Thesis (M.S.)--University of Missouri, School of Mines and Metallurgy, 1920. / K. K. Kershner determined to be Karl K. Kershner from "1874-1999 MSM-UMR Alumni Directory". The entire thesis text is included in file. Typescript. Illustrated by author. Title from title screen of thesis/dissertation PDF file (viewed May 25, 2009) Includes bibliographical references (p. 34-38).

Thesis (M.S. in Chemical Engineering)--University of California, Berkeley, June 1960. / UCRL-9145. Includes bibliographical references (leaves 49-50).

Thesis (M.S.)--University of Missouri, School of Mines and Metallurgy, 1938. / The entire thesis text is included in file. Typescript. Title from title screen of thesis/dissertation PDF file (viewed May 3, 2010) Includes bibliographical references (p. 41-43) and index (p. 44-46).

Thesis (Ph. D.)--Columbia University, 1925. / Vita. Bibliography: p. [39]-40, [61].

A series of Cu(II)-63 dithiocarbamates with alkyl and cycloalkyl substituents of various shape, size and rigidity has been prepared. Their rotational correlation times (Ƭ₂) were measured (in the fast motional regime) in toluene using the line-widths of their ESR spectra. The ESR spectra were recorded on paper tape with a digital acquisition system and analysed on an Amdahl 470 computer utilising specially written programs. This procedure results in a substantial improvement in precision over earlier manual methods. The observed correlation times were compared with those calculated by the QLRF model, the conditional free rotation model, the Stokes-Einstein and Perrin 'stick' hydrodynamic models and the 'slip' hydro- -dynamic model. The results in relation to Pecora's extension of the hydrodynamic model are also discussed. The statistical mechanical and 'stick' hydrodynamic models proved unsatisfactory. The results are adequately described by the 'slip' hydrodynamic model with an additional term ascribable to a free-rotation correlation time (Ƭ₀); i.e. Ƭ₂ = Cn + Ƭ₀ ¯¯¯ Ƭ where n is the viscosity of the solvent and C is a function of the size and shape of the molecule calculated from the ' slip ' theory. / Science, Faculty of / Chemistry, Department of / Graduate

The reactions of aromatic hydrocarbons represent a major area of uncertainty in urban atmospheric photochemistry. Much effort has been spent studying the simulated atmospheric oxidation chemistry of model aromatics, such as toluene, in order to delineate their reaction mechanisms. These studies are motivated both by interest in fundamental processes and a desire to discover an aromatic's contribution to the formation of ozone in polluted ambient atmospheres. Previous work on toluene includes both product studies and proposed mechanisms. In all previous studies, the combined product yields are half or less of the initially reacted toluene. A major reason for the poor carbon balances found in these studies in the precipitation of intermediate reaction products from the gas phase to the reaction walls. We have studied the oxidation process by blacklight irradiation of 1-10 ppm each of toluene and oxides of nitrogen in 22-liter pyrex flasks, in zero-air at 50% relative humidity. The products were recovered from the walls by exrtraction with methanol or dichloromethane. Some gas-phase products were recovered in the solvent as well. The extracts were analyzed on a Finnigan MAT triple stage quadrupole mass spectrometer/data system by direct probe injection. Once their molecular weights were determined, the products were fragmented by collision-induced-dissociation (CID) in the middle quadrupole to produce characteristic daughter ions. To assist in the spectral interpretation, toluene in three isomeric forms was subjected to simulated atmospheric reaction. In addition to normal (H8) toluene, methyl-deuterated (D3) and per-deuterated (D8) toluene were used. This study confirmed the existence of a number of products identified in past studies, confirmed the formation of some products which have been hypothesized in several proposed mechanisms for toluene oxidation, identified a number of previously unidentified and unproposed products. Detailed mechanistic steps have been outlined for all reaction products' formation and destruction. Other analytical techniques including GC, GC/MS, and HPLC, have supplemented the MS/MS analysis. These results and the further study of the types of compounds identified should make a significant contribution to the understanding of atmospheric aromatic systems.

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