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The kinetics and mechanisms of chlorohydrin formation.

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Craw, Donald Alan (1953) The kinetics and mechanisms of chlorohydrin formation. PhD thesis, University of Tasmania.

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Abstract

The reaction between a halogen or hydrogen halide and an
olefinic substance is one of the fundamental reactions of organic
chemistry. It is not surprising, therefore, that considerable
attention has been given to the kinetics of the electrophilic and
nucleophilic addition of halogens or hydrogen halides to olefins
under the influence of both thermal and photochemical activation
(1-6). The factors most likely to influence the rate of the
reaction viz., the nature of the olefin and its substituent groups,
the particular halogen or hydrogen halide employed, the temperature,
the influence of catalysts and the powerful solvent effects have
all been investigated in detail with the result that this seemingly
straightforward class of reactions has been shown to possess
considerable complexity.
On the other hand, the kinetics of the reactions of
hypohalous acids, and in particular hypochlorous acid, with olefins
has received rather scant attention. In some ways this is
remarkable in view of the fact that the formation of chlorohydrins
by this reaction has been known for at least seventy years when
Erlenmeyer and Muller (7) and Melikov (8.9) investigated the
addition of hypochlorous acid to the isomeric crotonic acids.
Perhaps the most important contribution to our knowledge of
reactions of this kind is due to Bloomfield and co-workers (10,11)
who, while investigating the addition of olefinic acids and esters
towards hypochlorous acid and ethyl hypochlorite, isolated, identified and estimated the relative amounts of the isomeric chlorohydrins formed in this reaction.
At about the same time, Shilov and collaborators began
an investigation of the kinetics of the reactions involving the
addition of hypochlorous acid to olefinic compounds and during
the past eighteen years, a series of papers from this source
have been published Ca- 30. It is unfortunate that these
investigators should have studied the catalytic effect of added
chloride ion, usually from hydrochloric acid, in the majority of
their reaction systems as the intervention of molecular chlorine
formed in this way would seriously interfere with the true nature
of hypochlorous acid additions. The results of early work by
Shilov et al. (14) on the addition to ethene, indicated that the
addition of chlorine to the double bond was about 100,000 times
greater than that of hypochlorous acid, yet it was only in later
papers (10.- 22) that this complicating factor seemed to be fully
appreciated. However, during their early work they concluded
that the addition reaction was a complex one and could not be
described by a simple bimolecular or termolecular process.
It seemed, therefore, that a detailed investigation of the kinetics
of chlorohydrin formation was desirable and would prove a profitable
and useful subject for research.

Item Type: Thesis (PhD)
Keywords: Chlorohydrin, Halogens
Copyright Holders: The Author
Copyright Information:

Copyright 1953 the Author - The University is continuing to endeavour to trace the copyright
owner(s) and in the meantime this item has been reproduced here in good faith. We
would be pleased to hear from the copyright owner(s).

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Thesis (Ph.D)--University of Tasmania, 1953

Date Deposited: 08 Dec 2014 23:58
Last Modified: 11 Mar 2016 05:56
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