Direct measurement and calculation of the second refractivity virial coefficients of gases

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Abstract
Values of second refractivity virial coefficients B R, obtained by differential measurement of the optical path in a gas when a sample is decompressed, are reported for Ne, Ar, Kr, Xe; CH4, CH3F, CH2F2, CHF3, CF4; CO2, N2 and SF6, at four wavelengths 632·8, 514·5, 488·0 and 457·9 nm. There is evidence of a possible wavelength dependence of B R. First refractivity virial coefficients A R are also reported for helium and the above gases at the same four wavelengths. The classical statistical-mechanical theory of B R is briefly reviewed and extended, and the leading contributions to B R have been evaluated numerically by computer for eleven of the twelve gases. Agreement between theory and experiment is often within the large experimental limits, but there is a tendency for the calculated values to exceed the observed.

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