nucleation

LIT-1889: Nonequilibrium Thermodynamics of Chemical Reaction Networks: Wisdom from Stochastic Thermodynamics

1 min read

Properties5
StatusActive — read in full 2026-10-31 (NOTE-1464); worth reading as the standard deterministic thermodynamics of open reaction networks, and for what it makes exact in the exchange's A13: sustained turnover needs an emergent fuel-to-waste cycle with nonzero affinity, and costs its current times that affinity (THEORY-1266).
Version2
Tagsthermodynamics, complex-systems
Cited as “paper” byNOTE-1464 — Rao & Esposito — Thermodynamics of open chemical reaction networks
Cited as “source” byTHEORY-1248 — Catalysts cancel out of the stoichiometric matrix, so a cycle of mutual catalytic production among species is not a stoichiometric cycle: the cycles that carry a reaction network's steady currents and affinities are fuel-to-waste pathways through it, and who catalyses whom enters only the rates, never the thermodynamic driving, THEORY-1266 — In an open reaction network of reversible elementary mass-action reactions, sustained currents need an emergent cycle with nonzero affinity: each chemostatted species either breaks a conservation law or opens an emergent cycle, so one chemostat never suffices; with every emergent affinity zero the network relaxes to a unique equilibrium fixed by its unbroken conserved quantities; and a nonequilibrium steady state dissipates exactly the sum over emergent cycles of current times affinity

Graph View

Rao, R., & Esposito, M. (2016). Nonequilibrium thermodynamics of chemical reaction networks: Wisdom from stochastic thermodynamics. Physical Review X, 6, 041064.

Read in full in NOTE-1464.

Why this is here

A13’s first toolkit for putting the toy production models on a thermodynamic footing: a production term written as a catalysed reaction must be paid for by an affinity, so a positive production rate is not yet a physically realizable maintenance mechanism. The reading bears A13 out and makes it exact (THEORY-1266). Rewritten as reversible elementary chemistry, CASE-189’s first construction needs a fuel and a waste chemostat. At zero affinity it has a single equilibrium with no current. It is bistable only above 3.52 RT, and recovers the case’s equilibria only as the affinity goes to infinity, which is also the limit in which CLAIM-516’s “no basal production” holds (NOTE-1464). It bears on CLAIM-273, whose missing thermodynamic quantity is shown to need a stoichiometry, local detailed balance and reservoirs, and on THEORY-692: complex-balanced networks are a far-from-equilibrium case with a Lyapunov function, so a chemical dissipative structure needs nonzero deficiency.

Backlinks