Chemical properties of alcohol

• Reactions involving entire alcoholic group.

 (i) Oxidation of alcohols.
• Oxidation of primary and secondary
alcohols can be brought about by a variety of
oxidizing agents. The product(s) differ depending
upon the type of the alcohol and oxidizing agent
used. Oxidation of 3° alcohol require severe
conditions and results in mixture of products.
• A primary alcohol first gives an aldehyde and then an
acid, both containing the same number of carbon
atoms as the original alcohol.
• Chromic acid (H2CrO4 prepared by dissolving
sodium dichromate in a mixture of sulfuric
acid and water) oxidizes 1° alcohol directly to
carboxylic acid.
 A better reagent for the oxidation of 1° alcohol to aldehyde
is pyridinium chlorochromate (PCC), a complex of CrO3 with
pyridine and CH2Cl2.

• Collins reagent is a complex of chromium trioxide

pyridine and is the original version of PCC.
• Secondary alcohols are easily oxidized to ketones
containing the same number of carbon atoms. The
chromic acid reagent is often best for laboratory
oxidation of secondary alcohols.

• PCC can also be used for the oxidation of 2° alcohol to

ketones.
• Tertiary alcohols are resistant to oxidation under
moderate conditions. Since, they have no H atoms on the
carbinol carbon atom, so oxidation must take place by
breaking C-C bond. These oxidations require severe
conditions and result in mixture of products.
 Limitations of chromium reagents:
• Chromium reagents are expensive and result in the formation of
environmentally hazardous oxidation byproducts so other
reagents are also recommended. (i) KMnO4 and HNO3 can be used
in place of chromium reagents. Since they are strong enough so
the reaction conditions have to be controlled, otherwise it would
lead to the cleavage of C-C bond. (ii) The Swern oxidation uses
DMSO and oxalyl chloride at low temperature, followed by a
hindered base. This is an alternative to KMNO4 and HNO3
reagents. This oxidises 1° alcohols to aldehyde and 2° alcohols to
ketones.
 Breath Analyser Test.
• The oxidation of alcohols to carboxylic acids have been recently
used as a breath analyzer test for detecting the level of ethanol in
the breath (and therefore blood) of suspected alcohol intoxicated
persons, especially drivers. The following reaction is involved,

• In the simplest version of this test, the culprit is asked to blow into
a tube containing K2Cr2O7 and H2SO4 supported on powdered silica
gel for a duration of 10-20 seconds. Any alcohol present in the
breath is oxidized to acetic acid, which results in change of colour
from orange to green in the tube. But, if the test is positive, it is
taken as justification by law or enforcement officers to administer a
more accurate blood or urine screening. The test works because of
the diffusion of blood alcohol through the lungs into the breath. If
the green develops beyond the half way mark, a blood alcohol
concentration greater than 0.08% is indicated, which is considered
as a criminal offense in many countries.
 Action of reduced copper
• Primary, secondary and tertiary alcohols give different
products when their vapours are passed over reduced copper
at 300°C. Two atoms of hydrogen are eliminated producing a
carbon-oxygen double bond. The process is known as catalytic
dehydrogenation.
• A primary alcohol is dehydrogenated to an aldehyde
• A secondary alcohol is dehydrogenated to a
ketone

• A tertiary alcohol is dehydrogenated to an

olefin
 Distinction between Primary,
Secondary and Tertiary Alcohols
• The three classes of alcohols may be
distinguished from one another by the
following methods:
• (i) Oxidation test. The mode of oxidation of
three types of alcohols is characteristic of each
type. Thus, the identification of the oxidation
products of a given alcohol indicates whether
it was primary, secondary or tertiary.
 Victor Meyer’s method
• The test is carried out as follows:
• The alcohol is first treated with phosphorusiodide (or
P+I2) and converted into the corresponding iodide.
• The alkyl iodide is then treated with silver nitrite and
converted into the corresponding nitrocompound.
• The nitroparaffin is finally treated with nitrous acid
(NaNO2+HCl) and then made alkaline. Primary alcohol
gives red colour, secondary alcohol gives blue colour
while the tertiary alcohol gives no colour.
Victor Meyer’s test