Physical Sciences and Mathematics Commons^™

Kinetics Of Ternary Complex Formation Reactions Of The Nickel(Ii) Complexes Of Ethylenediaminediacetate And Triethylenetetramine With Bidentate Donors, Lawrence H. Kolopajlo

Dissertations

The stopped-flow technique was used to measure rate constants for ternary complex formation involving both NiEDDA and Ni(trien)('2+), and bidentate donors. The reactions of both NiEDDA and Ni(trien)('2+) with bipy, phen, en, and sar were studied. In addition the reaction of NiEDDA and gly was studied. The reactions were of the first-order with respect to either nickel complex, and with respect to enH('+), bipy, and phen. The reactions involving phen and bipy were independent of pH and were reversible. The formation rate constants for the systems containing diamine reactants are as follows:

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Determination Of Organophosphorus Compounds By Hplc With Post-Column Photochemical Degradation Followed By The Formation Of Reduced Heieropolymolybdate, Stephen R. Priebe

Dissertations

A novel method for the determination of organophosphorus (OP) compounds by HPLC with post-column photochemical and chemical derivatization reactions has been developed. The OP compounds eluted from the column were photochemically degraded to orthophosphate by the use of a 450 W xenon lamp in conjunction with an auxiliary photodegradation reagent. The photodegradation reaction was studied extensively by means of batch irradiations with triethylphosphate as a model compound. The effects of the initial concentrations of triethylphosphate and ammonium peroxydisulfate, and of varying the pH of the reaction medium were determined. A survey of potential interferences was performed. Copper(II) ion was found …

Micellarly Catalyzed Reaction Of Substituted Benzohydroxamic Acids, Nop Utrapiromsuk

Dissertations

The rate constants for hydrolysis of ten derivatives of benzohydroxamic acid, namely, p-H, p-CH(,3), m-CH(,3), p-CH(,3)CH(,2), p-OCH(,3), p-NO(,2), p-Cl, and m-Cl, in 0.160 and 0.158 M HCl at 67.9-68.2(DEGREES)C without and with sodium 1-dodecanesulfonate were determined. There is a good linear correlation between log k(,w) and the Hammett substituent constants, (sigma), for all para and meta derivatives where k(,w) is the rate constant in the bulk aqeous phase. In the presence of micelles all the compounds, except the meta-nitro derivative, followed the standard pseudophase model of micellar catalysis. However, correlations of log k(,m) or log K/N, where k(,m) is the …