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.

The ozone transfer between atmosphere and vegetation. A study on Scots pine in the field

Ozone (O3) is a reactive gas present in the troposphere in the range of parts per billion (ppb), i.e. molecules of O3 in 109 molecules of air. Its strong oxidative capacity makes it a key element in tropospheric chemistry and a threat to the integrity of materials, including living organisms. Knowledge and control of O3 levels are an issue in relation to indoor air quality, building material endurance, respiratory human disorders, and plant performance. Ozone is also a greenhouse gas and its abundance is relevant to global warming. The interaction of the lower troposphere with vegetated landscapes results in O3 being removed from the atmosphere by reactions that lead to the oxidation of plant-related components. Details on the rate and pattern of removal on different landscapes as well as the ultimate mechanisms by which this occurs are not fully resolved. This thesis analysed the controlling processes of the transfer of ozone at the air-plant interface. Improvement in the knowledge of these processes benefits the prediction of both atmospheric removal of O3 and its impact on vegetation. This study was based on the measurement and analysis of multi-year field measurements of O3 flux to Scots pine (Pinus sylvestris L.) foliage with a shoot-scale gas-exchange enclosure system. In addition, the analyses made use of simultaneous CO2 and H2O exchange, canopy-scale O3, CO2 and H2O exchange, foliage surface wetness, and environmental variables. All data was gathered at the SMEAR measuring station (southern Finland). Enclosure gas-exchange techniques such as those commonly used for the measure of CO2 and water vapour can be applied to the measure of ozone gas-exchange in the field. Through analysis of the system dynamics the occurring disturbances and noise can be identified. In the system used in this study, the possible artefacts arising from the ozone reactivity towards the system materials in combination with low background concentrations need to be taken into account. The main artefact was the loss of ozone towards the chamber walls, which was found to be very variable. The level of wall-loss was obtained from simultaneous and continuous measurements, and was included in the formulation of the mass balance of O3 concentration inside the chamber. The analysis of the field measurements in this study show that the flux of ozone to the Scots pine foliage is generated in about equal proportions by stomatal and non-stomatal controlled processes. Deposition towards foliage and forest is sustained also during night and winter when stomatal gas-exchange is low or absent. The non-stomatal portion of the flux was analysed further. The pattern of flux in time was found to be an overlap of the patterns of biological activity and presence of wetness in the environment. This was seen to occur both at the shoot and canopy scale. The presence of wetness enhanced the flux not only in the presence of liquid droplets but also during existence of a moisture film on the plant surfaces. The existence of these films and their relation to the ozone sinks was determined by simultaneous measurements of leaf surface wetness and ozone flux. The results seem to suggest ozone would be reacting at the foliage surface and the reaction rate would be mediated by the presence of surface wetness. Alternative mechanisms were discussed, including nocturnal stomatal aperture and emission of reactive volatile compounds. The prediction of the total flux could thus be based on a combination of a model of stomatal behaviour and a model of water absorption on the foliage surfaces. The concepts behind the division of stomatal and non-stomatal sinks were reconsidered. This study showed that it is theoretically possible that a sink located before or near the stomatal aperture prevents or diminishes the diffusion of ozone towards the intercellular air space of the mesophyll. This obstacle to stomatal diffusion happens only under certain conditions, which include a very low presence of reaction sites in the mesophyll, an extremely strong sink located on the outer surfaces or stomatal pore. The relevance, or existence, of this process in natural conditions would need to be assessed further. Potentially strong reactions were considered, including dissolved sulphate, volatile organic compounds, and apoplastic ascorbic acid. Information on the location and the relative abundance of these compounds would be valuable. The highest total flux towards the foliage and forest happens when both the plant activity and ambient moisture are high. The highest uptake into the interior of the foliage happens at large stomatal apertures, provided that scavenging reactions located near the stomatal pore are weak or non-existent. The discussion covers the methodological developments of this study, the relevance of the different controlling factors of ozone flux, the partition amongst its component, and the possible mechanisms of non-stomatal uptake.

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.

Hydrothermal phase equilibria in Ln2O3-H2O-CO2 systems for Tm, Yb and Lu

Phase diagrams for Tm2O3-H2O-CO2. Yb2O3-H2O-CO2 and Lu2O3-H2O-CO2 systems at 650 and 1300 bars have been investigated in the temperature range of 100–800°C. The phase diagrams are far more complex than those for the lighter lanthanides. The stable phases are Ln(OH)3, Ln2(CO3)3.3H2O (tengerite phase), orthorhombic-LnOHCO3, hexagonal-Ln2O2CO3. LnOOH and cubic-Ln2O3. Ln(OH)3 is stable only at very low partial pressures of CO2. Additional phases stabilised are Ln2O(OH)2CO3and Ln6(OH)4(CO3)7 which are absent in lighter lanthanide systems. Other phases, isolated in the presence of minor alkali impurities, are Ln6O2(OH)8(CO3)3. Ln4(OH)6(CO3)3 and Ln12O7(OH)10,(CO3)6. The chemical equilibria prevailing in these hydrothermal systems may be best explained on the basis of the four-fold classification of lanthanides.

Multiple liquid-crystals and NMR

The use of more than one liquid crystal solvents to determine molecular structure and conformation is discussed. Liquid crystals of similar and opposite signs of diamagnetic anisotropies are considered separately since they lead to different novel applications. Advantages of such experiments over those employing single solvents are pointed out with illustrative examples.

Effect of surface resistance on gas absorption accompanied by a chemical reaction in a gas - liquid contactor

An analysis of gas absorption accompanied by chemical reaction in the presence of interfacial resistance is presented. The analysis indicates that the effect of interfacial resistance on interphase mass transfer is significantly higher in presence of a reaction compared to the pure absorption case. For fixed values of surface resistance and contact time, the difference between the amount of gas transferred across the interface with and without surface resistance increases as the value of reaction velocity increases. For ranges of contact time and surface resistance of practical relevance, the influence of surface resistance is too high to be neglected while designing gas-liquid contactors.

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 epsilon (Porson) 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 Image consistent with the theoretically predicted t−α singularity. However, over the full range of t an exponent ≈0.35 is obtained.

Liquid phase oxidation of propionaldehyde: Kinetics of initiation step

A method of determining the rate of the initiation reaction in the liquid phase oxidation of propionaldehyde is described.

Novel fluorinated surfactants tentatively identified in firefighters using liquid chromatography quadrupole time-of flight tandem mass spectrometry and a case-control approach

Fluorinated surfactant-based aqueous film-forming foams (AFFFs) are made up of per- and polyfluorinated alkyl substances (PFAS) and are used to extinguish fires involving highly flammable liquids. The use of perfluorooctanesulfonic acid (PFOS) and other perfluoroalkyl acids (PFAAs) in some AFFF formulations has been linked to substantial environmental contamination. Recent studies have identified a large number of novel and infrequently reported fluorinated surfactants in different AFFF formulations. In this study, a strategy based on a case-control approach using quadrupole time-of-flight tandem mass spectrometry (QTOF-MS/MS) and advanced statistical methods has been used to extract and identify known and unknown PFAS in human serum associated with AFFF-exposed firefighters. Two target sulfonic acids [PFOS and perfluorohexanesulfonic acid (PFHxS)], three non-target acids [perfluoropentanesulfonic acid (PFPeS), perfluoroheptanesulfonic acid (PFHpS), and perfluorononanesulfonic acid (PFNS)], and four unknown sulfonic acids (Cl-PFOS, ketone-PFOS, ether-PFHxS, and Cl-PFHxS) were exclusively or significantly more frequently detected at higher levels in firefighters compared to controls. The application of this strategy has allowed for identification of previously unreported fluorinated chemicals in a timely and cost-efficient way.

Liquid bubble manometer for low differential heads

The development of a highly sensitive liquid bubble manometer which can measure low differential heads to an accuracy of 0.01 mm of water is reported in this paper. The liquid bubble consists of two miscible liquids,benzaldehyde and normal hexane (each of which is immiscible in water) in such a proportion that the bubble density is within ±2 % of the density of water. The movement of the liquid bubble, which occupies the full cross-sectional area of the glass tube containing water in the manometer, is indicative of the applied differential head to a magnified scale. The manometer is found to give excellent results in open channel flow and is recommended for use for differential heads up to 2 cm of water. The manometer is economical, simple in fabrication and with simple modifications the sensitivity of the manometer can be increased to more than 0.01 mm of water.