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Pressure-volume-temperature data, along with dielectric relaxationmeasurements, are reported for a series of polychlorinated biphenyls (PCB),differing in the number of chlorine atoms on their phenyl rings. Analysis ofthe results reveals that with increasing chlorine content, the relaxation timesof the PCB become governed to a greater degree by density, rho, relative to theeffect of temperature, T. This result is consistent with the respectivemagnitudes of the scaling exponent, gamma, yielding superpositioning of therelaxation times measured at various temperatures and pressures, when plottedversus rho^gamma/T. While at constant (atmospheric) pressure, fragilities forthe various PCB are equivalent, the fragility at constant volume variesinversely with chlorine content. Evidently, the presence of bulkier chlorineatoms on the phenyl rings magnifies the effect density has on the relaxationdynamics.Comment: 20 pages 5 figure

Effect of chemical structure on the isobaric and isochoric fragility in polychlorinated biphenyls