Random Field Ising Model Criticality in a Complex Binary Liquid System.

While Ising criticality in classical liquids has been firmly established both theoretically and experimentally, much less is known about criticality in liquids in which the growth of the correlation length is frustrated by finite-size effects. A theoretical approach for dealing with this issue is the random-field Ising model (RFIM). While experimental critical-exponent values have been reported for magnetic samples (here, we consider γ, ν and η), little experimental information is available for critical fluctuations in corresponding liquid systems.

Thermal Conductivity of Metastable Ionic Liquid [Cmim][CHSO].

Ionic liquids have been suggested as new engineering fluids, namely in the area of heat transfer, as alternatives to current biphenyl and diphenyl oxide, alkylated aromatics and dimethyl polysiloxane oils, which degrade above 200 °C and pose some environmental problems. Recently, we have proposed 1-ethyl-3-methylimidazolium methanesulfonate, [Cmim][CHSO], as a new heat transfer fluid, because of its thermophysical and toxicological properties. However, there are some interesting points raised in this work, namely the possibility of the existence of liquid metastability below the melting point (303 K) or second order-disorder transitions (-type) before reaching the calorimetric freezing point.

Frame-invariant Fick diffusion matrices of multicomponent fluid mixtures.

Extension of a description of mass diffusion in binary fluids based on Fick's law to multicomponent fluids requires introduction of diffusion matrices. A problem is that Fick diffusion matrices commonly adopted for multicomponent fluids depend on the velocity frame of reference. In this paper we show how one can define Fick diffusion matrices for multicomponent fluids that are frame invariant.

Nonequilibrium Casimir pressures in liquids under shear.

In stationary nonequilibrium states coupling between hydrodynamic modes causes thermal fluctuations to become long ranged inducing nonequilibrium Casimir pressures. Here we consider nonequilibrium Casimir pressures induced in liquids by a velocity gradient. Specifically, we have obtained explicit expressions for the magnitude of the shear-induced pressure enhancements in a liquid layer between two horizontal plates that complete and correct results previously presented in the literature.

Unusual Transformation of Polymer Coils in a Mixed Solvent Close to the Critical Point.

We have discovered unusual behavior of polymer coils in a binary solvent (nitroethane+isooctane) near the critical temperature of demixing. The exceptionally close refractive indices of the solvent components make the critical opalescence relatively weak, thus enabling us to simultaneously observe the Brownian motion of the polymer coils and the diverging correlation length of the critical fluctuations. The polymer coils exhibit a collapse-reswelling-expansion-reshrinking transition upon approaching the critical temperature.

Work probability distribution for a ferromagnet with long-ranged and short-ranged correlations.

Work fluctuations and work probability distributions are fundamentally different in systems with short-ranged versus long-ranged correlations. Specifically, in systems with long-ranged correlations the work distribution is extraordinarily broad compared to systems with short-ranged correlations. This difference profoundly affects the possible applicability of fluctuation theorems like the Jarzynski fluctuation theorem.

Mesoscopic Diffusion of Poly(ethylene oxide) in Pure and Mixed Solvents.

We present results from an experimental dynamic light-scattering study of poly(ethylene oxide) (PEO) in both a pure solvent (water) and a mixed solvent (tert-butanol + water). The concentration dependence of the diffusive relaxation of the PEO molecules is found to be typical of polymers in a good solvent. However, the mesoscopic diffusive behavior of PEO in the mixed solvent is very different, indicating an initial collapse and subsequent reswelling of PEO caused by co-nonsolvency.

Contrasting Work Fluctuations and Distributions in Systems with Short-Range and Long-Range Correlations.

It is shown that the work fluctuations and work distribution functions are fundamentally different in systems with short-range versus long-range correlations. The two cases considered with long-range correlations are magnetic work fluctuations in an equilibrium isotropic ferromagnet and work fluctuations in a nonequilibrium fluid with a temperature gradient. The long-range correlations in the former case are due to equilibrium Goldstone modes, while in the latter they are due to generic nonequilibrium effects.

Non-local fluctuation phenomena in liquids.

Fluids in non-equilibrium steady states exhibit long-range fluctuations which extend over the entire system. They can be described by non-equilibrium thermodynamics and fluctuating hydrodynamics that assume local equilibrium for the thermophysical properties as a function of space and time. The experimental evidence for the consistency between this assumption of local equilibrium in the equations and the non-local fluctuation phenomena observed is reviewed.

Work, work fluctuations, and the work distribution in a thermal nonequilibrium steady state.

Long-ranged correlations generically exist in nonequilibrium fluid systems. In the case of a nonequilibrium steady state caused by a temperature gradient, the correlations are especially long-ranged and strong. The anomalous light scattering predicted to exist in these systems is well-confirmed by numerous experiments.

Nonequilibrium fluctuation-induced Casimir pressures in liquid mixtures.

In this article we derive expressions for Casimir-like pressures induced by nonequilibrium concentration fluctuations in liquid mixtures. The results are then applied to liquid mixtures in which the concentration gradient results from a temperature gradient through the Soret effect. A comparison is made between the pressures induced by nonequilibrium concentration fluctuations in liquid mixtures and those induced by nonequilibrium temperature fluctuations in one-component fluids.

Physical origin of nonequilibrium fluctuation-induced forces in fluids.

Long-range thermal fluctuations appear in fluids in nonequilibrium states leading to fluctuation-induced Casimir-like forces. Two distinct mechanisms have been identified for the origin of the long-range nonequilibrium fluctuations in fluids subjected to a temperature or concentration gradient. One is a coupling between the heat or mass-diffusion mode with a viscous mode in fluids subjected to a temperature or concentration gradient.

Non-equilibrium concentration fluctuations in binary liquids with realistic boundary conditions.

Because of the spatially long-ranged nature of spontaneous fluctuations in thermal non-equilibrium systems, they are affected by boundary conditions for the fluctuating hydrodynamic variables. In this paper we consider a liquid mixture between two rigid and impervious plates with a stationary concentration gradient resulting from a temperature gradient through the Soret effect. For liquid mixtures with large Lewis and Schmidt numbers, we are able to obtain explicit analytical expressions for the intensity of the non-equilibrium concentration fluctuations as a function of the frequency ω and the wave number q of the fluctuations.

Nonequilibrium Casimir-like Forces in Liquid Mixtures.

In this Letter, we consider a liquid mixture confined between two thermally conducting walls subjected to a stationary temperature gradient. While in a one-component liquid nonequilibrium fluctuation forces appear inside the liquid layer, nonequilibrium fluctuations in a mixture induce a Casimir-like force on the walls. The physical reason is that the temperature gradient induces large concentration fluctuations through the Soret effect.

Fluctuation-induced pressures in fluids in thermal nonequilibrium steady states.

Correlations in fluids in nonequilibrium steady states are long range. Hence, finite-size effects have important consequences in the nonequilibrium thermodynamics of fluids. One consequence is that nonequilibrium temperature fluctuations induce nonequilibrium Casimir-like pressures proportional to the square of the temperature gradient.

Communication: minimum in the thermal conductivity of supercooled water: a computer simulation study.

We report the results of a computer simulation study of the thermodynamic properties and the thermal conductivity of supercooled water as a function of pressure and temperature using the TIP4P-2005 water model. The thermodynamic properties can be represented by a two-structure equation of state consistent with the presence of a liquid-liquid critical point in the supercooled region. Our simulations confirm the presence of a minimum in the thermal conductivity, not only at atmospheric pressure, as previously found for the TIP5P water model, but also at elevated pressures.

Giant Casimir effect in fluids in nonequilibrium steady states.

In this Letter, we consider the fluctuation-induced force exerted between two plates separated by a distance L in a fluid with a temperature gradient. We predict that for a range of distances L, this nonequilibrium force is anomalously large compared to other Casimir forces. The physical reason is that correlations in a nonequilibrium fluid are generally of longer range than other correlations, even than those near an equilibrium critical point.

Thermal conductivity of supercooled water.

The heat capacity of supercooled water, measured down to -37°C, shows an anomalous increase as temperature decreases. The thermal diffusivity, i.e.

Thermodynamics of supercooled water.

We review the available experimental information on the thermodynamic properties of supercooled water and demonstrate the possibility of modeling these thermodynamic properties on a theoretical basis. We show that by assuming the existence of a liquid-liquid critical point in supercooled water, the theory of critical phenomena can give an accurate account of the experimental thermodynamic-property data up to a pressure of 150 MPa. In addition, we show that a phenomenological extension of the theoretical model can account for all currently available experimental data in the supercooled region, up to 400 MPa.

Concentration fluctuations in non-isothermal reaction-diffusion systems. II. The nonlinear case.

In this paper, we consider a simple reaction-diffusion system, namely, a binary fluid mixture with an association-dissociation reaction between two species. We study fluctuations at hydrodynamic spatiotemporal scales when this mixture is driven out of equilibrium by the presence of a temperature gradient, while still being far away from any chemical instability. This study extends the analysis in our first paper on the subject [J.

Critical behavior of the dielectric constant in asymmetric fluids.

By applying a thermodynamic theory that incorporates the concept of complete scaling, we derive the asymptotic temperature dependence of the critical behavior of the dielectric constant above the critical temperature along the critical isochore and below the critical temperature along the coexistence curve. The amplitudes of the singular terms in the temperature expansions are related to the changes of the critical temperature and the critical chemical potential upon the introduction of an electric field. The results of the thermodynamic theory are then compared with the critical behavior implied by the classical Clausius-Mossotti approximation.

Mesoscopic non-equilibrium thermodynamics of non-isothermal reaction-diffusion.

We show how the law of mass action can be derived from a thermodynamic basis, in the presence of temperature gradients, chemical potential gradients and hydrodynamic flow. The solution gives the law of mass action for the forward and the reverse contributions to the net chemical reaction. In addition we derive the fluctuation-dissipation theorem for the fluctuating contributions to the reaction rate, heat flux and mass fluxes.

Asymmetric criticality in weakly compressible liquid mixtures.

The thermodynamics of asymmetric liquid-liquid criticality is updated by incorporating pressure effects into the complete-scaling formulation earlier developed for incompressible liquid mixtures [C. A. Cerdeirina et al.

Nonequilibrium velocity fluctuations and energy amplification in planar Couette flow.

In this paper we investigate intrinsic thermally excited nonequilibrium velocity fluctuations in laminar planar Couette flow. For this purpose we have complemented the solution of the stochastic Orr-Sommerfeld equation for the intensity of the fluctuations of the wall-normal velocity, presented in a previous publication, with a solution of the stochastic Squire equation for the intensity of the fluctuations of the wall-normal vorticity. We have obtained exact solutions of these equations without boundary conditions and solutions in a Galerkin approximation when appropriate boundary conditions are included.

Phenomenological description of phase inversion.

We propose an extended Ginzburg-Landau model for a description of the ambivalence region associated with the phenomenon of phase inversion observed in dispersed water-oil flow through a pipe. In analogy to the classical mean-field theory of phase transitions, it is shown that a good quantitative representation of the ambivalence region is obtained by using the injected phase volume fraction and a friction factor as the appropriate physical parameters.