Search results for " Free energy"
showing 10 items of 137 documents
Estimation of individual Gibbs energies of cation transfer employing the insertion electrochemistry of solid Prussian blue
2011
Abstract A novel method to determine the Gibbs energy of cation transfer between two miscible solvents is described. This method uses electrochemical data for the reversible cation-assisted solid-state reduction of Prussian blue using ferrocene as internal potential standard. Voltammetric data can be used for a direct measurement of the Gibbs energy of ion transfer from one solvent to another using midpeak potentials in solutions of suitable salts in each one of the solvents separately or mixtures of the solvents. Excess Gibbs energies of solvation in solvent mixtures can also be directly estimated. Gibbs energies of cation transfer of Li+, Na+ and K+ ions from water to MeOH, MeCN and DMSO …
PREDICTION OF THERMODYNAMIC INSTABILITIES OF PROTEIN SOLUTIONS FROM SIMPLE PROTEIN-PROTEIN INTERACTIONS
2013
Statistical thermodynamics of protein solutions is often studied in terms of simple, microscopic models of particles interacting via pairwise potentials. Such modelling can reproduce the short range structure of protein solutions at equilibrium and predict thermodynamics instabilities of these systems. We introduce a square well model of effective protein-protein interaction that embeds the solvent's action. We modify an existing model [45] by considering a well depth having an explicit dependence on temperature, i.e. an explicit free energy character, thus encompassing the statistically relevant configurations of solvent molecules around proteins. We choose protein solutions exhibiting dem…
Classical and quantum vortex leapfrogging in two-dimensional channels
2020
The leapfrogging of coaxial vortex rings is a famous effect which has been noticed since the times of Helmholtz. Recent advances in ultra-cold atomic gases show that the effect can now be studied in quantum fluids. The strong confinement which characterizes these systems motivates the study of leapfrogging of vortices within narrow channels. Using the two-dimensional point vortex model, we show that in the constrained geometry of a two-dimensional channel the dynamics is richer than in an unbounded domain: alongsize the known regimes of standard leapfrogging and the absence of it, we identify new regimes of backward leapfrogging and periodic orbits. Moreover, by solving the Gross-Pitaevskii…
Thermodynamic predictions of the formation of chalcogenide glasses
1985
The understanding of glass forming ability requires quantitative information on the stable and metastable phase equilibria of binary and multicomponent systems, particularly as a function of composition and temperature. This paper discusses the success of the use of Gibbs free energy curves for the supercooled liquid relative to the stable crystalline phases to describe glass forming ability. Applications are reported for the systems GeSe2-Se, Sb2Se3-Se and GeSe2-Sb2Se3 for which experimental minimal quenching rates are available. A strongly associated regular solution model for the liquid phase gives a predicted behaviour consistent with experimental data. The method is intended to apply t…
Propan-2-ol dehydration on H-ZSM-5 and H-Y zeolite: a DFT study
2012
The catalytic dehydration of propan-2-ol over H-Y and H-ZMS-5 aluminated zeolite models, mimicking both internal cavities and external surfaces, was studied by DFT calculations to investigate the reaction mechanism. After the adsorption of propan-2-ol on the zeolite, the dehydration mechanism starts with alcohol protonation, occurring by one acidic –OH group of the zeolite fragment, followed by a concerted β-elimination to give propene. The catalytic activity is affected by the size of the zeolite cavity, which is larger in the H-Y than in the H-ZMS-5 zeolite. The adsorption energy of the reagent, as an example, decreases in the order: H-Y cavity ≃ H-ZMS-5 surface > H-ZMS-5 cavity, pointing…
Pd-catalyzed hydrodehalogenation of chlorinated olefins: Theoretical insights to the reaction mechanism
2012
Abstract Density functional theory calculations are applied to study energetics of trichloroethene (TCE) hydrodechlorination over pure Pd(1 1 1), chlorine-covered Pd(1 1 1), and Pd island supported by Au(1 1 1). Our results show that in all cases C Cl bond breakings take place more readily than C H bond formations and that TCE dechlorinates fully producing CCH precursors for the hydrogenations. The reaction pathway through radical-like species provides a possible explanation to the experimental product distributions that show a nominal amount of lesser chlorinated species in the presence of excess hydrogen. The surface chlorine resulted from the TCE decomposition weakens the binding of the …
From CO2 to dimethyl carbonate with dialkyldimethoxystannanes: the key role of monomeric species.
2011
International audience; The formation of dimethyl carbonate (DMC) from CO(2) and methanol with the dimer [n-Bu(2)Sn(OCH(3))(2)](2) was investigated by experimental kinetics in support of DFT calculations. Under the reaction conditions (357-423 K, 10-20 MPa), identical initial rates are observed with three different reacting mixtures, CO(2)/toluene, supercritical CO(2), and CO(2)/methanol, and are consistent with the formation of monomeric di-n-butyltin(iv) species. An intramolecular mechanism is, therefore, proposed with an Arrhenius activation energy amounting to 104 ± 10 kJ mol(-1) for DMC synthesis. DFT calculations on the [(CH(3))(2)Sn(OCH(3))(2)](2)/CO(2) system show that the exothermi…
Application of reverse electrodialysis to site-specific types of saline solutions: A techno-economic assessment
2019
Abstract Salinity gradients are a non-conventional source of renewable energy based on the recovery of the Gibbs free energy related to the mixing of solutions at different concentrations. Reverse Electrodialysis is a promising and innovative technology able to convert this energy directly into electric current. The worldwide availability of salinity gradients is limited to those locations where water bodies at different salinity levels are present. The present work analyses a number of different scenarios worldwide, in locations where salinity gradients are naturally available or generated by anthropogenic activities. A techno-economic model of the Reverse Electrodialysis process is presen…
Techno-economic evaluation of Reverse Electrodialysis process in different real environments
2018
Salinity Gradient Power is a promising renewable energy source based on the recovery of the chemical potential released from the mixing of solutions at different concentrations. Natural salinity gradients are extensively available worldwide in natural reservoirs. Reverse Electrodialysis is an innovative technology able to perform a direct conversion of the energy of mixing into electricity. Salinity gradients coming from natural resources or from human activities are worldwide available. In the present work a number of different scenarios, including natural resources (e.g. rivers, seas, lakes and salt ponds), industrial/urban wastes (e.g. brine and treated wastewaters) are analysed. The aim…
Porous silicon based photoluminescence immunosensor for rapid and highly-sensitive detection of Ochratoxin A.
2017
A rapid and low cost photoluminescence (PL) immunosensor for the determination of low concentrations of Ochratoxin A (OTA) has been developed. This immunosensor was based on porous silicon (PSi) and modified by antibodies against OTA (anti-OTA). PSi layer was fabricated by metal-assisted chemical etching (MACE) procedure. Main structural parameters (pore size, layer thickness, morphology and nanograins size) and composition of PSi were investigated by means of X-Ray diffraction (XRD), scanning electron microscopy (SEM) and Raman spectroscopy. PL-spectroscopy of PSi was performed at room temperature and showed a wide emission band centered at 680 ± 20nm. Protein A was covalently immobilized …