Departamento de Química Física, Facultad de Ciencia y Tecnología, Universidad del País Vasco/Euskal Herriko Unibertsitatea, Campus de Leioa, B. Sarriena, s/n, Leioa 48940, Spain.
J Phys Chem A. 2010 May 27;114(20):6124-30. doi: 10.1021/jp101149k.
Atmospheric aerosols typically consist of inorganic and organic material. Although the organic fraction can affect the behavior of mixed organic/inorganic particles, their physical properties are not well-understood. In this work, infrared spectra of internally mixed submicrometer particles of ammonium sulfate and succinic acid have been studied at ambient temperature in an aerosol flow cell. The spectra of dried particles show distinct features relative to the pure components, as a result of ion-molecule interactions between the inorganic and organic species. The hygroscopic behavior of the particles has been followed for several organic/inorganic mass ratios, showing that around equimolar composition, the mixed particles uptake water in a broad range of relative humidities (30-80%), substantially lower than the deliquescence relative humidity of the mixed system near 80%. Infrared spectra at predeliquescence relative humidities reveal that succinic acid is partially or completely in the liquid phase at much higher concentrations that those corresponding to a saturated solution of succinic acid. This behavior is proposed to arise from the ion-molecule interactions between the organic and inorganic components, which unstabilize the crystal structure relative to the pure solids and cause loss of translational order in the crystal, bringing about an increase in the Gibbs energy of the solid particles and allowing the uptake of water molecules prior to the deliquescence point. The obtained results show that water absorption prior to full deliquescence in this system has to be taken into account because it extends the range of relative humidities at which particles are partially or completely liquid.
大气气溶胶通常由无机和有机物质组成。虽然有机部分可以影响混合有机/无机颗粒的行为,但它们的物理性质还不是很清楚。在这项工作中,在气溶胶流动池中,研究了在环境温度下硫酸铵和琥珀酸的亚微米级混合颗粒的红外光谱。与纯组分相比,干燥颗粒的光谱显示出明显的特征,这是由于无机和有机物种之间的离子-分子相互作用。研究了几个有机/无机质量比的颗粒吸湿性,结果表明,在等摩尔组成附近,混合颗粒在较宽的相对湿度范围内(30-80%)吸收水分,远低于混合体系在 80%附近的吸湿相对湿度。在预吸湿相对湿度下的红外光谱表明,琥珀酸在比琥珀酸饱和溶液高得多的浓度下部分或完全处于液相。这种行为是由于有机和无机成分之间的离子-分子相互作用引起的,这种相互作用使晶体结构相对于纯固体不稳定,并导致晶体中平移有序的丧失,导致固体颗粒的吉布斯能增加,并允许水分子在达到吸湿点之前吸收。得到的结果表明,在这个体系中,在完全吸湿之前吸收水分必须考虑在内,因为它扩大了颗粒部分或完全处于液态的相对湿度范围。