The Third law of thermodynamics

         This law was first formulated by the German chemist Walther Nernst in the year1906. According to this law,

         The entropy of all perfectly crystalline solids is zero at the absolute zero temperature. As entropy is a measure of disorder, it can be interpretated that at the absolute zero, the perfectly crystalline solid posses a perfect order of its constituent particles.

         The most essential application of the third law of thermodynamics is that it helps in the calculation of absolute entropies of the substance at any temperature T.

         S=2.303 C_p log T

    Where C_P is the heat capacity of the substance at constant pressure and is supposed to remain constant in the range of 0 to T.  

Limitations of the law

         (1) Glassy solids even at 0^oK has entropy greater than zero.

         (2) Solids having mixtures of isotopes do not have zero entropy at 0^oK. For instance, entropy of solid chlorine is not zero at 0^oK.

         (3) Crystals of CO, N₂O, NO, H₂O, etc. do not have perfect order even at 0^oK thus their entropy is not equal to zero.

Thermochemistry

 Thermochemistry is the branch of physical chemistry which is concerned with energy changes accompanying chemical transformation. It is also called as chemical energetics. It is based on the first law of the thermodynamics.

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