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Heterogeneous Reaction of Nitric Acid with Nitric Oxide on Glass Surfaces under Simulated Atmospheric Conditions

机译:模拟大气条件下玻璃表面上硝酸与一氧化氮的非均相反应

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The heterogeneous reaction of nitric acid (HNO_3) with nitric oxide (NO) on borosilicate glass surfaces was studied in a flow system at relative humidity levels in the range 21-86%.Reactant concentrations were kept closer to ambient atmospheric levels as compared to all previous studies of this reaction.Within experimental error,no formation of the proposed reaction products nitrous acid (HONO) and nitrogen dioxide (NO_2) was observed.Upper limits of the reactive uptake coefficients of NO on borosilicate glass surfaces,covered with approx 1 monolayer of HNO_3,were determined:gamma (NO->HONO)<4.0x10~(-11) and gamma(NO->NO_2)<2.5x10~(-9).These values are significantly lower than previously reported values,which were determined at higher reactant concentrations.Results obtained upon investigation of the secondary heterogeneous reaction of the proposed product HONO with HNO_3 under identical experimental conditions show that HONO should be observed in the study of the reaction HNO_3+NO,if it is formed.Thus,the obtained upper limit gamma(NO->HONO) is representative for the reaction HNO_3+NO->HONO+NO_2.Under the assumption that the glass surfaces,typically used in laboratory studies of this reaction,are representative for environmental surfaces,the latter reaction is unimportant for atmospheric HONO formation and for a "renoxification" of the atmosphere.
机译:在相对湿度为21-86%的流动系统中研究了硝酸(HNO_3)与一氧化氮(NO)在硼硅酸盐玻璃表面上的异相反应,与所有反应物相比,反应物浓度保持更接近环境大气水平该反应以前的研究。在实验误差范围内,未观察到拟议的反应产物亚硝酸(HONO)和二氧化氮(NO_2)的形成。硼硅酸盐玻璃表面上NO的反应性吸收系数的上限,被约1个单层覆盖确定HNO_3的值:γ(NO-> HONO)<4.0x10〜(-11)和gamma(NO-> NO_2)<2.5x10〜(-9)。这些值明显低于先前报告的值在相同的实验条件下研究拟议产品HONO与HNO_3的次要异质反应获得的结果表明,在研究HNO_3 + NO的反应中应观察到​​HONO因此,所获得的上限γ(NO-> HONO)代表了反应HNO_3 + NO-> HONO + NO_2。在通常用于该反应的实验室研究的玻璃表面为代表的假设下对于环境表面而言,后一种反应对于大气中HONO的形成和大气的“再氧化”并不重要。

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