The experimental work described in this thesis is aimed primarily towards elucidation of the speciation of zinc-cyanide systems at elevated pH. In this study the formation and stability of H+-eN-, binary Zn2+-eN- and ternary Zn2+-CN--QH- complexes were studied by glass electrode potentiometry in aqueous solutions at 25.0°0 and in a medium of ionic strength of 0.1 mol dm-3. The solution pH was varied to cover the range 4 to 11. The study was undertaken with a view to establishing whether and under what conditions soluble binary zinc-cyanide complexes and ternary zinc-cyanide-hydroxide complexes form, and to determine formation constants for any such species that are found. This information would be useful in defining more precisely the speciation of solutions containing zinc and cyanide ions at elevated pH values. A titration method was used, in which hydrogen ion concentration was monitored by means of a glass indicating electrode. The cell was calibrated to allow measurements of hydrogen ion concentration rather than hydrogen ion activity. Owing to precipitation difficulties, the reagents were used at sub-millimolar concentration levels. The potentiometric data was interpreted with the aid of various formation function plots together with the use of various computer programs, such as HALTAFALL and ESTA. The results show that the ternary complex Zn(ON)3(OH)2- is formed in significant amounts in solutions of pH > 8.5. Some evidence was also obtained for the existence of the five coordinated species Zn(CN)3(OH)~- and Zn(CN)~- in these solutions, but existence of the latter two species cannot yet be regarded as firmly established. No polynuclear complexes were detected at the sub-millimolar concentrations used. Formation constants are reported for H+-eN- and both binary Zn2+-eN- and ternary Zn2+-eN--QH- species. / Thesis (M.Sc.)-University of Natal, Durban, 1990.

Dissertation (PhD)--University of Stellenbosch, 2000. / ENGLISH ABSTRACT: Silver/Zinc batteries are extensively used for applications where a power source with a high energy density is needed. A reactor was developed to manufacture the zinc electrodes for these batteries. The parameters for the control of this reactor were identified. The interaction and relationships between the set of parameters were established and quantified. The novel design of the reactor includes features such as continuous replenishment of the constituting chemicals, parallel flow of the plating fluid, inert anodes and a serial electrical layout. The controlling parameters consist of both chemical and physical parameters. They are - zincate concentration, hydroxyl concentration, density, temperature, flow rate of the plating fluid, and current density. The unique solubility characteristics of zinc oxide in potassium hydroxide lend themselves to a novel approach for the determination of the zincate concentration in· the plating solution. A set of conditions for the manufacturing of electrodes, with the required characteristics, was identified. The requirements are densely packed zinc dendrite morphology with high porosity and mechanical stability. The designed reactor complies with the industries safety requirements. The batteries were successfully applied in their operational domain (torpedoes) after this extensive research project was completed. / AFRIKAANSE OPSOMMING: Silwer/Sink batterye word intensief aangewend in gebruike waar 'n kragbron met hoë energie digtheid benodig word. 'n Reaktor is ontwikkel wat die sink elektrodes van die tipes batterye vervaardig. Die veranderlikes vir die beheer van die reaktor is bepaal. Die interaksie en verwantskap tussen die stel veranderlikes is verkry en gekwantifiseer. Die unieke ontwerp van die reaktor het die volgende karakteristieke, nl. aaneenlopende vervanging van die chemikalië verbruik, parallelle vloei van die plateringsvloeistof, inerte anodes en elektriese uitleg in serie. Die chemiese en fisiese veranderlikes is beide beherende veranderlikes. Hierdie fisiese en chemiese veranderlikes wat die proses beheer is die sinkaat konsentrasie, hidroksiel konsentrasie, digtheid, temperatuur, vloeitempo van die plateringsvloeistof en die stroomdigtheid. Die unieke oplossingskarakteristieke van sinkoksied in kalsium· hidroksied leen hom tot die unieke proses om die sinkaat konsentrasie in die plateringsvloeistof te bepaal. 'n Steloperasionele kondisies vir die vervaardiging van die elektrodes met die spesifieke spesifikasies soos verlang, is geïdentifiseer. Hierdie kondisies is die diggepakte sinkdendriet morfologie met 'n hoë porositeit en meganiese stabiliteit. Die ontwerpte reaktor voldoen aan die industriële veiligheidsvereistes en die ergonomiese maatstawwe. Die batterye is suksesvol gebruik in hulle industriële aanwending as gevolg van die suksesvolle afhandeling van die stuk navorsing.