Search results for "Standard enthalpy of formation"
showing 10 items of 19 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…
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…
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.
Equilibrium properties of the reaction H2⇌ 2H by classical molecular dynamics simulations
2013
We have developed a classical molecular dynamics model for the hydrogen dissociation reaction, containing two- and three-particle potentials derived by Kohen, Tully and Stillinger. Two fluid densities were investigated for a wide range of temperatures, and 11 fluid densities were considered for one temperature. We report the temperature range where the degree of reaction is significant, and also where a stable molecule dominates the population in the energy landscape. The three-particle potential, which is essential for the reaction model and seldom studied, together with the two-particle interaction lead to a large effective excluded volume diameter of the molecules in the molecular fluid.…
HEAT: High accuracy extrapolated ab initio thermochemistry.
2004
A theoretical model chemistry designed to achieve high accuracy for enthalpies of formation of atoms and small molecules is described. This approach is entirely independent of experimental data and contains no empirical scaling factors, and includes a treatment of electron correlation up to the full coupled-cluster singles, doubles, triples and quadruples approach. Energies are further augmented by anharmonic zero-point vibrational energies, a scalar relativistic correction, first-order spin-orbit coupling, and the diagonal Born-Oppenheimer correction. The accuracy of the approach is assessed by several means. Enthalpies of formation (at 0 K) calculated for a test suite of 31 atoms and mole…
Metal complex-DNA binding: Insights from molecular dynamics and DFT/MM calculations.
2012
Molecular dynamics (MD) simulations, followed by density functional theory/molecular mechanics (DFT/MM) calculations, provided a detailed structure of the binding site between the cationic metallointercalator (dipyrido [3,2-a:2',3'-c]phenazine)(glycinato)copper(II), [Cu(gly)(dppz)](+), and the two dodeca-deoxynucleotide duplexes [dodeca(dG-dC)]2 and [dodeca(dA-dT)]2. Three simultaneous DNA binding types were detected in the fully optimized DFT/MM structures: 1) metal coordination through exocyclic oxygen atoms of nitrogen bases; 2) intercalation of the dppz chromophore between stacked Watson-Crick AT-AT and GC-GC bases; and 3) hydrogen bonding between the glycinato ligand and amine groups o…
Cyclooctadienine — hoch gespannte C 8 H 8 ‐Kohlenwasserstoffe
1985
Mit Hilfe der MNDO-Methode werden die energiearmsten Konformationen der vier strukturisomeren Cyclooctadienine 1–4 berechnet. Aus ihren Bildungswarmen ΔHf konnen durch Bezug zu den Cyclooctatrienen 5 und 6 die geometrischen Ringspannungen Eg abgeschatzt werden. Als experimentelle Sonde fur die Ringspannung dienen die UV-, IR (Raman)- und 13C-NMR-Spektren. Cyclooctadienynes — Highly Strained C8H8-Hydrocarbons Applying the MNDO-method the conformations with lowest energy of the isomeric cyclooctadienynes 1–4 are calculated. The geometrical ring strains Eg can be evaluated from the enthalpies of formation ΔHf in relation to the cyclooctatrienes 5 and 6. UV, IR (Raman) and 13C NMR spectra serve…