Thermodynamic Discrimination between Energy Sources for Chemical Reactions
Thermodynamic Discrimination between Energy Sources for Chemical Reactions
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DOI：
10.1016/j.joule.2020.12.014
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发表时间：
2021-01-20
期刊：
影响因子：
39.8
通讯作者：
Manthiram, Karthish
中科院分区：
文献类型：
--
作者：
Schiffer, Zachary J.;Limaye, Aditya M.;Manthiram, Karthish
化学转化跨越巨大的能量差异，然而驱动反应的能量来源的比较通常是在个案的基础上进行的；没有一个基本驱动的、通用的框架来分析和比较化学反应的驱动力。在这项工作中，我们提出了一个与反应无关的平衡常数的表达式，作为温度、压力和电压的函数。对于一组特定的轴，所有的反应都用一个ox来表示；电化学和热化学驱动的反应之间的定量区分是显而易见的。此外，我们表明，我们的表达式在系统的功和能量通量方面具有很强的物理基础，尽管需要有关操作条件的具体数据来提供定量的能量分析。总的来说，这个通用方程和化学反应的简单可视化提供了一个一致的热力学框架，可以在不了解详细过程参数的情况下比较电化学和热化学能源。
Chemical transformations traverse large energy differences, yet the comparison of energy sources to drive a reaction is often done on a case-by-case basis; there is no fundamentally driven, universal framework with which to analyze and compare driving forces for chemical reactions. In this work, we present a reaction-independent expression for the equilibrium constant as a function of temperature, pressure, and voltage. With a specific set of axes, all reactions are represented by a single ox; yTHORN point, and a quantitative divide between electrochemically and thermochemically driven reactions is visually evident. Additionally, we show that our expression has a strong physical basis in work and energy fluxes to the system, although specific data about operating conditions are necessary to provide a quantitative energy analysis. Overall, this universal equation and facile visualization of chemical reactions provides a consistent thermodynamic framework for comparing electrochemical versus thermochemical energy sources without knowledge of detailed process parameters.