Investigation of the correlation between structural relaxation time and configurational entropy under high pressure in a chlorinated biphenyl

被引:47
作者
Casalini, R
Paluch, M
Fontanella, JJ
Roland, CM
机构
[1] USN, Res Lab, Div Chem, Washington, DC 20375 USA
[2] George Mason Univ, Dept Chem, Fairfax, VA 22030 USA
[3] Silesian Univ, Inst Phys, PL-40007 Katowice, Poland
[4] USN Acad, Dept Phys, Annapolis, MD 21402 USA
关键词
D O I
10.1063/1.1499484
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
Dielectric relaxation measurements on a chlorinated biphenyl (PCB62) were carried out over a broad frequency range, with variation of both temperature and pressure. In combination with calorimetric determinations of the configurational entropy, these data could be described using the Adam-Gibbs model. Specifically, the experimental results were interpreted using a recently introduced equation for both the temperature and pressure dependencies of the structural relaxation time. The tau(T,P) data for PCB62 yielded values of the fitting parameters consistent with known physical properties of the material. A change of the dynamics was evident in isobaric measurements at atmospheric pressure, corresponding to a value of the relaxation time tau(B)similar to5x10(-5) s. A related change of dynamics was observed in isothermal experiments at varying pressures. It is noteworthy that the latter transpired at a very similar tausimilar totau(B). Moreover, the shape of the relaxation function depended only on the value of tau. We believe this is the first reported evidence of such a change of dynamics in experiments using pressure as a variable. These results suggest that this change is governed by the time scale of the relaxation, independently of any particular combination of T and P. (C) 2002 American Institute of Physics.
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页码:4901 / 4906
页数:6
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