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Laws of thermodynamics

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Thermodynamics
The classical Carnot heat engine
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Laws
Systems
State
Processes
Cycles
System propertiesNote: Conjugate variables in italics
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Specific heat capacity  c = {\displaystyle c=}
T {\displaystyle T} S {\displaystyle \partial S}
N {\displaystyle N} T {\displaystyle \partial T}
Compressibility  β = {\displaystyle \beta =-}
1 {\displaystyle 1} V {\displaystyle \partial V}
V {\displaystyle V} p {\displaystyle \partial p}
Thermal expansion  α = {\displaystyle \alpha =}
1 {\displaystyle 1} V {\displaystyle \partial V}
V {\displaystyle V} T {\displaystyle \partial T}
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The laws of thermodynamics in principle describe the specifics for the transport of heat and work in thermodynamic processes. Since their conception, however, these laws have become some of the most important in all of physics and many other branches of science. They are often associated with concepts far beyond what is directly stated in the wording.

Zeroth law

Main article: Zeroth law of thermodynamics

If systems A and B are in thermodynamic equilibrium, and systems B and C are in thermodynamic equilibrium, then systems A and C are also in thermodynamic equilibrium.

When two systems are put in contact with each other, there will be a net exchange of energy and/or matter between them unless they are in thermodynamic equilibrium. While this is a fundamental concept of thermodynamics, the need to state it explicitly as a law was not perceived until the first third of the 20th century, long after the first three laws were already widely in use, hence the zero numbering.

Thermodynamic equilibrium includes thermal equilibrium (associated to heat exchange and parameterized by temperature), mechanical equilibrium (associated to work exchange and parameterized generalized forces such as pressure), and chemical equilibrium (associated to matter exchange and parameterized by chemical potential).

First law

Main article: First law of thermodynamics

The increase in the internal energy of a system is equal to the amount of energy added by heating the system, minus the amount lost as a result of the work done by the system on its surroundings.

This is the statement of the conservation of energy for a thermodynamic system. It refers to the two main ways that a system transfers energy between itself and its surroundings - by the process of heating (or cooling) and the process of mechanical work. The rate of gain or loss in the internal, or stored, energy of a system is determined by the rates of these two processes. In fact, these are only the two most well known processes. Other processes (e.g. adding more particles) may contribute to the gain or loss of internal energy, and for these cases, extra terms must be included in the expression of the first law.

A second aspect of the first law is to clarify the nature of the internal energy. It is a stored quantity. The amount does not depend on which processes put it there. More generally, the amount is independent of the history of the system. If a thermodynamic system goes through changes, becoming warmer, cooler, larger, smaller, whatever, but returns to its original state, then it will have the same amount of internal energy as it did to begin with. Mathematically speaking, the internal energy is a state function and infinitesimal changes in the internal energy are exact differentials.

Second law

Main article: Second law of thermodynamics

It is impossible to obtain a process that, operating in cycle, produces no other effect than the subtraction of a positive amount of heat from a reservoir and the production of an equal amount of work. (the so-called Kelvin-Planck Statement)

The entropy of a thermally isolated macroscopic system never decreases (see Maxwell's demon), however a microscopic system may exhibit fluctuations of entropy opposite to that dictated by the second law (see Fluctuation Theorem). In fact the mathematical proof of the Fluctuation Theorem from time-reversible dynamics and the Axiom of Causality, constitutes a proof of the Second Law. In a logical sense the Second Law thus ceases to be a "Law" of Physics and instead becomes a theorem which is valid for large systems or long times.

Third law

Main article: Third law of thermodynamics

As temperature goes to absolute 0, the entropy of a system approaches a constant.

It is important to remember that, except for the first law, the laws of thermodynamics are only statistical generalizations. That is, they simply describe the tendencies of macroscopic systems. For microsopic systems with few particles, the variations in the parameters become larger than the parameters themselves, and the assumptions of thermodynamics become meaningless. The first law of thermodynamics, however, i.e. the law of conservation, has become the most sound of all laws in science. Its validity has never been disproved.

Extended Interpretations

The laws of thermodynamics are sometimes interpreted to have a wider significance and implication than simply encoding the experimental results upon which the science of thermodynamics is based. See for example:

See also

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