MODULE 4
ALCOHOLS(ALKANOLS)
Learning outcomes
By the end of this module, you will be able to:
Name common alcohols and phenols using the IUPAC system
Discuss the preparation, physical and chemical properties of alcohols and
phenols
Compare the properties of phenol and other alcohols
State the uses of alcohols and phenols
Introduction
In module three, you learnt that haloalkanes consist of a halogen
replacing at least one hydrogen in the parent alkane. In this module,
you are going to discuss another group of compounds called alcohols.
Alcohols are a group of organic compounds containing a hydroxyl
group (OH) in their molecules. The most prominent member of this
series is ethanol(alcohol) commonly consumed in beers, whiskey, wine
and other alcoholic drinks. However, the group includes a variety of
other alcohols including glycerol, cholesterol, Panadol and other
compound known and sometimes used in everyday life.
The different kinds of alcohols
Alcohols fall into different classes depending on how the -OH group is
positioned on the chain of carbon atoms. There are some chemical
differences between the various types.
Primary alcohols
In a primary (1°) alcohol, the carbon which carries the -OH group is
only attached to one alkyl group.
In each of the examples considered above, there is only one linkage to
an alkyl group from the CH2 group holding the -OH group. However,
Methanol (CH3OH), the simplest alcohol, is counted as a primary
alcohol even though there are no alkyl groups attached to the carbon
with the -OH group on it.
Secondary alcohols
In secondary (2°) alcohols, the carbon containing the -OH group is
attached directly to two alkyl groups, which may be the same or
different. Examples:
Tertiary alcohols
In tertiary (3°) alcohols, the carbon atom holding the -OH group is
attached directly to three alkyl groups, which may be any combination
of same or different.
Examples:
Nomenclature of alcohols
Simple alcohols are named by adding the suffix ‘ol’ to the name
indicating the number of carbon atoms in the molecule. However, for
complex alcohols, there is emphasis on the position of the hydroxyl
(OH) group. Some examples and names of alcohols are shown in the
table below:
Alcohol IUPAC name
Methanol
Ethanol
Propan-1-ol
Propan-2-ol
Phenyl methanol
Physical properties of alcohols
1. Physical state
Alcohols are generally colourless liquids with a spirity smell. They are
mainly liquids or solids at room temperature. The change of state
from liquids to solids becomes more likely with increase in chain
length and increase in the number of hydroxyl groups in the
molecule. For example, glycerol is solid while propanol is a
liquid(figure4.1).
Glycerol Propanol
Figure 4.1: Glycerol is a solid while propanol is a liquid
2. Melting points and Boiling Points
The melting and boiling points of alcohols are generally higher than
those of alkanes with similar molecular mass and carbon chain length.
This is because the alcohols have intermolecular hydrogen bonds
which attract the different molecules towards one another. Figure 4.2
shows the existence of hydrogen bonds in ethanol.
Figure 4.2: Hydrogen bonds in ethanol
The chart shows the boiling points of some simple primary alcohols
with up to 4 carbon atoms.
Figure 4.3: Boiling points of similar alkanes and alcohols compared
They are compared with the equivalent alkane (methane to butane)
with the same number of carbon atoms.
From the chart, we observe that:
The boiling point of an alcohol is always much higher than that of
the alkane with the same number of carbon atoms.
The boiling points of the alcohols increase as the number of
carbon atoms increases. The patterns in boiling point reflect the
patterns in intermolecular attractions.
Solubility of alcohols in water
The small alcohols are completely soluble in water. Whatever
proportions you mix them in, you will get a uniform mixture. However,
the solubility of alcohols decreases as the length of the hydrocarbon
chain in the alcohol increases. Once you get to four carbons and
beyond, the fall in solubility is noticeable, and you may well end up
with partial miscibility or even complete immiscibility. The decrease in
miscibility with increasing chain length is due to the increase in length
of the hydrophobic alkyl chain of the alcohols.
Methods of preparation of alcohols
1. From alkyl halides
When Haloalkanes (alkyl halides) are heated with aqueous sodium
or potassium hydroxide, alcohols are formed.
2. Preparation from alkenes
Alcohols can be produced from Alkenes by their Hydration, by passing
alkenes through concentrated H2SO4 and then hydrolysis with boiling
water.
Mechanism
The steps involved in the formation of alcohol are shown below:
(i) Electrophilic attack by hydroxyl union on alkenes gives a
carbocation intermediate
(ii) Nucleophilic attack by water on 20 carbocation
(iii) Deprotonation or loss of proton to form alcohol
3. Preparation from carbonyl compounds
a. By reduction of aldehyde and ketones.
The aldehydes or ketones are reduced to alcohols using Hydrogen in
nickel, sodium in ethanol, Lithium aluminium hydride in ether or
sodium borohydride to form alcohols. Aldehydes give primary alcohols
while ketones give secondary alcohols.
b. By reduction of Carboxylic acids and esters
Carboxylic acids and esters can be reduced by strong reducing
agents such as lithium aluminium hydride to give alcohols.
4. Grignard Synthesis
All three types of alcohol (primary, secondary and tertiary) can be
prepared from the Grignard reagents by interaction with suitable
carbonyl compounds.
Grignard Synthesis
The reaction of the Grignard reagent with formaldehyde leads to
primary alcohols, that with aldehydes other than formaldehyde yield
secondary alcohols and that with ketones give tertiary alcohols.
Manufacture of ethanol by fermentation
Chemical properties of alcohols
The reactions of alcohols can be grouped into the following categories:
• Reactions involving the cleavage of O – H bond.
• Reactions involving the cleavage of C – OH bond.
• Reactions involving both the alkyl and hydroxyl group.
A. Reactions involving the cleavage of O – H bond:
1. Reaction with active metals ( acidic nature of alcohols)
Alcohols react with electropositive metals like Na, K, Mg, Al, Zn etc. to
form metal alkoxide with the evolution of hydrogen gas.
In this reaction, alcohol acts as a (weak) acid. The acidic nature is
mainly due to the presence of the highly polar O – H bond, which
allows the ionisation of hydrogen atom (hydrogen as H+ ion).
The acidic nature of alcohols is in the order: Methyl alcohol > 10 alcohol
> 20 alcohol > 30 alcohols.
The alkyl group is an electron releasing group, which releases
electrons toward O-atom thereby increasing the electron density at O-
atom. As a result, O-atom shows lesser tendency to withdraw electrons
from H-atom. This decreases the polarity of O – H bond due to which
breaking of O – H bond becomes difficult. Thus, acidic nature
decreases with the increase in alkyl group.
Water is a stronger acid than alcohols
Although water and alcohols have similar structure, -OH group is
attached to a H-atom in water while in alcohols-OH group is bonded to
an alkyl group.
The alkyl group is an electron releasing group, which releases
electrons toward O-atom thereby increasing the electron density at O-
atom. As a result, O-atom shows lesser tendency to withdraw electrons
from H-atom. This decreases the polarity of O – H bond due to which
breaking of O – H bond becomes difficult. Thus, acidic nature
decreases with the increase in alkyl group.
2. Reaction with carboxylic acid (Esterification reaction)
Alcohols react with carboxylic acids in the presence of few drops of
conc. H2SO4 to form esters. This reaction is known as esterification
reaction.
Here, conc.H2SO4 absorbs water formed and shifts the equilibrium in
forward direction.
3. Reaction with acid chloride and acid anhydride
When alcohols are heated with an acid chloride or acid anhydride,
esters are formed. Eg.
4. Reaction with Grignard reagent
Alcohols react with Grignard reagent to form alkane.
B. Reactions involving the cleavage of C – OH bond:
The –OH group of alcohol has two lone pair of electrons on O-atom and
thus behave as Lewis base. The Lewis base nature of alcohols show the
order:
30 > 20 > 10 > methyl alcohol
In tertiary alcohols the partial –ve charge on oxygen atom is intensified
due to +I effect of alkyl group. This increases the tendency of oxygen
atom to donate electron pair or to show the cleavage og C-O bond.
1. Reaction with halogen acid
Alcohols react with halogen acids to form the haloalkanes. Eg.
2. Reaction with phosphorus halides
Alcohols react with phosphorus halides to give the corresponding alkyl
halides.
3. Reaction with thionyl chloride
C. Reactions involving both alkyl and hydroxyl group
1. Dehydration of alcohol
When alcohol is heated with conc. H 2SO4 or when vapour of alcohol is
passed over heated alumina (Al 2O3), it undergoes dehydration to give
alkenes or ethers.
For example,
Mechanism
However, it is possible to obtain an ether instead of the alkene. The
nature of product depends upon the reaction conditions.
With excess alcohol at about 1400C, the product is instead an ether.
With heated alumina:
2. Dehydrogenation of alcohols
When alcohol vapours are passed over heated copper at 300 0C,
different types of alcohols give different products.
a. Primary alcohols are dehydrogenated to aldehydes. Eg.
b. Secondary alcohols are dehydrogenated to ketones. Eg.
c. Tertiary alcohols doesn’t get dehydrogenated due to the absence of
α-hydrogen but it undergoes dehydration to give alkene.
3. Oxidation of alcohols:
Identification of primary, secondary and tertiary alcohol by
oxidation method:
Alcohols are oxidized by different oxidizing agents like acidic or
alkaline KMnO4, acidified K2Cr2O7, dil. HNO3, etc. to give different
products.
Oxidation reactions of alcohols
The oxidising agent used in these reactions is normally a solution of
sodium or potassium dichromate (VI) acidified with dilute sulphuric
acid. If oxidation occurs, the orange solution containing the dichromate
(VI) ions is reduced to a green solution containing chromium (III) ions.
The electron-half-equation for this reaction is
Primary alcohols
Primary alcohols can be oxidised to either aldehydes or carboxylic
acids depending on the reaction conditions. In the case of the
formation of carboxylic acids, the alcohol is first oxidised to an
aldehyde which is then oxidised further to the acid.
Partial oxidation to aldehydes
An aldehyde is obtained if you use an excess of the alcohol, and distil
off the aldehyde as soon as it forms. The excess of the alcohol means
that there isn't enough oxidising agent present to carry out the second
stage. Removing the aldehyde as soon as it is formed means that it
doesn't hang around waiting to be oxidised by excess oxidising agent.
For example, the use of ethanol as a typical primary alcohol, produces
the aldehyde ethanal, CH3CHO. The equation for this reaction can
easily be obtained using oxidation numbers as shown below:
Or simply, it can be represented as:
If an excess of the oxidising agent is used and the aldehyde formed as
the half-way product stays in the mixture the product is a carboxylic
acid.
Or simply,
The alcohol is heated under reflux with an excess of the oxidising
agent. When the reaction is complete, the carboxylic acid is distilled
off.
Secondary alcohols
Unlike primary alcohols which produce aldehydes or carboxylic acids
on oxidation, secondary alcohols are only oxidised to ketones. For
example, the heating of propan-2-ol with sodium or potassium
dichromate (VI) solution acidified with dilute sulphuric acid, forms
propanone.
Or simply,
Tertiary alcohols
Tertiary alcohols aren't oxidised by acidified sodium or potassium
dichromate (VI) solution. There is no reaction whatsoever because the
tertiary alcohols lack a hydrogen atom attached to the carbon atom
containing the OH group. Generally, the oxidation of alcohols involves
removal of the hydrogen atoms attached to the OH group.
Uses of alcohols
Identify any 6 uses of alcohols
Question
Discuss the chemistry of Phenols under the following headings:
a. Meaning of phenols
b. Preparation of phenol
c. Physical properties
d. Chemical properties
e. Uses of phenols