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Register a new userThe third law of thermodynamics or an absolute definition for Entropy. Part 2 : definitions and applications
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Pascal Marquet
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This paper is the second part of a previous paper (Marquet, 2019) dealing with the need to define the entropy with an absolute way, by using the third law of thermodynamics. In this second part it is shown that there is a need and interest to define a potential temperature which is a synonym of the moist-air absolute entropy, with several possible novel applications to study meteorology and climate processes.
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This article describes the third law of thermodynamics. This law is often poorly known and is often decried, or even considered optional and irrelevant to describe weather and climate phenomena. This, however, is inaccurate and contrary to scientific facts. A rather exhaustive historical study is proposed here in order to better understand, in another article to come, why the third principle can be interesting for the atmosphere sciences.
Calculations of entropy fluxes and production rate have been evaluated with some success to study atmospheric processes. However, recurring questions arise as to how best to take into account entropy flux due to radiation, for example. This article raises another kind of question: how to define the entropy of the atmosphere itself, which is composed of variable proportions of dry air (nitrogen, oxygen, argon, etc.) and water (vapour, liquid, ice). The specific values of the entropy for such a variable composition system depend on the reference values of its components. Most of the current definitions are based on entropies set at zero for dry air and liquid water at zero degrees Celsius. Differently, the third law of thermodynamics assumes that the entropy of all species cancels out for the more stable solid state at the zero of absolute temperatures. In this paper, we analyze the possible consequences of this absolute definition of entropy of moist air on the calculation of entropy fluxes. The impacts of moisture are significant and these new calculation methods seem to be able to modify the budgets of atmospheric entropy, with possible impacts on the nature of the equilibrium of the atmosphere resulting from entropic imbalances induced by radiations.
It is important to be able to calculate the moist-air entropy of the atmosphere with precision. A potential temperature has already been defined from the third law of thermodynamics for this purpose. However, a doubt remains as to whether this entropy potential temperature can be represented with simple but accurate first- or second-order approximate formulas. These approximations are rigorously defined in this paper using mathematical arguments and numerical adjustments to some datasets. The differentials of these approximations lead to simple but accurate formulations for tendencies, gradients and turbulent fluxes of the moist-air entropy. Several physical consequences based on these approximations are described and can serve to better understand moist-air processes (like turbulence or diabatic forcing) or properties of certain moist-air quantities (like the static energies).
The exergy of the dry atmosphere can be considered as another aspect of the meteorological theories of available energies. The local and global properties of the dry available enthalpy function, also called flow exergy, were investigated in a previous paper (Marquet, Q. J. R. Meteorol. Soc., Vol 117, p.449-475, 1991). The concept of exergy is well defined in thermodynamics, and several generalizations to chemically reacting systems have already been made. Similarly, the concept of moist available enthalpy is presented in this paper in order to generalize the dry available enthalpy to the case of a moist atmosphere. It is a local exergy-like function which possesses a simple analytical expression where only two unknown constants are to be determined, a reference temperature and a reference pressure. The moist available enthalpy, $a_m$, is defined in terms of a moist potential change in total entropy. The local function $a_m$ can be separated into temperature, pressure and latent components. The latent component is a new component that is not present in the dry case. The moist terms have been estimated using a representative cumulus vertical profile. It appears that the modifications brought by the moist formulation are important in comparison with the dry case. Other local and global properties are also investigated and comparisons are made with some other available energy functions used in thermodynamics and meteorology.
We consider open quantum systems consisting of a finite system of independent fermions with arbitrary Hamiltonian coupled to one or more equilibrium fermion reservoirs (which need not be in equilibrium with each other). A strong form of the third law of thermodynamics, $S(T) rightarrow 0$ as $Trightarrow 0$, is proven for fully open quantum systems in thermal equilibrium with their environment, defined as systems where all states are broadened due to environmental coupling. For generic open quantum systems, it is shown that $S(T)rightarrow gln 2$ as $Trightarrow 0$, where $g$ is the number of localized states lying exactly at the chemical potential of the reservoir. For driven open quantum systems in a nonequilibrium steady state, it is shown that the local entropy $S({bf x}; T) rightarrow 0$ as $T({bf x})rightarrow 0$, except for cases of measure zero arising due to localized states, where $T({bf x})$ is the temperature measured by a local thermometer.
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