Part I. The Kinetics of the Fast Reaction Between Ozone and Nitrogen Dioxide. Part II. A Mechanism for the Formation of Red Phosphorous from White Phosphorus in Solution

Citation

Johnston, Harold Sledge (1948) Part I. The Kinetics of the Fast Reaction Between Ozone and Nitrogen Dioxide. Part II. A Mechanism for the Formation of Red Phosphorous from White Phosphorus in Solution. Dissertation (Ph.D.), California Institute of Technology. doi:10.7907/P40Q-X050. https://resolver.caltech.edu/CaltechETD:etd-04262004-153834

Abstract

NOTE: Text or symbols not renderable in plain ASCII are indicated by [...]. Abstract is included in .pdf document. Part I. 1. A system has been designed and constructed which will mix two gaseous reactants, isolate them in a reaction cell, and follow the entire course of the reaction photoelectrically in one-tenth of a second. The output of the photoelectric tube is recorded by a time-exposure photograph of the screen of an oscilloscope. 2. The kinetics of the fast reaction between ozone and nitrogen dioxide mas studied over a ten-fold range of each reactant. The rate law was found to be [...] over the entire course of the reaction. As expected from the speed of the reaction, the energy of activation was found to be low, 6.4 kilocalories per mole. A simple two-step mechanism is proposed to account for the observations. Part II. 1. In an effort to obtain information about the mechanism of the formation of red phosphorus from white phosphorus in a solution of phosphorus tribromide, a radioactive tracer study was made of that system. Tentative explanations are advanced for certain features of the process. 2. A great variety of colors of polymerized phosphorus were observed in this study, and correlations between presumed size and color are discussed.

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