Maximal entropy in an isolated system implies thermodynamic equilibrium
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Peer-reviewed physics literature and reference texts indicate that isolated systems evolve such that their entropy increases and reaches a maximum, corresponding to a state of thermodynamic equilibrium.
Throughout Earth's history, life has increased greatly in abundance, complexity, and diversity. At the same time, it has substantially altered the Earth's environment, evolving some of its variables to states further and further away from thermodynamic equilibrium. For instance, concentrations in atmospheric oxygen have increased throughout Earth's history, resulting in an increased chemical disequilibrium in the atmosphere as well as an increased redox gradient between the atmosphere and the Earth's reducing crust. These trends seem to contradict the second law of thermodynamics, which states for isolated systems that gradients and free energy are dissipated over time, resulting in a state of thermodynamic equilibrium. This seeming contradiction is resolved by considering planet Earth as a coupled, hierarchical and evolving non-equilibrium thermodynamic system that has been substantially altered by the input of free energy generated by photosynthetic life. Here, I present this hierarchical thermodynamic theory of the Earth system. I first present simple considerations to show that thermodynamic variables are driven away from a state of thermodynamic equilibrium by the transfer of power from some other process and that the resulting state of disequilibrium reflects the past net work done on the variable. This is applied to the processes of planet Earth to characterize the generation and transfer of free energy and its dissipation, from radiative gradients to temperature and chemical potential gradients that result in chemical, kinetic, and potential free energy and associated dynamics of the climate system and geochemical cycles. The maximization of power transfer among the processes within this hierarchy yields thermodynamic efficiencies much lower than the Carnot efficiency of equilibrium thermodynamics and is closely related to the proposed principle of Maximum Entropy Production (MEP). The role of life is then discussed as a photochemical process that generates substantial amounts of chemical free energy which essentially skips the limitations and inefficiencies associated with the transfer of power within the thermodynamic hierarchy of the planet. This perspective allows us to view life as being the means to transform many aspects of planet Earth to states even further away from thermodynamic equilibrium than is possible by purely abiotic means. In this perspective pockets of low-entropy life emerge from the overall trend of the Earth system to increase the entropy of the universe at the fastest possible rate. The implications of the theory are discussed regarding fundamental deficiencies in Earth system modeling, applications of the theory to reconstructions of Earth system history, and regarding the role of human activity for the future of the planet.
The unitary dynamics of isolated quantum systems does not allow a pure state to thermalize. Because of that, if an isolated quantum system equilibrates, it will do so to the predictions of the so-called “diagonal ensemble” ρ DE . Building on the intuition provided by Jaynes’ maximum entropy principle, in this paper we present a novel technique to generate progressively better approximations to ρ DE . As an example, we write down a hierarchical set of ensembles which can be used to describe the equilibrium physics of small isolated quantum systems, going beyond the “thermal ansatz” of Gibbs ensembles.
Molecular Theory of Irreversibility
A generalization of the Gibbs entropy postulate is proposed based on the BBGKY hierarchy as the nonequilibrium entropy for a system of N interacting particles. This entropy satisfies the basic principles of thermodynamics in the sense that it reaches its maximum at equilibrium and is coherent with the second law. By using a generalization of the Liouville equation describing the evolution of the distribution vector, it is demonstrated that the entropy production is a non-negative quantity. Moreover, following the procedure of non-equilibrium thermodynamics a transport matrix is introduced and a microscopic expression for this is derived. This framework allows one to perform the thermodynamic analysis of non-equilibrium steady states which, as proven here, constitute the states of minimum entropy production when one considers small departures from stationarity.
Published as: The Journal of Chemical Physics 123, 204108 (2005)
DOI: 10.1063/1.2131059
arXiv categories: cond-mat.stat-mech
The nonlinear equation of motion that accomplishes a self-consistent unification of quantum mechanics (QM) and thermodynamics conceptually different from the (von Neumann) foundations of quantum statistical mechanics (QSM) and (Jaynes) quantum information theory (QIT), but which reduces to the same mathematics for the thermodynamic equilibrium (TE) states, and contains standard QM in that it reduces to the time-dependent Schrödinger equation for zero entropy states is discussed in full mathematical detail. By restricting the discussion to a strictly isolated system (noninteracting, disentangled and uncorrelated), we show how the theory departs from the conventional QSM/QIT rationalization of the second law of thermodynamics, which instead emerges in QT (quantum thermodynamics) as a theorem of existence and uniqueness of a stable equilibrium state for each set of mean values of the energy and the number of constituent particles. To achieve this, the theory assumes Trρ lnρ B −k for the physical entropy and is designed to implement two fundamental ansatzs: (1) that in addition to the standard QM states described by idempotent density operators (zero entropy), a strictly isolated and uncorrelated system admits also states that must be described by non-idempotent density operators (nonzero entropy); (2) that for such additional states the law of causal evolution is determined by the simultaneous action of a Schrödinger-von Neumann-type Hamiltonian generator
equilibrium with a third system, the two original systems are in thermal equilibrium with each other. Basically, if system A is in thermal equilibrium with system C and system B is also in thermal equilibrium with system C, system A and system B are in thermal equilibrium with each other. - 1st Law of Thermodynamics
- The First Law of Thermodynamics states that energy can be converted from one form to another with the interaction of heat, work and internal energy, but it cannot be created nor destroyed, under any circumstances. - 2nd Law of Thermodynamics
- The Second Law of Thermodynamics states that the state of entropy of the entire universe, as an isolated system, will always increase over time. The second law also states that the changes in the entropy in the universe can never be negative. - 3rd Law of Thermodynamics
- The 3rd law of thermodynamics will essentially allow us to quantify the absolute amplitude of entropies. It says that when we are considering a totally perfect (100% pure) crystalline structure, at absolute zero (0 Kelvin), it will have no entropy (S).
that the entropy of isolated systems left to spontaneous evolution cannot decrease, as they always tend toward a state of thermodynamic equilibrium where
The second law of thermodynamics is a physical law based on universal empirical observation concerning heat and energy interconversions. A simple statement of the law is that heat always flows spontaneously from hotter to colder regions of matter (or 'downhill' in terms of the temperature gradient). Another statement is: "Not all heat can be converted into work in a cyclic process." These are info
This…
where
Ω
(
E
)
{\displaystyle \Omega \left(E\right)}
is the number of quantum states in a small interval between
E
{\displaystyle E}
and
E
+
δ
E
{\displaystyle E+\delta E}
. Here
δ
E
{\displaystyle \delta E}
is a macroscopically small energy interval that is kept fixed. Strictly speaking this means that the entropy depends on the choice of
δ
E
{\displaystyle \delta E}
. However, in the thermodynamic limit (i.e. in the limit of infinitely…
As elaborated above, it is thought that the second law of thermodynamics is a result of the very low-entropy initial conditions at the Big Bang. From a statistical point of view, these were very special conditions. On the other hand, they were quite simple, as the universe – or at least the part thereof from which the observable universe developed – seems to have been extremely uniform.
This may seem somewhat paradoxical, since in many physical systems uniform conditions (e.g. mixed rather than separated gases) have high entropy. The paradox is solved once realizing that gravitational systems have negative heat capacity, so that when gravity is important, uniform conditions (e.g. gas of uniform density) in fact have lower entropy compared to non-uniform ones (e.g. black holes in empty space). Yet another approach is that the universe had high (or even maximal) entropy given its size, but as the universe grew it rapidly came out of thermodynamic equilibrium, its entropy only slightly increased compared to the increase in maximal possible entropy, and thus it has arrived at a very low entropy when compared to the much larger possible maximum given its later size.
As for the reason why initial conditions were such, one suggestion is that cosmological inflation was enough to wipe off non-smoothness, while another is that the universe was created spontaneously where the mechanism of creation implies low-entropy initial conditions.
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