I. A Study of the Catalytic Decomposition of Nitric Oxide. II. A Chromatographic Apparatus and Technique for the Analysis of Nitric Oxide in Nitrogen. III. Kinetics and Mechanism of the Air Oxidation of the Dithionite Ion (S₂0₄⁼) in Aqueous Solution

Citation

Sakaida, Roy Ryosuke (1960) I. A Study of the Catalytic Decomposition of Nitric Oxide. II. A Chromatographic Apparatus and Technique for the Analysis of Nitric Oxide in Nitrogen. III. Kinetics and Mechanism of the Air Oxidation of the Dithionite Ion (S₂0₄⁼) in Aqueous Solution. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/VQEV-BW35. https://resolver.caltech.edu/CaltechETD:etd-07112006-080753

Abstract

Part I: The study of the catalytic decomposition of nitric oxide at a concentration of 0.5% by volume in nitrogen was conducted over a packed bed in a tubular flow reactor. The packed bed was in the form of alumina pellets impregnated with 0.1% by weight of platinum oxide and 3.0% by weight of nickel oxide. Tests which were conducted at pressures of 1 to 15 atm and temperatures of 800 to 1000°F showed that the rate is second-order with respect to the nitric oxide and is retarded by the adsorption of atomic oxygen on the surface of the catalyst. Part II: In conjunction with the decomposition studies, a gas chromatographic technique for the analysis of nitric oxide at a concentration of less than 0.5% by volume in nitrogen was developed. The chromatograph column with a length of 8 ft contained silica gel and was operated in a temperature range of 65 to 85°C. Helium was used as the carrier gas, and the eluted components were measured by means of a thermal conductivity cell with dual thermistors. Part III: A study of the air oxidation of sodium dithionite in aqueous solution was made. A mechanism was proposed in which the SO2- freeradical ion was the reactive intermediate. The rate of oxidation was found to be half-order with respect to the dithionite ion and first-order with respect to molecular oxygen.

Thesis Files