Critical behavior of the aqueous electrolytic system 3-methylpyridine+D2O+NaBr

Abstract

The system 3-methylpyridine(3MP) + water(H2O)+NaBr has been the subject of an intense scientific debate since the work of Jacob et al. [Phys. Rev. E. 58, 2188 (1988)] and Anisimov et al. [Phys. Rev. Lett. 85, 2336 (2000)]. The crossover critical behavior of this system seemed to show remarkable sensitivity to the weight fraction (X) of the ionic impurity NaBr. In the range X< or =0.10 the system displayed Ising behavior and a pronounced crossover to mean-field behavior in the range 0.10< or =X< or =0.16. A complete mean-field behavior was observed at X=0.17, a result that was later attributed to the existence of long-living nonequilibrium states in this system [Kostko et al., Phys. Rev. E. 70, 026118 (2004)]. In this paper, we report the near-critical behavior of osmotic susceptibility in the isotopically related ternary system, 3MP+heavy water(D2O)+NaBr. Detailed light-scattering experiments performed at exactly the same NaBr concentrations as investigated by Jacob et al. reveal that the system 3MP + D2O + NaBr shows a simple Ising-type critical behavior with gamma approximately 1.24 and nu approximately 0.63 over the entire NaBr concentration range 0< or =X< or =0.1900. The crossover behavior is predominantly nonmonotonic and is completed well outside the critical domain. An analysis in terms of the effective susceptibility exponent (gammaeff) reveals that the crossover behavior is nonmonotonic for 0< or =X< or =0.1793 and tends to become monotonic for X>0.1793. The correlation length amplitude xio, has a value of approximately 2 A for 0.0250< or =X< or =0.1900, whereas for X=0, xio approximately 3.179 A. Since isotopic H-->D substitution is not expected to change the critical behavior of the system, our results support the recent results obtained by Kostko et al. [Phys. Rev. E. 70, 026118 (2004)] that 3MP + H2O + NaBr exhibits universal Ising-type critical behavior typical for other aqueous solutions.