School of Chemistry - Theses

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    Heavy metal ion activation of zinc sulphide
    Ralston, John ( 1978)
    This thesis deals with the activation of zinc sulphide by the heavy metal ions Cu ll, Cd 11 and Pb II over a wide range of pH, metal ion concentration, zinc sulphide concentration and incident light conditions. At acid to neutral pH values the uptake of a heavy metal ion has been observed to take place in two stages: a fast, initial step followed by a second, slower step. Kinetic data have shown that heavy metal ion uptake generally follows a logarithmic dependence on time. At alkaline pH values heavy metal ion uptake is complicated by hydrolysis effects. A sensitive mass spectrometric technique has been developed and is capable of quantitatively detecting down to 1% of a nominal monolayer of elemental sulphur on a mineral of surface area 0.7 m2 g-1. Elemental sulphur was detected on sphalerite surfaces activated by Cu11 and Pb II up to pH 6.6, both in the dark and under UV irradiation. Elemental sulphur was only detected on Cd II activated and unactivated zinc sulphide surfaces under UV irradiation. A mechanism for the activation of zinc sulphide is advanced at acid, neutral and alkaline pH values. At acid to neutral pH values, metal ion uptake occurs by an exchange reaction This is coupled with a surface redox process, which is linked with the semiconductor properties of zinc sulphide. As a result of this surface redox process, elemental sulphur may form on the zinc sulphide surface, depending on the type of metal ion involved and on the incident light conditions. It is proposed that the rate determining step in the exchange reaction is the transfer of an adsorbed metal ion from a surface, adsorbed site to a lattice site. This leads to a logarithmic dependence of metal ion uptake on time, as observed experimentally. At alkaline pH values, the mechanism at acid to neutral pH values is complicated by metal ion hydrolysis, adsorption and precipitation effects. An overall mechanism is proposed which accounts for the observed behaviour.
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    Orientated water under insoluble monolayers
    Ralston, John ( 1970)
    The fact that oil could calm a rough sea was recorded by Pliny the Elder and by Plutarch. More quantitative information was provided by Benjamin Franklin in 1774 when he reported to the Royal Society that a teaspoonful of oil made a half-acre surface of pond ".... as smooth as a looking glass" (24). Subsequent experimentation showed that a similar effect could be observed when small amounts of insoluble soaps or "fatty" organic compounds were spread on water surfaces. Willard Gibbs published his thermodynamic treatment of surface tension and adsorption in 1878, providing the necessary theoretical background for explaining experimental results (66). In 1891 Fraulein Pockels developed the technique of manipulating these insoluble films between "barriers" extending across the entire width of a trough of water, filled so that it almost overflowed. This permitted quantitative information about surface tension and surface area to be obtained and led Rayleigh to propose, in 1899, that surface films were only one molecule thick. The basis for contemporary understanding of the behaviour of molecules in insoluble monolayers was provided in 1817 by Irving Langmuir (97), who devised the surface balance which still bears his name and whose results verified the theories of molecular orientation at surfaces. (From introduction)