Properties of Alkyl Halides.

(1) Physical properties

(i) CH 3 F, CH 3 Cl , CH 3 Br and C 2 H 5 Cl are gases at room temperature. The alkyl halides upto C18
are colourless liquids while higher members are colourless solids.
(ii) Alkyl halides are insoluble in water but soluble in organic solvents.
(iii) They burn on copper wire with green edged flame (Beilstein test for halogens).
(iv) Alkyl bromides and iodides are heavier than water. Alkyl chlorides and fluorides are lighter
than water.
(v) Alkyl iodides become violet or brown in colour on exposure as they decompose in light.
Light
2 RI   R  R  I2
(vi) For a given alkyl group, the boiling points of alkyl halides are in the order
RI  RBr  RCl  RF and for a given halogen the boiling points of alkyl halides increase with
the increase of the size of the alkyl group.
(vii) Alkyl halides are in general toxic compounds and bring unconsciousness when inhaled in
large amounts.

(2) Chemical properties: The alkyl halides are highly reactive, the order of reactivity is,
Iodide > Bromide > Chloride (Nature of the halogen atom)
Tertiary > Secondary > Primary (Type of the halogen atom)
Amongst the primary alkyl halide, the order of reactivity is : CH 3 X  C 2 H 5 X  C 3 H 7 X , etc.
The high reactivity of alkyl halides can be explained in terms of the nature of C  X bond which
is highly polarised covalent bond due to large difference in the electronegativities of carbon and
halogen atoms.

The halogen is far more electronegative than carbon and tends to pull the electrons away from
carbon, i.e., halogen acquires a small negative charge and carbon a small positive charge.
 
 C X

This polarity gives rise to two types of reactions,

(i) Nucleophilic substitution reactions(ii) Elimination reactions

(i) Nucleophilic substitution reactions: The C  site is susceptible to attack by nucleophiles (An
electron rich species). : Nu   R  X  Nu  R  X  :
 
X
R  X  R   R  Nu ( S N 1 Reaction)
Nu
Slow Fast
 Slow
 Nu  R  X  ( S N 2 Reaction)
Fast
Nu  R  X  Nu ..... R..... X 
Transition state
Examples of SN reactions,
(a) Hydrolysis: Alkyl halides are hydrolyzed to corresponding alcohols by moist silver oxide
(AgOH ) or by boiling with aqueous alkali solution (NaOH or KOH). The attacking nucleophile is
OH  .
RX  AgOH  ROH  AgX ; RX  KOH (aq )  ROH  KX
Alkyl halide Alcohol

Note: With the help of this reaction an alkene can be converted into alcohol. Alkene is first reacted with
HBr to form alkyl bromide and then hydrolysis is done.

HBr AgOH
CH 2  CH 2  CH 3 CH 2 Br   CH 3 CH 2 OH
Ethylene Ethyl brom ide Ethyl alcohol

(b) Reaction with alkoxides or dry silver oxide: Ethers are formed by heating alkyl halides with
sodium or potassium alkoxides or dry silver oxide. The attacking nucleophile is OR 
(Williamson's synthesis).

 ROR '  NaX ; 2 RX  Ag 2 O  R  O  R  2 AgX

Heat
RX  NaOR ' 
Unsym. ether Sym. ether

(c) Reaction with sodium or potassium hydrogen sulphide: Alkyl halides form thioalcohols with
aqueous alcoholic sodium hydrogen sulphide or potassium hydrogen sulphide. The nucleophile
is SH  .

RX  NaSH  RSH  NaX

Sodium hydrogen Thioalcoho l
sulphide or Alkanethio l
or Alkyl mercaptan

(d) Reaction with alcoholic potassium cyanide and silver cyanide: Alkyl cyanides are formed as
the main product when alkyl halides are heated with alcoholic potassium cyanide. The
nucleophile is CN  .

Alcohol
RX  KCN    RCN  KX
Alkylcyanide or
Alkane nitrile

(e) Reaction with potassium nitrite or silver nitrite: On heating an alkyl halide with potassium
nitrite in an aqueous ethanolic solution, alkyl nitrite is obtained as the main product though
some nitro alkane is also formed. The nucleophile is NO 2 .
RX  K  O  N  O  R  O  N  O  KX
Alkyl nitrite

However, when alkyl halide is heated with silver nitrite in an aqueous ethanolic solution, nitro-
alkane is the main product. Some alkyl nitrite is also obtained.

O
RX  AgNO 2  R  N  AgX
O
Nitro -alkane

(f) Reaction with ammonia: On heating with aqueous or alcoholic solution of ammonia in a
sealed tube at 100°C, alkyl halides yield a mixture of amines and quaternary ammonium salt. The
nucleophile is NH 2 in the first reaction.

C 2 H 5 Br  H  NH 2  C 2 H 5 NH 2  HBr ; C 2 H 5 NH 2  BrC 2 H 5  C 2 H 5 NHC 2 H 5  HBr

Ethylamine (p.) Diethylami ne(sec.)

 
(C 2 H 5 )2 NH  BrC 2 H 5  (C 2 H 5 )3 N  HBr ; (C 2 H 5 )3 N  BrC 2 H 5  (C 2 H 5 ) 4 NBr
Triethylam ine(tert.) Tetraethyl ammonium
bromide(Qu aternary)

(g) Reaction with silver salts of fatty acids: On heating with silver salts of fatty acids in alcoholic
solution, alkyl halides yield esters. The nucleophile is R' COO  .

R ' COOAg  XR  R ' COOR  AgX

Ester

(h) Reaction with sodium acetylide: Alkyl halides react with sodium acetylide to form higher
alkynes. The nucleophile is CH  C  .
RX  NaC  CH  R  C  CH  NaX
Sodium acetylide Alkyne

(i) Reaction with sodium or potassium sulphide: Alkyl halides react with sodium or potassium
sulphide in alcoholic solution to form thioethers.
2 RX  Na 2 S  R  S  R  2 NaX
Thioether

Thioethers can also be obtained by heating alkyl halides with alcoholic solution of sodium
mecaptide (NaSR ' ) , i.e., metallic derivative of a thioalcohol.
RX  NaSR '  R  S  R ' NaX

C 2 H 5 Br  NaSCH 3  C 2 H 5  S  CH 3  NaBr

Ethyl methyl thi oether

(j) Reaction with halides: Alkyl chlorides react with sodium bromide or sodium iodide to form
alkyl bromide or alkyl iodide. Similarly, alkyl bromides react with sodium iodide in acetone or
methanol to form alkyl iodides.
NaI
RCl  NaBr  RBr  RI
Alkyl chloride Alkyl brom ide Alkyl iodide
(ii) Elimination reactions: The positive charge on carbon is propagated to the neighboring
carbon atoms by inductive effect. When approached by a strongest base (B), it tends to lose a
proton usually from the -carbon atom. Such reactions are termed elimination reactions. They
are also E1 and E2 reactions.
B
..
H H H H H
| | | | |
E1reaction: R  C  C  H 
Slow

Fast
 R  C  C  H  R  C  C  H  B  H
| | X |  |
H X H H
B : H H BH H H
| | | | |
Slow
 R  C  C  H  B  H  X 
E2Reaction: R  C  C  H  R  C  C  H  Fast
| | | | |
H X H X H
Transiton state

As the above reactions involve leaving of X  , the reactivity of alkyl halides (Same alkyl group,
different halogens) should be limited with C  X bond strength.
Type of bond C  I C  Br C  Cl
Bond strength (kcal/mol) 45.5 54 66.5
Bond strength increases

The breaking of the bond becomes more and more difficult and thus, the reactivity decrease.
The order of reactivity (Tertiary > Secondary > Primary) is due to +I effect of the alkyl groups
which increases the polarity of C  X bond.
R R
R C X, CH X, R CH 2 X
R R

The primary alkyl halides undergo reactions either by S N 2 or E2 mechanisms which involve the
formation of transition state. The bulky groups cause steric hinderance in the formation of
transition state. Therefore, higher homologues are less reactive than lower homologues.
CH 3 X  C 2 H 5 X  C 3 H 7 X , etc.

Example of elimination reaction

(a) Dehydrohalogenation: When alkyl halides are boiled with alcoholic potassium hydroxide,
alkenes are formed.
Cn H 2 n 1 X  KOH  Cn H 2 n  KX  H 2 O
(Alcoholic ) Alkene

In this reactions, ether is a by-product as potassium ethoxide is always present in small quantity.
C 2 H 5 Br  KOC 2 H 5  C 2 H 5  O  C 2 H 5  KBr

(b) Action of heat: Alkyl halides when heated above 300°C, tend to lose a molecule of hydrogen
halide forming alkenes.
300  C 300  C
RCH 2 CH 2 X   RCH  CH 2  HX ; C 2 H 5 Br   CH 2  CH 2  HBr
Alkene Ethene

The decomposition follows the following order,

Iodide > Bromide > Chloride (When same alkyl group is present) and
Tertiary > Secondary > Primary (When same halogen is present).

(iii) Miscellaneous reactions

(a) Reduction: Alkanes are formed when alkyl halides are reduced with nascent hydrogen
obtained by Zn / HCl or sodium and alcohol or Zn/Cu couple or LiAlH 4 .
RX  2 H  R  H  HX
Reaction is used for the preparation of pure alkanes

(b) Wurtz reaction: An ether solution of an alkyl halide (Preferably bromide or iodide) gives an
alkane when heated with metallic sodium.
2 RX  2 Na  R  R  2 NaX

(c) Reaction with magnesium: Alkyl halides form Grignard reagent when treated with dry
magnesium powder in dry ether.
Dry ether
Rx  Mg   R  Mg  X
(Powder ) Grignard reagent

Grignard reagents are used for making a very large number of organic compounds.

(d) Reaction with other metals: Organometallic compounds are formed.

 When heated with zinc powder in ether, alkyl halides form dialkyl zinc compounds. These are
called Frankland reagents.
Ether
2C 2 H 5 Br  2 Zn  (C 2 H 5 )2 Zn  ZnBr2
Heat

 When heated with lead-sodium alloy, ethyl bromide gives tetra ethyl lead which is used an
antiknock compound in petrol.
4 C 2 H 5 Br  4 Pb( Na ) (C 2 H 5 ) 4 Pb  4 NaBr  3 Pb
 Alkyl halides form dialkyl mercury compounds when treated with sodium amalgam.
2C 2 H 5 Br  Na  Hg  (C 2 H 5 )2 Hg  NaBr
Diethyl mercury
 Reaction with lithium: Alkyl halides react with lithium in dry ether to form alkyl lithiums.
 R  Li  LiX ; C 2 H 5 Br  2 Li  C 2 H 5  Li  LiBr
Ether
RX  2 Li 
Ethyl bromide

Alkyl lithiums are similar in properties with Grignard reagents. These are reactive reagents also.
(e) Friedel-Craft's reaction: Alkyl halides react with benzene in presence of anhydrous aluminium
halides to form a homologue of benzene.
C 6 H 6  RCl   C6 H 5 R  HCl ; C 6 H 6  C 2 H 5 Br 
AlCl 3 AlBr 3
 C 6 H 5 C 2 H 5  HBr
Benzene Alkyl benzene

(f) Substitution (Halogenation): Alkyl halides undergo further halogenation in presence of

sunlight, heat energy or peroxide.
Br2 Br2
C 2 H 5 Br  C 2 H 4 Br2  C 2 H 3 Br3 .....
hv hv