Isomorphism of critical vaporization phenomena in pure substances and binary mixtures

By integration with respect to a noncritical order parameter (the concentration of the mixture), a model Hamiltonian of Landau-Ginzburg type for a binary mixture is reduced to the Hamiltonian of a single-component fluid. The conditions under which this isomorphism is possible are considered. It is shown that taking into account fluctuations of a critical order parameter (the total density of the mixture) by Wilson's approximate method leads, in an approximation linear in ( =4 – d; d is the dimensionality of the space), to the renormalization of the Hamiltonian parameters and to values of the critical indices, , , , which for = 1 are close to those observed experimentally.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 11, pp. 35–40, November, 1976.     

Simple views on critical binary liquid mixtures in porous glass

A simple scenario, different from previous attempts, is proposed to resolve the problem of the slow phase separation dynamics of binary liquid mixtures confined in porous Vycor glass. We demonstrate that simply mutual diffusion, renormalized by critical composition fluctuations and geometrical hindrance of the porous glass, accounts for the slow phase separation kinetics. Capillary invasion studies of porous Vycor glass by the critical isobutyric acid-water mixture, close to the consolute solution temperature, corroborate our analysis.     

Experimental study of critical thermal load during boiling of binary liquid mixtures

The critical thermal load q _cr is experimentally studied as a function of the composition of an aqueous solution of ethanol, isopropanol, n-butanol, isobutanol, and isoamyl alcohol during pool boiling of saturated and subcooled liquids at atmospheric pressure.     

Ultrasonic absorption in binary liquid mixtures

Ultrasonic absorption in binary liquid mixtures containing benzene, chloroform, cyclohexane and toluene with triethylamine, a rotational isomeric relaxing liquid, as a common component has been studied at a frequency of 7.56 MHz. A pulse techrique has been used for the measurement of absorption with an accuracy of ±5%. Bauer-Sette formula has been used to calculate the absorption of these liquid mixtures at different concentrations. The theoretical values evaluated on the basis of Bauer-Sette theory appear to have good agreement with experimental values. In view of the discrepancy pointed out by Mallikarjuna Rao and Suryanarayana, the mixtures of benzene and ethylacetate have been studied in this context and found the theoretical values coinciding with experimental values.     

Relaxation phenomena in water - n-methylmorpholin n-oxide binary mixtures

Binary mixtures composed of water and N-methylmorpholin N-oxide (NMMNO) were studied in the concentration range 0.19 m to 26.5 m with shear and longitudinal waves. The dependence on temperature and molality of 1)the ultrasonic spectrum, 2)the real part of the complex mechanical impedance and 3)the ultrasonic velocity indicates equilibrium between bulk and solvated water with increasing NMMNO concentration and organisation of the structure of the system.     

Ultrasonic studies in binary liquid mixtures of benzene and coconut oil near the critical region

Velocity and attenuation of ultrasonic waves have been measured in complex binary mixtures of benzene and multicomponent coconut oil near the critical temperature in the low MHz region. The experimental results are analysed in terms of theories developed by Kawasaki and Mistura. The characteristic frequency and amplitude parameter determined by fitting the data in the relations proposed by Kawasaki-Mistura are scaled at reduced temperature and these agree with scaling exponents. A small velocity dispersion is also observed.     

Impurity effects on the critical behaviour of the electrical resistance of binary liquid mixtures

The electrical resistance of the binary liquid system cyclohexane + acetic anhydride is measured, in the critical region, both in the pure mixture and when the mixture is doped with small amounts (≈ 100 ppm) of H₂O/D₂O impurities.T _c was approached to aboutt=3×10⁻⁶ wheret=(T −T _c )/T _c . The critical exponentb ≈ 0.35 in the fit of the resistance data to the equationdR/dT ∼t ^−b does not seem to be affected appreciably by the impurities. There is a sign reversal ofdR/dt in the non-critical region. Binary liquid systems seem to violate the universality of the critical resistivity.     

Osmotic pressure and models of binary liquid mixtures

Correction terms are explicitly exhibited to a relation proposed by Hammel between the compressibility K_T of a liquid binary mixture and the values of K_T in the pure species 1 and 2.     

NpT-ensemble Monte Carlo calculations for binary liquid mixtures

A Monte Carlo method for the calculation of thermodynamic properties in the isothermal-isobaric ensemble is described. Application is made to the calculation of excess thermodynamic properties (enthalpy, volume and Gibbs free energy) of binary mixtures of Lennard-Jones 12-6 liquids. Comparison is made with the predictions of a number of theories of liquid mixtures; the so-called van der Waals one-fluid model and the variational theory of Mansoori and Leland are both found to give excellent results. The accuracy attainable in estimates of the excess properties is discussed in terms of statistical fluctuations in various calculated quantities and the advantages and disadvantages of the method are examined in relation to calculations by the more familiar constant-volume method.     

Sound velocity in binary liquid mixtures and the statistical mechanical theories

Sound velocity in three binary liquid mixtures benzene+cyclohexane (I), cyclohexane+carbontetrachloride (II) and benzene+carbontetrachloride (III) has been measured. Significant structure and Flory — Patterson theories have been employed to evaluate ultrasonic velocity in the systems. The values are in good agreement with the experimental ones. A comparative study of significant structure theory and Flory-Patterson Theory has been made. Both the theories give satisfactory results for the three liquid mixtures.     

Kinetic fragility of binary and ternary glass forming liquid mixtures

The experimental studies of liquid fragility in miscible binary and ternary glass forming mixtures reveal a general observation of the negative deviation in fragility upon mixing from the linear average of those of the components. Further analyses from ideal, near ideal to non-ideal mixing modes show that the deviation magnitude does not increase monotonically with mixing enthalpy, and a moderate intermolecular interaction would generate a largest reduction in fragility. Four eutectic systems, methyl-o-toluate-methyl-p-toluate, ZnCl₂-AlCl₃, glycerol-water, and fructose-water, are studied to locate the composition where the largest fragility deviation occurs in phase diagrams. It is found that the compositions with the fragility minima do not coincide with the eutectic points. The results partly explain the experimental observation that the best glass forming region is not located at the eutectic composition.     

On the theory of spinodal decomposition in solid and liquid binary mixtures

The kinetics of phase separation is discussed with emphasis on the transition between spinodal decomposition and nucleation. A reanalysis of the theory of Langer, Baron and Miller shows that it exhibits a spinodal line somewhat closer to the coexistence curve than the meanfield spinodal. There the same (as we think unphysical) critical singularities occur as in Cahn-Hilliard theory. The precise location of this spinodal line depends on the cell size of the coarse graining. For concentrations less than the spinodal one the structure factorS(k, t) converges then towards the structure factor of the metastable onephase state, implying an infinite lifetime of the latter.In order to include the effects of nucleation and growth we hence present an alternative treatment, extending our previous work on cluster dynamics. From a simple approximation for the radial concentration distribution function of clustersS(k, t) is computed numerically. Even at rather low concentrations the time evolution ofS(k, t) is then similar to what Langer et al. find at high concentrations, implying a very gradual transition from nucleation and growth to spinodal decomposition, at least for parameter values appropriate to the Ising model. This treatment, which is consistent with Lifshitz-Slyozov's coarsening law at late times, is extended to the early stages of phase separation in liquid mixtures.     

Diffusion-stress coupling in liquid phase during rapid solidification of binary mixtures

An analytical model has been developed to describe the diffusion-viscous stress coupling in the liquid phase during rapid solidification of binary mixtures. The model starts with a set of evolution equations for diffusion flux and viscous pressure tensor, based on extended irreversible thermodynamics. It has been demonstrated that the diffusion-stress coupling leads to non-Fickian diffusion effects in the liquid phase. With only diffusive dynamics, the model results in the nonlocal diffusion equations of parabolic type, which imply the transition to complete solute trapping only asymptotically at an infinite interface velocity. With the wavelike dynamics, the model leads to the nonlocal diffusion equations of hyperbolic type and describes the transition to complete solute trapping and diffusionless solidification at a finite interface velocity in accordance with experimental data and molecular dynamic simulation.     

Photopyroelectric investigation of binary mixtures of liquid crystals in contact preparations

The photopyroelectric (PPE) method is proposed as a sensitive technique to study a binary mixture of liquid crystals in a contact preparation. The photothermal signal is generated while scanning the contact preparation. The crystal (K)/smectic-A (S _A), smectic-A/nematic (N), and nematic/isotropic (I) interphase boundaries are detected. The displacement of these boundaries due to the variation of the temperature is monitored. Received: 13 Oktober 1998 / Accepted: 7 July 1999 / Published online: 3 December 1999     

Ultrasonic study on binary liquid mixtures between some bromoalkanes and hydrocarbons

Densities and ultrasound velocities for the binary mixtures of 1-bromobutane+benzene and 1,4-dimethylbenzene and of 1-bromopentane+cyclohexane and benzene have been measured at 308.15 K. Adiabatic compressibilities (beta(ad)), and Wada's constants (W) have also been evaluated as a function of composition. The ultrasound velocities decrease, attains a minimum and then increase with increase in mole fractions of hydrocarbons in the binary mixtures except in the case of 1-bromopentane+benzene binary mixtures where the variation is just the reverse. Dependence of adiabatic compressibilities with mole fractions of hydrocarbons is sigmoid. The non-ideal behaviour of the systems studied is explained on the basis of dipole-induced dipole interactions.