Thesis (Ph. D.)--University of Texas at Austin, 2004. / Supervisor: John G. Ekerdt. Vita. Includes bibliographical references. Also available from UMI.

Thesis (M.Sc. (Chemistry)) - Rhodes University, 2009.

Diss. (sammanfattning) Göteborg : Univ. , 2010.

Thesis (M.Sc.(Chemistry))--University of Pretoria, 2003. / Summaries in Afrikaans and English. Includes bibliographical references.

Thesis (M.Sc.(Chemistry))--University of Pretoria, 2005. / Includes abstract in English. Includes bibliographical references. Electronic copy also available.

Thesis (M.Sc.)--Memorial University of Newfoundland, 2003. / Includes bibliographical references. Also available online.

Thesis (Ph. D.)--West Virginia University, 2006. / Title from document title page. Document formatted into pages; contains xx, 149 p. : ill. (some col.). Includes abstract. Includes bibliographical references (p. 144-149).

>Magister Scientiae - MSc / This thesis focuses on the electroanalysis of some dienes (2-methyl-1.3-butadiene (MBD), tran-1.3-pentadiene (PD), 1.3-cyclohexadiene (CHD) and 3-cyclooctadiene (COD)) found in gasoline and the development of simple electrochemical diene sensors. The detection of dienes in fuels is important as they readily polymerise and form gum in fuel tanks. The electroctivity of the dienes was studied with glassy carbon electrode (GCE) and Pt electrode in tetrabutylammonium perchlorate (TBAP)/acetonitrile solution. Polyaniline-polystyrene sulfonic acid (PANi-PSSA) composite films were electro-deposited or drop-coated on GCE, with and without gold nanoparticles (AuNPs) and characterized by cyclic voltammetry (CV), high resolution transmission electron microscopy (HRTEM) and ultraviolet-visible (UV-vis) spectroscopy. Both composite polymers were found to be of nanofibral structure, and the spherical gold nanoparticles were dispersed uniformly within the polymer. The dienes exhibited no redox peaks on GCE/PANi-PSSA and GCE/PANi-PSSA/AuNPs electrode systems from -1.0 V to +1.5 V, beyond which PANi would overoxidize and lose its electroactivity. Therefore, cyclic voltammetry and steady state amperometry of the four dienes (MBD, PD, CHD and COD) were studied with unmodified Pt and GCE electrodes. Subtractively normalised interfacial-fourier transform infra-red (SNIFTIR) spectroscopic studies of the dienes were performed with Pt electrode. SNIFTIR data showed that there was a definite electro-oxidation of 1.3-cyclohexadiene as electrode potential was changed from E = 770 mV to E = 1638 mV. Severe electrode fouling was observed when steady state amperometric detection of CHD, as a representative diene, was performed on Pt electrode. Randel-Sevčik analysis of the CVs of the dienes on Pt electrode gave diffusion coefficient (Dox) values of 10.65 cm²/s, 9.55 cm²/s, 3.20 cm²/s and 3.96 cm²/s for CHD, COD, PD, and MBD, respectively. The corresponding detection limits (3σn-1) were 0.0106 M, 0.0111 M, 0.0109 M, and 0.0107 M.

An experiment has been completed which demonstrated quantum mechanical tunneling of electrons between two gold electrodes separated in vacuum. The tunneling current between the gold electrodes has been measured, for fixed voltages of 0.1 and 0.01 volts, as the electrode spacing was varied from a distance of approximately 2.0 nm down to a point where the electrodes touched. Current-voltage characteristics for fixed electrode spacing in the direct tunneling region have also been measured. Numerical calculations of the tunneling current based on the free-electron model of the electrodes and the barrier, an image-potential reduced barrier, and a WKB approximation for the tunneling probability have been performed and compared with Simmons' theory and with the experimental results. Within experimental error the results indicate that an image potential reduced barrier with the modifications suggested by Lang and Kohn gives a close approximation to the true barrier for metal-vacuum-metal tunneling. For the first time, the work function of the electrodes in a tunneling experiment has been deduced from experimental parameters independent of the tunneling device.

Made available in DSpace on 2014-11-10T11:09:58Z (GMT). No. of bitstreams: 0 Previous issue date: 2014-05-07Bitstream added on 2014-11-10T11:58:20Z : No. of bitstreams: 1 000774432_20150530.pdf: 1155206 bytes, checksum: 75ba8f4ab9965441201ba92669b126ba (MD5) Bitstreams deleted on 2015-06-03T11:42:44Z: 000774432_20150530.pdf,. Added 1 bitstream(s) on 2015-06-03T11:44:10Z : No. of bitstreams: 1 000774432.pdf: 2712576 bytes, checksum: 93c3b29a0b848195159ba8b85d09eed4 (MD5) / Neste trabalho desenvolveu-se um método eletroanalítico em superfície de eletrodo sólido com filme intermetálico Ag2Hg3.02 (AgSIE), para a determinação do ácido fólico (FA). O AgSIE foi utilizado em substituição ao eletrodo de Hg líquido de modo a atender ao conceito da “química verde”. Aplicou-se a técnica de Voltametria de Onda Quadrada Adsortiva de Redissolução (SWAdSV - do inglês: Square Wave Adsorptive Stripping Voltammetry), considerando-se a frequência analítica, seletividade e sensibilidade do método. O FA apresentou um pico de redução em -0,6 V vs. Esce , com características de processo adsortivo. Otimizou-se os parâmetros experimentais e as curvas analíticas (n= 5) foram construídas por diluição da solução padrão, no intervalo de 0,2 x 10-7 a 10,6 x 10-7 mol L-1. Os limites de detecção e de quantificação obtidos para o FA foram LD= 6,79 x 10-10 mol L-1 e LQ= 2 x 10-8 mol L-1, respectivamente. O método de adição de padrão foi aplicado para a determinação do FA em fármacos de ácido fólico contendo 5,0 mg/tablet, resultando numa recuperação de R%= 98,4  2,7 %, (m= 4,9 ± 0,1) mg (FAFI), R%= 99,9  2,9 %, (m= 4,9 ± 0,15) mg (FAFII) e para o multivitamínico de 0,25 mg/tablete: R%= 99,4  1,54 % (m= 0,24 ± 0,03) mg (FAFIII) e nas amostras de sucos de frutas in natura e industrializados, foram obtidas as concentrações de 0,3 a 84,4 g L-1. A técnica de Cromatografia Líquida de Alta Eficiência (HPLC - do inglês: High Performance Liquid Chromatography), foi utilizada na determinação de FA em fármacos e sucos de frutas para comparação dos resultados, assim, foi conduzida em coluna ODS-C18, de 150 x 4,6 mm (5 m), fase móvel de ACN/HAC-KOH, eluição por gradiente (10:90, v/v), pH 2,88, fluxo 0,5 mL min -1 e detector UV-vis máx. 280 nm. A curva analítica (n= 3) do ácido fólico, foi construída no intervalo de 1,41 x 10-6 a 4,53 x 10-5 mol L-1 e calculou-se... / In this work we developed na electroanalytical method on the surface of solid intermetallic electrode film Ag2Hg3.02 (AgSIE) for the determination of folic acid (FA). The AgSIE was used instead of liquid Hg electrode in order to attend to the concept of green chemistry . We applied the technique of square wave voltammetry toAdsorptive Stripping Voltammetry (SWAdSV), considering the analytical frequency selectivity and sensitivity of the method. The FA showed a peak reduction in -0,6 vs. Esce, with characteristics of adsorptive process. Optimized the experimental parameters and the analytical curves (n = 5) were constructed by diluting the standard solution in the range from 0.2 x 10-7 to 10.6 x 10-7 mol L- 1. The limits of detection and quantification were obtained for the FA LD = 6.79 x 10-10 mol L -1 and LQ = 2 x 10-8 mol L- 1, respectively. The standard addition method was used for determination of FA in folate pharmaceutical containing 5.0 mg / tablet , resulting in recovery of R % = 98.4  2.7% (mean = 4.9 ± 0 1 ) mg ( FAFI ), R = 99.9 %  2.9% (mean = 4.9 ± 0.15) mg ( FAFII ) and the multivitamin 0.25 mg / tablet : R % = 99.4  1.54 % ( m = 0.24 ± 0.03 ) mg ( FAFIII) and in samples of fruit juices in natura and processed , the concentrations from 0.3 to 84.4 mg L- 1 were obtained. The technique of High Efficiency Liquid Chromatography (HPLC), was utilized in the determination of FA in pharmaceutical and fruit juices for comparison, so the results was conducted in ODS - C18 column, 150 x 4.6 mm ( 5 m) mobile phase ACN / HAC-KOH, elution gradient (10:90, v / v ), pH 2.88, flow of 0.5 mL min -1 and UV-vis detector máx. 280 nm. The analytical curve (n = 3) of folic acid was built in the range from 1.41 x 10-6 to 4.53 x 10-5 mol L- 1 and calculated, LD = 8.38 x 10-8 mol L- 1 and LQ = 2.49 x 10-7 mol L- 1 . Accuracy was assessed pharmaceutical (5.0 mg / tablet ) for two dilutions 5:10 g mL -1, FAFI in obtaining the...