Thesis (Ph. D.)--Northwestern University, 1922.

Thesis (M.S.)--University of South Florida, 2003. / Title from PDF of title page. Document formatted into pages; contains 64 pages. Includes bibliographical references.

Thesis (Ph. D.)--University of Chicago, 1921. / "Private edition distributed by the University of Chicago Libraries, Chicago, Illinois, 1922." "This work was carried out in cooperation with Dr. M.S. Kharasch." "Reprinted from the Journal of the American Chemical Society, vol. XLIII, no. 8, August, 1921, and vol. XLIV, no. 4, April, 1922." Also available on the Internet.

Thesis (Ph. D.)--University of Chicago, 1921. / "Private edition distributed by the University of Chicago Libraries, Chicago, Illinois, 1922." "This work was carried out in cooperation with Dr. M.S. Kharasch." "Reprinted from the Journal of the American Chemical Society, vol. XLIII, no. 8, August, 1921, and vol. XLIV, no. 4, April, 1922."

The kinetics of the homogeneous reduction of mercuric salts by-molecular hydrogen in aqueous solution have been examined over a wide range of solution composition, temperature and hydrogen partial pressure. In perchlorate solutions, where Hg⁺⁺and Hg₂⁺⁺ are uncomplexed the kinetic results can be expressed by the equation: -d[H₂]J/dt = k₁[H₂][Hg⁺⁺] + k₂[H₂][Hg₂⁺⁺] where k₁ = 4.2 x 10¹⁰ exp [-18100/RT] 1.mole⁻¹ sec.⁻¹ and k₂ = 1.2 x 10¹¹ exp [-20400/RT] 1.mole⁻¹ sec.⁻¹ It was concluded that the rate-determining process of the reaction involves the bimolecular interaction of one H₂ molecule with either Hg⁺⁺ or Hg₂⁺⁺ , i.e., Hg⁺⁺ + H₂ [symobal omitted] Hg + 2H⁺ Hg₂⁺⁺ + H₂ [symbol omitted] 2Hg + 2H⁺ The Hg atoms thus formed undergo further rapid reactions to yield the observed products (Hg₂⁺⁺ or metallic mercury) the nature of which is determined by •' thermodynamic considerations. Mercuric complexes also reacted homogeneously with hydrogen but in most cases more slowly than the simple Hg⁺⁺ ions. The order of decreasing reactivity of the complexes, HgAc₂ > HgCl₂ > HgBr₂ > Hg(ethylenediamine)₂⁺⁺, is the same as the order of their increasing stability. This is attributed to the reduction of the electron affinity of Hg⁺⁺ through electron donation from the complexing ligand. The reactivity of mercuric complexes such as HgAc₂ and Hg(ethylenediamine)₂⁺⁺ is increased by anions such as 0H⁻, CO₃⁼, Ac⁻, etc., the influence of which increases in the same order as their basicity. This is attributed to stabilization, by the anions, of the H⁺ ions which are released in the rate-determining step of the reaction. Some conclusions are drawn concerning the mechanism of heterogeneous activation of hydrogen by solid catalysts. / Applied Science, Faculty of / Materials Engineering, Department of / Graduate

[From Introduction]. In 1955, Dry and Gledhill, both formerly of this Department, published their paper on the Solubility of Mercurous Chloride in Water at 25°0, and it was originally intended that this thesis should be an extension of the study to cover the temperature range from 5 t o 55°0. A preliminary investigation at 25°0, however, failed to yield results which were consistent with their findings, even though their apparatus and experimental technique were used. In an effort to resolve these difficulties their method of saturating the calomel in the conductance cell was thoroughly investigated, and as this procedure was found to be responsible, it was necessary to evolve an entirely new approach. The technique finally adopted was to saturate the mercurous chloride solutions by mechanical stirring in siliconed vessels and to carry out the conductance, pH, and total mercury concentration measurements on the filter ed solution. This method gave good results, and was free from the many extrapolations prevalent in the original procedure.

Call number: LD2668 .T4 1955 B75 / Master of Science

Thesis--University of Louisville. / At head of title: Chemical Technology Division. Chemical Development Section B. Includes bibliographical references (p. 55-56).

Thesis (Ph. D.)--University of Chicago, 1929. / Lithoprinted. "Private edition, distributed by the University of Chicago libraries, Chicago, Illinois."

A variable temperature ^13 C and ^199 Hg NMR study has been conducted for diphenyl-, bis(o-tolyl)-, bis(m-tolyl)-, and bis(2, 6-xylyl)mercury in dimethyl sulfoxide and 1,1,2,2 tetrachloroethane; ^13 C T1 relaxation times are reported as a function of temperature. Barriers to rotation of the aryl rings are obtained. Chemical shifts and couplings in CDCl_3 are given for bis(p-tolyl)-, bis(2, 5-xylyl)-, bis(mesityl)-,phenyl(o-tolyl)-, phenyl(m-tolyl)mercury, and the compounds listed above. The steric interactions of these aryl mercury compounds are discussed.