We have studied the temperature dependence of the extent of dimerization of NO2 dissolved in a mixture of perfluoromethylcyclohexane+carbon tetrachloride near the mixture liquid–liquid critical point. We used the static dielectric constant as a measure of the extent of dimerization. We find that the dimerization decreases near the critical temperature by about 4% and that the functional form of the temperature dependence can be described by a critical exponent of (1−α), where α is the exponent for the heat capacity at constant pressure and composition and has the value 0.11. Such a temperature dependence is in agreement with the theoretical analysis of J. C. Wheeler and R. G. Petschek [Phys. Rev. A 28, 2442 (1983)].
We have measured the dielectric constant as a function of temperature and frequency near the liquid-liquid critical point of a mixture of polystyrene (molecular weight 1.02 X lo5) in diethyl malonate at the critical composition. The range of the frequency was 20 kHz to 1 MHz. For the one-phase region above the critical point, the range of the temperature was 1.1 X lod < t < 7.9 X where t is the reduced temperature, IT-TcI/Tc, and T, is the critical temperature. The dielectric constant in the one-phase region near the critical point shows an anomalous increase of about 0.3% above the "background" behavior far from the critical point. This anomaly is consistent with the theoretical prediction of a leading critical exponent (1 -a ) , where a is 0.11. The amplitude of the dielectric constant anomaly decreases with increasing frequency, an effect not yet considered in the theory. Below the critical temperature, the dielectric constants of the coexisting phases were measured as functions of temperature and frequency. The frequency ranged from 20 kHz to 1 MHz. The temperature ranged from 1.4 X The difference between the dielectric constants of coexisting phases is consistent with a critical exponent @ of 0.325, where @ describes the vanishing of the order parameter at the critical point. The average of the dielectric constants of coexisting phases is nearly linear but shows a critical contribution that can be described by an exponent 2p. Neither above nor below the critical temperature was there any evidence of the theoretically predicted critical anomaly in the dielectric relaxation time.< t < 3.5 X IntroductionModern theories of critical phenomena are based on the idea that the origin of the anomalies in the thermodynamic and transport properties near critical points is the growth of large and long-lived fluctuations in the order parameters.lY2 We present here experiments to test these theories for the description of dielectric properties near a liquidliquid critical point in a polymer solution.One-Phase Region: Temperature Dependence. Both phenomen~logical~,~ and m i c r o s~o p i c~~~ approaches predict that the dielectric constant, e, at zero frequency in the one-phase region near a liquid-liquid critical point should have the functional form:
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