Purification:

Chloroform thus prepared in the laboratory

is not in pure form. To make it free from
impurities, first of all it is separated from
the aqueous layer using a separating
funnel and then washed thoroughly with
dilute solution of caustic soda and then
with water. Finally it is dried over
anhydrous calcium chloride and redistilled
in between 60ᵒC -65ᵒC.
 Aqueous layer
Chloroform
 Oxidation
In the presence off sunlight chloroform oxidizes in
air to give poisonous carbonyl chloride gas commonly
known as phosgene gas.
CHClȝ+ Oշ hϑ COClշ + HCl
chloroform Phosgene gas

Chloroform produces toxic carbonyl chloride commonly called as

phosgene gas when exposed to air in the presence of sunlight. So,
chloroform to be used for anaesthetic purpose is stored with the
following precautions.

It is always kept in i) dark coloured bottles (so as to prevent

the entry of sunlight) and is ii) filled upto the brim with well
stoppered lid (to exclude air inside the bottle) so as to
prevent the formation of toxic phosgene gas.
 Besides iii) 1% ethanol is added at the time of
bottling so as to convert phosgene gas if formed any
into non poisonous diethyl carbonate.

Phosgene gas
1% ethanol
 Carbylamine reaction
a. When chloroform is slowly warmed with primary amines in the
presence of an alcoholic solution of KOH.
b. on a water bath
c. produces foul smelling compounds known as alkyl or aryl
isocyanide.
d. Commonly called as carbylamines
e. Distinctive test for both chloroform and primary amines
f. Known as isocyanide test or carbylamine reaction.

Methyl carbylamine
OR Methyl isocyanide
alcoholic

and chloroform.

N
Ethyl carbylamine
 Reimer –Tiemann reaction
• When a mixture of phenol and chloroform is refluxed
in the presence of an aqueous solution of caustic alkali
at a constant temperature of 70ᵒC followed by acid
hydrolysis produces ortho- hydroxybenzaldehyde
commonly known as salicyldehyde.
• In this reaction a small amount of para isomer is also
obtained. Instead of chloroform if carbon tetrachloride
is used then the same reaction produces o-hydroxy
benzoic acid commonly known as salicylic acid
together with a small amount of p- isomer.
 O- hydroxybenzaldehyde
(salicyldehyde)

p- hydroxybenzaldehyde
 Hydrolysis:
Chloroform on warming with a hot and conc. solution of
caustic alkali hydrolyzes to form formate salt of caustic
alkali, which when acidified with dilute acid results formic acid.
+NaOH

-NaCl
 Nitration:
• The hydrogen of the chloroform is replaced by nitro
group when it is treated with concentrated nitric
acid. The product formed is chloropicrin or
trichloronitromethane or nitrochloroform. It is a
liquid, poisonous and used as an insecticide and a
war gas.

•
CHClȝ + HNOȝ = NOշCClȝ + HշO
chloroform Conc. Nitrochloroform
Or chloropicrin