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Conductivity Maxima vs. Temperature: Grotthuss Conductivity in Aprotic Molten Salts

机译:电导率最大与温度:非质子熔盐的射线电导率

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摘要

The phenomenon of electrical conductivity maxima of molten salts versus temperature during orthobaric (closed-vessel) conditions is further examined. First, we summarize results from density-functional-based molecular dynamics simulations of molten SnCl_2 and HgBr_2, which provided structural information but also succeeded in reproducing (i) previously published experimental conductivities to within an order of magnitude, and (ii) the conductivity maxima. The "hopping" mechanism we previously proposed is now termed a Grotthuss mechanism, which became quite clear in the simulations of the molecular liquid HgBr_2 which exhibited Grotthuss chains of bromide transfers. Second, we fit the experimental conductivities of 12 different molten salts with the equation σ = e~(-aT) e~b e~(-c/T), which fits well in most cases, and mapped the density-dependent Arrhenius equation σ(T, ρ) = A(ρ)e~(-Ea(ρ)/RT) onto it in a particular way, generating A and E_a curves for each molten salt for physical insight.
机译:进一步研究了熔融盐的电导率最大值现象,在正交(闭合容器)条件下的温度。首先,我们总结了来自熔融SnCl_2和HgBr_2的密度功能的分子动力学模拟的结果,其提供了结构信息,但也成功地在幅度内再现(i)以前公布的实验导体,并且(ii)电导率最大值。我们以前提出的“跳跃”机制现在被称为麦克风机制,该机制在展示溴化物转移的麦克风链中的分子液体HGBR_2的模拟中变得非常清楚。其次,我们将12个不同熔盐的实验导体与等式σ= e〜(-AT)E〜(-C / T)拟合,这在大多数情况下都适合,并映射了密度依赖的Arhenius方程σ (t,ρ)=(ρ)e〜( - ρ)/ Rt)以特定的方式,为每个熔盐产生A和E_A曲线,用于物理洞察力。

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