A New Rare-Gas Compound: HXeOXeH

Rare-gas chemistry is of growing interest, and the recent advances include the "insertion" of a Xe atom into OH and water in the rare-gas hydrides HXeO and HXeOH. The insertion of Xe atoms into the H-C bonds of hydrocarbons was also demonstrated for HXeCC, HXeCCH and HXeCCXeH, the last of which was the first rare-gas hydride containing two rare-gas atoms. We describe the preparation and characterization of a new rare-gas compound, HXeOXeH. HXeOXeH was prepared in solid xenon by photolysis of a suitable precursor, for example water, and subsequent mobilization of the photoproducts. The experimental identification was carried out by FTIR spectroscopy, isotopic substitution and by use of various precursors. The photolytical and thermal stability of the new rare-gas hydride was also studied. The experimental work was supported by extensive quantum chemical calculations provided by our co-workers. HXeOXeH forms in a cryogenic xenon matrix from neutral O and H atoms in a two-step diffusion-controlled process involving HXeO as an intermediate [reactions (1) and (2)]. This formation mechanism is unique in that a rare-gas hydride is formed from another rare-gas hydride. H + Xe + O → HXeO (1) HXeO + Xe + H → HXeOXeH (2) Similarly to other rare-gas hydrides, HXeOXeH has a strongly IR-active H-Xe stretching vibration, allowing its spectral detection at 1379.3 cm-1. HXeOXeH is a very high-energy metastable species, yet thermally more stable than many other rare-gas hydrides. The calculated bending barrier of 0.57 eV, is not enough to explain the observed stability, and HXeOXeH might be affected by additional stabilization from the solid xenon environment. Chemical bonding between xenon and environmentally abundant species like water is of particular importance due to the “missing-xenon” problem. The relatively high thermal stability of HXeOXeH compared to other oxygen containing rare-gas compounds is relevant in this respect. Our work also raises the possibility of polymeric (–Xe–O)n networks, similarly to the computationally studied (XeCC)n polymers.

Does manure management affect the latent greenhouse gas emitting potential of livestock manures?

With livestock manures being increasingly sought as alternatives to costly synthetic fertilisers, it is imperative that we understand and manage their associated greenhouse gas (GHG) emissions. Here we provide the first dedicated assessment into how the GHG emitting potential of various manures responds to the different stages of the manure management continuum (e.g., from feed pen surface vs stockpiled). The research is important from the perspective of manure application to agricultural soils. Manures studied included: manure from beef feedpen surfaces and stockpiles; poultry broiler litter (8-week batch); fresh and composted egg layer litter; and fresh and composted piggery litter. Gases assessed were methane (CH4) and nitrous oxide (N2O), the two principal agricultural GHGs. We employed proven protocols to determine the manures’ ultimate CH4 producing potential. We also devised a novel incubation experiment to elucidate their N2O emitting potential; a measure for which no established methods exist. We found lower CH4 potentials in manures from later stages in their management sequence compared with earlier stages, but only by a factor of 0.65×. Moreover, for the beef manures this decrease was not significant (P < 0.05). Nitrous oxide emission potential was significantly positively (P < 0.05) correlated with C/N ratios yet showed no obvious relationship with manure management stage. Indeed, N2O emissions from the composted egg manure were considerably (13×) and significantly (P < 0.05) higher than that of the fresh egg manure. Our study demonstrates that manures from all stages of the manure management continuum potentially entail significant GHG risk when applied to arable landscapes. Efforts to harness manure resources need to account for this.

Ion exchange of sodium chloride and sodium bicarbonate solutions using strong acid cation resins in relation to coal seam water treatment

Coal seam gas production has resulted in the production of large volumes of associated water which contains dissolved salts dominated by sodium chloride and sodium bicarbonate. Ion exchange using synthetic resins has been proposed as a method for desalination of coal seam water to make it suitable for various beneficial reuse options. This study investigated the behaviour of solutions of sodium chloride and sodium bicarbonate with respect to exchange with Lanxess S108H strong acid cation (SAC) resin. Equilibrium isotherms were created for solutions of NaCl and NaHCO3 and an actual sample of coal seam water from the Surat Basin in southern Queensland. The exchange of sodium ions arising from sodium bicarbonate was found to be considerably more favourable than exchange of sodium ions from sodium chloride solutions. This latter behaviour was attributed to the secondary decomposition of bicarbonate species under acidic conditions which resulted in the evolution of carbon dioxide and formation of water. The isotherm profiles could not be satisfactorily fitted by a single isotherm model such as the Langmuir expression. Instead, two Langmuir equations had to be simultaneously applied in order to fit the sections of the isotherm attributable to sodium ion exchange from sodium bicarbonate and sodium chloride. The shape of the isotherm profile was dependent upon the ratio of sodium chloride to sodium bicarbonate in solution and there was a high degree of correlation between simulated and actual coal seam water solutions.

Liquid Sheet Breakup in Gas-Centered Swirl Coaxial Atomizers

The study deals with the breakup behavior of swirling liquid sheets discharging from gas-centered swirl coaxial atomizers with attention focused toward the understanding of the role of central gas jet on the liquid sheet breakup. Cold flow experiments on the liquid sheet breakup were carried out by employing custom fabricated gas-centered swirl coaxial atomizers using water and air as experimental fluids. Photographic techniques were employed to capture the flow behavior of liquid sheets at different flow conditions. Quantitative variation on the breakup length of the liquid sheet and spray width were obtained from the measurements deduced from the images of liquid sheets. The sheet breakup process is significantly influenced by the central air jet. It is observed that low inertia liquid sheets are more vulnerable to the presence of the central air jet and develop shorter breakup lengths at smaller values of the air jet Reynolds number Re-g. High inertia liquid sheets ignore the presence of the central air jet at smaller values of Re-g and eventually develop shorter breakup lengths at higher values of Re-g. The experimental evidences suggest that the central air jet causes corrugations on the liquid sheet surface, which may be promoting the production of thick liquid ligaments from the sheet surface. The level of surface corrugations on the liquid sheet increases with increasing Re-g. Qualitative analysis of experimental observations reveals that the entrainment process of air established between the inner surface of the liquid sheet and the central air jet is the primary trigger for the sheet breakup.

Effect of Bottom Bubbling Conditions on Surface Reaction Rate in Oxygen-Water System

In secondary steelmaking, the enhancement of the reaction rate in the low carbon period during the decarburization of steel is considered the most effective method to produce ultralow carbon steel. In a previous study, it was revealed that the surface reaction is dominant during the final stage of the actual refining process. In order to improve the surface reaction rate, it is necessary to enlarge the reaction region, which is usually achieved by increasing the plume eye area. In this study, water model experiments were carried out to estimate the influence of bottom stirring conditions on the gas-liquid reaction rate; for this purpose, the deoxidation rate during the bottom bubbling process was measured. Five types of nozzle configurations were used to study the effect of the plume eye area on the reaction rate at various gas flow rates. The results reveal that the surface reaction rate is influenced by the gas flow rate and the plume eye area. An empirical correlation was developed for the reaction rate and the plume eye area. This correlation was applied to estimate the gas-liquid reaction rate mat the bath surface.

BDST modelling of sodium ion exchange column behaviour with strong acid cation resin in relation to coal seam water treatment

Reverse osmosis is the dominant technology utilized for desalination of saline water produced during the extraction of coal seam gas. Alternatively, ion exchange is of interest due to potential cost advantages. However, there is limited information regarding the column performance of strong acid cation resin for removal of sodium ions from both model and actual coal seam water samples. In particular, the impact of bed depth, flow rate, and regeneration was not clear. Consequently, this study applied Bed Depth Service Time (BDST) models to reveal that increasing sodium ion concentration and flow rates diminished the time required for breakthrough to occur. The loading of sodium ions on fresh resin was calculated to be ca. 71.1 g Na/kg resin. Difficulties in regeneration of the resin using hydrochloric acid solutions were discovered, with 86% recovery of exchange sites observed. The maximum concentration of sodium ions in the regenerant brine was found to be 47,400 mg/L under the conditions employed. The volume of regenerant waste formed was 6.2% of the total volume of water treated. A coal seam water sample was found to load the resin with only 53.5 g Na/kg resin, which was consistent with not only the co-presence of more favoured ions such as calcium, magnesium, barium and strontium, but also inefficient regeneration of the resin prior to the coal seam water test.

Effect of surfactants on the fluorescence spectra of water-soluble MEHPPV derivatives having grafted polyelectrolyte chains

Poly(2-methoxy-5-[2'-ethylhexyoxy]-1,4-phenylenevinylene) (MEHPPV) derivatives with polyacrylic acid (PAA) chains grafted onto their backbone were found to be water soluble, and they exhibited a dramatic increase in their fluorescence intensity in the presence of a variety of surfactants, even at concentrations far below their critical micelle concentrations (CMC). This increase was accompanied by a blue-shift in the emission maximum. These observations are rationalized based on the postulate that the backbone conformation of the conjugated polymer is modulated upon interaction of the surfactant molecules with the polyelectrolytic tethers, which in turn results in a significant depletion of intra-chain interchromophore interactions that are known to cause red-shifted emission bands with significantly lower emission yields.

Vibrational phase relaxation of O–H stretch in bulk water: Role of large amplitude angular jumps and negative cross-correlations among the forces on the O–H bond

The ultrafast vibrational phase relaxation of O–H stretch in bulk water is investigated in molecular dynamics simulations. The dephasing time (T2) of the O–H stretch in bulk water calculated from the frequency fluctuation time correlation function (Cω(t)) is in the range of 70–80 femtosecond (fs), which is comparable to the characteristic timescale obtained from the vibrational echo peak shift measurements using infrared photon echo [W.P. de Boeij, M.S. Pshenichnikov, D.A. Wiersma, Ann. Rev. Phys. Chem. 49 (1998) 99]. The ultrafast decay of Cω(t) is found to be responsible for the ultrashort T2 in bulk water. Careful analysis reveals the following two interesting reasons for the ultrafast decay of Cω(t). (A) The large amplitude angular jumps of water molecules (within 30–40 fs time duration) provide a large scale contribution to the mean square vibrational frequency fluctuation and gives rise to the rapid spectral diffusion on 100 fs time scale. (B) The projected force, due to all the atoms of the solvent molecules on the oxygen (FO(t)) and hydrogen (FH(t)) atom of the O–H bond exhibit a large negative cross-correlation (NCC). We further find that this NCC is partly responsible for a weak, non-Arrhenius temperature dependence of the dephasing rate.

Carbon dynamics in peatlands under changing hydrology : Effects of water level drawdown on litter quality, microbial enzyme activities and litter decomposition rates

Pristine peatlands are carbon (C) accumulating wetland ecosystems sustained by a high water level (WL) and consequent anoxia that slows down decomposition. Persistent WL drawdown as a response to climate and/or land-use change directly affects decomposition: increased oxygenation stimulates decomposition of the old C (peat) sequestered under prior anoxic conditions. Responses of the new C (plant litter) in terms of quality, production and decomposability, and the consequences for the whole C cycle of peatlands are not fully understood. WL drawdown induces changes in plant community resulting in shift in dominance from Sphagnum and graminoids to shrubs and trees. There is increasing evidence that the indirect effects of WL drawdown via the changes in plant communities will have more impact on the ecosystem C cycling than any direct effects. The aim of this study is to disentangle the direct and indirect effects of WL drawdown on the new C by measuring the relative importance of 1) environmental parameters (WL depth, temperature, soil chemistry) and 2) plant community composition on litter production, microbial activity, litter decomposition rates and, consequently, on the C accumulation. This information is crucial for modelling C cycle under changing climate and/or land-use. The effects of WL drawdown were tested in a large-scale experiment with manipulated WL at two time scales and three nutrient regimes. Furthermore, the effect of climate on litter decomposability was tested along a north-south gradient. Additionally, a novel method for estimating litter chemical quality and decomposability was explored by combining Near infrared spectroscopy with multivariate modelling. WL drawdown had direct effects on litter quality, microbial community composition and activity and litter decomposition rates. However, the direct effects of WL drawdown were overruled by the indirect effects via changes in litter type composition and production. Short-term (years) responses to WL drawdown were small. In long-term (decades), dramatically increased litter inputs resulted in large accumulation of organic matter in spite of increased decomposition rates. Further, the quality of the accumulated matter greatly changed from that accumulated in pristine conditions. The response of a peatland ecosystem to persistent WL drawdown was more pronounced at sites with more nutrients. The study demonstrates that the shift in vegetation composition as a response to climate and/or land-use change is the main factor affecting peatland ecosystem C cycle and thus dynamic vegetation is a necessity in any models applied for estimating responses of C fluxes to changes in the environment. The time scale for vegetation changes caused by hydrological changes needs to extend to decades. This study provides grouping of litter types (plant species and part) into functional types based on their chemical quality and/or decomposability that the models could utilize. Further, the results clearly show a drop in soil temperature as a response to WL drawdown when an initially open peatland converts into a forest ecosystem, which has not yet been considered in the existing models.

Two-Phase Thermodynamic Model for Efficient and Accurate Absolute Entropy of Water from Molecular Dynamics Simulations

Presented here is the two-phase thermodynamic (2PT) model for the calculation of energy and entropy of molecular fluids from the trajectory of molecular dynamics (MD) simulations. In this method, the density of state (DoS) functions (including the normal modes of translation, rotation, and intramolecular vibration motions) are determined from the Fourier transform of the corresponding velocity autocorrelation functions. A fluidicity parameter (f), extracted from the thermodynamic state of the system derived from the same MD, is used to partition the translation and rotation modes into a diffusive, gas-like component (with 3Nf degrees of freedom) and a nondiffusive, solid-like component. The thermodynamic properties, including the absolute value of entropy, are then obtained by applying quantum statistics to the solid component and applying hard sphere/rigid rotor thermodynamics to the gas component. The 2PT method produces exact thermodynamic properties of the system in two limiting states: the nondiffusive solid state (where the fluidicity is zero) and the ideal gas state (where the fluidicity becomes unity). We examine the 2PT entropy for various water models (F3C, SPC, SPC/E, TIP3P, and TIP4P-Ew) at ambient conditions and find good agreement with literature results obtained based on other simulation techniques. We also validate the entropy of water in the liquid and vapor phases along the vapor-liquid equilibrium curve from the triple point to the critical point. We show that this method produces converged liquid phase entropy in tens of picoseconds, making it an efficient means for extracting thermodynamic properties from MD simulations.

Critical micelle concentration from a lattice gas model

The temperature dependence of the critical micelle concentration (CMC) and a closed-loop coexistence curve are obtained, via Monte Carlo simulations, in the water surfactant limit of a two-dimensional version of a statistical mechanical model for micro-emulsions, The CMC and the coexistence curve reproduce various experimental trends as functions of the couplings. In the oil-surfactant limit, there is a conventional coexistence cure with an upper consolute point that allows for a region of three-phase coexistence between oil-rich, water-rich and microemulsion phases.

Studies in biogas technology. Part IV. A novel biogas plant incorporating a solar water-heater and solar still

A reduction in the heat losses from the top of the gas holder of a biogas plant has been achieved by the simple device of a transparent cover. The heat losses thus prevented have been deployed to heat a water pond formed on the roof of the gas holder. This solar-heated water is mixed with the organic input for ‘ hot-charging ’ of the biogas plant. A thermal analysis of such a solar water-heater ‘ piggy-backing ’ on the gas holder of a biogas plant has been carried out.To test whether the advantages indicated by the thermal analysis can be realised in practice, a biogas plant of the ASTRA design was modified to incorporate a roof-top solar water-heater. The operation of such a modified plant, even under ‘ worst case ’ onditions, shows a significant improvement in the gas yield compared to the unmodified plant. Hence, the innovation reported here may lead to drastic reductions in the sizes and therefore costs of biogas plants. By making the transparent cover assume a tent-shape, the roof-top solar heater can serve the additional function of a solar still to yield distilled water. The biogas plant-cum-solar water-heater-cum-solar still described here is an example of a spatially integrated hybrid device which is extremely cost-effective.

Room-temperature gas sensors based on gallium nitride nanoparticles

Room-temperature sensing characteristics for H-2, ethanol, NH3, H2S and water have been investigated with thick-film sensors based on GaN nanoparticles, prepared by a simple chemical route. In general, GaN nanoparticles exhibit satisfactory sensor properties for these gases and vapors even at room temperature. The sensitivity for ethanol is found to be highest, the sensitivity and recovery times being smallest. Gas sensor properties of GaN seem to be related to intrinsic defects, which act as sorption sites for the gas molecules. (c) 2010 Elsevier Ltd. All rights reserved.

Entropy and dynamics of water in hydration layers of a bilayer

We compute the entropy and transport properties of water in the hydration layer of dipalmitoylphosphatidylcholine bilayer by using a recently developed theoretical scheme two-phase thermodynamic model, termed as 2PT method; S.-T. Lin et al., J. Chem. Phys. 119, 11792 (2003)] based on the translational and rotational velocity autocorrelation functions and their power spectra. The weights of translational and rotational power spectra shift from higher to lower frequency as one goes from the bilayer interface to the bulk. Water molecules near the bilayer head groups have substantially lower entropy (48.36 J/mol/K) than water molecules in the intermediate region (51.36 J/mol/K), which have again lower entropy than the molecules (60.52 J/mol/K) in bulk. Thus, the entropic contribution to the free energy change (T Delta S) of transferring an interface water molecule to the bulk is 3.65 kJ/mol and of transferring intermediate water to the bulk is 2.75 kJ/mol at 300 K, which is to be compared with 6.03 kJ/mol for melting of ice at 273 K. The translational diffusion of water in the vicinity of the head groups is found to be in a subdiffusive regime and the rotational diffusion constant increases going away from the interface. This behavior is supported by the slower reorientational relaxation of the dipole vector and OH bond vector of interfacial water. The ratio of reorientational relaxation time for Legendre polynomials of order 1 and 2 is approximately 2 for interface, intermediate, and bulk water, indicating the presence of jump dynamics in these water molecules. (C) 2010 American Institute of Physics. doi:10.1063/1.3494115]

Protein Hydration and Water Structure: X-ray Analysis of a Closely Packed Protein Crystal with Very Low Solvent Content

Low-humidity monoclinic lysozyme, resulting from a water-mediated transformation, has one of the lowest solvent contents (22% by volume) observed in a protein crystal. Its structure has been solved by the molecular replacement method and refined to an R value of 0.175 for 7684 observed reflections in the 10–1.75 Å resolution shell. 90% of the solvent in the well ordered crystals could be located. Favourable sites of hydration on the protein surface include side chains with multiple hydrogen-bonding centres, and regions between short hydrophilic side chains and the main-chain CO or NH groups of the same or nearby residues. Major secondary structural features are not disrupted by hydration. However, the free CO groups at the C terminii and, to a lesser extent, the NH groups at the N terminii of helices provide favourable sites for water interactions, as do reverse turns and regions which connect β-structure and helices. The hydration shell consists of discontinuous networks of water molecules, the maximum number of molecules in a network being ten. The substrate-binding cleft is heavily hydrated, as is the main loop region which is stabilized by water interactions. The protein molecules are close packed in the crystals with a molecular coordination number of 14. Arginyl residues are extensively involved in intermolecular hydrogen bonds and water bridges. The water molecules in the crystal are organized into discrete clusters. A distinctive feature of the clusters is the frequent occurrence of three-membered rings. The protein molecules undergo substantial rearrangement during the transformation from the native to the low-humidity form. The main-chain conformations in the two forms are nearly the same, but differences exist in the side-chain conformation. The differences are particularly pronounced in relation to Trp 62 and Trp 63. The shift in Trp 62 is especially interesting as it is also known to move during inhibitor binding.