Reactions of NH radicals. I. Photolysis of HN3 vapor at 313nm.
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Photolysis of HN<SUB>3</SUB> vapor was studied at 313 nm as a function of HN<SUB>3</SUB> and Xe pressures, light intensity, and temperature. The photolysis of hydrazoic acid labeled with <SUP>15</SUP>N was also studied. The quantum yields of N<SUB>2</SUB>, H<SUB>2</SUB>, and NH<SUB>4</SUB>N<SUB>3</SUB> as a product were 4.85, 0.494, and 0.842 at 30 °C and 6.7 kPa of HN<SUB>3</SUB>, respectively. The mechanism for the main reactions was postulated as follows: HN<SUB>3</SUB>+<I>h</I>ν(313 nm)→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 (2); NH(<I>a</I><SUP>1</SUP>Δ)+HN<SUB>3</SUB>→N<SUB>3</SUB>+NH<SUB>2</SUB> (3); 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> (4). The rate constant ratios of <I>k</I><SUB>3</SUB>⁄<I>k</I><SUB>2</SUB>=0.746 and <I>k</I><SUB>4</SUB>⁄<I>k</I><SUB>2</SUB>=1.23 were obtained at 30°C. (<I>k</I><SUB>3</SUB>+<I>k</I><SUB>4</SUB>)⁄<I>k</I><SUB>2</SUB> decrease drastically with rising temperature. Xe is effective for the collisional deactivation, NH(<I>a</I><SUP>1</SUP>Δ)+Xe→NH(<I>X</I><SUP>3</SUP>Σ<SUP>−</SUP>)+Xe (15), and <I>k</I><SUB>15</SUB>⁄(<I>k</I><SUB>2</SUB>+<I>k</I><SUB>3</SUB>+<I>k</I><SUB>4</SUB>)=0.187 was obtained at 30 °C.
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