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首页> 外文期刊>The journal of physical chemistry, A. Molecules, spectroscopy, kinetics, environment, & general theory >Adsorption of Atmospheric Gases at the Air-Water Interface. 4: The Influence of Salts
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Adsorption of Atmospheric Gases at the Air-Water Interface. 4: The Influence of Salts

机译：空气-水界面处的大气气体吸附。 4：盐的影响

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摘要

We have measured the standard free energies and standard enthalpies of adsorption as well as saturated surface coverages for hexanoic acid and 1-propanol adsorbed at the air-aqueous interface of sodium chloride (NaCl) and ammonium sulfate ((NH_4)_2SO_4) solutions of concentrations between 0 and 4 mol L~(-1). Temperature-dependent surface tension measurements are used to obtain ΔG_(aq→σ)~0 and ΔH_(aq→σ)~0; using known Henry's law constants and estimated values of the salting-out coefficient we calculate the gas-interface adsorption parameters ΔG_(g→σ)~0 and ΔH_(g→σ)~0. A small (～1-2 kJ mol~(-1)) decrease in ΔG_(aq→σ)~0 with increasing salt concentration is accompanied by an increase (～10-30%) in saturated surface coverage, consistent with the expected "salting-out" behavior. Adsorption from the gas phase becomes somewhat less favorable with increasing salt concentration for both organic species. The standard enthalpy of adsorption from the gas phase decreases with increasing salt concentration for hexanoic acid, but not for 1-propanol. This may be a consequence of acid dimer formation at the interface becoming important at higher coverages.
机译：我们已经测量了在浓度为氯化钠（NaCl）和硫酸铵（（NH_4）_2SO_4）的空气-水界面处吸附的己酸和1-丙醇的标准自由能和标准吸附焓以及饱和表面覆盖率在0至4 mol L〜（-1）之间。随温度变化的表面张力测量值用于获得ΔG_（aq→σ）〜0和ΔH_（aq→σ）〜0;利用已知的亨利定律常数和盐析系数的估计值，我们计算出气界面吸附参数ΔG_（g→σ）〜0和ΔH_（g→σ）〜0。随着盐浓度的增加，ΔG_（aq→σ）〜0的小幅下降（〜1-2 kJ mol〜（-1））伴随着饱和表面覆盖率的增加（〜10-30％），与预期一致“出盐”行为。对于两种有机物质，随着盐浓度的增加，气相的吸附变得有些不利。气相的标准吸附焓随己酸而不是1-丙醇的盐浓度的增加而降低。这可能是由于在较高覆盖率下界面处形成酸二聚体变得重要的结果。

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