:—Behaviors of NH<SUB>3</SUB> and N<SUB>2</SUB>O in NH<SUB>3</SUB>-air and NH<SUB>3</SUB>-N<SUB>2</SUB>O-air under the UV irradiation—
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The behaviors of NH<SUB>3</SUB> and N<SUB>2</SUB>O in NH<SUB>3</SUB>-O<SUB>2</SUB>-N<SUB>2</SUB> and NH<SUB>3</SUB>-N<SUB>2</SUB>O-O<SUB>2</SUB>-N<SUB>2</SUB> mixture were studied under UV irradiation at room temperature. NH<SUB>3</SUB> in NH<SUB>3</SUB>-O<SUB>2</SUB>-N<SUB>2</SUB> mixture decomposed to N<SUB>2</SUB>, N<SUB>2</SUB>O and H<SUB>2</SUB>O under a high pressure mercury lamp irradiation. The selectivity of N<SUB>2</SUB>O formation was constant independent of O<SUB>2</SUB> concentration in the presence of excess O<SUB>2</SUB> and was approximately 14 % of the amount of NH<SUB>3</SUB> decomposed. The decomposition rate of NH<SUB>3</SUB> was independent of O<SUB>2</SUB> concentration and proportional to the concentration of NH<SUB>3</SUB>. While, under a low pressure mercury lamp irradiation, NH<SUB>4</SUB>NO<SUB>3</SUB> formed with N<SUB>2</SUB>, N<SUB>2</SUB>O and H<SUB>2</SUB>O. The decomposition rate increased remarkably with increasing the concentration of O<SUB>2</SUB> and expressed by the following equation<BR>- <I>d</I> (NH<SUB>3</SUB>) /<I>d</I>θ= <I>k</I> [NH<SUB>3</SUB>] + <I>k'</I> [O<SUB>2</SUB>] <SUP>1/2</SUP> [θ = <I>W/F</I> (watt⋅min⋅l<SUP>-1</SUP>) ] <BR>The selectivity of N<SUB>2</SUB>O formation increased with increasing the concentration of O<SUB>2</SUB> and decreased rapidly with further increasing over than 10 %. The results may be caused by the oxidative consumption of the intermediate HNO for N<SUB>2</SUB>O formation to give NH<SUB>4</SUB>NO<SUB>3</SUB>. No effect of N<SUB>2</SUB>O was observed in the decomposition of NH<SUB>3</SUB> in NH<SUB>3</SUB>-O<SUB>2</SUB>-N<SUB>2</SUB> mixture under a high and low pressure mercury lamp irradiation. N<SUB>2</SUB>O increased a little by the oxidative decomposition of NH<SUB>3</SUB> in N<SUB>2</SUB>O-NH<SUB>3</SUB>-O<SUB>2</SUB>-N<SUB>2</SUB> mixture under a high pressure mercury lamp irradiation and in the early stage under a low pressure mercury lamp irradiation, while decreased in the later stage under a low pressure mercury lamp irradiation. The decomposition rate of N<SUB>2</SUB>O was not affected by the presence of NH<SUB>3</SUB>.
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