Reactions of NH radicals. IV. Photolysis of HN3 in the presence of CH4 at 313 nm.
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The photolysis of HN<SUB>3</SUB> vapor in the presence of CH<SUB>4</SUB> was studied at 313 nm, 30 °C, and a low light intensity. The reaction products were N<SUB>2</SUB>, H<SUB>2</SUB>, NH<SUB>4</SUB>N<SUB>3</SUB>, CH<SUB>3</SUB>NH<SUB>2</SUB>·HN<SUB>3</SUB>, and CH<SUB>3</SUB>N<SUB>3</SUB>. CH<SUB>3</SUB> radicals were also detected as intermediates. The quantum yields of these products were measured as a function of the CH<SUB>4</SUB> and HN<SUB>3</SUB> pressures. The following mechanisms for the main reactions were proposed: HN<SUB>3</SUB>+<I>h</I>ν(313nm)→N<SUB>2</SUB>+NH(<I>a</I><SUP>1</SUP>Δ); NH(<I>a</I><SUP>1</SUP>Δ)+HN<SUB>3</SUB>→2N<SUB>2</SUB>+2H(2a); NH(<I>a</I><SUP>1</SUP>Δ)+HN<SUB>3</SUB>→N<SUB>3</SUB>+NH<SUB>2</SUB> (2b); NH(<I>a</I><SUP>1</SUP>Δ)+HN<SUB>3</SUB>→N<SUB>2</SUB>+N<SUB>2</SUB>H<SUB>2</SUB><SUP>*</SUP> (2c); NH(<I>a</I><SUP>1</SUP>Δ)+ CH<SUB>4</SUB>→CH<SUB>3</SUB>NH<SUB>2</SUB><SUP>*</SUP> (3); NH(<I>a</I><SUP>1</SUP>Δ)+CH<SUB>4</SUB>→NH(X<SUP>3</SUP>Σ<SUP>−</SUP>)+CH<SUB>4</SUB> (4); CH<SUB>3</SUB>NH<SUB>2</SUB><SUP>*</SUP>→H+CH<SUB>2</SUB>NH<SUB>2</SUB> or CH<SUB>3</SUB>NH (5); CH<SUB>3</SUB>NH<SUB>2</SUB><SUP>*</SUP>→CH<SUB>3</SUB>+NH<SUB>2</SUB> (6). The rate-constant ratios at 30°C were: <I>k</I><SUB>3</SUB>⁄<I>k</I><SUB>2</SUB>=0.175; <I>k</I><SUB>4</SUB>⁄<I>k</I><SUB>2</SUB>=0.177; <I>k</I><SUB>6</SUB>⁄<I>k</I><SUB>5</SUB>=0.133. The collisional deactivation of CH<SUB>3</SUB>NH<SUB>2</SUB><SUP>*</SUP> was not found in the total pressure range, from 6.4 to 24.3 kPa.
- 公益社団法人 日本化学会の論文
公益社団法人 日本化学会 | 論文
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