Electrostatic Cancellation of Gravity Effects in Liquid Mixtures

We point out that a spatially-varying electric field can be used to cancel the effect of gravity in liquid mixtures by coupling to the different components' permittivities. Cancellation occurs if the system under consideration is small enough. For a simple ``wedge'' electrode geometry we show that the required system size and voltage are practical, easily realizable in the Lab. Thus this setup might be a simple alternative to more expensive or hazardous options such as the space-shuttle, drop-tower, or magnetic levitation experiments.Comment: 1.5 pages, one figure. Accepted to PRE brief report

Thermodynamics of gas–liquid colloidal equilibrium states: hetero-phase fluctuations

Following on from two previous JETC (Joint European Thermodynamics Conference) presentations, we present a preliminary report of further advances towards the thermodynamic description of critical behavior and a supercritical gas-liquid coexistence with a supercritical fluid mesophase defined by percolation loci. The experimental data along supercritical constant temperature isotherms (T >= T-c) are consistent with the existence of a two-state mesophase, with constant change in pressure with density, rigidity, (dp/d rho) (T), and linear thermodynamic state-functions of density. The supercritical mesophase is bounded by 3rd-order phase transitions at percolation thresholds. Here we present the evidence that these percolation transitions of both gaseous and liquid states along any isotherm are preceded by pre-percolation hetero-phase fluctuations that can explain the thermodynamic properties in the mesophase and its vicinity. Hetero-phase fluctuations give rise to one-component colloidal-dispersion states; a single Gibbs phase retaining 2 degrees of freedom in which both gas and liquid states with different densities percolate the phase volume. In order to describe the thermodynamic properties of two-state critical and supercritical coexistence, we introduce the concept of a hypothetical homo-phase of both gas and liquid, defined as extrapolated equilibrium states in the pre-percolation vicinity, with the hetero-phase fractions subtracted. We observe that there can be no difference in chemical potential between homo-phase liquid and gaseous states along the critical isotherm in mid-critical isochoric experiments when the meniscus disappears at T = T-c. For T > T-c, thermodynamic states comprise equal mole fractions of the homo-phase gas and liquid, both percolating the total phase volume, at the same temperature, pressure, and with a uniform chemical potential, stabilised by a positive finite interfacial surface tension.info:eu-repo/semantics/publishedVersio

Thermodynamic fluid equations-of-state

As experimental measurements of thermodynamic properties have improved in accuracy, to five or six figures, over the decades, cubic equations that are widely used for modern thermodynamic fluid property data banks require ever-increasing numbers of terms with more fitted parameters. Functional forms with continuity for Gibbs density surface (p,T) which accommodate a critical-point singularity are fundamentally inappropriate in the vicinity of the critical temperature (T-c) and pressure (p(c)) and in the supercritical density mid-range between gas- and liquid-like states. A mesophase, confined within percolation transition loci that bound the gas- and liquid-state by third-order discontinuities in derivatives of the Gibbs energy, has been identified. There is no critical-point singularity at T-c on Gibbs density surface and no continuity of gas and liquid. When appropriate functional forms are used for each state separately, we find that the mesophase pressure functions are linear. The negative and positive deviations, for both gas and liquid states, on either side of the mesophase, are accurately represented by three or four-term virial expansions. All gaseous states require only known virial coefficients, and physical constants belonging to the fluid, i.e., Boyle temperature (T-B), critical temperature (T-c), critical pressure (p(c)) and coexisting densities of gas ((cG)) and liquid ((cL)) along the critical isotherm. A notable finding for simple fluids is that for all gaseous states below T-B, the contribution of the fourth virial term is negligible within experimental uncertainty. Use may be made of a symmetry between gas and liquid states in the state function rigidity (dp/d)(T) to specify lower-order liquid-state coefficients. Preliminary results for selected isotherms and isochores are presented for the exemplary fluids, CO2, argon, water and SF6, with focus on the supercritical mesophase and critical region.info:eu-repo/semantics/publishedVersio

The Nature of Asymmetry in Fluid Criticality

By combining accurate liquid-vapor coexistence and heat-capacity data, we have unambiguously separated two non-analytical contributions of liquid-gas asymmetry in fluid criticality and proved the validity of "complete scaling" [Fisher et al., Phys. Rev. Lett. 85, 696 (2000); Phys. Rev. E, 67, 061506, (2003)]. We have also developed a method to obtain two scaling-field coefficients, responsible for the two sources of the asymmetry, from mean-field equations of state. Since the asymmetry effects are completely determined by Ising critical exponents, there is no need for a special renormalization-group theoretical treatment of asymmetric fluid criticality.Comment: 4 pages, 3 figure

Relationship between Diffusion, Selfdiffusion and Viscosity

We investigate the experimental limits of validity of the Stokes-Einstein equation. There is an important difference between diffusion and self-diffusion. There are experimental evidences, that in the case of self-diffusion the product D /T is constant and the equation is still valid. However, comparison of existing experimental data on viscosity and diffusion coefficients D of small, fast moving ions unambiguously show that the product D /T depends strongly on temperature T. The temperature dependence of diffusion coefficient declines from that of viscosity. Therefore, the Stokes-Einstein equation is not valid in this case

Asymmetric Fluid Criticality I: Scaling with Pressure Mixing

The thermodynamic behavior of a fluid near a vapor-liquid and, hence, asymmetric critical point is discussed within a general ``complete'' scaling theory incorporating pressure mixing in the nonlinear scaling fields as well as corrections to scaling. This theory allows for a Yang-Yang anomaly in which \mu_{\sigma}^{\prime\prime}(T), the second temperature derivative of the chemical potential along the phase boundary, diverges like the specific heat when T\to T_{\scriptsize c}; it also generates a leading singular term, |t|^{2\beta}, in the coexistence curve diameter, where t\equiv (T-T_{\scriptsize c}) /T_{\scriptsize c}. The behavior of various special loci, such as the critical isochore, the critical isotherm, the k-inflection loci, on which \chi^{(k)}\equiv \chi(\rho,T)/\rho^{k} (with \chi = \rho^{2} k_{\scriptsize B}TK_{T}) and C_{V}^{(k)}\equiv C_{V}(\rho,T)/\rho^{k} are maximal at fixed T, is carefully elucidated. These results are useful for analyzing simulations and experiments, since particular, nonuniversal values of k specify loci that approach the critical density most rapidly and reflect the pressure-mixing coefficient. Concrete illustrations are presented for the hard-core square-well fluid and for the restricted primitive model electrolyte. For comparison, a discussion of the classical (or Landau) theory is presented briefly and various interesting loci are determined explicitly and illustrated quantitatively for a van der Waals fluid.Comment: 21 pages in two-column format including 8 figure

Generic mechanism for generating a liquid-liquid phase transition

Recent experimental results indicate that phosphorus, a single-component system, can have two liquid phases: a high-density liquid (HDL) and a low-density liquid (LDL) phase. A first-order transition between two liquids of different densities is consistent with experimental data for a variety of materials, including single-component systems such as water, silica and carbon. Molecular dynamics simulations of very specific models for supercooled water, liquid carbon and supercooled silica, predict a LDL-HDL critical point, but a coherent and general interpretation of the LDL-HDL transition is lacking. Here we show that the presence of a LDL and a HDL can be directly related to an interaction potential with an attractive part and two characteristic short-range repulsive distances. This kind of interaction is common to other single-component materials in the liquid state (in particular liquid metals), and such potentials are often used to decribe systems that exhibit a density anomaly. However, our results show that the LDL and HDL phases can occur in systems with no density anomaly. Our results therefore present an experimental challenge to uncover a liquid-liquid transition in systems like liquid metals, regardless of the presence of the density anomaly.Comment: 5 pages, 3 ps Fig

Isotropic soft-core potentials with two characteristic length scales and anomalous behaviour

Isotropic soft-core potentials with two characteristic length scales have been used since 40 years to describe systems with polymorphism. In the recent years intense research is showing that these potentials also display polyamorphism and several anomalies, including structural, diffusion and density anomaly. These anomalies occur in a hierarchy that resembles the anomalies of water. However, the absence of directional bonding in these isotropic potentials makes them different from water. Other systems, such as colloidal suspensions, protein solutions or liquid metals, can be well described by these family of potentials, opening the possibility of studying the mechanism generating the polyamorphism and anomalies in these complex liquids