No description available.

The rate of oxidation of copper metal to copper (I) by copper (II) in the presence of organic ligands has been determined for a variety of ligands using a flow injection analysis system to sample the reaction. The results obtained using the FIA sampling method compare favorably with those obtained in eariler work when allyl alcohol was used as the ligand. The mechanism proposed in that earlier work has been shown to be a general mechanism for the oxidation of copper metal in the presence of complexing ligands. It was found that some ligands increase the rate of the reaction beyond the ability of conventional FIA to sample many data points before the reaction reaches equilibrium. A method has been developed that allows for more rapid sampling of the reaction mixture by the FIA system, resulting in overlapping FIA peaks. These overlapping peaks can then be deconvolved by an iterative curve fitting/digital subtraction technique in which each peak in the FIA output is fitted to a model function and subtracted from the output, thus removing its effect on the peak height of subsequent peaks. The iodination of acetylacetone in acidic solution was also studied by the fast injection FIA technique. Iodine was generated coulometrically in the solution containing acetylacetone and hydrochloric acid. By this method, the keto-enol equilibrium constant of acetylacetone was determined over a range of pH's. They ranged from 2.3 x 10⁻⁵ at a pH of 2.63 to 1.8 x 10⁻⁴ at a pH of 4.03. It was also found that the reaction was first order with respect to the acetylacetone concentration.

An apparatus utilizing a constant pressure flow system was developed for measuring the effect of pressure on the diffusion rates, and therefore diffusion coefficients, of binary gas mixtures passing through porous solids. Hydrogen and nitrogen were employed for testing ceramic porous solids at room temperature, with various pressures from 1 to 14.6 atmospheres absolute. The values obtained for the products of the effective diffusion coefficients and absolute pressures were substantially constant, with a maximum deviation of ±5%. It seemed that the diffusion rate of hydrogen increased with pressure, while that of nitrogen decreased. At atmospheric pressure the ratio of diffusion rates {N(H₂)/N(N₂)} was in good agreement with the theoretical value proposed by Hoogschagen i.e. √M(N₂)/M(H₂). However, the experimental diffusion ratio increased with pressure. This behavior might be due to some degree of forced flow present in the diffusion process, although it was not possible to determine a cause for such a flow. This apparatus is suitable for the study of diffusion rates in the transition region, between Knudsen and ordinary diffusion, by simply changing pressure and hence the mean free path of the gases involved. Forced flow would not be a factor in this region. / Applied Science, Faculty of / Chemical and Biological Engineering, Department of / Graduate