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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Mixing of the Organic Aerosol Fractions: Liquids as the Thermodynamically Stable Phases
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Mixing of the Organic Aerosol Fractions: Liquids as the Thermodynamically Stable Phases

机译：有机气溶胶馏分的混合：液体为热力学稳定相

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An increasing number of single-particle measurements show that organic and inorganic constituents of the atmospheric aerosol are internally mixed within the particles. Therefore, the phases of the aerosol will be influenced by both mixing of the organic substances with each other and mixing between organic and inorganic constituents. In this work, the mixing properties of the organic aerosol fractions have been investigated theoretically and experimentally with respect to melting and deliquescence. We show that a liquid (or an amorphous solid) is the thermodynamically stable phase-even in the absence of water as a solvent-provided that a sufficiently high number of miscible components are present. Furthermore, we show experimentally that the deliquescence relative humidity of aqueous solutions of dicarboxylic acids decreases with an increasing number of components present in the solution. A five-component mixture consisting of malic, malonic, maleic, glutaric, and methylsuccinic acids deliquesces at a relative humidity (RH) as low as 45.4% RH, while the pure dicarboxylic acids exhibit deliquescence points between 72 and 96% RH. A further reduction of the deliquescence relative humidity is observed when an inorganic salt is added to the dicarboxylic acid five-component mixture. For NaCl, deliquescence of the eutonic composition occurred at 41.3%, for ammonium sulfate at 36.4%, and for ammonium nitrate even at 27.1% RH. Interactions between the solutes lead to either higher or lower solubilities in the multicomponent mixture as compared to the respective single-component aqueous solutions. In the mixed dicarboxylic acids/inorganic salt solutions, the solubilities of ammonium nitrate and sulfate are increased by ~40%, the one of sodium chloride is decreased by a similar amount. In summary, these mixing properties suggest that small fractions of organic species prevent tropospheric aerosols from becoming fully solid, and the organic fraction may even stay fully liquid irrespective of tropospheric humidity.
机译：越来越多的单颗粒测量结果表明，大气气溶胶的有机和无机成分在颗粒内部内部混合。因此，气溶胶的相将受到有机物质相互混合以及有机和无机成分之间混合的影响。在这项工作中，已经从熔融和潮解的角度对有机气溶胶馏分的混合特性进行了理论和实验研究。我们证明，即使存在不存在作为溶剂的水，液体（或无定形固体）也是热力学稳定的相，前提是存在足够数量的可混溶组分。此外，我们通过实验表明，二羧酸水溶液的潮解性相对湿度随溶液中存在的组分数量的增加而降低。由苹果酸，丙二酸，马来酸，戊二酸和甲基琥珀酸组成的五组分混合物，在相对湿度（RH）低至45.4％RH的条件下潮解，而纯二羧酸的潮解点在RH的72％至96％之间。当将无机盐添加到二羧酸五组分混合物中时，观察到潮解相对湿度的进一步降低。对于NaCl，甚至在27.1％RH时，自律成分的潮解性为41.3％，对于硫酸铵为36.4％，对于硝酸铵。与相应的单组分水溶液相比，溶质之间的相互作用导致多组分混合物中的溶解度更高或更低。在混合的二羧酸/无机盐溶液中，硝酸铵和硫酸盐的溶解度增加〜40％，氯化钠之一的溶解度减少相似的量。总之，这些混合特性表明，一小部分有机物会阻止对流层气溶胶变成完全固态，并且无论对流层湿度如何，有机物甚至可能保持完全液态。

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