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Chemical processes in rigid media at low temperatures

Citation

DeMore, William B. (1958) Chemical processes in rigid media at low temperatures. Dissertation (Ph.D.), California Institute of Technology. http://resolver.caltech.edu/CaltechETD:etd-10072004-114343

Abstract

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An apparatus has been developed for studying chemical processes in rigid inert media at low temperatures (4.2[degrees]K, 20[degrees]K., or 77[degrees]K. The materials to be studied are deposited as a thin film on a cold surface by vacuum effusion. Infrared and visible-ultraviolet absorption spectroscopy were used for detection.

The CS molecule and the benzyl radical were isolated in hydrocarbon films at 77[degrees]K. CF2 and NO3 were trapped in films of nitrogen at 20[degrees]K. Visible-ultraviolet spectra of these species were obtained.

The photolysis of diazomethane in films of nitrogen at 20[degrees]K has been extensively studied. By adding various reactants to the films, evidence for the following reactions has been obtained: [...].

Ozone in nitrogen films is decomposed by ultraviolet light and some nitrous oxide is produced. This is attributed to the reaction [...], which is a hot atom reaction.

Irradiation of mixtures of O3 and NO2 in nitrogen films yields NO3, N2O5, NO, and HNO3 (due to the presence of water). Irradiation of NO2 and O2 in nitrogen films yields O3 and NO.

The results obtained indicate that (1) hot atom or radical reactions occur in the film, and (2) photochemical fragments are energy-rich and may diffuse for a distance of at least a few molecular diameters in the rigid media.

Item Type:Thesis (Dissertation (Ph.D.))
Degree Grantor:California Institute of Technology
Division:Chemistry and Chemical Engineering
Major Option:Chemistry
Thesis Availability:Public (worldwide access)
Research Advisor(s):
  • Davidson, Norman R.
Thesis Committee:
  • Unknown, Unknown
Defense Date:1 January 1958
Record Number:CaltechETD:etd-10072004-114343
Persistent URL:http://resolver.caltech.edu/CaltechETD:etd-10072004-114343
Default Usage Policy:No commercial reproduction, distribution, display or performance rights in this work are provided.
ID Code:3966
Collection:CaltechTHESIS
Deposited By: Imported from ETD-db
Deposited On:07 Oct 2004
Last Modified:26 Dec 2012 03:04

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