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The critical behavior of osmotic susceptibility is investigated in the re-entrant complex mixture 1-propanol (P)+water (W)+potassium chloride (KCl) through light-scattering measurements. The measurements are performed on approaching a special critical point [i.e., the double critical point (DCP)] in this mixture, along the line of upper critical solution temperatures (TU’s), by varying t from the high temperature one-phase region. The light-scattering data analysis emphasizes the need for corrections to the asymptotic Ising behavior and yields very large magnitudes for the correction-to-scaling amplitudes A1 and A2, with the first-correction amplitude A1 being negative, signifying a nonmonotonic crossover behavior of the susceptibility exponent in this mixture. For the TU closest to the DCP, the effective susceptibility exponent γeff displays a nonmonotonic crossover from its nearly doubled three dimensional (3D)-Ising value toward its nearly double mean-field value with an increase in t. While for that far away from the DCP, it displays a nonmonotonic crossover from its single-limit Ising value toward a value slightly lower than its mean-field value of 1 with an increase in t. This feature of the effective susceptibility exponent is interpreted in terms of the possibility of a nonmonotonic crossover to the mean-field value from lower values in the nonasymptotic high t region. The renormalized Ising regime extends over a larger t range for the sample (or TU) closest to the DCP when compared to that far away from it. The in-between TU’s display a trend toward shrinkage in the renormalized Ising regime as TU shifts away from the DCP. Nevertheless, the crossover to the mean-field behavior is completed only beyond t>10-2 for the TU’s studied. The observed crossover behavior is attributed to the presence of strong ion-induced clustering in this mixture, as revealed by various structure probing techniques, while the observed unique trend in the crossover behavior is discussed in terms of the varying influence of the DCP on the critical behavior along the TU line. The crossover behavior for the TU’s is pronounced and more sharp compared to the TL’s (lower critical solution temperatures) [U. K. Pradeep, J. Chem. Phys. 129, 134506 (2008)] in this mixture, although there exists no difference in the growth of the mesoscale clusters in the lower and upper one-phase regions in this mixture. Our observations suggest the need to look at the crossover behavior probably from two perspectives, namely, the dielectric effect and the clustering effect. The effective susceptibility exponent as a function of the field variable tUL, instead of the conventional variable t, displays a sharp nonmonotonic crossover from its asymptotic 3D-Ising value (∼1.24) toward a value slightly lower than its nonasymptotic mean-field value of 1, as that observed in the t analysis for the TU far away from the influence of the DCP. [ABSTRACT FROM AUTHOR]

The critical behavior of osmotic susceptibility in an aqueous electrolyte mixture 1-propanol (1P)+water (W)+potassium chloride is reported. This mixture exhibits re-entrant phase transitions and has a nearly parabolic critical line with its apex representing a double critical point (DCP). The behavior of the susceptibility exponent is deduced from static light-scattering measurements, on approaching the lower critical solution temperatures (TL’s) along different experimental paths (by varying t) in the one-phase region. The light-scattering data analysis substantiates the existence of a nonmonotonic crossover behavior of the susceptibility exponent in this mixture. For the TL far away from the DCP, the effective susceptibility exponent γeff as a function of t displays a nonmonotonic crossover from its single limit three-dimensional (3D)-Ising value (∼1.24) toward its mean-field value with increase in t. While for that closest to the DCP, γeff displays a sharp, nonmonotonic crossover from its nearly doubled 3D-Ising value toward its nearly doubled mean-field value with increase in t. The renormalized Ising regime extends over a relatively larger t range for the TL closest to the DCP, and a trend toward shrinkage in the renormalized Ising regime is observed as TL shifts away from the DCP. Nevertheless, the crossover to the mean-field limit extends well beyond t>10-2 for the TL’s studied. The observed crossover behavior is attributed to the presence of strong ion-induced clustering in this mixture, as revealed by various structure probing techniques. As far as the critical behavior in complex or associating mixtures with special critical points (like the DCP) is concerned, our results indicate that the influence of the DCP on the critical behavior must be taken into account not only on the renormalization of the critical exponent but also on the range of the Ising regime, which can shrink with decrease in the influence of the DCP and with the extent of structuring in the system. The utility of the field variable tUL in analyzing re-entrant phase transitions is demonstrated. The effective susceptibility exponent as a function of tUL displays a nonmonotonic crossover from its asymptotic 3D-Ising value toward a value slightly lower than its nonasymptotic mean-field value of 1. This behavior in the nonasymptotic, high tUL region is interpreted in terms of the possibility of a nonmonotonic crossover to the mean-field value from lower values, as foreseen earlier in micellar systems. [ABSTRACT FROM AUTHOR]