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Third Law of Thermodynamics

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

Tipo

Sistema astratto

Interruzione

Sostanziale

Utilizzo

Uso diffuso

Precursori

  • formulation of the Second Law and the concept of entropy
  • experimental advances in liquefying gases (oxygen, nitrogen, hydrogen) and reaching low temperatures
  • development of statistical mechanics by Ludwig Boltzmann and J. Willard Gibbs
  • the emergence of quantum theory from Max Planck’s work on black-body radiation

Applicazioni

  • cryogenics and low-temperature physics
  • calculating chemical affinities and reaction equilibrium constants
  • materials science for understanding crystal structures, defects, and residual entropy
  • research into superconductivity and superfluidity, phenomena that occur near absolute zero
  • determination of absolute entropy values for chemical substances

Brevetti:

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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