Laws of Thermodynamics

The four laws of thermodynamics define fundamental physical quantities (temperature, energy, and entropy) that characterize thermodynamic systems. The laws describe how these quantities behave under various circumstances, and forbid certain phenomena (such as perpetual motion).

The four laws of thermodynamics are:

• Zeroth law of thermodynamics: If two systems are in thermal equilibrium with a third system, they must be in thermal equilibrium with each other. This law helps define the notion of temperature.

• First law of thermodynamics: Heat and work are forms of energy transfer. Energy is invariably conserved but the internal energy of a closed system changes as heat and work are transferred in or out of it. Equivalently, perpetual motion machines of the first kind are impossible.

• Second law of thermodynamics: The entropy of any isolated system not in thermal equilibrium almost always increases. Isolated systems spontaneously evolve towards thermal equilibrium—the state of maximum entropy of the system—in a process known as "thermalization". Equivalently, perpetual motion machines of the second kind are impossible.

• Third law of thermodynamics: The entropy of a system approaches a constant value as the temperature approaches zero. The entropy of a system at absolute zero is typically zero, and in all cases is determined only by the number of different ground states it has. Specifically, the entropy of a pure crystalline substance at absolute zero temperature is zero.

Classical thermodynamics describes the exchange of work and heat between systems. It has a special interest in systems that are individually in states of thermodynamic equilibrium. Thermodynamic equilibrium is a condition of systems which are adequately described by only macroscopic variables. Every physical system, however, when microscopically examined, shows apparently random microscopic statistical fluctuations in its thermodynamic variables of state (entropy, temperature, pressure, etc.). These microscopic fluctuations are negligible for systems which are nearly in thermodynamic equilibrium and which are only macroscopically examined. They become important, however, for systems which are nearly in thermodynamic equilibrium when they are microscopically examined, and, exceptionally, for macroscopically examined systems that are in critical states, and for macroscopically examined systems that are far from thermodynamic equilibrium.

There have been suggestions of additional laws, but none of them achieve the generality of the four accepted laws, and they are not mentioned in standard textbooks.

The laws of thermodynamics are important fundamental laws in physics and they are applicable in other natural sciences.