Search results for "Thermodynamic"
showing 10 items of 2971 documents
Reactor model for fast reactions in the micro-bubble column and validation
2007
A simple reactor model for predicting conversions in a micro-bubble column is described. It assumes fast reactions so that the gaseous component is readily consumed at the gas-liquid interface. Then, gas-liquid mass transfer becomes determining. As input parameters for the model, the hydrodynamics, specific interfacial area, and mass transport need to be described. Two fast model reactions, the catalytic oxidation of butyraldehyde and the absorption of CO2 in aqueous NaOH, show the applicability of the model but also its limits. The model was used for predicting reaction performance in dependence of operating conditions, in particular to get maximum conversion with the antagonistic paramete…
Viscous Synergy of Pure Monoalcohol Mixtures in Water and Its Relation to Concentration
2004
Pure or aqueous alcohols are the solvents most widely used in industry, including in the manufacture of pharmaceuticals and cosmetic products. However, water–alcohol mixtures generate hydrogen-bonded molecular associations that lead to volume contraction and an increase in viscosity greater than that expected in the absence of any interaction between the components of the mixture. This phenomenon is referred to as viscous synergy. The present study investigates viscous synergy in monoalcohol systems containing up to five carbon atoms, since beyond hexanol all alcohols are practically insoluble in water. In all cases, determinations were made of the proportions of water and alcohol for which…
Interaction of methyltin(IV) compounds with carboxylate ligands. Part 2: Formation thermodynamic parameters, predictive relationships and sequesterin…
2008
Thermodynamic data of mono-, di- and tri-methyltin(IV)-carboxylate complexes (acetate, malonate, succinate, oxydiacetate, diethylenetrioxydiacetate, malate, citrate, 1,2,3-tricarballylate, 1,2,3,4-butanetetracarboxylate, 1,2,3,4,5,6-benzenehexacarboxylate) in aqueous solution are reported at t = 25 °C and I = 0 mol l−1. Thermodynamic parameters obtained were analysed to formulate empirical predictive relationships as a function of different parameters, such as the number of carboxylate groups of the ligand and the charge of the alkyltin(IV) cation. Sequestration diagrams of citrate and 1,2,3-tricarballylate towards alkyltin(IV) cations at different pH values are also reported and discussed.…
A simple model for barrier frequencies for enzymatic reactions.
2010
We present a simple model to rationalize the effects of environment on the reaction barrier frequencies derived from free energy profiles. These frequencies are relevant in deviations of a rate constant from its transition state theory value and in determining which environmental dynamics participate in the reaction. In particular, this simple model can be used to understand the changes in the reaction barrier frequencies of an enzymatic catalyzed reaction and the corresponding uncatalyzed process in aqueous solution, a change which has implications for dynamical environmental effects on the enzymatic reaction. Two possible cases are analyzed, in which the polarity (charge separation/locali…
Entropy of transfer of n-nitroalkanes from n-octane to water at 25�C
1984
Entropy of transfer of nitromethane, nitroethane, 1-nitrobutane, 1-nitropentane, and 1-nitrohexane from n-octane to water at 25°C is calculated using an electrostatic model. The calculations indicate that the electrostatic transfer entropy depends primarily on the dipole moment and the size of the-C−NO2 group, showing a trend which is similar to that previously found for the transfer free energy of the same process.
Calculation of the relative basicities of methylamines in solution
1990
Abstract The relative basicities in solution of the methylamines have been calculated using the model of Miertus, Scrocco and Tomasi to describe the solvent effect. The surface of the cavity is defined with the GEPOL method. The ab initio calculations have been performed using a 4-31G basis set. The relative order is reproduced using a combination of the gas-phase proton affinities obtained with quantum-mechanical methods by Eades, Weil, Dixon and Douglass and the solvation values obtained by us. The results seem to point out that the irregular order is not due to solvent but to basis-set effects.
Thermodynamics of titanium and vanadium reduction in non-aqueous environment calculated at various levels of theory.
2012
Reduction of titanium and vanadium compounds is a process accompanying the activation of coordinative olefin polymerization catalysts. Four density functional theory (DFT) functionals, coupled cluster with single, double, and perturbative triple excitations method CCSD(T) as well as complete active-space second-order perturbation theory method CASPT2 with a complete active-space self-consistent field CASSCF reference wave function were applied to investigate the thermodynamics of titanium and vanadium reduction. The performance of these theoretical methods was assessed and compared with experimental values. The calculations indicate that vanadium(IV) chloride is more easily reduced by trime…
Temperature at Small Scales: A Lower Limit for a Thermodynamic Description
2011
We analyze the concept of equilibrium temperature in a set of interacting argon atoms, confined in a nanostructure, a zeolite with an intricate distribution of channels through which the atoms may move. The temperature is computed following two procedures: by averaging over the kinetic energy of the particles and over the forces acting on them. It is shown that for external surfaces and for regions which do not fall under the whole pattern of potential energy distribution, smaller than a quarter of a crystal unit cell, both temperatures, kinetic and configurational, show significant differences. The configurational temperature accounts for the different interactions on the particles in the …
Application of SQMFF Vibrational Calculations to Transition States: DFT and ab Initio Study of the Kinetics of Methyl Azide and Ethyl Azide Thermoly…
1998
DFT including nonlocal corrections and ab initio calculations at MP2 and MP4 levels of theory have been performed in order to provide information concerning the mechanism of the rate limiting step of the thermal decomposition of methyl azide and ethyl azide. The chemically interesting points of the ground-state potential energy surface have been fully optimized, and a detailed normal-mode analysis for the reagents and the transition states is presented. The well-established scaled quantum mechanical force field method has been used to obtain reliable vibrational frequencies for these molecular structures. The force fields of transition states have been modified by using the scale factors co…
Anomalies in the temperature dependence of the 1.2-? absorption of liquid water
1975
The weakly absorbed 1.2-μ combination band of water was accurately studied as a function of temperature, in both its profile and first derivative, to obtain information on the bulk properties of liquid water. Arrhenius plots of integrated component intensity ratios showed well aligned experimental points, except for a neatly defined break occurring in the 30 to 40°C temperature interval for pure water A similar break, shifted by some 18°C towards lower temperature, was found in the case of 1M NaClO4 aqueous solutions. The breaks are tentatively assumed to result from abrupt though subtle changes involving low-frequency modes. This tentative, assumption appears independent of specific models…