Search results for "Enthalpy"
showing 10 items of 199 documents
Zur Autoxydation von Polystyrol
1971
Die mit Azoisobuttersauredinitril (AIBN) initiierte Autoxydation von Polystyrol (PS) in Chlorbenzol bei 60°C ist von der Ordnung 0,75, bezogen auf AIBN, und 0,34, bezogen auf PS. Der niedrige Exponent der Polystyrolkonzentration weist neben intermolekularen Wachstumsschritten auf intramolekulare Reaktionsschritte bei der Autoxydation hin. Die bei der Autoxydation am Polystyrol gebildeten Hydroperoxidgruppen zerfallen in Essigsathylester als Losungsmittel mit einer Aktivierungsenthalpie von 19,7 kcal/Mol und einer Aktivierungsentropie von −29 cal/Mol Grad. Das spricht fur einen monomolekularen bifunktionellen Zerfallsmechanismus. Als fluchtige Produkte bei diesem Hydroperoxidzerfall werden P…
Enthalpies of formation of isoprene’s major oxidation byproducts
2005
Abstract The theoretical enthalpies of formation ( Δ f H 298 . 15 ∘ ) of methyl vinyl ketone (MVK, CH 2 CHC(O)CH 3 ), methacrolein (MACR, CH 2 C(CH 3 )CHO), and the radical products formed in their corresponding OH radical oxidations have been calculated with DFT (MPW1K/6-31+G(d,p)) and multilevel (MCCM-UT-CCSD(T)//MPW1K/6-31+G(d,p)) methods. The bond dissociation energies ( BDE , DH 298 . 15 0 ) of the H-atoms that can be abstracted from the MVK and MACR molecules, and the C–O forming bonds of the OH addition products are also calculated. The regioselectivity of the global reaction is discussed in terms of bond strength.
Pressure-induced chemical decomposition of copper orthovanadate (α-Cu3V2O8)
2021
The high pressure stability of α-Cu3V2O8 has been investigated via complementary high pressure synchrotron X-ray diffraction experiments and theoretical density functional theory calculations. The results of both experiment and theory are in close agreement. The main result of this work is that α-Cu3V2O8 undergoes a pressure-induced chemical decomposition into CuO and V2O5 at a modest pressure of ∼1.35 GPa according to the experimental observations, and at ∼2.45 GPa according to the calculations. The decomposition is investigated with enthalpy calculations and one of the main driving factors is the stability of the octhedral oxygen-coordination of the metal atoms in the decompositon product…
Enthalpies of solution and dilution of butanol and pentanol in dodecyltrimethylammonium bromide micellar solutions
1987
The enthalpies of solution and of dilution of 1-butanol and 1-pentanol were measured in micellar solutions of dodecyltrimethylammonium bromide by systematically changing the concentration of alcohols and surfactant. The enthalpies of solution at infinite dilution of alcohols at each surfactant concentration were evaluated from a linear plot. This quantity increases with surfactant concentration (up to 0.8m) with a curvature which depends on the alcohol alkyl chain length. The difficulties arising for a quantitative treatment of both the enthalpies of dilution and of solution at finite alcohol concentrations are discussed. The dependence on the surfactant concentration of the standard enthal…
Fluid geochemistry in a low-enthalpy geothermal field along a sector of southern Apennines chain (Italy)
2020
Abstract The chemical and isotopic features of the fluids (water and gases) in the Lucane thermal area (southern Italy) have been investigated in order to verify their origin, water temperature in the geothermal reservoir, and to recognize the main natural processes concerning the water composition during ascent towards the surface. The Lucane geothermal system is placed in the southern sector of the Apennines chains, a seismically active area, close to the southern base of the Mt. Alpi carbonate massif. Along the study area, two main sets of high-angle faults form an almost orthogonal fault system that, as suggested by local structural geology, acts as a preferential pathway for uprising d…
Speciation of Al3+ in fairly concentrated solutions (20 to 200 mmol L-1) at I = 1 mol L-1 (NaNO3), in the acidic pH range, at different temperatures.
2011
AbstractThe hydrolysis of Al3+ was studied in aqueous 1 mol L−1 NaNO3 solution at different concentrations (20–200 mmol L−1) and temperatures (283.15–343.15 K) by potentiometry (ISE-H+, glass electrode). Many different speciation models were considered in the calculations and it was found that the best model is represented by the following species: Al(OH)2+, Al(OH)45+, Al13(OH)327+. Hydrolysis constants and enthalpy changes at different temperatures are reported.
New Pressure-Induced Polymorphic Transitions of Anhydrous Magnesium Sulfate
2017
The effects of pressure on the crystal structure of the three known polymorphs of magnesium sulfate have been theoretically study by means of DFT calculations up to 45 GPa. We determined that at ambient conditions gamma MgSO4 is an unstable polymorph, which decompose into MgO and SO3, and that the response of the other two polymorphs to hydrostatic pressure is non isotropic. Additionally we found that at all pressures beta MgSO4 has a largest enthalpy than alpha MgSO4. This indicates that beta MgSO4 is thermodynamically unstable versus alpha MgSO4 and predicts the occurrence of a beta alpha phase transition under moderate compression. Our calculations also predict the existence under pressu…
Transport coefficients of n-butane into and through the surface of silicalite-1 from non-equilibrium molecular dynamics study
2009
We have studied coupled heat and mass transfer of n-butane through a membrane of silicalite-1. A description of the surface was given using non-equilibrium thermodynamics, and transport coefficients were determined. Three independent coefficients were found for the whole surface: the resistance to heat transfer, the coupling coefficient and the resistance to mass transfer. These coefficients were defined in stationary state. All resistances are significant, and show that the surface acts as a barrier to transport. A new scheme was devised to find the enthalpy of adsorption, from two particular coupling coefficients, namely the measurable heats of transfer. The method yields the enthalpy of …
DSC study on hyaluronan drying and hydration
2011
Abstract The processes of hyaluronan (HYA) drying and hydration were studied using differential scanning calorimetry. In the first approach the isoconversional Kissinger–Akahita–Sunose (KAS) method was applied in order to determine actual activation energies of evaporation of pure water and water from concentrated HYA solutions. Since the evaporation is a single-step process, the activation energies for pure water provided results consistent with tabulated values of evaporation enthalpies. In the course of water evaporation from hyaluronan solution a break in increasing enthalpy followed by a decrease below 0.34 g of water per 1 g of HYA was observed. This result confirmed earlier observati…
Micellization in Model Surfactant Systems
1999
Formation of micelles in model lattice surfactant systems was studied by a novel methodology based on grand-canonical Monte Carlo simulations. The methodology involves combining free-energy information from a series of simulations in small systems by histogram reweighting. The solution osmotic pressure as a function of overall volume fraction of surfactant shows a sharp break at the critical micelle concentration (cmc) at sufficiently low temperatures. Studies in larger systems at appropriate values of the surfactant chemical potential are used to investigate the size distribution of micellar aggregates. The methodology allows for a clear distiction between micellization and macroscopic pha…