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Thermodynamics

Contents

Idea

From Wikipedia:

Thermodynamics is the science of energy conversion involving heat and other forms of energy, most notably mechanical work. It studies and interrelates the macroscopic variables, such as temperature, volume and pressure, which describe physical, thermodynamic systems.

Details

On this Azimuth page we will mainly focus on the modern interpretation of thermodynamics, including:

Non-equilibrium thermodynamics is a branch of thermodynamics that deals with systems that are not in thermodynamic equilibrium. Most systems found in nature are not in thermodynamic equilibrium; for they are changing or can be triggered to change over time, and are continuously and discontinuously subject to flux of matter and energy to and from other systems. For their thermodynamic study, more general concepts are required for non-equilibrium systems than for equilibrium systems. Non-equilibrium systems can be in stationary states that are not homogeneous even when there is no externally imposed field of force; in this case, the description of the internal state of the system requires a field theory. Many natural systems still today remain beyond the scope of currently known macroscopic thermodynamic methods.

A dissipative structure is characterized by the spontaneous appearance of symmetry breaking (anisotropy) and the formation of complex, sometimes chaotic, structures where interacting particles exhibit long range correlations. The term dissipative structure was coined by Russian-Belgian physical chemist Ilya Prigogine, who was awarded the Nobel Prize in Chemistry in 1977 for his pioneering work on these structures. The dissipative structures considered by Prigogine have dynamical régimes that can be regarded as thermodynamically steady states, and sometimes at least can be described by suitable extremal principles in non-equilibrium thermodynamics. Simple examples include convection, cyclones and hurricanes. More complex examples include lasers, Rayleigh-Bénard convection, the Belousov–Zhabotinsky reaction and at the most sophisticated level, life itself.

One way of mathematically modeling a dissipative system is given in the article on wandering sets: it involves the action of a group on a measurable set.

In thermodynamics, the Onsager reciprocal relations express the equality of certain ratios between flows and forces in thermodynamic systems out of equilibrium, but where a notion of local equilibrium exists.“Reciprocal relations” occur between different pairs of forces and flows in a variety of physical systems. For example, consider fluid systems described in terms of temperature, matter density, and pressure. In this class of systems, it is known that temperature differences lead to heat flows from the warmer to the colder parts of the system; similarly, pressure differences will lead to matter flow from high-pressure to low-pressure regions. What is remarkable is the observation that, when both pressure and temperature vary, temperature differences at constant pressure can cause matter flow (as in convection) and pressure differences at constant temperature can cause heat flow. Perhaps surprisingly, the heat flow per unit of pressure difference and the density (matter) flow per unit of temperature difference are equal. This equality was shown to be necessary by Lars Onsager using statistical mechanics as a consequence of the time reversibility of microscopic dynamics. The theory developed by Onsager is much more general than this example and capable of treating more than two thermodynamic forces at once, with the limitation that “the principle of dynamical reversibility does not apply when (external) magnetic fields or Coriolis forces are present”, in which case “the reciprocal relations break down”.

Modeling

One way of mathematically modeling a dissipative system is given in the article on wandering sets: it involves the action of a group on a measurable set.

In those branches of mathematics called dynamical systems and ergodic theory, the concept of a wandering set formalizes a certain idea of movement and mixing in such systems. When a dynamical system has a wandering set of non-zero measure, then the system is a dissipative system. This is very much the opposite of a conservative system, for which the ideas of the Poincaré recurrence theorem apply. Intuitively, the connection between wandering sets and dissipation is easily understood: if a portion of the phase space “wanders away” during normal time-evolution of the system, and is never visited again, then the system is dissipative. The language of wandering sets can be used to give a precise, mathematical definition to the concept of a dissipative system. The notion of wandering sets in phase space was introduced by Birkhoff in 1927.

References

See also Extremal principles in non-equilibrium thermodynamics here on the Azimuth Library.