Polyhaloalkanes
The haloalkanes containing more than two halogen atoms are known as polyhalkanes.
Example: CHCl3, CCl4 etc.
Chloroform
Chloroform is an example of polyhaloalkane. It's molecular formula is CHCl3 and the IUPAC
name is Trichloromethane.
Cl
I
H — C — Cl
I
Cl
(Chloroform)
Preparation of trichloromethane [chloroform]
Chloroform is prepared by heating bleaching powder paste with ethyl alcohol or acetone.
This method is employed for the manufacture of chloroform laboratory as well as in
industries.
The bleaching powder used in the process acts as source of chlorine and calcium
hydroxide.
CaOCl2 + H2O Ca(OH)2 + Cl2
Preparation with the help of ethyl alcohol
The reaction completes in three different steps.
Step I: Cl2 evolved from beaching powder paste oxidises ethyl alcohol to acetaldehyde.
CH3 CH2 OH + Cl2 CH3CHO + 2HCl
acetaldehyde
Step II: Acetaldehyde is then chlorinated to trichloro acetaldehyde (Chloral).
O
II
CH3CHO + 3Cl2 CCl3 — C — H + 3 HCl
Chloral
Step III: Finally, chloral is hydrolysed in presence of Ca(OH)2 and evolved chloroform.
O
II
2 CCl3 — C — H + Ca(OH)2 2 CHCl3 + (HCOO)2 Ca
Chloroform Calcium formate
Preparation with the help of acetone
Reaction of acetone with bleaching powder paste completes in the following two steps;
Step I: Cl2 evolved from bleaching powder paste acts as a chlorinating agent and converts
acetone to trichloroacetone.
O O
II II
CH3 — C — CH3 + 3 Cl2 CCl3 — C — CH3 + 3 HCl
Trichloroacetone
264 | P a g e © J a y P r a k a s h P a u d e l // Department of Chemistry
Step II: Trichloroacetone is hydrolysed in presence of Ca(OH)2 and evolves chloroform.
O
II
2 CCl3 — C — CH3 + Ca(OH)2 2 CHCl3 + (CH3COO)2 Ca
Chloroform Calcium acetate
Chemical Properties of trichlromethane
1. Oxidation : [Action with air]
Chloroform undergoes show oxidation by oxygen of air, in presence of sunlight to form
highly poisonous phosgene gas.
O
Sun light II
CHCl3 + O2 (air) Cl — C — Cl + HCl
Carbonyl chlorine
(Phosgen gas)
Therefore, chloroform is stored in dark brown bottles and filled upto the brim to avoid the
formation of poisonous phosgene gas.
Also, 1% ethyl alcohol is added to the bottles of the chloroform. Ethyl alcohol converts
poisonous phosgene gas if formed to non-poisonous diethyl carbonate.
2. Action with aqueous alkali
When chloroform is heated with aqueous alkali (aq. NaOH), sodium formate is obtained
which on acidification gives Formic acid.
3. Nitration
When chloroform is heated with conc. HNO3, chloropicrin (nitrochloroform) is obtained.
Chloropicrin was manufactured for use as poisonous gas in World War I. It is also used as
an insecticide.
265 | P a g e © J a y P r a k a s h P a u d e l // Department of Chemistry
4. Action with propanone (acetone)
When chloroform is treated with acetone in presence of aqueous alkali, chloretone is
obtained.
It is used as hypnotic drug (sleep inducing drug) and as a weak local anesthetic.
5. Action with silver powder
When chloroform is heated with silver powder, acetylene gas is obtained:
6. Reduction reaction
On reduction with Zn / HCl (acidic medium), chloroform gives methylene chloride while
on reduction with Zn/H2O (neutral medium), chloroform gives methane.
Uses of Chloroform
1. It can be used as an anaesthetic agent during surgical process.
2. It is used as a solvent for fats, waxes, rubbers, iodine, medicines etc.
3. It is used in the preparation of chloropicrin, chloretone, Salicyaldehyde etc.
266 | P a g e © J a y P r a k a s h P a u d e l // Department of Chemistry
