Thesis (Ph. D.)--University of Chicago, 1916. / Includes bibliographical references.

Thesis (Ph. D.)--University of Chicago, 1916. / Includes bibliographical references. Also available on the Internet.

Thesis (Ph. D.)--Columbia University, 1930. / Vita. eContent provider-neutral record in process. Description based on print version record. Bibliography: p. 33-35.

Thesis (Ph. D.)--University of Chicago, 1918. / "A Private edition, distributed by the University of Chicago Libraries, Chicago, Ill." "Reprinted from the Journal of the American chemical society, Vol. XLI, No. 12, December, 1919." Includes bibliographical references.

Thesis (Ph. D.)--Columbia University, 1930. / Vita. Bibliography: p. 33-35.

Thesis (Ph. D.)--University of Chicago, 1918. / "A Private edition, distributed by the University of Chicago Libraries, Chicago, Ill." "Reprinted from the Journal of the American chemical society, Vol. XLI, No. 12, December, 1919." Includes bibliographical references.

Thesis (Ph. D.)--Columbia University, 1921. / Vita. Includes bibliographical references.

Thesis (Ph. D.)--University of Chicago, 1918. / "A Private edition, distributed by the University of Chicago Libraries, Chicago, Ill." "Reprinted from the Journal of the American chemical society, Vol. XLI, No. 12, December, 1919." Includes bibliographical references. Also available on the Internet.

The kinetics of the oxidation of formic acid by permanganate in aqueous perchloric acid solution, i.e., 2MnO¯₄ + 3HCOOH + 2H⁺ → 2MnO₂ + 3CO₂ + 4H₂O were studied in the temperature range 15 to 35°C. The variables examined included the reactant and hydrogen ion concentrations, ionic strength, the presence of various metal ions, and solvent and reactant deuterium isotope effects. The reaction appears to proceed through two independent paths in which the rate-determining steps are bimolecular reactions of permanganate with formic acid and with formate ion, respectively. The kinetics are thus of the form -d [MnO₄¯] / dt = [M nO₄¯] [HCOOH] (kA + kBKi / [H⁺] ) where kA and kg are rate constants of the two bimolecular reactions involving formic acid and formate ion, respectively, and Ki is the ionization constant of formic acid. The Arrhenius expressions for the rate constants were found to be kA = 1.1 x 10⁹exp. (-16400/RT) 1.mole¯¹sec¯¹ and kB = 7.8 x 10⁹exp. (-13000/RT) 1.mole¯¹sec¯¹. The formate ion reaction exhibits a large deuterium (HCOO¯:DCOO¯) isotope effect which suggests cleavage of the C-H bond in the rate-determining step. The absence of a corresponding isotope effect in the formic acid reaction suggests that it proceeds by a different mechanism. Fe⁺⁺⁺(but not Ag⁺, Cu⁺⁺, Co⁺⁺ or Na⁺) was found to catalyze the reaction, possibly by a mechanism involving a FeMnO₄⁺⁺ complex. Previous investigations of the formic acid-permanganate system have been confined to lower acidities than the present one, and only the formate ion contribution to the reaction had been detected. / Science, Faculty of / Chemistry, Department of / Graduate

The kinetics of the oxidation of HCOOH by thallium (ill) in aqueous perchloric acid solution were studied in the temperature range 65 to 85°C. The effects of concentration variation, ionic strength, pH and various salts on the rate of reaction were determined. The kinetics suggest that the reaction proceeds through the formation of an intermediate complex Tl.HCOOH⁺⁺⁺ by the following mechanism T1⁺⁺⁺ + HCOOH ⇄T1.HCOOH⁺⁺⁺ (K fast equilibrium) T1HCOOH⁺⁺⁺ → T1⁺ + 2H⁺ + CO₂ (k slow) On the basis of this mechanism, the following rate equation was derived and found to fit the experimental data. [Equation omitted] where a and b are the initial T1⁺⁺⁺ and HCOOH concentrations, respectively, while x is the concentration of T1⁺ at time t. The constants k and K were evaluated kinetically and found to have the values: K = 16.2 liter mole¯¹ (between 65 and 85°C.) and k = 1.2 x 10¹³ exp, [-26,600/RT] sec.¯¹. The absorption spectra of the solutions also provided evidence for the presence of the postulated complex. The inhibiting effects of chloride and sulphate ions on the reaction were attributed to their ability to tie up thallium (III) by complexing with it. / Science, Faculty of / Chemistry, Department of / Graduate