Third Law of Thermodynamics - History

History

The third law was developed by the chemist Walther Nernst during the years 1906-1912, and is therefore often referred to as Nernst's theorem or Nernst's postulate. The third law of thermodynamics states that the entropy of a system at absolute zero is a well-defined constant. This is because a system at zero temperature exists in its ground state, so that its entropy is determined only by the degeneracy of the ground state.

In 1912 Nernst stated the law thus:

"It is impossible for any procedure to lead to the isotherm T = 0 in a finite number of steps."

An alternative version of the third law of thermodynamics as stated by Gilbert N. Lewis and Merle Randall in 1923:

If the entropy of each element in some (perfect) crystalline state be taken as zero at the absolute zero of temperature, every substance has a finite positive entropy; but at the absolute zero of temperature the entropy may become zero, and does so become in the case of perfect crystalline substances.

This version states not only ΔS will reach zero at 0 K, but S itself will also reach zero as long as the crystal has a ground state with only one configuration. Some crystals form defects which causes a residual entropy. This residual entropy disappears when the kinetic barriers to transitioning to one ground state are overcome.

With the development of statistical mechanics, the third law of thermodynamics (like the other laws) changed from a fundamental law (justified by experiments) to a derived law (derived from even more basic laws). The basic law from which it is primarily derived is the statistical-mechanics definition of entropy for a large system:

where S is entropy, k_B is the Boltzmann constant, and is the number of microstates consistent with the macroscopic configuration.