Entropy is a thermodynamic state variable that quantifies the probabilistic distribution of accessible microstates in a system. The term and the concept are used in diverse fields, from classical thermodynamics (where it was first recognized), to the microscopic description of nature in statistical physics, and the principles of information theory. It has far-ranging applications in chemistry and physics, in biological systems and their relation to life, in cosmology, economics, and information systems including the transmission of information in telecommunication. Entropy is central to the second law of thermodynamics, which states that the entropy of an isolated system left to spontaneous evolution cannot decrease with time. As a result, isolated systems evolve toward thermodynamic equilibrium, where the entropy is highest. "High" entropy means that energy is more disordered or dispersed, while "low" entropy means that energy is more ordered or concentrated. A consequence of the second law of thermodynamics is that certain processes are irreversible. The thermodynamic concept was referred to by Scottish scientist and engineer William Rankine in 1850 with the names thermodynamic function and heat-potential. In 1865, German physicist Rudolf Clausius, one of the leading founders of the field of thermodynamics, defined it as the quotient of an infinitesimal amount of heat to the instantaneous temperature. He initially described it as transformation-content, in German Verwandlungsinhalt, and later coined the term entropy from a Greek word for transformation. Austrian physicist Ludwig Boltzmann explained entropy as the measure of the number of possible microscopic arrangements or states of individual atoms and molecules of a system that comply with the macroscopic condition of the system. He thereby introduced the concept of statistical disorder and probability distributions into a new field of thermodynamics, called statistical mechanics, and found the link between the microscopic interactions, which fluctuate about an average configuration, to the macroscopically observable behaviour, in the form of a simple logarithmic law, with a proportionality constant, the Boltzmann constant, which has become one of the defining universal constants for the modern International System of Units.
History
In his 1803 paper Fundamental Principles of Equilibrium and Movement, the French mathematician Lazare Carnot proposed that in any machine, the accelerations and shocks of the moving parts represent losses of moment of activity; in any natural process there exists an inherent tendency towards the dissipation of useful energy. In 1824, building on that work, Lazare's son, Sadi Carnot, published Reflections on the Motive Power of Fire, which posited that in all heat-engines, whenever "caloric" (now known as heat) falls through a temperature difference, work or motive power can be produced from the actions of its fall from a hot to cold body. He used an analogy with how water falls in a water wheel. That was an early insight into the second law of thermodynamics. Carnot based his views of heat partially on the early 18th-century "Newtonian hypothesis" that both heat and light were types of indestructible forms of matter, which are attracted and repelled by other matter, and partially on the contemporary views of Count Rumford, who showed in 1789 that heat could be created by friction, as when cannon bores are machined. Carnot reasoned that if the body of the working substance, such as a body of steam, is returned to its original state at the end of a complete engine cycle, "no change occurs in the condition of the working body". The first law of thermodynamics, deduced from the heat–friction experiments of James Joule in 1843, expresses the concept of energy and its conservation in all processes; the first law, however, is unsuitable for separately quantifying the effects of friction and dissipation. In the 1850s and 1860s, German physicist Rudolf Clausius objected to the supposition that no change occurs in the working body, and gave that change a mathematical interpretation, by questioning the nature of the inherent loss of usable heat when work is done, e.g., heat produced by friction. He described his observations as a dissipative use of energy, resulting in a transformation-content (Verwandlungsinhalt in German), of a thermodynamic system or working body of chemical species during a change of state. That was in contrast to earlier views, based on the theories of Isaac Newton, that heat was an indestructible particle that had mass. Clausius discovered that the non-usable energy increases as steam proceeds from inlet to exhaust in a steam engine. From the prefix en-, as in 'energy', and from the Greek word τροπή [tropē], which is translated in an established lexicon as turning or change and that he rendered in German as Verwandlung, a word often translated into English as transformation, in 1865 Clausius coined the name of that property as entropy. The word was adopted into the English language in 1868. Later, scientists such as Ludwig Boltzmann, Josiah Willard Gibbs, and James Clerk Maxwell gave entropy a statistical basis. In 1877, Boltzmann visualized a probabilistic way to measure the entropy of an ensemble of ideal gas particles, in which he defined entropy as proportional to the natural logarithm of the number of microstates such a gas could occupy. The proportionality constant in this definition, called the Boltzmann constant, has become one of the defining universal constants for the modern International System of Units (SI). Henceforth, the essential problem in statistical thermodynamics has been to determine the distribution of a given amount of energy E over N identical systems. Constantin Carathéodory, a Greek mathematician, linked entropy with a mathematical definition of irreversibility, in terms of trajectories and integrability.
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