Search results for "Enthalpy"
showing 10 items of 199 documents
Beyond the Vegard's law: solid mixing excess volume and thermodynamic potentials prediction, from end-members
2020
Abstract A method has been developed, herein presented, to model binary solid solutions' volume, enthalpy and Gibbs energy using the energy state functions, E ( V , S ) , of the end-members only. The E ( V , S ) s are expanded around an unknown mixing volume, V Mix , and the fundamental equilibrium equation − ( ∂ E / ∂ V ) S = P is used to determine V Mix . V Mix allows us to model enthalpy, straightforwardly. The same argument holds using Helmholtz energy, F ( V , T ) , in place of E ( V , S ) , and the equilibrium equation becomes − ( ∂ F / ∂ V ) T = P . One can readily determine the Gibbs free energy, too. The method presented remarkably simplifies computing of solid mixings' thermodynam…
Calculating thermodynamic properties from fluctuations at small scales.
2011
We show how density and energy fluctuations of small nonperiodic systems embedded in a reservoir can be used to determine macroscopic thermodynamic properties like the enthalpy density and the thermodynamic correction factor. For mixtures, the same formalism leads to a very convenient method to obtain so-called total correlation function integrals, also often referred to as Kirkwood-Buff integrals. Using finite size scaling, the properties obtained for small systems can be extrapolated to the macroscopic system limit provided that the system is sufficiently far from the critical point. As derived in our previous work (Chem. Phys. Lett. 2011, 504, 199-201), the finite size scaling is signifi…
Computer simulation of models for the structural glass transition
2008
In order to test theoretical concepts on the glass transition, we investigate several models of glassy materials by means of Monte Carlo (MC) and Molecular Dynamics (MD) computer simulations. It is shown that also simplified models exhibit a glass transition which is in qualitative agreement with experiment and that thus such models are useful to study this phenomenon. However, the glass transition temperture as well as the structural properties of the frozen-in glassy phase depend strongly on the cooling history, and the extrapolation to the limit of infinitely slow cooling velocity is nontrivial, which makes the identification of the (possible) underlying equilibrium transition very diffi…
Ab initiostudy of compressedAr(H2)2: Structural stability and anomalous melting
2010
We study the structural stability and dynamical properties of $\text{Ar}{({\text{H}}_{2})}_{2}$ under pressure using first-principles and ab initio molecular-dynamics techniques. At low temperatures, $\text{Ar}{({\text{H}}_{2})}_{2}$ is found to stabilize in the cubic C15 Laves structure $({\text{MgCu}}_{2})$ and not in the hexagonal C14 Laves structure $({\text{MgZn}}_{2})$ as it has been assumed previously. Based on enthalpy energy and phonon calculations, we propose a temperature-induced ${\text{MgCu}}_{2}\ensuremath{\rightarrow}{\text{MgZn}}_{2}$ phase transition that may rationalize the existing discrepancies between the sets of Raman and infrared vibron measurements. Our AIMD simulati…
A Chemical Index Inspired by Biological Plastic Evolution: Valence-Isoelectronic Series of Aromatics
2004
Plastic evolution is a new perspective of the evolutionary process conjugating the effect, on one hand, of the acquired characters and, on the other, of the relationships that emerge among the principle of evolutionary indeterminacy, the principle of morphologic determination, and natural selection. Plastic evolution is applied to design the coordination index Ic. Ic is used to characterize the valence-isoelectronic series of cyclopentadiene, benzene, toluene, and styrene and compared to charge indices for dipole moment. The parameters needed to calculate Ic are minus the standard enthalpy of formation T, molecular surface area S, and molecular weight W. With the exception of the O heteromo…
Environmentally Relevant Properties of All 209 Polychlorinated Biphenyl Congeners for Modeling Their Fate in Different Natural and Climatic Conditions
2009
The temperature dependence of physical properties and degradation lifetimes in the environment of all polychlorinated biphenyl (PCB) congeners (N = 209) were determined. For physical properties, the coefficients A and B in equations log(property) = A(property) − B(property)/T(K) were determined by thermodynamic and QSPR methods and compared with the results of independent methods in the literature. The coefficients Apl and Bpl for liquid state vapor pressure PL, As and Bs for solubility in water SW, Ah and Bh for volatility kH (or kH = PL/SW), and Aow and Bow for lipophilicity (KOW), stored in the database of the fate model program, allowed automatic temperature corrections for realistic fa…
Study of the molecular origin of the mechanical and dielectric β relaxation of methyl methacrylate/isopropenyl methyl ketone copolymers
1988
Resultats de l'etude dielectrique, mecanique et par TSC en faveur d'une combinaison d'une barriere intra- et intermoleculaire dans la relaxation beta
Enthalpy and Entropy Contributions to Solvent Quality and Inversions of Heat Effects with Polymer Concentration
2006
Vapor pressures above the solutions of polystyrene in either cyclohexane (32-60 °C) or toluene (10-70 °C) have been measured by a combination of head space sampling and gas chromatography as a function of the volume fraction φ of the polymer. The thus obtained Flory-Huggins interaction parameters Χ (φ; T) were complemented by data for three other systems (tert-butyl acetate/polystyrene, cyclohexane/poly(vinyl methyl ether), 2-propanol/poly(butyl methacrylate)) reported in the literature and analyzed in terms of their enthalpy and entropy parts Χ H and Χ s . Furthermore these experimental findings were modeled by means of an approach splitting the mixing process conceptually into two parts a…
Calorimetric and Volumetric Investigations of the Effect of the Hydrophobicity of the Surfactant on the Binding between (Ethylene oxide)13-(propylene…
2004
The enthalpy and the volume of transfer (DeltaY(t)) of the unassociated (ethylene oxide)(13)-(propylene oxide)(30)-(ethylene oxide)(13) (L64) from water to the aqueous sodium alkanoate solutions as functions of the surfactant concentrations (m(S)) were determined at 298 K. The surfactants studied are sodium hexanoate, sodium heptanoate, sodium octanoate, sodium undecanoate, and sodium dodecanoate. As a general feature, for the short alkyl chain surfactants, DeltaY(t) describes an S-shaped curve in the range of m(S) analyzed whereas for the more hydrophobic surfactants the DeltaY(t) vs m(S) trends exhibit maxima which appear at ms values very close to the critical micellar concentration in w…
Temperature-controlled poly(propylene) glycol hydrophobicity on the formation of inclusion complexes with modified cyclodextrins. A DSC and ITC study.
2011
The study highlighted the main forces driving the formation of hydroxypropyl-cyclodextrins (HP-CDs) + poly(propylene) glycol 725 g mol(-1) inclusion complexes. The temperature parameter was chosen as the variable to modulate the hydrophobicity of the polymer, and consequently ITC experiments as functions of temperature as well as DSC measurements were done in a systematic way. The polymer is not included into HP-α-CD, it is strongly bound to HP-β-CD and it is floating in HP-γ-CD. The stability of the inclusion complexes is entropy controlled. The gain of the entropy is a unique result compared to the opposite literature findings for inclusion complexes based on polymers and CDs. This peculi…