Third Law Of Thermodynamics
The third law of thermodynamics states that absolute zero can not be achieved in a finite number of stages. The third law of thermodynamics can also be defined as that when reaching absolute zero, 0 degrees Kelvin, any process of a physical system stops and when reaching absolute zero the entropy reaches a minimum and constant value.
This principle states that the entropy of a system at the absolute zero temperature is a well-defined constant. This is because, at the temperature of absolute zero, a system is in a basic state and entropy increases are achieved by degeneration from this basic state.
Nernst's theorem states that the entropy of a perfect crystal of any element at the absolute zero temperature is zero. However, this observation does not take into account that the real crystals have to be formed at temperatures above zero. Consequently, they will have defects that will not be eliminated when cooled down to absolute zero. As they are not perfect crystals, the information needed to describe the existing defects will increase the entropy of the crystal.
Theorems and statements of the third law of thermodynamics
Nernst Terorema: A chemical reaction between pure crystalline phases that occurs at absolute zero does not produce any change in entropy.
Nernst-Simon statement: The entropy change that results from any reversible isothermal transformation of a system tends to zero as the temperature approaches zero.
Planck statement: For T → 0, the entropy of any system in equilibrium approximates a constant that is independent of the other thermodynamic variables.
Absolute zero inaccessibility theorem: There is no process capable of reducing the temperature of a system to absolute zero in a finite number of steps.
4th Postulate of Callen: The entropy of any system is canceled in the state for which
History of the third law of thermodynamics
The third law was developed by the chemist Walther Nernst during the years 1906-12, and that is why it is 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 there is a system at zero temperature in its ground state, so that its entropy is determined only by the degeneration of the ground state.
In 1912, Nernst declared the law thus: "It is impossible for a procedure to lead to the isotherm T = 0 in a finite number of steps".
An alternative version of the third principle of the laws of thermodynamics as established by Gilbert N. Lewis and Merle Randall in 1923: "If the entropy of each element in some crystalline (perfect) state is taken as zero in the absolute zero of temperature, each substance has a finite positive entropy; but at the absolute zero of the temperature, the entropy can become zero, and it is in the case of the perfect crystalline substances. "
This version indicates that not only ΔS will reach zero at 0 degrees Kelvin, but that S will also reach zero as long as the crystal has a ground state with a single configuration. Some crystals form defects that cause a residual entropy. This residual entropy disappears when the kinetic barriers for the transition to a ground state are overcome.
Last review: April 12, 2018