Linking solution and solid state studies of bismuth and cadmium complexes

Show simple item record Vieira, Vanessa Lourenco 2014-08-01T08:47:32Z 2014-08-01T08:47:32Z 2014-08-01
dc.description.abstract In this project the link between species in solution and the solid state was considered. This is relevant due to the many applications in life where there is this interchange between solid and solution state, for example drug design, environmental metal speciation and the manufacture of materials that are in contact with solution (such as outdoor surface coatings, containers and so on). Complexation of two metal ions, namely cadmium(II) and bismuth(III), was studied. With bismuth showing so much promise in medicinal applications it was pertinent to investigate this interchange since the intake of medication is generally in the solid form which then converts to solution species as it dissolves in the body where it becomes active. For cadmium it is mainly the environmental concerns which we are faced with that call for the examination of speciation of complexes in solution, as well as their disposition upon precipitation or crystallization. A correlation was found between solution species and the complex that was isolated in the crystalline form with regards to pH for a number of metal-ligand species. We show how the results from solution experiments (achieved using direct current polarography) and those of crystalline complexes can complement each other when using species distribution diagrams as the intermediary. The distribution of species can be varied by changing the concentration and ligand-to-metal ratio at which the species distribution diagram is plotted. It is this characteristic which allows the solution and crystalline complexes – which are achieved using differing experimental conditions – to be correlated. The speciation diagram for a metal-ligand system, calculated using formation constants derived from solutions studies, was used in most instances to target specific species for their growth in the solid state. In some cases the solid state structure was used to confirm a suspected solution species, and in others the result was used to identify minor solution species which cannot be detected by the techniques used in determining formation constants. Further, we show that doing solution experiments at a range of temperatures can also aid in elucidating these minor species. The growth of crystalline species at low pH was important for this work because the pH titrations used for solution experiments were conducted from below pH 2 where the diffusion junction potential is large and changing. An in-situ witness ion was incorporated into the experiment to monitor the shifts due to the diffusion junction potential so that they could be compensated for. Additionally, for bismuth-ligand systems, hydrolysis and complexation with nitrates occurs in this same pH region. The formation constants and the species identified below pH 2 therefore do carry some uncertainty, so obtaining crystalline complexes of these species provides further confidence in their prediction in solution. en_ZA
dc.language.iso en en_ZA
dc.subject.lcsh Solutions, Solid.
dc.subject.lcsh Metal ions.
dc.subject.lcsh Bismuth.
dc.subject.lcsh Cadmium.
dc.title Linking solution and solid state studies of bismuth and cadmium complexes en_ZA
dc.type Thesis en_ZA

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