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» Onsager 互惠关系

Onsager 互惠关系

1930
  • Lars Onsager
利用珀尔帖冷却器和发生器演示热电应用的实验室场景。.

(图片仅供参考)

这些关系是非平衡热力学中的一个关键定理,它们表达了能量和物质耦合流之间某些交叉系数的相等性。它们指出,在没有磁场的情况下,输运系数矩阵是对称的:[latex]L_{alphabeta} = L_{betaalpha}[/latex]。这使得看似无关的输运现象联系起来,例如: 塞贝克佩尔蒂埃 热电效应。

The Onsager reciprocal relations extend classical thermodynamics, which primarily deals with systems in equilibrium, to systems that are near equilibrium but experiencing irreversible processes. These processes are described by a set of linear equations relating thermodynamic ‘fluxes’ (like heat flow, electric current, or mass diffusion) to thermodynamic ‘forces’ (like temperature gradient, electric potential gradient, or chemical potential gradient). For example, a heat flux ([latex]J_q[/latex]) can be caused by a temperature gradient ([latex]X_q[/latex]) and an electric potential gradient ([latex]X_e[/latex]), so [latex]J_q = L_{qq}X_q + L_{qe}X_e[/latex].

The novelty of Onsager’s work, for which he won the 1968 Nobel Prize in Chemistry, was to prove that the cross-coefficient linking the electrical force to heat flow ([latex]L_{qe}[/latex]) is equal to the coefficient linking the thermal force to electric current ([latex]L_{eq}[/latex]). This symmetry is not obvious from macroscopic observation but arises from the principle of microscopic reversibility—the idea that the equations of motion for individual particles are symmetric with respect to time reversal. These relations dramatically simplified the study of complex transport phenomena by reducing the number of independent coefficients that need to be measured experimentally.

UNESCO Nomenclature: 2212
热力学、统计物理学和凝聚态物质

类型

抽象系统

中断

递增

用法

小众/专业

前体

  • 经典热力学(第一和第二定律)
  • 诸如傅里叶热传导定律和菲克扩散定律之类的经验定律
  • 发现各种交叉现象,如塞贝克效应、珀尔帖效应和汤姆森效应
  • 路德维希·玻尔兹曼和 J. 威拉德·吉布斯的统计力学
  • 爱因斯坦关于布朗运动和涨落耗散定理的工作

应用程序

  • 热电(珀尔帖冷却器、放射性同位素热电发电机)
  • 电动力学(微流体电渗透、流动电位)
  • 跨生物膜运输现象的分析
  • 设计多功能材料的材料科学
  • 地球物理学在模拟地壳中耦合热流体流动方面的应用

专利:

NA

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Related to: Onsager reciprocal relations, non-equilibrium thermodynamics, transport phenomena, fluxes, forces, thermoelectricity, seebeck effect, Peltier effect, microscopic reversibility, statistical mechanics.

历史背景

Onsager 互惠关系

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