Module 1: Introduction to Thermodynamics

Development of the Third Law of Thermodynamics

In the laws of thermodynamics, we are more familiar with the First and Second law of thermodynamics
more than the third one. Well, these laws are one of the foundations in the field of science and
research, among other things, they put constraints on how energy can be used in the universe. Let me
explain the concept of the third law.

Generally speaking, it is about the ability to create an absolute temperature scale, for which absolute
zero is the point at which the internal energy of a solid is precisely 0. The third law states that the
entropy of a perfect crystal of an element in its most stable form tends to zero as the temperature
approaches absolute zero. Meaning, entropy is determined only by the degeneracy of the ground state
since the system at zero temperature exists in its ground state.

This third law of thermodynamics was first developed by a German chemist and physicist Walther
Nernst, during the years 1906-1912. This was also known as the Nernst’s theorem or Nernst’s postulate
before. In 1912, Nernst stated that “It is impossible for any procedure to lead to the isotherm T=0 in a
finite number of steps.”

By 1923, American chemists Gilbert N. Lewis and Merle Randall restated the third law of
thermodynamics as:

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.

The problem that occurred to them was that some crystals formed defects which cause a residual entropy that
disappeared when kinetic barriers to transitioning to one ground state are overcome. Their version stated that ΔS
and S will reach zero at 0 K as long as the crystal has a ground state with only one configuration.

By the time that a fundamental tool named statistical mechanics was developed, the third law of
thermodynamics, along with other laws, changed from being a fundamental law to a derived law.
 𝑆 − 𝑆0 = 𝑘𝐵𝑙𝑛Ω

References:

Gaskell, D.R. (2018). Introduction to the Thermodynamics of Materials, 6th ed. New York: CRC Taylor
and Francis.

Abriata, J.P. and Laughlin, D.E. (2004). “The Third Law of Thermodynamics and low temperature phase
stability,” Progress in Materials Science 49, 367-387.

Goldstein, Martin, and Inge F. (1993). The Refrigerator and the Universe. Harvard Univ. Press. Chpt. 14