Quantum Statistical Mechanics of Isotope Effects. II. The Surface Tension and Internal Energy

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Abstract
The thermodynamic properties of a system with given intermolecular potential, including first quantum corrections, are shown to be identical to those for a classical system with an effective intermolecular potential. This technique, together with a statistical‐thermodynamic derivation of a molecular expression for the surface tension, enables one to calculate the classical and the first‐quantum‐corrected surface tension. The first quantum corrections are utilized to discuss the difference in the thermodynamic properties of isotopes. The agreement between the experimental and theoretical difference in surface tension of H2 and D2 is excellent. It has been found that the major difference is due to the difference in density along the vapor—liquid equilibrium line. The effect is similar though not as pronounced in the case of the energy of vaporization.

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