Reactions of NH radicals. V. Photolysis of HN3 in the presence of C3H8 at 313 nm.
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The photolysis of HN<SUB>3</SUB> vapor in the presence of C<SUB>3</SUB>H<SUB>8</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>, C<SUB>3</SUB>H<SUB>6</SUB>, NH<SUB>4</SUB>N<SUB>3</SUB>, CH<SUB>3</SUB>NH<SUB>2</SUB>·HN<SUB>3</SUB>, C<SUB>2</SUB>H<SUB>5</SUB>NH<SUB>2</SUB>·HN<SUB>3</SUB>, and <I>n</I>- and <I>i</I>-C<SUB>3</SUB>H<SUB>7</SUB>NH<SUB>2</SUB>·HN<SUB>3</SUB>. The quantum yields of these products were measured as a function of the pressure of HN<SUB>3</SUB> or C<SUB>3</SUB>H<SUB>8</SUB>. The following mechanisms for the main reactions was proposed: 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, NH<SUB>2</SUB>+N<SUB>3</SUB>, and N<SUB>2</SUB>+N<SUB>2</SUB>H<SUB>2</SUB><SUP>*</SUP> (2); NH(<I>a</I><SUP>1</SUP>Δ)+C<SUB>3</SUB>H<SUB>8</SUB>→C<SUB>3</SUB>H<SUB>7</SUB>NH<SUB>2</SUB><SUP>*</SUP>(<I>n</I>- and <I>i</I>-propylamine) (3); NH(<I>a</I><SUP>1</SUP>Δ)+C<SUB>3</SUB>H<SUB>8</SUB>→NH (X<SUP>3</SUP>Σ<SUP>−</SUP>)+C<SUB>3</SUB>H<SUB>8</SUB> (4); C<SUB>3</SUB>H<SUB>7</SUB>NH<SUB>2</SUB><SUP>*</SUP>→CH<SUB>3</SUB>+C<SUB>2</SUB>H<SUB>4</SUB>NH<SUB>2</SUB> (5); CH<SUB>4</SUB>+C<SUB>2</SUB>H<SUB>4</SUB>NH (6), C<SUB>2</SUB>H<SUB>4</SUB>+CH<SUB>3</SUB>NH<SUB>2</SUB> (7), C<SUB>2</SUB>H<SUB>5</SUB>+CH<SUB>2</SUB>NH<SUB>2</SUB> (8), C<SUB>2</SUB>H<SUB>6</SUB>+CH<SUB>2</SUB>NH (9), H<SUB>2</SUB>+C<SUB>3</SUB>H<SUB>6</SUB>NH (10), and NH<SUB>3</SUB>+C<SUB>3</SUB>H<SUB>6</SUB> (11); C<SUB>3</SUB>H<SUB>7</SUB>NH<SUB>2</SUB><SUP>*</SUP>+HN<SUB>3</SUB>→C<SUB>3</SUB>H<SUB>7</SUB>NH<SUB>2</SUB>+HN<SUB>3</SUB> (12); C<SUB>3</SUB>H<SUB>7</SUB>NH<SUB>2</SUB><SUP>*</SUP>+ C<SUB>3</SUB>H<SUB>8</SUB>→C<SUB>3</SUB>H<SUB>7</SUB>NH<SUB>2</SUB>+C<SUB>3</SUB>H<SUB>8</SUB> (13). The rate constant ratios are: <I>k</I><SUB>3</SUB>⁄<I>k</I><SUB>2</SUB>=1.28; <I>k</I><SUB>4</SUB>⁄<I>k</I><SUB>2</SUB>=0.262; <I>k</I><SUB>6</SUB>⁄<I>k</I><SUB>5</SUB>=0.109; <I>k</I><SUB>7</SUB>⁄<I>k</I><SUB>5</SUB>=0.050; <I>k</I><SUB>8</SUB>⁄<I>k</I><SUB>5</SUB>=1.39; <I>k</I><SUB>9</SUB>⁄<I>k</I><SUB>5</SUB>=0.040; <I>k</I><SUB>10</SUB>⁄<I>k</I><SUB>5</SUB>=1.20; <I>k</I><SUB>11</SUB>⁄<I>k</I><SUB>5</SUB>=4.72; <I>k</I><SUB>12</SUB>⁄<I>k</I><SUB>5</SUB>=666 dm<SUP>3</SUP> mol<SUP>−1</SUP>; <I>k</I><SUB>13</SUB>⁄<I>k</I><SUB>5</SUB>=860 dm<SUP>3</SUP> mol<SUP>−1</SUP>. The formation ratio of <I>n</I>-C<SUB>3</SUB>H<SUB>7</SUB>NH<SUB>2</SUB>/<I>i</I>-C<SUB>3</SUB>H<SUB>7</SUB>NH<SUB>2</SUB> was 1.55, regardless of the total pressure. The half-life of 1.78×10<SUP>−10</SUP> s for C<SUB>3</SUB>H<SUB>7</SUB>NH<SUB>2</SUB><SUP>*</SUP> was obtained by using the collision theory. The relative and absolute rate constants were compared for the reactions of NH(<I>a</I><SUP>1</SUP>Δ) with CH<SUB>4</SUB>, C<SUB>2</SUB>H<SUB>6</SUB>, and C<SUB>3</SUB>H<SUB>8</SUB>; it was found that the relative yield for the insertion of NH(<I>a</I><SUP>1</SUP>Δ) into a C–H bond increases with a decrease in the C–H bond dissociation energy.
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