Chemistry and Chemical Biology ETDs

Publication Date

5-18-1978

Abstract

Spectroscopic studies of the reactions of fluorine with silicon, silane and deuterated silane, and of oxygen with uranium are reported. Chemiluminescence and atomic absorption techniques have been employed to determine the kinetics, photon yields and branching ratios of the chemistry leading to the excited states of the radical SiF. The reaction of silicon vapor with fluorine occurs at nearly a gas kinetic rate (k2=1.3 x 10-16 cc molecule-1 sec-1). The overall system photon yield from the reaction of silane and fluorine to produce SiF(A➔X) and SiF(a➔X) emission were 5 x 10-2% and 3 x 10-5% respectively. The photon yields for the analagous reaction of deuterated silane with fluorine were about a factor of two lower. No emission attributable to the SiF(a➔A) transition was detectable. The results of these studies indicate that these reactions cannot be utilized to chemically pump an SiF electronic transition laser.

Infrared chemiluminescence techniques were used to probe the reaction of uranium and oxygen in the gas phase. The resulting infrared emission is reported and is in good agreement with previously reported matrix isolation results. An estimate of the U02(u3)nv=l➔0 lifetime is given as 100 µsec.

Language

English

Document Type

Dissertation

Degree Name

Chemistry

Level of Degree

Doctoral

Department Name

Department of Chemistry and Chemical Biology

First Committee Member (Chair)

Robert Tapscott

Second Committee Member

William Fletcher Coleman

Third Committee Member

Illegible

Fourth Committee Member

Thomas Michael Niemczyk

Fifth Committee Member

Howard Carnes Bryant

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