Entropy of fusion

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In thermodynamics, the entropy of fusion is the increase in entropy when melting a solid substance. This is almost always positive since the degree of disorder increases in the transition from an organized crystalline solid to the disorganized structure of a liquid; the only known exception is helium.^[1] It is denoted as ${\displaystyle \Delta S_{\text{fus}}}$ and normally expressed in joules per mole-kelvin, J/(mol·K).

A natural process such as a phase transition will occur when the associated change in the Gibbs free energy is negative.

${\displaystyle \Delta G_{\text{fus}}=\Delta H_{\text{fus}}-T\times \Delta S_{\text{fus}}<0,}$

where ⁠${\displaystyle \Delta H_{\text{fus}}}$⁠ is the enthalpy of fusion. Since this is a thermodynamic equation, the symbol ⁠${\displaystyle T}$⁠ refers to the absolute thermodynamic temperature, measured in kelvins (K).

Equilibrium occurs when the temperature is equal to the melting point ${\displaystyle T=T_{f}}$ so that

${\displaystyle \Delta G_{\text{fus}}=\Delta H_{\text{fus}}-T_{f}\times \Delta S_{\text{fus}}=0,}$

and the entropy of fusion is the heat of fusion divided by the melting point:

${\displaystyle \Delta S_{\text{fus}}={\frac {\Delta H_{\text{fus}}}{T_{f}}}}$

Helium-3 has a negative entropy of fusion at temperatures below 0.3 K. Helium-4 also has a very slightly negative entropy of fusion below 0.8 K. This means that, at appropriate constant pressures, these substances freeze with the addition of heat.^[2]

• Entropy of vaporization

• Atkins, Peter; Jones, Loretta (2008), Chemical Principles: The Quest for Insight (4th ed.), W. H. Freeman and Company, p. 236, ISBN 978-0-7167-7355-9
• Ott, J. Bevan; Boerio-Goates, Juliana (2000), Chemical Thermodynamics: Advanced Applications, Academic Press, ISBN 0-12-530985-6

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