Search results for " Enthalpy"
showing 10 items of 31 documents
Towards highly accurate ab initio thermochemistry of larger systems: benzene.
2011
The high accuracy extrapolated ab initio thermochemistry (HEAT) protocol is applied to compute the total atomization energy (TAE) and the heat of formation of benzene. Large-scale coupled-cluster calculations with more than 1500 basis functions and 42 correlated electrons as well as zero-point energies based on full cubic and (semi)diagonal quartic force fields obtained with the coupled-cluster singles and doubles with perturbative treatment of the triples method and atomic natural orbital (ANO) triple- and quadruple-zeta basis sets are presented. The performance of modifications to the HEAT scheme and the scaling properties of its contributions with respect to the system size are investiga…
Enthalpies of mixing of some nitriles aqueous solutions with dodecylsurfactants micellar solutions
1988
The enthalpies of mixing of some n-nitriles (from acetonitrile to valeronitrile) aqueous solutions with dodecyltzimethylammonium bromide, sodium dodecylsulfate and dodecyltzimethylammonium oxide micellar solutions were determined. The measurements were performed by systematically changing the surfactant concentration at a given solute concentration. The experimental enthalpies were rationalized in terms of the standard enthalpy of transfer of solute from the aqueous to the micellar phase and of the distribution constant between the two phase. Information on the effect of the nature of the surfactant on the standard thermodynamic quantities of transfer(ΔG t o , ΔH t o , TΔS t o ) is reported…
Hydrolysis of dioxouranium(VI): a calorimetric study in NaClaq and NaClO4aq, at 25°C
2004
Abstract We report the results of a calorimetric study on the hydrolysis of UO 2 2+ in different ionic media (NaClO 4 aq , NaCl aq ) at 25 °C. Experiments in NaCl were performed at different ionic strength, at I ≤1 mol l −1 . The species considered in both ionic media were UO 2 (OH) + , (UO 2 ) 2 (OH) 2 2+ and (UO 2 ) 3 (OH) 5 + , and in addition (UO 2 ) 3 (OH) 4 2+ and (UO 2 ) 3 (OH) 7 − in NaCl aq . The dependence on ionic strength of enthalpy changes in NaCl aq was expressed by the simple linear equation Δ H pq =Δ H ° pq + aI 1/2 ( a , empirical parameter). Comparison with literature findings is given and some recommended values are reported.
Protonation thermodynamics of 2,2'-bipyridyl in aqueous solution. Salt effects and weak complex formation
1993
Abstract Protonation constants of 2,2'-bipyridyl (bipy) have been determined potentiometrically, using (H + )-glass electrode, in different aqueous media (alkali and alkaline earth chlorides, tetramethylammonium chloride and tetramethylammonium iodide) at different temperatures and ionic strengths. The differences in log K H values are explained using a complex formation model. Formation thermodynamic parameters are given.
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.
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.
Some fundamentals of the vapor and solution growth of ZnSe and ZnO
1999
Abstract Some fundamentals of ZnSe and ZnO vapor and solution growth are investigated. Residual water present in gases or gaseous mixtures such as H 2 , Ar or H 2 +H 2 O is shown to act as a sublimation activator in the vapor-phase transport of both compounds. The processes involved in the growth by chemically activated sublimation with such gases and gas mixtures have been studied by close-spaced vapor transport (CSVT). The ZnSe growth rate is found to be constant, while in the ZnO case a high initial growth rate is followed by slower growth subsequently. Using a theoretical model, the thermodynamic constants of the transport – energies of activation, sublimation and condensation and entha…
Enthalpy of Solution of Nonionic Solutes in Organized Systems
1989
The standard enthalpies of solution of alcohols in micellar solutions of dodecyltrimethylammonium bromide were obtained by direct measurements and by enthalpies of mixing. The observed trends were analyzed with a previously reported model. From the resulting equations, the distribution constant, standard enthalpy of transfer from aqueous to the micellar phase and the standard enthalpy of solution in micellar phase can be calculated at the same time using a linear least-squares analysis. The model seems to hold well also in the case of short chain surfactants and microheterogeneities in spite of the fact that the micellization equilibrium is treated as a pseudo-phase transition.