الفهرس 
Chapter 1 IntroductionOnly 14 pages are availabe for public view
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Abstract
The first aim of this thesis is to estimate the solvation, cyclic voltammetry, kinetic and thermodynamic parameters for the interaction of copper bromide with 2-(2,7-Dioxo-2,3,4,5,6,7-hexahydro-1H-benzo[b]azonin-1-yl)-N’-(2-oxoindolin-3-ylidene)acetohydrazide (cpd. 404) in HCl and H3PO4 medium. The second aim is the evaluation of solvation parameters for CdCl2 with cpd. 404 in sodium acetate medium. The third aim is the oxidation of the natural polymers (pectin and sodium alginate) with KMnO4 cyclic voltammetrically in 0.1M NaOH supporting electrolyte. Part One: Part one is studying the cyclic voltammetry of CuBr2 in absence and presence of cpd. 404 in HCl solutions using glassy carbon electrodes at 291.15K. Two reduction waves for CuBr2 and two oxidation peaks are clear in absence and presence of ligand (cpd. 404). The thermodynamic stability constants, Gibbs free energies of complexation for the interaction between CuBr2 and cpd. 404 are increased by the increase in cpd. 404 concentration in 0.1M HCl medium but all the data given are in the range of electrostatic energy indicating small interaction strength between cpd. 404 and CuBr2. Effect of scan rates prove that the reaction between CuBr2 and cpd. 404 is diffusion mechanism. The analysis of the waves were proceeded by applying the equations used on the two couple of peaks for CuBr2. Third reduction wave was observed at ” ” " ~ " ” ”-0.5V which is due to the deposition of copper bromide at that voltage. Fourth catalytic hydrogen wave was also appeared in presence of cpd. 404 on CuBr2 and increased by increasing cpd. 404 concentration. We follow its analysis and found that it can be used in fuel cells. Part Two: Part two is the cyclic voltammetry of CuBr2 in absence and presence of cpd. 404 in 0.1M H3PO4 using glassy carbon electrode at 301.45K. Four reduction waves and two oxidation peaks were appeared for CuBr2 in presence of 0.1M H3PO4. The waves can be divided into two couples of reversible waves, couple (1) (wave 1) with one electron and couple (2) with (wave 2) also consumes one electron. Effect of cpd. 404 on CuBr2 in H3PO4 was discussed. The redox mechanism was suggested and consists of first irreversible wave, two redox couple of waves and lastly hydrogen irreversible reduction wave. The analysis of cyclic voltammetry data show that on applying wave (1) couple of peaks more data are obtained in comparison to wave (2) couple indicating easier of couple of peak (1) to happen. The stability constants β and Gibbs free energies of complexation for interaction of CuBr2 and cpd. 404 in 0.1M H3PO4 have greater values than on using 0.1M HCl not because of the small rise in temperature but is due to more complexation in the H3PO4 medium. Part Three: The cyclic voltammetry of cadmium chloride in absence and presence of cpd. 404 in 0.1M sodium acetate using glassy carbon electrode at 303.15K using glassy carbon electrode. Two main clear peaks were appeared at ” ” " ~ " ” ”-1.0V for reduction and at 0.14V for the oxidation peak consuming two electrons for each process. Most of the evaluated solvation parameters for the interaction of CdCl2 with cpd. 404 like electron rate constant ks, cathodic surface coverage Γc, cathodic quantity of electricity Qc, anodic quantity of electricity Qa,are decreased by more adding of cpd. 404 to CdCl2 favouring complexation reaction. The stability constants β and Gibbs free energies of complexation happened by the interaction of cpd. 404 with CdCl2 were estimated and found to be in the range of electrostatic energy aggregation. Part Four: Electrochemical redox reaction, kinetics for KMnO4, oxidation parameters for pectin in sodium hydroxide cyclic voltammetrically. The redox mechanism for KMnO4 alone in 0.1M NaOH were explained at different potassium permanganate concentration. Effect of time was obtained for the interaction of KMnO4 with pectin and the oxidation mechanism was suggested and it was proved that he reaction between KMnO4+pectin is oxidation and not complexation. The analysis data given in this part indicating the oxidation of pectin by KMnO4 in 0.1M NaOH medium and the mechanism took place by two steps, one fast followed by a slow one for each one electron consumed in each redox step. Part Five: Kinetic oxidation mechanism for sodium alginate by potassium permanganate in sodium hydroxide medium via cyclic voltammetry. By adding sodium alginate to potassium permanganate in 0.1M NaOH, The analysis cyclic voltammetric data obtained support of the oxidation of sodium alginate by KMnO4 and the oxidation mechanism was suggested. Effect of time intervals was discussed for the interaction of sodium alginate with potassium permanganate in 0.1M NaOH was studied and ks versus time relation show two mechanistic processes, first oxidation mechanism which is slow one (with small ks values) and then the fast process which is the complexation reaction after 27 minutes. The thesis gives alot of cyclic voltammetry, solvation, kinetic and thermodynamic data for some salts with ligands used in environmental studies.