The thermodynamic properties of biphenyl

Abstract Ideal-gas thermodynamic properties for biphenyl based on calorimetric measurements were determined between 300 and 700 K, well into the range of typical chemical-process temperatures. Experimental methods included adiabatic heat-capacity calorimetry, comparative ebulliometry, inclined-piston manometry, and differential-scanning calorimetry (d.s.c.). The derived values provide a firm basis for the prediction of thermodynamic properties for a large family of molecular structures including many substituted biphenyls—such as polychlorinated biphenyls (PCBs)—as well as polyphenyls of arbitrary size. Results also highlighted ambiguities common in the statistical calculation of thermodynamic properties of polycyclic molecules. Critical-property measurements with a d.s.c. indicated the commonly accepted assessed values to be in error. The biphenyl critical properties serve as a “cornerstone” in group-contribution estimation schemes, which are employed often by engineers in corresponding-states correlations for the estimation of a great variety of physical properties. Thermodynamically consistent sublimation vapor pressures were derived to show which of the many literature values are valid, an essential step in the validation of the many reported PCB vapor-pressure measurements, which are key to environmental-impact considerations.

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