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Michelle Roy

Order of Reactivity of Halogens in Electrophilic Addition

David Shaffer  Follow

The rate-determining step of halogenation of alkenes is the formation of cyclic intermediate.

The cyclohalonium intermediate of bromine will be more stable than that of chlorine owing to its lower electronegativity.

The following paragraph is taken from Peter Sykes [$1$, p.$181$-$182$]:

It is not normally possible to add fluorine directly to alkenes as the reaction is so exothermic that bond fission occurs. Many alkenes will not add iodine directly either and when the reaction does occur it is usually readily reversible.

As is clear $\ce{I2}$ will be more reactive than $\ce{F2}$.

Hence, the correct answer is D.

References:

  1. Peter Sykes; A Guidebook to Mechanism in Organic Chemistry 6th ed.; 2003 ISBN-10:8177584332

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Charles MacKay  Follow

Ans is (D) Since F+ is not possible andin case. of I2 it will be reversibleso In I2 &F2 the order is I2>F2So ans is (D)

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John Kenny  Follow
So how does Fluorine react ?More
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Bruce R. Miller  Follow

ans is d Normally not possible to F2 because it is highly exothermic with I2 reversible reaction takes placedue to more E.N of Cl2 compare to Br2. It does not give e pair to carbocation

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António José Rodrigues Rebelo  Follow

I would say (B).

The mechanism involves the breaking of the Halogen–Halogen bond. The strength of this bond decreases down the group because atomic radius increases. The attraction of the halogen nuclei on the electrons in the covalent bond decreases as the valence electrons are further away from the nucleus.

Therefore, the I–I bond is weakest while F–F is strongest. Hence, I2 is most reactive and F2 is least.

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