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.

Analysis of Daphnane Orthoesters in Poisonous Australian Pimelea Species by Liquid Chromatography-Tandem Mass Spectrometry.

Cattle grazing in arid rangelands of Australia suffer periodic extensive and serious poisoning by the plant species Pimelea trichostachya, P. simplex, and P. elongata. Pimelea poisoning (also known as St. George disease and Marree disease) has been attributed to the presence of the diterpenoid orthoester simplexin in these species. However, literature relating to previous studies is complicated by taxonomic revisions, and the presence of simplexin has not previously been verified in all currently recognized taxa capable of inducing pimelea poisoning syndrome, with no previous chemical studies of P. trichostachya (as currently classified) or P. simplex subsp. continua. We report here the isolation of simplexin from P. trichostachya and the development of a liquid chromatography-mass spectrometry/mass spectrometry (LC-MS/MS) method to measure simplexin concentrations in pimelea plant material. Simplexin was quantified by positive-ion atmospheric pressure chemical ionization (APCI) LC-MS/MS with selected reaction monitoring (SRM) of the m/z 533.3 > 253.3 transition. LC-MS/MS analysis of the four poisonous taxa P. trichostachya, P. elongata, P. simplex subsp. continua, and P. simplex subsp. simplex showed similar profiles with simplexin as the major diterpenoid ester component in all four taxa accompanied by varying amounts of related orthoesters. Similar analyses of P. decora, P. haematostachya, and P. microcephala also demonstrated the presence of simplexin in these species but at far lower concentrations, consistent with the limited reports of stock poisoning associated with these species. The less common, shrubby species P. penicillaris contained simplexin at up to 55 mg/kg dry weight and would be expected to cause poisoning if animals consumed sufficient plant material.

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.

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.

Use of a volatile buffer at ambient temperature *1: Versatile approach to the purification of self-complementary synthetic deoxyoligonucleotides by reversed-phase high-performance liquid chromatography

Abstract is not available.

Dynamic structure factor across the liquid-solid interface: appearance of a delta-function elastic peak

We present a theoretical calculation of the dynamic structure factor, S(k, ω), at the liquid-solid interface for large values of the wavevector k. An analytic expression is derived which shows the evolution of the elastic peak as the solid surface is approached from the liquid side.

The Influence of Bilayer Composition on the Gel to Liquid Crystalline Transition

We report molecular dynamics simulations of bilayers using a united atom model with explicit solvent molecules. The bilayer consists of the single tail cationic surfactant behenyl trimethyl ammonium chloride (BTMAC) with stearyl alcohol (SA) as the cosurfactant. We study the gel to liquid crystalline transitions in the bilayer by varying the amount of water at fixed BTMAC to SA ratio as well as by varying the BTMAC to SA ratio at fixed water content. The bilayer is found to exist in the tilted, Lβ′ phase at low temperatures, and for the compositions investigated in this study, the Lβ′ to Lα melting transition occurred in the temperature range 330−338 K. For the highest BTMAC to SA composition (2:3 molar ratio), a diffuse headgroup−water interface is observed at lower temperatures, and an increase in the d-spacing occurs prior to the melting transition. This pretransition swelling is accompanied by a sharpening in the water density variation across the headgroup region of the bilayer. Signatures of this swelling effect which can be observed in the alkane density distributions, area per headgroup, and membrane thickness are attributed to the hydrophobic effect. At a fixed bilayer composition, the transition temperature (>338 K) from the Lβ′ to Lα transition obtained for the high water content bilayer (80 wt %) is similar to that obtained with low water content (54.3 wt %), confirming that the melting transition at these water contents is dominated by chain melting.

Coexistence curve of acetonitrile and cyclohexane liquid system

The paper reports a detailed determination of the coexistence curve for the binary liquid system acetonitrile+cyclohexane, which have very closely matched densities and the data points get affected by gravity only for t=(Tc−T)/ Tc[approximately-equal-to]10−6. About 100 samples were measured over the range 10−6liquids. The extrapolation properties of the Wegner expansion procedure is somewhat inferior to the extrapolation obtained using a renormalization group (RG) crossover expansion. The use of the new variables proposed by Johnston et al. and Vnuk in making the coexistence curve appear symmetric in the new variables is pointed out. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.

Elastic constants of galena down to liquid helium temperatures

The elastic constants of single crystal galena have been determined from the measured ultrasonic velocities down to liquid helium temperature. A cryostat incorporating an arrangement to inject the liquid bonding material at low temperature is described. At 5 K, the values of elastic constants are C11=14.90, C12=3.51 and C44=2.92×1010 N/m2.