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H2O2 与亚利桑那试验粉尘的非均相相互作用。

Heterogeneous interaction of H2O2 with Arizona Test Dust.

机构信息

Institut de Combustion, Aérothermique, Réactivité et Environnement (ICARE), CNRS, 45071 Orléans Cedex 2, France.

出版信息

J Phys Chem A. 2014 Jan 16;118(2):441-8. doi: 10.1021/jp409946j. Epub 2013 Dec 31.

Abstract

The heterogeneous interaction of H2O2 with solid films of Arizona Test Dust (ATD) was investigated under dark conditions and in presence of UV light using a low pressure flow tube reactor coupled with a quadrupole mass spectrometer. The uptake coefficients were measured as a function of the initial concentration of gaseous H2O2 ([H2O2]0 = (0.18 - 5.1) × 10(12) molecules cm(-3)), irradiance intensity (JNO2 = 0.002 - 0.012 s(-1)), relative humidity (RH = 0.002 - 69%), and temperature (T = 268 - 320 K). The initial uptake coefficient was found to be independent of the concentration of H2O2 and UV irradiation intensity and to decrease with increasing RH and temperature according to the following expressions: γ0 = 4.8 × 10(-4)/(1+ RH(0.66)) at T = 275 K and γ0 = 3.2 × 10(-4)/(1 + 2.5 × 10(10)exp(-7360/T)) at RH = 0.35% (calculated using BET surface area, estimated conservative uncertainty of 30%). By contrast, the steady state uptake coefficient was found to be independent of temperature, to increase upon UV irradiation of the surface, and to be inversely (γSS ∼ H2O2) dependent on the concentration of H2O2. The RH independent steady state uptake coefficient was measured under dark and UV irradiation conditions: γSS(dark) = (0.95 ± 0.30) × 10(-5) and γSS(UV) = (1.85 ± 0.55) × 10(-5), for RH = (2 - 69)% and [H2O2]0 ≅ 1.0 × 10(12) molecules cm(-3). The present experimental data support current considerations that uptake of H2O2 on mineral aerosol is potentially an important atmospheric process.

摘要

在黑暗条件下并在存在紫外光的情况下,使用低压流动管反应器结合四极质谱仪研究了 H2O2 与亚利桑那试验粉尘(ATD)的固体膜的不均匀相互作用。测量了作为初始浓度的气态 H2O2([H2O2]0=(0.18-5.1)×10(12)分子 cm(-3))、辐照度强度(JNO2=0.002-0.012 s(-1))、相对湿度(RH=0.002-69%)和温度(T=268-320 K)的函数的吸收系数。发现初始吸收系数与 H2O2 的浓度和紫外辐射强度无关,并随着 RH 和温度的增加而降低,根据以下表达式:γ0=4.8×10(-4)/(1+RH(0.66))在 T=275 K 和 γ0=3.2×10(-4)/(1+2.5×10(10)exp(-7360/T))在 RH=0.35%(使用 BET 表面积计算,估计不确定度为 30%)。相比之下,发现稳态吸收系数与温度无关,在表面的紫外辐射下增加,并且与 H2O2 的浓度呈反比(γSS∼H2O2)。在黑暗和紫外辐射条件下测量了 RH 独立的稳态吸收系数:γSS(dark)=(0.95±0.30)×10(-5)和 γSS(UV)=(1.85±0.55)×10(-5),对于 RH=(2-69)%和[H2O2]0≈1.0×10(12)分子 cm(-3)。目前的实验数据支持当前的考虑,即 H2O2 在矿物气溶胶上的吸收可能是一种重要的大气过程。

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