Dynamics Of Thermotropic Liquid Crystals Across The Isotropic-Nematic Transition And Their Similarity With Glassy Relaxation In Supercooled Liquids

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A Conjecture Concerning Transformation Of A Supercooled Hard-Sphere Liquid To A Metastable Disordered Solid

It is conjectured that the hard sphere system has several distinct solid phases, all but one of which are metastable. The bifurcation theory analysis of freezing is extended to the description of the transition between a supercooled liquid and a disordered solid by defining a restricted phase space for the disordered solid. This approach leads to the prediction of a first order transition between a supercooled hard sphere fluid and a disordered metastable hard sphere solid. The results of the calculation are in qualitative agreement with the results of Woodcock's molecular dynamics computer simulations. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.

Interfacial area measurement in a gas - liquid ejector for a sodium chloride - air system

Interfacial area measurement has been carried out experimentally by measuring the bubble size and holdup for air-sodium chloride solution system. The size of the bubble is predominantly established by the air hold up. High speed photography technique for bubble size measurement and gamma ray attenuation method for holdup measurements are followed. The measured values are compared with the theoretically predicted values. Interracial area as a function of the liquid flow rate and also its distance from the nozzle of the ejector has been reported in this paper. The results obtained for this non-reactive system are also compared with those of air-water system.

Mechanistic studies on the pyrolysis and combustion of polystyrene/ammonium perchlorate propellants in the presence of transition metal oxides

The effect of transition metal oxides (Fe2O3, MnO2, Ni2O3 and Co2O3) on polystyrene/ammonium perchlorate propellant systems has been examined. The mechanism of action of the oxides in increasing the burning rate was examined by studying the effect of the oxides on the thermal decomposition and combustion of the oxidizer and the propellant. It has been concluded that one of the mechanisms by which the oxides act is by promoting the charge-transfer process, which is indicated by the enhancement of the electron-transfer process in ammonium perchlorate and by the correlation between the redox potential of the metal ions and the corresponding burning rates of the propellant.

Kinetics of Extraction of Iron(II1) by Bis(2-ethylhexyl Phosphate in a Laminar Liquid-Liquid Jet Reactor

The kinetics of iron(II1) extraction by bis(Zethylhexy1) phosphate (HDEHP, HA) in kerosene from sulfuric acid solutions has been studied in a liquid-liquid laminar jet reactor. The contact time of the interface in this reacting device is of the same order of magnitude as the surface renewal time in dispersion mixing and much less than that obtained in the relatively quiescent condition of the Lewis cell. Yet the analysis of the data in this study suggested a rate-controlling step involving surface saturation quite in conformity with that obtained in the Lewis cell and not with that in dispersion mixing as reported in the literature. Further, the mechanism suggested a weaker dependence of the rate on hydrogen ion concentration which was reported by other workers.

Heat transfer with solid liquid phase change initiating at a point in a semi infinite mold

Short-time analytical solutions of temperature and moving boundary in two-dimensional two-phase freezing due to a cold spot are presented in this paper. The melt occupies a semi-infinite region. Although the method of solution is valid for various other types of boundary conditions, the results in this paper are given only for the prescribed flux boundary conditions which could be space and time dependent. The freezing front propagations along the interior of the melt region exhibit well known behaviours but the propagations along the surface are of new type. The freezing front always depends on material parameters. Several interesting results can be obtained as particular cases of the general results.

Low-frequency dielectric constant measurements in the critical polar + non-polar binary liquid system: Methanol + n-heptane

The low-frequency (5–100 kHz) dielectric constant ε has been measured in the temperature range 7 × 10−5 < T = (T − Tc)/Tc < 8 × 10−2. Near Tc an exponent ≈0.11 characterizes the power law behaviour of dε/dt consistent with the theoretically predicted t−α singularity. However, over the full range of t an exponent ≈0.35 is obtained.

Enhancement of Tunneling Density of States at a Junction of Three Luttinger Liquid Wires

We study the tunneling density of states (TDOS) for a junction of three Tomonaga-Luttinger liquid wires. We show that there are fixed points which allow for the enhancement of the TDOS, which is unusual for Luttinger liquids. The distance from the junction over which this enhancement occurs is of the order of x=v/(2 omega), where v is the plasmon velocity and omega is the bias frequency. Beyond this distance, the TDOS crosses over to the standard bulk value independent of the fixed point describing the junction. This finite range of distances opens up the possibility of experimentally probing the enhancement in each wire individually.

Chemical changes during the aging and decomposition of composite solid propellants

During the thermal decomposition of orthorhombic ammonium perchlorate (AP) at 230°C, where the decomposition is only up to 30 wt %, there is an accumulation in the solid of acids, the concentration of which increases up to 15% decomposition, after which it decreases till it reaches the original value. Similar observations have been made in the polystyrene (PS)/AP propellant systems. Aging studies of PS/AP propellants have been carried out earlier [1], where it has been shown that for the aged propellants the thermal decomposition (TD) rate at 230°C and 260°C and ambient pressure burning rate (Image ) both increase and this increase is due to the formation of reactive intermediate “polystyrene peroxide (PSP).” In the present studies it has been observed that during the aging of the propellant at 150°C, the acid is formed and gets accumulated in the propellant, which may also be responsible for the increase in TD rate and perhaps may be more effective than PSP.

Vapour composition and activities in Mg-Zn liquid alloy at 923 K

Vapour species effusing from a magnesia Knudsen cell containing Mg-Zn alloy at 923 K were condensed on a water cooled copper plate. The equilibrium composition of the vapour phase over the alloy was determined from chemical analysis of the condensate. The activity coefficients of both components in the alloy have been derived from the data using a modified Gibbs-Duhem relation. The ratio of saturation vapour pressures of pure Zn and Mg obtained from the analysis of alloy data agree well with values from the literature, providing an internal check on the accuracy of data obtained in this study. Both components of the alloy exhibit negative deviations from Raoult's law. The concentration-concentration structure factor of Bhatia and Thomton at zero wave vector, evaluated from the measurements, indicate the presence of MgZn2 type complex in the liquid state. The associated regular solution model has been used for the thermodynamic description of liquid Mg-Zn alloys.

Permeation of gases through liquid films

Permeation of gases through single surfactant stabilized aqueous films has previously been studied in view of the potentiality of foam to separate gaseous mixtures. The earlier analysis assumed that the gas phase was well mixed and that the mass-transfer process was completely controlled by the liquid film. Permeabilities evaluated from single film data based on such analysis failed to predict the mass-transfer data obtained on permeation through two films. It is shown that the neglect of gas-phase resistance and the effect of film movement is the reason for the failure of the well-mixed gas models. An exact analysis of diffusion through two films is presented. It successfully predicts the experimental data on two films based on parameters evaluated from single film data.

ESR evidence for 2 coexisting liquid phases in deeply supercooled bulk water

Using electron spin resonance spectroscopy (ESR), we measure the rotational mobility of probe molecules highly diluted in deeply supercooled bulk water and negligibly constrained by the possible ice fraction. The mobility increases above the putative glass transition temperature of water, T-g = 136 K, and smoothly connects to the thermodynamically stable region by traversing the so called "no man's land" (the range 150-235 K), where it is believed that the homogeneous nucleation of ice suppresses the liquid water. Two coexisting fractions of the probe molecules are evidenced. The 2 fractions exhibit different mobility and fragility; the slower one is thermally activated (low fragility) and is larger at low temperatures below a fragile-to-strong dynamic cross-over at approximate to 225 K. The reorientation of the probe molecules decouples from the viscosity below approximate to 225 K. The translational diffusion of water exhibits a corresponding decoupling at the same temperature [Chen S-H, et al. (2006) The violation of the Stokes-Einstein relation in supercooled water. Proc Natl Acad Sci USA 103:12974-12978]. The present findings are consistent with key issues concerning both the statics and the dynamics of supercooled water, namely the large structural fluctuations [Poole PH, Sciortino F, Essmann U, Stanley HE (1992) Phase behavior of metastable water. Nature 360: 324-328] and the fragile-to-strong dynamic cross-over at approximate to 228 K [Ito K, Moynihan CT, Angell CA (1999) Thermodynamic determination of fragility in liquids and a fragile-tostrong liquid transition in water. Nature 398: 492-494].

Fluctuation Theory Of The Specific-Heat Of Normal Liquid-3He

The measured specific heat of normal liquid 3He shows a plateau for 0.15<1 K; below 0.15 K and above 1 K, it rises linearly with temperature. However, the slope on the high-temperature side is very much reduced compared with the free-Fermi-gas value. We explain these features through a microscopic, thermal spin- and density-fluctuation model. The plateau is due to spin fluctuations which have a low characteristic energy in 3He. Because of the low compressibility, the density fluctuations are highly suppressed; this leads to a reduced slope for CV(T) for high temperatures.

Gas-liquid interfacial area in stirred vessels: The effect of an immiscible liquid phase

The presence of an inert immiscible organic phase in gas�liquid dispersions in stirred vessels influences the interfacial area in a more complex fashion than hitherto reported. As the organic phase fraction is increased, the interfacial area expressed on the basis of a unit volume of dispersion or aqueous phase, first increases, passes through a maximum and then decreases. This trend is observed irrespective of whether the area is determined by chemical means or by physical method. It is found that for low values of inert phase fraction, the average bubble size decreases whereas the gas holdup increases, resulting in increased interfacial area. The lower average bubble size is found to be due to partial prevention of coalescence as the bubbles size generated in the impeller region actually increases with the organic phase fraction. The actual values of interfacial areas depend on the nature of the organic phase. It is also found that the organic phase provides a parallel path for mass transfer to occur, when the solubility of gas in it is high.