Kinetics of the gas phase reaction OH+NO(+M)->HONO(+M) and the determination of the UV absorption cross sections of HONO
Kinetics of the gas phase reaction OH+NO(+M)->HONO(+M) and the determination of the UV absorption cross sections of HONO
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DOI：
10.1016/s0009-2614(97)00576-9
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发表时间：
1997-07-04
影响因子：
2.8
通讯作者：
Sillesen, A
中科院分区：
文献类型：
--
作者：
Pagsberg, P;Bjergbakke, E;Sillesen, A
本文采用OH + NO（+ M）--> HONO（+ M）反应（M = SF_6）作为第三体，在不受其它吸收物种干扰的情况下，记录了HONO的近紫外吸收光谱。该反应是由SF6/H2O/NO混合物的脉冲辐解引发的，总压在10-1000 mbar范围内，298 K。速率系数的压力依赖性进行了研究，通过时间分辨紫外和红外光谱。通过对下降曲线的分析，我们导出了极限低压速率常数k（0）/[SF6] =（1.5 +/- 0.1）× 10（-30）cm（6）molecule（-2）s（-1）at 298 K，使用Tree和同事报道的k（无穷大）=（3.3 +/-0.3）× 10（-11）cm（3）molecule（-1）s（-1）和F-cent = 0.81的值。在320-400 nm范围内记录了HONO的紫外光谱，确定了HONO最强吸收带位于354.2 nm处的绝对吸收截面σ =（5.02 +/-0.76）× 10（-19）cm（2）分子（-1）。差分吸收截面用于现场测量的HONO进行了研究。(C)1997年Elsevier Science B.V.
The reaction OH + NO(+ M) --> HONO(+ M) with M = SF6 as a third body has been employed as a clean source for recording the near-ultraviolet absorption spectrum of HONO without interference from other absorbing species. The reaction was initiated by the pulse radiolysis of SF6/H2O/NO mixtures with total pressures in the range 10-1000 mbar at 298 K. The pressure dependence of the rate coefficient was studied by time-resolved UV and IR spectroscopy. By analysis of the fall-off curve we have derived a value for the limiting low pressure rate constant k(0)/[SF6] = (1.5 +/- 0.1) X 10(-30) cm(6) molecule(-2) s(-1) at 298 K, using the values of k(infinity) = (3.3 +/- 0.3) X 10(-11) cm(3) molecule(-1) s(-1) and F-cent = 0.81 reported by Tree and co-workers. The UV spectrum of HONO was recorded in the range 320-400 nm and an absolute absorption cross section of sigma = (5.02 +/- 0.76) X 10(-19) cm(2) molecule(-1) has been determined for the strongest band of HONO located at 354.2 nm. Differential absorption cross sections to be used for field measurements of HONO were also investigated. (C) 1997 Elsevier Science B.V.