Thermodynamics of Small Systems

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Evans, Denis J.
Williams, Stephen R.
Bernhardt, Debra
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G Radons, B Rumpf & H G Schuster

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2010
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Abstract

Thermodynamics is the study of the flow and transformation of heat into work. Until recently, our understanding of thermodynamics was largely confined to equi-librium states. Linear irreversible thermodynamics is a simple extension of the nineteenth century concepts of equilibrium thermodynamics to systems that are sufficiently close to equilibrium, that intensive thermodynamic variables can be ap-proximated by the same functions of local state variables as would be the case if the entire system was in complete thermodynamic equilibrium. Classical thermody-namics was limited in application to large systems where intensive thermodynam-ic functions do not change their values if the system size is increased. This is often referred to as the “thermodynamic limit”. In spite of these restrictions, thermodynamics is arguably the most widely appli-cable theory in physics. Its First and Second Laws are probably held with greater conviction that any other statements in physics. In the last fifteen years, three new theorems have been proven that revolution-ize our understanding of thermodynamics. Firstly, these new theorems remove the need to take the thermodynamic limit. This allows the application of thermody-namic concepts to finite, and even “nano” systems. Secondly, these new theorems can be applied to systems that are arbitrarily far from equilibrium. Thirdly, and for the first time, these theorems explain how macroscopic irreversibility appears naturally in systems that obey time reversible microscopic dynamics. Resolution of the Loschmidt (Irreversibility) Paradox had defied our best efforts for more than 100 years. These theorems remove the need for the Second Law of thermodynam-ics. That “law” now becomes a limiting (thermodynamic limit) consequence of the laws of mechanics and the Axiom of Causality: that an event A, can only influence event B, if A occurred prior to B.

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Nonlinear dynamics of nanosystems

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Thermodynamics and statistical physics

Condensed matter physics not elsewhere classified

Chemical thermodynamics and energetics

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