Search results for "enthalpy"
showing 10 items of 199 documents
Elastic properties of the sigma W-Re phase: A first principles investigation
2017
Abstract We perform density functional theory (DFT) calculations to obtain the formation enthalpy and six independent elastic constants for the 32 possible occupations of the five non-equivalent sites of the σ -phase. The obtained results suggest linear correlation between bulk modulus and Re concentration and between shear modulus and formation enthalpy. The results are used to parameterize a sublattice model with ideal mixing on each sublattice for the free energy and elastic constants. The model allows one to predict the equilibrium composition on each sublattice and hence elastic constants as a function of global Re concentration and temperature of the W-Re alloy.
Modeling self-sustaining waves of exothermic dissolution in nanometric Ni-Al multilayers
2016
Abstract The self-sustained propagating reaction occurring in nanometric metallic multilayers was studied by means of molecular dynamics (MD) and numerical modeling. We focused on the phenomenon of the exothermic dissolution of one metallic reactant into the less refractory one, such as Ni into liquid Al. The exothermic character is directly related to a negative enthalpy of mixing. An analytical model based on the diffusion-limited dissolution [1] coupled with heat transfer was derived to account for the main aspects of the process. Together, several microscopic simulations were carried out. The first series were set up to obtain all the parameters governing the process, including the heat…
Arsenic diffusion in relaxedSi1−xGex
2003
The intrinsic As diffusion properties have been determined in relaxed ${\mathrm{Si}}_{1\ensuremath{-}x}{\mathrm{Ge}}_{x}$ epilayers. The properties were studied as a function of composition x for the full range of materials with $x=0,$ 0.20, 0.35, 0.50, 0.65, 0.8, and 1. The activation enthalpy ${E}_{a}$ was found to drop systematically from 3.8 eV $(x=0)$ to 2.4 eV $(x=1).$ Comparisons with other impurity atom- and self-diffusion results in Si, Ge, and SiGe show that both interstitials and vacancies contribute as diffusion vehicles in the composition range $0l~xl~0.35$ and that vacancy mechanism dominates diffusion in the composition range $0.35lxl~1.$
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…
Unravelling the kinetics and molecular mechanism of the degenerate Cope rearrangement of bullvalene
2020
The kinetics and molecular mechanism of the gas phase degenerate Cope rearrangement (DCR) of bullvalene have been investigated by applying quantum mechanical calculations. Highly accurate energies (CBS-QB3 and CBS-APNO) and RRKM calculations were employed to study the kinetics and ‘fall-off’ behavior. It was found that the DCR of bullvalene (C3v) occurs through a bishomoaromatic transition structure (C2v) with an energy barrier of ∼49 kJ mol−1. The calculated activation energy and enthalpy were in good agreement with the available values in the literature, but lower than those of common Cope rearrangement; this result is related to the high stabilization energy due to the interaction of the…
Specific and highly efficient condensation of GC and IC DNA by polyaza pyridinophane derivatives
2018
Abstract Two bis-polyaza pyridinophane derivatives and their monomeric reference compounds revealed strong interactions with ds-DNA and RNA. The bis-derivatives show a specific condensation of GC- and IC-DNA, which is almost two orders of magnitude more efficient than the well-known condensation agent spermine. The type of condensed DNA was identified as ψ-DNA, characterized by the exceptionally strong CD signals. At variance to the almost silent AT(U) polynucleotides, these strong CD signals allow the determination of GC-condensates at nanomolar nucleobase concentrations. Detailed thermodynamic characterisation by ITC reveals significant differences between the DNA binding of the bis-deriv…
Co-adsorption of 1,2-dichloroethane and 1-bromo,2-chloroethane on zeolite ZSM-5 from the liquid and vapour phases, using the Myers-Prausnitz-Dubinin …
2002
Abstract The adsorption/co-adsorption of 1,2-dichloroethane (DCA) and 1-bromo,2-chloroethane (BCA) from the vapour and the liquid phases by zeolite ZSM-5 at ambient temperature is reported, using Dubinin's theory and the recent Myers-Prausnitz-Dubinin (MPD) theory. For adsorption from the liquid phase, the activity coefficients in the adsorbed and the liquid states are the same and no selectivity is observed. This is confirmed by the absence of an excess enthalpy of immersion of ZSM-5 into the mixtures. Adsorption from the vapour phase proceeds in two stages, as indicated by double Dubinin-Astakhov (DA) plots. If one considers only the domain of high relative pressure, co-adsorption is desc…
Calculation of the chemical potential and the activity coefficient of two layers of CO2 adsorbed on a graphite surface.
2014
We study the adsorption of carbon dioxide at a graphite surface using the new Small System Method, and find that for the temperature range between 300 K and 550 K most relevant for CO2 separation; adsorption takes place in two distinct thermodynamic layers defined according to Gibbs. We calculate the chemical potential and the activity coefficient of both layers directly from the simulations. Based on thermodynamic relations, the entropy and enthalpy of the CO2 adsorbed layers are also obtained. Their values indicate that there is a trade-off between entropy and enthalpy when a molecule chooses for one of the two layers. The first layer is a densely packed monolayer of relatively constant e…
Thermodynamic Characterization Of Two Layers Of CO2 On A Graphite Surface
2014
We find by examination of density profiles that carbon dioxide adsorbs on graphite in two distinct layers. We report the activity coefficient, entropy and enthalpy for CO2 in each layer using a convenient computational method, the Small System Method, thereby extending this method to surfaces. This opens up the possibility to study thermodynamic properties for a wide range of surface phenomena. © 2014 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).
Energetics of sodium dodecylsulfate-dodecyldimethylamine oxide mixed micelle formation
1994
Enthalpies of dilution and osmotic coefficients of the sodium dodecyl-sulfate (NaDS)-dodecyldimethylamine oxide (DDAO) mixtures in water have been measured at 25 and 37°C, respectively. From the enthalpies of dilution the apparent molar relative enthalpies LΦ were calculated. The change of the LΦ vs. total molality mt profiles with the mole fraction reflects the variation of the ionic character of the mixed micelles. From the osmotic coefficients the nonideal free energy G2ni were calculated. By combining G2ni with the partial molar relative enthalpies, the nonideal entropies TS2ni were determined. At a given mole fraction, G2ni and TS2ni values are decreasing and increasing respectively, t…