Consistent Modelling of Non-Equilibrium Thermodynamic Processes in the Atmosphere

<p>Approximations in the moist thermodynamics of atmospheric/weather models are often inconsistent. Different parts of numerical models may handle the thermodynamics in different ways, or the approximations may disagree with the laws of thermodynamics. In order to address these problems we may derive all relevant thermodynamic quantities from a defined thermodynamic potential; approximations are then instead made to the potential itself --- this guarantees self-consistency. This concept is viable for vapor and liquid water mixtures in a moist atmospheric system using the Gibbs function but on extension to include the ice phase an ambiguity exists at the triple-point. In order to resolve this the energy function must be used instead; constrained maximisation methods may be used on the entropy in order to solve the system equilibrium state. Once this is done however, a further extension is necessary for atmospheric systems. In the Earth's atmosphere many important non-equilibrium processes take place; for example, freezing of super-cooled water, evaporation, and precipitation. To fully capture these processes the equilibrium method must be reformulated to involve finite rates of approach towards equilibrium. This may be done using various principles of non-equilibrium thermodynamics, principally Onsager reciprocal relations. A numerical scheme may then be implemented which models the competing finite processes in a moist thermodynamic system.</p>

Necessary and Sufficient Conditions for Time Reversal Symmetry in Presence of Magnetic Fields

Time reversal invariance (TRI) of particles systems has many consequences, among which the celebrated Onsager reciprocal relations, a milestone in Statistical Mechanics dating back to 1931. Because for a long time it was believed that (TRI) dos not hold in presence of a magnetic field, a modification of such relations was proposed by Casimir in 1945. Only in the last decade, the strict traditional notion of reversibility that led to Casimir’s work has been questioned. It was then found that other symmetries can be used, which allow the Onsager reciprocal relations to hold without modification. In this paper we advance this investigation for classical Hamiltonian systems, substantially increasing the number of symmetries that yield TRI in presence of a magnetic field. We first deduce the most general form of a generalized time reversal operation on the phase space of such a system; secondly, we express sufficient conditions on the magnetic field which ensure TRI. Finally, we examine common examples from statistical mechanics and molecular dynamics. Our main result is that TRI holds in a much wider generality than previously believed, partially explaining why no experimental violation of Onsager relations has so far been reported.

Consistent Modelling of Non-Equilibrium Thermodynamic Processes in the Atmosphere

<p>Approximations in the moist thermodynamics of atmospheric/weather models are often inconsistent. Different parts of numerical models may handle the thermodynamics in different ways, or the approximations may disagree with the laws of thermodynamics. In order to address these problems, we may derive all relevant thermodynamic quantities from a defined thermodynamic potential; approximations are then instead made to the potential itself — this guarantees self-consistency. This concept is viable for vapor and liquid water mixtures in a moist atmospheric system using the Gibbs function but on extension to include the ice phase an ambiguity presents itself at the triple-point. In order to resolve this the energy function must be utilised instead; constrained maximisation methods can then be used on the entropy in order to solve the system equilibrium state. Once this is done however, a further extension is necessary for atmospheric systems. In the Earth’s atmosphere many important non-equilibrium processes take place; for example, freezing of super-cooled water, evaporation, and precipitation. To fully capture these processes the equilibrium method must be reformulated to involve finite rates of approach towards equilibrium. This may be done using various principles of non-equilibrium thermodynamics, principally Onsager reciprocal relations. A numerical scheme may then be implemented which models competing finite processes in a moist thermodynamic system.</p>

Gradient Dynamics and Entropy Production Maximization

We compare two methods for modeling dissipative processes, namely gradient dynamics and entropy production maximization. Both methods require similar physical inputs–-how energy (or entropy) is stored and how it is dissipated. Gradient dynamics describes irreversible evolution by means of dissipation potential and entropy, it automatically satisfies Onsager reciprocal relations as well as their nonlinear generalization (Maxwell–Onsager relations), and it has statistical interpretation. Entropy production maximization is based on knowledge of free energy (or another thermodynamic potential) and entropy production. It also leads to the linear Onsager reciprocal relations and it has proven successful in thermodynamics of complex materials. Both methods are thermodynamically sound as they ensure approach to equilibrium, and we compare them and discuss their advantages and shortcomings. In particular, conditions under which the two approaches coincide and are capable of providing the same constitutive relations are identified. Besides, a commonly used but not often mentioned step in the entropy production maximization is pinpointed and the condition of incompressibility is incorporated into gradient dynamics.