CLASS : XII

SUBJECT : CHEMISTRY
CHAPTER : 10
MODULE :3
PHASE : 1
TEACHER : ARYA T S
:
PREAPARATION OF HALOALKANES FROM
ALCOHOLS

CLASS: XII SUBJECT : CHEMISTRY CHAPTER: 10 MODULE :3 PHASE: 1 2

 USING HALOGEN ACIDS (HX)
Alcohols react with halogen acids to form haloalkanes. The
rate of the reaction differs for primary, secondary,
and tertiary alcohols.

CLASS: XII SUBJECT : CHEMISTRY CHAPTER: 10 MODULE :3 PHASE: 1 3

CLASS: XII SUBJECT : CHEMISTRY CHAPTER: 10 MODULE :3 PHASE: 1 4
 PREPARATION OF CHLOROALKANES
In this case, primary alcohol and
secondary alcohol react with HCl acid
gas to form halo alkane in the presence
of anhydrous ZnCl2, which act as
a catalyst in this reaction.

CLASS: XII SUBJECT : CHEMISTRY CHAPTER: 10 MODULE :3 PHASE: 1 5

CLASS: XII SUBJECT : CHEMISTRY CHAPTER: 10 MODULE :3 PHASE: 1 6
CLASS: XII SUBJECT : CHEMISTRY CHAPTER: 10 MODULE :3 PHASE: 1 7
 PREPARATION OF BROMO ALKANES
Bromoalkanes are prepared by
reacting hydrogen bromide (HBr)
with alcohols. HBr needed for this
purpose can be generated using
sodium or potassium bromide with
sulphuric acid (H2SO4).
CLASS: XII SUBJECT : CHEMISTRY CHAPTER: 10 MODULE :3 PHASE: 1 8
 PREPARATION OF IODOALKANES
Iodo oalkanes are prepared by reacting
hydrogen iodide (HI) with
alcohols.Hydroiodic acid (HI) needed for
the preparation of iodoalkanes can be
generated in situ by the action of 95%
phosphoric acid on potassium or soidum
iodides (KI or NaI).
CLASS: XII SUBJECT : CHEMISTRY CHAPTER: 10 MODULE :3 PHASE: 1 9
 Additionally, the reactivity of haloacids
follows the order HI > HBr > HCl > HF. HI is
easily and highly reacting haloacid among
all of them because the HI bond is weaker
than the other three. Therefore, it can be
broken easily in comparison to the other
halogen bonds to form H+ and I− ions.

CLASS: XII SUBJECT : CHEMISTRY CHAPTER: 10 MODULE :3 PHASE: 1 10

 USING PHOSPHROUS HALIDES(PX3/PX5)
This reaction helps in the formation of
Chloroalkanes, bromoalkanes, and iodoalkanes.
In this reaction Phosphrous halides interchange
the functional group of alcohols (–OH) with the
corresponding halides. The reaction is as
follows:
ROH + PCl5 → RCl + POCL3 + HCl

CLASS: XII SUBJECT : CHEMISTRY CHAPTER: 10 MODULE :3 PHASE: 1 11

 Alkyl bromide or alkyl iodide formation is
possible by the reaction of an alcohol with
phosphorus tribromide and triiodide. To
achieve the reaction, red phosphorus reacts
with bromine or iodine by in-situ
preparation (during the reaction) of
phosphorus tribromide and triiodide.

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CLASS: XII SUBJECT : CHEMISTRY CHAPTER: 10 MODULE :3 PHASE: 1 13
 USING THIONYL CHLORIDE
This reagent is the most preferred and suitable
in between the three reactions of alcohols. Alcohol
reacts with Thionyl chloride (SOCl2) to form alkyl
chlorides. However, the by-products formed in this
reaction are gaseous in nature. Therefore, the by-
products can easily escape into the atmosphere,
leaving the pure alkyl halide. This method helps in
the generation of pure alkyl halide.
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CLASS: XII SUBJECT : CHEMISTRY CHAPTER: 10 MODULE :3 PHASE: 1 15
 Question : Why is sulphuric acid not used
during the reaction of alcohols with KI?

Answer : Sulphuric acid (H2SO4) is an oxidising agent. It

oxidises HI produced during the reaction to I2.
2KI + H2SO4 → 2KHSO4 + 2HI
2HI + H2SO4 → H2O + I2 + SO2
To prepare an alkyl iodide, a non oxidising agent
such as H3PO4 is used instead of sulphuric acid.
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THANK YOU

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