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The return of supercooled water to a stable equilibrium condition is an irreversible process which, in large enough samples, takes place adiabatically. We investigated this phenomenon in water by fast imaging techniques. As water freezes, large energy and density fluctuations promote the spatial coexistence of solid and liquid phases at different temperatures. Upon synchronously monitoring the time evolution of the local temperature, we observed a sharp dynamic transition between a fast and a slow decay regime at about 266.6 K. We construe the observed phenomenon in terms of the temperature dependence of heat transfers from solid and liquid volumes already at their bulk coexistence temperature towards adjacent still supercooled liquid regions. These findings can be justified by observing that convective motions induced by thermal gradients in a supercooled liquid near coexistence are rapidly suppressed as the nucleated solid fraction overcomes, at low enough temperatures, a characteristic percolation threshold. [ABSTRACT FROM AUTHOR]

We revisit the concavity property of the thermodynamic entropy in order to formulate a general proof of the minimum energy principle as well as of other equivalent extremum principles that are valid for thermodynamic potentials and corresponding Massieu functions under different constraints. The current derivation aims at providing a coherent formal framework for such principles which may be also pedagogically useful as it fully exploits and highlights the equivalence between different schemes. We also elucidate the consequences of the extremum principles for the general shape of thermodynamic potentials in relation to first-order phase transitions. [ABSTRACT FROM AUTHOR]

A formula expressing the statistical entropy of a lattice-gas model as a multiparticle correlation expansion is derived in the grand-canonical and in the canonical ensembles. The differences from the analogous expansion in the continuum case are elucidated. The Ising model in one dimension is discussed as a case study. [ABSTRACT FROM AUTHOR]