Clinoptilolite is a natural zeolite which can be used favorably in heavy metal removal. The main mechanisms for metal removal via clinoptilolite are adsorption and ion exchange. Several sources propose to keep the normality constant to obtain equilibrium isotherms for ion exchange systems, while many studies use constant sorbent mass with varying normalities of the sorbate. The objective of this study is to investigate the prevailing mechanisms of clinoptilolite during cadmium removal and the impact of the methodology for obtaining equilibrium isotherms. Batch Cd2+ removal experiments were conducted by using the two different methodologies (i.e. keeping the sorbent mass constant vs. keeping the normality constant) with clinoptilolite in as-received (AsC) and conditioned form (CnC), an ion exchange resin and granulated activated carbon. Exchangeable and framework cations, conductivity and pH were monitored during experiments. The equilibrium results were then fitted to isotherm models. The prevailing mechanisms for Cd2+ removal with clinoptilolite are discussed considering all monitored parameters and isotherm model fits. Use of the methodology was seen to have an effect on the overall Cd2+-clinoptilolite interaction. For example, differences between methodologies are observed regarding maximum sorbed Cd2+ and the distribution of exchangeable cations. Conductivity profiles provided a good indication of presence of ion exchange and demonstrated that it is more dominating for CnC than for AsC. The Cd2+ removal capacities observed in this study (0.65 meq/g for AsC and 1.46 meq/g for CnC) are the highest recorded for a clinoptilolite sample, as can be found in the literature.

The significant root inhibition of growth in Cd-treated soybean (Glycine max) seedling correlated with the increase of H2O2 levels, PODs and laccases activity. The increase of the activities of PODs (pI 8.8, pI 7.7, pI 5.2, pI 4.5, pI 4.4 and pI 3.7) and laccases (pI 9.2, pI 8.9 and pI 8.3, pI 5.4, pI 4.2 and pI 3.7) are accompanied by a rise of lignin contents in Cd-treated tissues. Our results suggested that laccases work during the early stage of Cd treatment. Laccases and peroxidases work cooperatively in lignin synthesis when the time of Cd treatment was prolonged.

In our previous studies on modeling methyl transfer protein, Ada protein, we found that zinc complexes of tri(2-thiophenyl)phosphine (PS3), (A), have similar methyl transfer behavior as its biological counter part. In order to probe the role of zinc in methylation process, we used tin and cadmium in model study to compare their chemistry relative to that of zinc. We found that all three metal complexes have similar chemistry and assume similar dimeric anion structure. For example, [Cd(PS3)]22-(1) and [Cd(SiPS3)]22-(2) have been successfully characterized crystallographically to possess the same structure as zinc dimer (A). However , in attempt to crystallize the tin analogue, the accidental oxidation product [SnIV(OH)2(SiPS3)]2, (5), was obtained. Its crystal structure gave clue to the mechanism of oxidation of the original tin dimer. The reactions with alkylating reagent of (1) have been compared with those of zinc dimer (A), and we found that the metal (Zn or Cd) center causes the dimers to produce different degree of methylation products toward different alkylating reagents. For the reactions with CH3I, the different degree of methylation between Cd and Zn dimers shows that the presence of zinc center has higher methylation selectivity and weaker reactivity.

For the theory of electrochemical analysis, a kinetic model that considers the ion transport limitations near the cathode of electrode is based upon a generalized Butler-Volmer equation and has been modified in theory and developed. The subjects of this study are the investigation of the kinetics mechanism of CdTe electrodeposition from an aqueous solution containing CdSO4, TeO2, and H2SO4 in cyclic voltammetry and applied to the optimal control of the composition and stoichiometric deviation of CdTe thin film by electrodeposition. The computer simulation is performed to understand the influences of electrodeposited parameters in the process, such as deposition temperature, pH value and concentrations of Cd2+ and HTeO2+ ions, is one of the focuses in this study. In this investigation, a novel electrochemical method for simultaneously measuring diffusion coefficient and ion transference number is applied in the simulation of CdTe electrodeposition for the first time. From the fitting of the experimental data, the values of the thermodynamic, kinetic and mass transport parameters of the electrodeposition process are obtained. In addition, the modified Butler-Volmer model predicts the potential of perfect stoichiometry (PPS) for electrodeposition of CdTe thin film, and a good agreement has been found between the calculated and experimental results. It also predicts the composition of electrodeposits for the electrodeposition of CdTe and other II-VI and III-V compounds from solutions containing reducible ions. Furthermore, the one that is worth mentioning in this investigation, a novel algorithm of stoichiometric deviation is also developed and applied to the electrodeposition for the first time. With the change of the parameter, the deviation of stoichiometry can be estimated accurately. The simulated results of mathematical model are verified experimentally using electrodeposition and can obtain two aspects. They are the accurate potential perfect stoichiometry (PPS) in which the intrinsic CdTe thin film can be electrodeposited and the stoichiometric deviation which can be dominated accurately in the adjustment of electrodeposited potential. Besides, the native non-degenerate p-type and n-type CdTe thin film can also be deposited. At PPS, well-connected granular CdTe thin films can be deposited and are predicted to be intrinsic, but are slightly p-type due to cadmium vacancies (VCd). The conversion of conductive type occurs only by defect redistribution and local defect reactions after annealing; the converted n-type layer shows lower resistivity and higher mobility. A film annealed at 350oC exhibits excellent crystallization.

We have successfully used the cadmium ion with (2-thiophenyl)phenylphosphine(PS2) or Bis(3-trimethylsilyl-2-thiophenyl)phenylphosphine(SiPS2) to synthesize [(PS2)Cd(TMEDA)](2) and [(SiPS2)Cd(TMEDA)](4) that were structurally similar to [(PS2)Zn(TMEDA)](1). We also obtained a series of zinc complxes [NEt4][(PS2)Zn(SC6H5)](6), [NEt4][{[(PS2)Zn](SC6H11)[(PS2)Zn]}](7) and [NEt4][(PS2)Zn(SCH2C6H5)](8) with systematically varied thiolates. From studying of the methylation reactions of these complexeswith methyliodine or trimethylphosphate, we found that the metal center(zinc or cadmium), ligand(PS2 or SiPS2) or the net charge (neutral ornegative) can influence the reaction time, selectivity of reaction site ormechanism. The zinc complexes (6), (7), and (8) are capable of completingthe catalytic cycle of mthylation-demethylation and hence a good model for related enzyme system.

Title from PDF of title page. / Document formatted into pages; contains 71 pages. / Thesis (M.S.E.E.)--University of South Florida, 2003. / Includes bibliographical references. / Text (Electronic thesis) in PDF format. / ABSTRACT: The CdTe solar cell is a leading candidate for cost-effective thin-film solar cells having demonstrated small area cell effciencies of 16.4%. A Key issue associated with CdTe thin film photovoltaic modules is the analysis of degradation behavior of the device. The analysis is complicated as changes due to degradation may be reversible. Solar cell measurement techniques were used to understand the changes in device parameters after light soaking for 1000 hours. An automated measurement setup was implemented as part of this thesis work. The main objective of this thesis was to study the effect of CdCl&esc;b2&esc;s heat treatment on the device stability. The temperature for this heat treatment was varied from 360oC to 400oC. Cells were stressed under illumination at both short circuit and open circuit conditions. It was found that the increase CdCl&esc;b2&esc;s heat treatment temperature slowed down the degradation rate.This was true for both short and open circuit stress conditions. Also short circuit stress condition slowed down the degradation of the device when compared with the open circuit condition. It became evident that the recombination current mainly got affected when the device was said to be degraded. / System requirements: World Wide Web browser and PDF reader. / Mode of access: World Wide Web.

Thèse de doctorat : Géosciences : Nancy 1 : 2009. / Titre provenant de l'écran-titre.

Thesis (Ph. D.)--University of Missouri--Columbia, 2002. / "December 2002." Typescript. Vita. Includes bibliographical references (leaves 109-118). Also issued on the Internet.

Thesis (Ph. D.)--University of Missouri--Columbia, 2002. / Typescript. Vita. Includes bibliographical references (leaves 109-118). Also issued on the Internet.

We report here a study of a specific doublet of de Haas-van Alphen frequencies in pure Mg and very dilute Mg(Cd) alloys with the magnetic field aligned with the c-axis. The work involved three stages. First, the use of extremely strain-free crystals, temperatures down to 40 millidegree Kelvin, large amplitude modulation, and the fast Fourier transform allowed the components of this doublet to be well resolved. This resolution allowed measurement of the changes in the cross-sectional area as a function of magnetic field orientation to verify the assignment of this doublet to the cap and monster arm junction at the top of the Brillouin zone. Third, with the magnetic field aligned with the c-axis, the splitting of this doublet offered a direct and sensitive indication of any symmetry breaking changes in the 0001 Fourier component of the ionic lattice potential in Mg upon the introduction of Cd. C. B. Friedberg's analysis of his electron interference lineshape data from the quantum interferometer in Mg had indicated that the energy of this band gap should increase by 40% with the introduction of 15 ppm Cd. Our data indicate that any change in the energy of the band gap must be at least three orders of magnitude smaller than that indicated by Friedberg. Our data are, in fact, consistent with there being no changes in the electronic band structure or the Fermi surface of Mg(Cd) alloys (with up to 0.02% (At) Cd), from that of pure Mg.