shown below.
 5. The remaining positively charged oxygen is deprotonated,
giving the required ester as product as shown below.

5. OXIDATION OF THE ALCOHOL

Oxidation of alcohol can give different product that depends
on the class of alcohol and the oxidizing agent (oxidant).
Primary alcohols can be oxidized to aldehydes by dilute
solution of acidified potassium dichromate, (K2Cr2O7) or
alkaline potassium permanganate (KMnO4). If the condition
is not controlled, further oxidation will take place easily
leading to the production of carboxylic acid.

Under mild conditions also, secondary alcohol can be

oxidized to ketones. Prolonged oxidation with strong
oxidizing agent produces fragmentation. Oxidation of both
primary (RCH2OH) and secondary (R2CHOH) alcohols,
requires the removal of two hydrogen atoms from the alcohol
molecule, one from the OH group and other from the carbon
atom that bears the OH group.
Tertiary alcohols are resistant to oxidation. This is because
the OH bearing carbon does not have a hydrogen atom
attached but is instead bonded to other carbon atoms. Since
oxidation involves the formation of a carbon-to-oxygen
double bond, the OH bearing carbon must be able to release
one of its attached atoms to form the double bond. But while
the carbon-to-hydrogen bonding is easily broken under
oxidative conditions, the carbon-to-carbon bonds are not.
Therefore, tertiary alcohols are not easily oxidized. However,
under forced oxidation the products are usually ketones and
acid with less number of carbons than the initial reacting
alcohol

USES OF ALCOHOL
1. It is used as solvent to dissolve resins, varnishes, lacquer,
soap, perfumes etc
2. It is used to produce other chemicals e.g alkene, aldehyde,
ketone, carboxylic acids etc.
3. It is used to produced alcoholic beverages
4. It is used as an anti-freeze in automobile radiator because
of its low freezing point
5. It is used as fuel either by itself or mixed with petrol in
racing cars and rocket
6. It is used as an antiseptic and in sterilisation such as
cleaning the skin prior to being injected and sterilisation of
surgical equipments.
7. It is for preservation of biological specimen and food
 8. Ethanol is used in drugs. Solutions of drugs in ethanol are
called tinctures eg iodine tinctures and quinine tinctures.
9. Ethanol is used in the production of soap. Transparent
soaps are made by dissolving soap in ethanol and allowing
the solvent to evaporate.

REVIEW QUESTIONS
1. Suggest the reaction condition needed for the conversion of
bromoethene to ethanol.
2. A compound with molecular formula CH3CHOHCH3
is catalytically dehydrated with sulphuric acid at 140°C
i. Suggest the IUPAC name and structure of the product.
ii. State the use of the product
iii. State the chemical equation of the reaction.
3. An alcohol shares the same molecular formula (C 4H10O) with
ether. Give an account of the difference in their boiling points.
4. Show how cyclohexanol can react by:
i. Combustion
ii. Dehydration

5. Write chemical equation and experimental conditions for the

following reactions of pentan-2-ol. i. Dehydration ii.
Oxidation iii. Hydrobromination iv. With CH 3COOH iv.
Combustion
 6a. Suggest reaction mechanism for the hydration of 2-
methylpropene.
b. What is the significance of the method?
7. Write the equation for the oxidation of each alcohol. Use [O]
above the arrow to indicate an oxidizing agent. If achohol is
resistant to oxidation reaction, write “no reaction” after the
arrow.

8. Write equations each for the dehydration and oxidation of

2-butanol to yield the corresponding alkene, ether and
carbonyl compound type.

1. Suggest reaction mechanism for the dehydration of 2-

propanol to yield each compound type.
a. an alkene
b. an ether
1. 10. Suggest reaction mechanism reaction.
2. Suggest reaction mechanism reaction.