ORIENT COLLEGES TALAGANG

BS Zoology Semester II
Chemistry-II
On-Screen Lectures
Unsaturated Hydrocarbons
Lecture # 3
 Chemical Reactions of Alkenes

Heat of Hydrogenation and Stability of Alkenes

Heat of hydrogenation can be used to determine relative
stability of alkenes. the more heat is released, the less

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stable is the alkene
Consider the following reactions

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 Chemical Reactions of Alkenes

Heat of Hydrogenation and Stability of Alkenes

Now compare the structure of three alkenes with ethene H2C=CH2 the simplest
alkene

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 In 3-methyl-1-butene, one of the four H-atoms of ethene has been replaced with
iso-propyl group i.e. it is monosubstituted. Also, it releases largest heat
 In 2-methyl-1-butene, two of the four H-atoms of ethene have been replaced with
methyl and an ethyl i.e. it is disubstituted
 In 2-methyl-2-butene, three of the four H-atoms of ethene have been replaced
with three methyl groups i.e., it is trisubstituted. Also, it releases smallest heat

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 Chemical Reactions of Alkenes

Heat of Hydrogenation and Stability of Alkenes

Now compare the structure of three alkenes with ethene H2C=CH2 the simplest
alkene

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Therefore, we can conclude that the more alkyl groups are bonded to double bonded
carbons, the lesser the heat is released and the more stable the alkene is
Thus, order of stability of alkenes is

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 Chemical Reactions of Alkenes

Halogenation
Addition of halogen molecule across double bond is
called halogenation of alkenes

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 Chemical Reactions of Alkenes

Halogenation (in non-polar solvents)

When alkenes are treated with halogens (chlorine or bromine) in
non-polar solvent, two halogen atoms add to two double bonded

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carbons and a vicinal dihalide (compound having two halogen
atoms on two adjacent C-atoms) is formed. Reddish brown of
bromine is discharged so it is used to check the presence of double/
triple bond

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 Chemical Reactions of Alkenes

Halogenation (in non-polar solvents)

Mechanism

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 Chemical Reactions of Alkenes

Halogenation (in non-polar solvents) at high

temperature
When halogenation is carried out at high temperature, substitution

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instead of addition takes place. Substitution takes place at allylic
carbon (carbon atom next to double bond) and an allylic halide is
formed

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 Chemical Reactions of Alkenes
Addition of Hypohalous Acid
(Halogenation in the presence of water)
When alkenes are treated with halogens in water,

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addition of hypohalous acid (HOX) occurs; OH,
group and halogen atom add to two double
bonded carbons and halohydrins are formed
where X is halogen

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 Chemical Reactions of Alkenes
Addition of Hypohalous acid HOX
(Halogenation in water) Mechanism

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 Chemical Reactions of Alkenes
Halogenation in the presence of alcohols
Mechanism

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 Chemical Reactions of Alkenes

Addition of halogen acid HX (Hydrohalogenation)

When alkenes are treated with halogen acids (such as
HCl, HBr etc.), hydrogen and halogen atom add to two

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double bonded carbons and alkyl halides are formed

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 Chemical Reactions of Alkenes
Addition of halogen acid HX (Hydrohalogenation)
If the alkenes is unsymmetrical, additions occurs
according to Morkonikov’s rule which states that

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“In case of addition of unsymmetrical reagent to an
unsymmetrical alkenes/ alkyne, positive part of reagent
adds to C-atom constituting double bond which has
greater number of H-atoms”

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 Chemical Reactions of Alkenes
Addition of halogen acid HX (Hydrohalogenation)
More examples of Morkonikov’s rule

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 Chemical Reactions of Alkenes
Addition of halogen acid HX (Hydrohalogenation)
Explanation of Morkonikov’s rule
Addition of halogen acid to an alkene involves formation of carbocation. Every
carbocation has its own stability. Thus, when more than one carbocation can be

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formed that carbocation will be actually formed (and will lead to product) which is
more stable. For example, consider

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 Chemical Reactions of Alkenes
Explanation of Morkonikov’s rule
Thus, actual product will be formed when H+ adds to C-2 and Cl- adds to C-3

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 Chemical Reactions of Alkenes
Addition of halogen acid HX (Hydrohalogenation)
Anti-Morkonikov’s rule
Addition of HF, HCl or HI always takes place according

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to Morkonikov’s rule. But the addition of HBr depends
on presence or absence of peroxides such as benzoyl
peroxide. If there is no peroxide, addition takes place
according to Morkonikov’s rule but in absence of
peroxide, it takes place opposite to Morkonikov’s rule
called Anti-Morkonikov’s rule or peroxide effect

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 Chemical Reactions of Alkenes
Anti-Morkonikov’s rule

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 Chemical Reactions of Alkenes
Anti-Morkonikov’s rule: Mechanism

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