Vibrational Energy Distribution through Chemical Laser Studies. II. Fluorine Atoms plus Chloroform

Abstract

Laser emission by HF from the UF₆–CCl₃H chemical laser system and by DF from the UF₆–CCl₃D system has been studied, the latter by the equal‐gain temperature technique. For HF, $\text{υ\hspace{0.17em}=\hspace{0.17em}2\hspace{0.17em}→\hspace{0.17em}1}\mathrm{and}\text{3\hspace{0.17em}→\hspace{0.17em}2}$ transitions were observed, with $P_{\text{2–1}}\text{(3)}$ reaching threshold first at room temperature. For DF, $\text{υ\hspace{0.17em}=\hspace{0.17em}2\hspace{0.17em}→\hspace{0.17em}1, 3\hspace{0.17em}→\hspace{0.17em}2,}\mathrm{and}\text{4\hspace{0.17em}→\hspace{0.17em}3}$ transitions were observed, with $P_{\text{3–2}}\text{(4)}$ reaching threshold first at room temperature. The abstraction reaction F+CCl₃H(CCl₃D) is about 8 kcal more exothermic than the corresponding methane reaction, which accounts for the appearance of the higher $\upsilon$ transitions. The DF zero‐pressure, equal‐gain temperature of 386 ± 10°K establishes $k_3{\mathrm{\hspace{0.17em}/\hspace{0.17em}k}}_2\text{\hspace{0.17em}=\hspace{0.17em}1.54}$ , the same, within experimental uncertainty, as that observed for the less exothermic F+CD₄ reaction.