Friday, June 27, 2025

Thermodynamics and emergence

Novelty. 

Temperature and entropy are emergent properties. Classically, they are defined by the zeroth and second laws of thermodynamics, respectively. The individual particles that make up a system in thermodynamic equilibrium do not have these properties. Kadanoff provided an example illustrating the qualitative difference between macro- and micro-perspectives. He pointed out how deterministic behaviour can emerge at the macroscale from stochastic behaviour at the microscale. The many individual molecules in a dilute gas can be viewed as undergoing stochastic motion. However, collectively they are described by an equation of state such as the ideal gas law.

 Primas gave a technical argument, involving C* algebras, that temperature is emergent: it belongs to an algebra of contextual observables but not to the algebra of intrinsic observables.44 Following this perspective, Bishop argued that temperature and the chemical potential are (contextually) emergent.

Intra-stratum closure. 

The laws of thermodynamics, the equations of thermodynamics (such as TdS = dU + pdV), and state functions such as S(U,V), provide a complete description of processes involving equilibrium states. A knowledge of microscopic details, such as the atomic constituents or forces of interaction, is not necessary for the description.

Irreducibility. 

A common view is that thermodynamics can be derived from statistical mechanics. However, this is contentious. David Deutsch claimed that the second law of thermodynamics is an “emergent law”: it cannot be derived from microscopic laws, like the principle of testability.

Lieb and Yngvason stated that the derivation from statistical mechanics of the law of entropy increase “is a goal that has so far eluded the deepest thinkers.”  In contrast, Weinberg claimed that Maxwell, Boltzmann, and Gibbs “showed that the principles of thermodynamics could in fact be deduced mathematically, by an analysis of the probabilities of different configurations… Nevertheless, even though thermodynamics has been explained in terms of particles and forces, it continues to deal with emergent concepts like temperature and entropy that lose all meaning on the level of individual particles.” (Dreams of A Final Theory, pages 40-41)

I agree that thermodynamic properties (e.g., equations of state, the temperature dependence of heat capacity, and phase transitions) can be deduced from statistical mechanics. However, thermodynamic principles, such as the second law, are not thermodynamic properties. Furthermore, these thermodynamic principles are required to justify the equations of statistical mechanics, such as the partition function, that are used to calculate thermodynamic properties. 

Macro hints of microscopics.

The Sackur-Tetrode equation for the entropy of an ideal gas hinted at the quantisation of phase space. The Gibbs paradox hinted that fundamental particles are indistinguishable. The third law of thermodynamics hints at quantum degeneracy.

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Thermodynamics and emergence

Novelty.  Temperature and entropy are emergent properties. Classically, they are defined by the zeroth and second laws of thermodynamics, re...