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The stability of the polyhalides.


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Nunn, Ernest Keith 1965 , 'The stability of the polyhalides.', PhD thesis, University of Tasmania.

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Molecular halogens or inter halogens compounds have, for
many years, been known to be capable of associating with halide
ions either in the solid state or in solution to form stable univalent
species. The classic example of this is the enhanced solubility
of iodine in an aqueous potassium iodide solution to form the
triiodide anion. This was crysjallired by Johnson ( 1) in 1877 and
was the first inorganic triiodide identified. The earliest reference
to a triiodide was however the strychnine triiodide of Pelletier and
Caventore (2) in 1819. Filhol ( 3) made the first reference to an
inorganic poly halide in 18 39. This was the mixed poly halide KIC14.
Lowig and Roozeboom also investigated polyhalides during the
nineteenth century ( 4, 5). It is interesting that whilst Roozeboom
was one of the leaders in the use of ternary phase rule investigation,
his work on ammonium tribromide was not pursued in this manner.
At the close of the nineteenth century Wells, Penfield and
Wheeler (6-8) began pioneering investigations into the polyhalide
field. Much of the work was of a qualitative nature, dealing with
the preparation of a particular compound or studying specific physical
properties. This work was followed up by Abegg and Hamburger,
Foote and Chalker, Parsons and Whittemore and Kremann and
Schoulz over the period 1908 - 1912. They were mainly interested
in the controversy over the formula of the potassium polyiodide (9-121_.

Most of the preparative methods at this stage involved crystallisation
from an aqueous solution. It was not realized that solvation could occur
and although analysis often suggested this, conflicting reports were
given based on an anhydrous polyhalide. It was not until 1931 when
Grace (13) recognized the possibility of solvation that many of these
earlier discrepancies were resolved.
In the period 1910 - 1930 interest in the polyhalides lapsed
to some extent apart from a review of structural considerations by
Clark (14) in 1923, the results of which however were inconclusive.
The early 1930's saw a revival of interest in both the homogeneous and
mixed polyhalides. In England, Grace, Cheesman, Duncan, Harris
and coworkers and in America Briggs and coworkers began studying
the former type of polyhalide by using phase rule techniques, in
particular three component systems, which characterized solvates.
At this time Cremer and Duncan (15 - 16) reviewed the polyhalide work
up to this stage and re examined the preparative methods, properties
and reactions of this type of compound. Their main interest was in
the mixed poly halide of the type MIBr2, but they did. deal with._CsBr3
and CsI3.

Item Type: Thesis - PhD
Authors/Creators:Nunn, Ernest Keith
Keywords: Halogens
Copyright Holders: The Author
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Copyright 1964 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
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Thesis (Ph.D.) - University of Tasmania, 1965. Includes bibliography

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