Reactions of NH radicals. III. Photolysis of HN3 in the presence of C2H4 at 313nm.
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Photolysis of HN<SUB>3</SUB> vapor in the presence of C<SUB>2</SUB>H<SUB>4</SUB> was studied at 313 nm and 30 °C. The main products were N<SUB>2</SUB>, H<SUB>2</SUB>, CH<SUB>4</SUB>, C<SUB>2</SUB>H<SUB>6</SUB>, NH<SUB>4</SUB>N<SUB>3</SUB>, C<SUB>2</SUB>H<SUB>5</SUB>N·HN<SUB>3</SUB> (salt of C<SUB>2</SUB>H<SUB>5</SUB>N (azomethines) with HN<SUB>3</SUB>), HCN, CH<SUB>3</SUB>CN, CH<SUB>3</SUB>N<SUB>3</SUB>, and C<SUB>2</SUB>H<SUB>5</SUB>N<SUB>3</SUB>. The quantum yields of these products were measured as a function of the light intensity and pressures of HN<SUB>3</SUB> and C<SUB>2</SUB>H<SUB>4</SUB>. The following mechanism for the main reactions was infered: HN<SUB>3</SUB>+<I>h</I>ν(313 nm)→NH(<I>a</I><SUP>1</SUP>Δ)+N<SUB>2</SUB>; 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>→NH<SUB>2</SUB>+N<SUB>3</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)+C<SUB>2</SUB>H<SUB>4</SUB>→C<SUB>2</SUB>H<SUB>5</SUB>N<SUP>*</SUP> (aziridine and vinylamine) (3); C<SUB>2</SUB>H<SUB>5</SUB>N<SUP>*</SUP>→CH<SUB>3</SUB>+CH<SUB>2</SUB>N (4); C<SUB>2</SUB>H<SUB>5</SUB>N<SUP>*</SUP>→H<SUB>2</SUB>+CH<SUB>3</SUB>CN (5); C<SUB>2</SUB>H<SUB>5</SUB>N<SUP>*</SUP>→H+C<SUB>2</SUB>H<SUB>4</SUB>N (6); C<SUB>2</SUB>H<SUB>5</SUB>N<SUP>*</SUP>→C<SUB>2</SUB>H<SUB>3</SUB>+NH<SUB>2</SUB> (7). The rate constant ratios at 30 °C are: <I>k</I><SUB>3</SUB>⁄<I>k</I><SUB>2</SUB>=1.64; <I>k</I><SUB>5</SUB>⁄<I>k</I><SUB>4</SUB>=0.102; <I>k</I><SUB>6</SUB>⁄<I>k</I><SUB>4</SUB>=0.564; <I>k</I><SUB>7</SUB>⁄<I>k</I><SUB>4</SUB>=0.734. The collisional deactivation from NH(<I>a</I><SUP>1</SUP>Δ) to NH(<I>X</I><SUP>3</SUP>Σ<SUP>−</SUP>) by C<SUB>2</SUB>H<SUB>4</SUB> was not found. The lifetime of C<SUB>2</SUB>H<SUB>5</SUB>N<SUP>*</SUP> is much shorter than 6.8×10<SUP>−11</SUP> s for C<SUB>2</SUB>H<SUB>5</SUB>NH<SUB>2</SUB><SUP>*</SUP>(←NH(<I>a</I><SUP>1</SUP>Δ)+C<SUB>2</SUB>H<SUB>6</SUB>). The relative and absolute rates for the reactions of NH(<I>a</I><SUP>1</SUP>Δ) with HN<SUB>3</SUB>, Xe, C<SUB>2</SUB>H<SUB>6</SUB>, and C<SUB>2</SUB>H<SUB>4</SUB> are discussed.
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