Studies in hydrogen bonding: Association within mixed dimers of water,methanol, ammonia,and methylamine using the empirical potential EPEN

An empirical potential EPEN has been used to find the stable geometries and approximate hydrogenbond energies of the mixed dimers formed between molecules of water, methanol, ammonia, and methylamine. These results are compared with results in the literature obtained using ab initio methods.     

Isospin fractionation in nuclear multifragmentation

Isotopic distributions for light particles and intermediate mass fragments have been measured for 112Sn+112Sn, 112Sn+124Sn, 124Sn+112Sn, and 124Sn+124Sn collisions at E/A = 50 MeV. Isotope, isotone, and isobar yield ratios are utilized to estimate the isotopic composition of the gas phase at freeze-out. Analyses within the equilibrium limit imply that the gas phase is enriched in neutrons relative to the liquid phase represented by bound nuclei. These observations suggest that neutron diffusion is commensurate with or more rapid than fragment production.     

Specific heat of electron gas of arbitrary dimensionality

The exchange contribution to the specific heat of an electron gas in d dimensions is calculated and is shown to lead to a logarithmic temperature dependence at low temperatures in all dimensions (d > 1).     

Oxygen and water vapor permeability of fully substituted long chain cellulose esters (LCCE)

Fully-substituted cellulose esters with acyl substituents ranging in size from C2 to C18 were synthesized using the acyl chloride method. Films were prepared from the purified esters by either solvent-casting or compression-molding at elevated temperatures. Oxygen and water vapor permeability was determined under different conditions of pressure and moisture. The relationship between cellulose ester structure and barrier properties was examined. The results revealed linear relationships between water vapor and oxygen permeabilities and molar ester substituent volume as well as several structural factors relating to polymer polarity and hydrophobicity, such as aliphatic (methylene) content, solubility parameter, and contact angle. Films from long chain cellulose esters (LCCE) with acyl substituents in the size range between C8 and C18 were found to represent effective barriers to water vapor transport while their obstruction to the transfer of oxygen remained low. It was concluded that the hydrophobic nature of LCCEs is responsible for the control of water vapor transport, and that spatial factors dominate the transfer of oxygen.     

Born-Haber-Fajans cycle generalized: linear energy relation between molecules, crystals, and metals

Classical procedures to calculate ion-based lattice potential energies (U(POT)) assume formal integral charges on the structural units; consequently, poor results are anticipated when significant covalency is present. To generalize the procedures beyond strictly ionic solids, a method is needed for calculating (i) physically reasonable partial charges, delta, and (ii) well-defined and consistent asymptotic reference energies corresponding to the separated structural components. The problem is here treated for groups 1 and 11 monohalides and monohydrides, and for the alkali metal elements (with their metallic bonds), by using the valence-state atoms-in-molecules (VSAM) model of von Szentpály et al. (J. Phys. Chem. A 2001, 105, 9467). In this model, the Born-Haber-Fajans reference energy, U(POT), of free ions, M(+) and Y(-), is replaced by the energy of charged dissociation products, M(delta)(+) and Y(delta)(-), of equalized electronegativity. The partial atomic charge is obtained via the iso-electronegativity principle, and the asymptotic energy reference of separated free ions is lowered by the "ion demotion energy", IDE = -(1)/(2)(1 - delta(VS))(I(VS,M) - A(VS,Y)), where delta(VS) is the valence-state partial charge and (I(VS,M) - A(VS,Y)) is the difference between the valence-state ionization potential and electron affinity of the M and Y atoms producing the charged species. A very close linear relation (R = 0.994) is found between the molecular valence-state dissociation energy, D(VS), of the VSAM model, and our valence-state-based lattice potential energy, U(VS) = U(POT) - (1)/(2)(1 - delta(VS))(I(VS,M) - A(VS,Y)) = 1.230D(VS) + 86.4 kJ mol(-)(1). Predictions are given for the lattice energy of AuF, the coinage metal monohydrides, and the molecular dissociation energy, D(e), of AuI. The coinage metals (Cu, Ag, and Au) do not fit into this linear regression because d orbitals are strongly involved in their metallic bonding, while s orbitals dominate their homonuclear molecular bonding.     

Applying thermodynamics to digestion/gasification processes: the Attainable Region approach

The research shows theoretical calculations on the thermodynamics of digestion/gasification processes where glucose is used as a surrogate for biomass. The change in Enthalpy (?H) and Gibbs Free Energy (?G) is used to obtain the Attainable Region (AR) that shows the overall thermodynamic limits for digestion/gasification from 1 mol of glucose. Gibbs Free Energy and Enthalpy (G–H) plots were calculated for the temperature range 25–1500 °C. The results show the effect of temperature on the AR for the processes when water is in both liquid and gas states using 25 °C, 1 bar as the reference state. The AR results show that the production of CO, H₂, CH₄ and CO₂ are feasible at all temperatures studied. The minimum Gibbs Free Energy becomes more negative from ?418.68 kJ mol^?1 at 25 °C to ?3024.34 kJ mol^?1 at 1500 °C while the process shifts from exothermic (?141.90 kJ mol^?1) to endothermic (1161.80 kJ mol^?1) for the respective temperatures. Methane and carbon dioxide are favoured products (minimum Gibbs Free Energy) for temperatures up to about 600 °C, and this therefore includes Anaerobic Digestion. The process is exothermic below 500 °C, and thus Anaerobic Digestion requires heat removal. As the temperature continues to increase, hydrogen production becomes more favourable than methane production. The production of gas is endothermic above 500 °C, and it needs a supply of heat that could be done, either by combustion or by electricity (plasma gasification). The calculations show that glucose conversion at temperatures around 700 °C favours the production of carbon dioxide and hydrogen at minimum G. Generally, the results show that the gas from high-temperature gasification (>~800 °C) typically carries the energy mainly in syngas components CO and H₂, whereas at low-temperature gasification (<500 °C) the energy is carried in CH₄. The overall analysis for the temperature range (25–1500 °C) also suggests a close relationship between biogas production/digestion and gasification as biogas production can be referred to as a form of low-temperature gasification.