Ingram Stephen, Rovelli Grazia, Song Young-Chul, Topping David, Dutcher Cari S, Liu Shihao, Nandy Lucy, Shiraiwa Manabu, Reid Jonathan P
School of Chemistry, University of Bristol, Cantock's Close, Bristol BS8 1TS, U.K.
Department of Earth and Environmental Sciences, University of Manchester, Oxford Rd, Manchester M13 9PL, U.K.
J Phys Chem A. 2021 Apr 29;125(16):3444-3456. doi: 10.1021/acs.jpca.1c00986. Epub 2021 Apr 16.
Organic aerosol can adopt a wide range of viscosities, from liquid to glass, depending on the local humidity. In highly viscous droplets, the evaporation rates of organic components are suppressed to varying degrees, yet water evaporation remains fast. Here, we examine the coevaporation of semivolatile organic compounds (SVOCs), along with their solvating water, from aerosol particles levitated in a humidity-controlled environment. To better replicate the composition of secondary aerosol, nonvolatile organics were also present, creating a three-component diffusion problem. Kinetic modeling reproduced the evaporation accurately when the SVOCs were assumed to obey the Stokes-Einstein relation, and water was not. Crucially, our methodology uses previously collected data to constrain the time-dependent viscosity, as well as water diffusion coefficients, allowing it to be predictive rather than postdictive. Throughout the study, evaporation rates were found to decrease as SVOCs deplete from the particle, suggesting path function type behavior.
有机气溶胶可以呈现出从液体到玻璃的广泛粘度范围,这取决于局部湿度。在高粘性液滴中,有机成分的蒸发速率会受到不同程度的抑制,但水的蒸发仍然很快。在这里,我们研究了在湿度控制环境中悬浮的气溶胶颗粒中半挥发性有机化合物(SVOCs)及其溶剂化水的共蒸发情况。为了更好地复制二次气溶胶的组成,还存在非挥发性有机物,从而产生了一个三组分扩散问题。当假设SVOCs服从斯托克斯-爱因斯坦关系而水不服从时,动力学模型准确地再现了蒸发过程。至关重要的是,我们的方法使用先前收集的数据来约束随时间变化的粘度以及水扩散系数,使其具有预测性而非事后预测性。在整个研究过程中,发现随着SVOCs从颗粒中耗尽,蒸发速率会降低,这表明存在路径函数类型的行为。