Nernst Heat Theorem

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Nernst Heat Theorem

formulated by Walther Nernst early in the twentieth century and was used in
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Nernst Heat Theorem

Graph of energies at low temperatures 7/15/12

Nernst Heat Theorem

In the limit of T = 0 the equation reduces to just G = H, as illustrated in the figure shown fromthermodynamics, the slope of the G curve is S Since the slope shown here reaches the horizontal limit of 0 as T 0 then the implication is that S 0, which is the Nernst heat theorem The significance of the Nernst heat
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Nernst Heat Theorem

ConsiderGibbs-Helmholtzequation G H = T ( (G)/T)P .. (1) Where G -> change infree energy H -> change in enthalpy Atabsolutezero i.e. T = 0, Equation(1) will become: G = H A scientist Richard measures the E.M.F. of thecellsat differenttemperatures He found that the value of (G)/T
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Nernst Heat Theorem

Mathematically, The Nernst Heat Theorem can be expressed as:

Lt (T > 0) [ (G) / T]P= Lt (T > 0) [ (H) / T]P= 0 .. (2) Where Lt means limiting value

From the second law of thermodynamics, [ (G) / T]P= S (3) From Kirchoffs equation, [ (H) / T]P= 7/15/12

Theentropyof a perfectcrystalat absolute zerois exactly equal to zero Lt T 0 S=0

Third Law of Thermodynamics

The entropy of a system approaches a constant value as the temperature approaches zero At the absolute zero, entropy of every substance may becomes zero and it does becomes zero in the case of perfectly
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Residual Entropy

Residual entropyis small amount of entropywhich is present even after a substance is cooled arbitrarily close to absolute zero It occurs if a material can exist in many different microscopic states when cooled to absolute zero Egs: NO, CO, N2O, H2O, H2
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Residual Entropy
NO, CO, N2O

Two alternative arrangements are possible in crystal lattice NO & ON CO & OC NNO & ONN Crystal does not have one definite structure no perfect order at 0K 7/15/12 entropy not zero

Residual Entropy
Water

Uncertainity in the position of Hbonds/rotational motion of molecules in the solid state does not have perfect order at 0K

Hydrogen

Existence of ortho and para hydrogen in the solid state at 0K 7/15/12