The third law of thermodynamics is a statistical law of nature regarding entropy: The entropy of a perfect crystal approaches zero

as temperature approaches absolute zero. For other materials, the residual entropy is not necessarily zero,[1] although it is always zero for a perfect crystal in which there is only one possible ground state.

The entropy of a substance is zero if the absolute temperature is zero

1 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. It means that "it is impossible by any procedure, no matter how idealised, to reduce any system to the absolute zero of temperature in a finite number of operations". 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 S 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. [2] 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, kB is the Boltzmann constantand is the number of microstates consistent with the macroscopic configuration. The third law of thermodynamics is essentially a statement 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. Various sources show the following three potential formulations of the third law of thermodynamics: It is impossible to reduce any system to absolute zero in a finite series of operations. The entropy of a perfect crystal of an element in its most stable form tends to zero as the temperature approaches absolute zero. As temperature approaches absolute zero, the entropy of a system approaches a constant, of Third Law of Thermodynamics in Low Temperature Physics The principle of third law is widely used in low temperature physics which use techniques like liquid cryogens, evaporative cooling, adiabatic demagnetization. The Third Law of Thermodynamics states that the entropy of any pure substance in thermodynamic equilibrium approaches zero as the temperature approaches zero (Kelvin), or conversely the temperature (Kelvin) of any pure substance in thermodynamic equilibrium approaches zero when the entropy approaches zero

Applications

The Third Law of Thermodynamics can mathematically be expressed as

lim ST0 = 0 (1) where S = entropy (J/K) T = absolute temperature (K) At a temperature of absolute zero there is no thermal energy or heat. At a temperature of zero Kelvin the atoms in a pure crystalline substance are aligned perfectly and do not move. There is no entropy of mixing since the substance is pure. The temperature of absolute zero is the reference point for determination entropy. The absolute entropy of a substance can be calculated from measured thermodynamic properties by integrating the differential equations of state from absolute zero. For a gas this requires integrating through solid, liquid and gaseous phases.