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Henry's and non-Henry's law behavior of Br in simple marine systems

机译:Br在简单海洋系统中的亨利定律和非亨利定律行为

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摘要

Experimental studies for the partitioning of Br as a trace element between aqueous and solid solutions were carried out in simple marine systems. The evaporation experiments were pet-formed at 25degreesC and 1 atm in the systems of halite (NaCl), sylvite (KCl), kainite (KMgClSO4 . 2.75H(2)O), carnallite (KMgCl3 . 6H(2)O), and bischofite (MgCl2 . 6H(2)O). The partition coefficients for the systems investigated are constant only at a restricted concentration range. For concentrations lower than 100 to 300 mug Br/g aqueous solutions, D-Br increases with decreasing concentrations. Various evaporation experiments indicate that this observation is not due to kinetic effects (evaporation rates). To find a link between the partition coefficient and the Henry's law behavior, the activity coefficients of the trace components in the solid solutions were recalculated from the experimentally derived data. It can be shown from these calculations that constant activity coefficients or Henry's law behavior is reached for higher mole fractions of the trace component in the solid solution in halite and sylvite and thus correspond to constant partition coefficients. For bischofite and carnallite, Henry's law behavior is restricted to the lower mole fractions, where D-Br is not constant. This behavior is caused by the activity of the trace component in the aqueous solution, which is powered by the stoichiometric factor of this component in the Br-end-member solid solution. For halite, sylvite, and kainite, this factor equals 1 and is 2 for bischofite and 3 for carnallite. However, it is thus impossible to correlate Henry's law behavior with constant partition coefficients for solid solution systems where the stoichiometric factor of the trace component is greater than 1. Copyright (C) 2002 Elsevier Science Ltd. [References: 29]
机译:在简单的海洋系统中进行了将Br作为痕量元素在水溶液和固溶体之间分配的实验研究。蒸发实验是在25摄氏度和1个大气压下在盐岩(NaCl),钾盐(KCl),钾盐岩(KMgClSO4.2.75H(2)O),角钠石(KMgCl3.6H(2)O)和重钙钛矿(MgCl 2·6H(2)O)。研究的系统的分配系数仅在有限的浓度范围内是恒定的。对于浓度低于100至300马克杯的Br / g水溶液,D-Br随浓度降低而增加。各种蒸发实验表明,这种观察不是由于动力学效应(蒸发速率)引起的。为了找到分配系数与亨利定律行为之间的联系,从实验得出的数据中重新计算了固溶体中痕量组分的活度系数。从这些计算中可以看出,对于在石盐和钾盐中的固溶体中的痕量组分的较高摩尔分数,达到了恒定的活度系数或亨利定律行为,因此对应于恒定的分配系数。对于双锂辉石和钠盐岩,亨利定律的行为仅限于较低的摩尔分数,其中D-Br不是恒定的。此行为是由水溶液中微量组分的活性引起的,该活性由Br-端元固溶体中该组分的化学计量因子提供动力。对于岩盐,钾盐和钾盐岩,该系数等于1,对于Bischofite,该系数等于2,对于钠盐岩,该系数等于3。但是,对于痕量组分的化学计量系数大于1的固溶系统,不可能将亨利定律行为与恒定分配系数相关联。(C)2002 Elsevier Science Ltd. [参考:29]

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