» 热力学第三定律

热力学第三定律

1910
  • Walther Nernst
  • Max Planck
Laboratory scene demonstrating the Third Law of Thermodynamics in cryogenics.

The Third Law states that the entropy of a perfect crystal approaches a constant minimum as its temperature approaches absolute zero ([latex]0[/latex] Kelvin). This minimum value is defined as zero. A key consequence is the unattainability of absolute zero in a finite number of steps. This law provides a fundamental reference point for determining the absolute entropy of a substance.

The Third Law originated from Walther Nernst’s work on chemical reactions at low temperatures, formulated as the Nernst Heat Theorem in 1906. He observed that the change in entropy for chemical reactions approaches zero as the temperature approaches absolute zero. Max Planck later extended this to state that the entropy of each individual perfect crystalline substance is itself zero at absolute zero. This provides an absolute, rather than relative, scale for entropy.

The law’s novelty lies in its connection between thermodynamics and the quantum-mechanical nature of matter. At absolute zero, a system is in its ground state, which for a perfect crystal is a unique, non-degenerate state, corresponding to zero entropy ([latex]S = k_B \ln(1) = 0[/latex]). Amorphous materials like glass, however, have residual entropy at absolute zero due to their disordered structure. The law also implies that as [latex]T \rightarrow 0[/latex], specific heats ([latex]C_p[/latex], [latex]C_v[/latex]) and the coefficient of thermal expansion also approach zero. The unattainability principle arises because each step in a cooling process removes a smaller and smaller amount of entropy, requiring an infinite number of steps to reach zero entropy.

UNESCO Nomenclature: 2212
– Thermodynamics, statistical physics, and condensed matter

类型

抽象系统

中断

实质性

使用方法

广泛使用

前体

  • formulation of the Second Law and the concept of entropy
  • 液化气体(氧气、氮气、氢气)和达到低温的实验进展
  • 路德维希·玻尔兹曼和 J. 威拉德·吉布斯对统计力学的发展
  • the emergence of quantum theory from Max Planck’s work on black-body radiation

应用

  • 低温学和低温物理学
  • 计算化学亲和力和反应平衡常数
  • 材料科学,用于了解晶体结构、缺陷和残余熵
  • 研究超导性和超流体性,即在绝对零度附近发生的现象
  • 化学物质绝对熵值的测定

专利:

NA

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Related to: third law, absolute zero, entropy, perfect crystal, Nernst heat theorem, unattainability principle, cryogenics, ground state, quantum mechanics, zero-point energy.

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