Search results for "Gibbs"
showing 10 items of 164 documents
Batch-to-Melt Conversion Kinetics in Sodium Aluminosilicate Batches Using Different Alumina Raw Materials
2016
The batch-to-melt conversion in batches of sand, soda ash and corundum (C), alumina spinel (A), boehmite (B), or gibbsite (G) as Al2O3 carrier are studied using thermal analysis, X-ray diffraction, and 27Al nuclear magnetic resonance spectroscopy. Laboratory-scaled batches are either heated continuously or quenched from 1600°C in a series of increasing dwell times. The results show that the conversion from the raw materials to the fresh melt proceeds in two kinetic stages. During the first stage (3–5 min), fast conversion of nearly 95% by mass occurs and the conversion coefficient increases in the order G < C ≈ A < B. The second stage is controlled by the slow dissolution of intermediate cr…
Quasi-RRHO approximation and DFT study for understanding the mechanism and kinetics of nitration reaction of benzonitrile with nitronium ion
2021
Abstract The nitration reaction of benzonitrile with nitronium cation, NO2+, has been studied within the Molecular Electron Density Theory at the MN15-L/aug-cc-pVTZ level of theory. For this electrophilic aromatic substitution (EAS) reaction, three regioisomeric reaction paths have been studied. Quasi-RRHO approximation was applied to consider the vibrational contribution to entropy and correct the Gibbs free energy profile of the reaction in the solvent phase. Benzonitrile is less nucleophilically activated than benzene due to the presence of the electron-withdrawing CN group the meta position is the more favorable reaction path of this EAS reaction. The analysis of ELF and AIM demonstrate…
Stability of a Split Streptomycin Binding Aptamer
2016
Here we investigated the stability of an aptamer, which is formed by two RNA strands and binds the antibiotic streptomycin. Molecular dynamics simulations in aqueous solution confirmed the geometry and the pattern of hydrogen bond interactions that was derived from the crystal structure (1NTB). The result of umbrella sampling simulations indicated a favored streptomycin binding with a free energy of ΔGbind° = −101.7 kJ mol–1. Experimentally, the increase in oligonucleotide stability upon binding of streptomycin was probed by single-molecule force spectroscopy. Rate dependent force spectroscopy measurements revealed a decrease in the natural off-rate (koff-COMPLEX = 0.22 ± 0.16 s–1) for the …
Fractional hereditariness of lipid membranes: Instabilities and linearized evolution
2016
In this work lipid ordering phase changes arising in planar membrane bilayers is investigated both accounting for elas- ticity alone and for effective viscoelastic response of such assemblies. The mechanical response of such membranes is studied by minimizing the Gibbs free energy which penalizes perturbations of the changes of areal stretch and their gradients only [1]. As material instabilities arise whenever areal stretches characterizing homogeneous configurations lie inside the spinoidal zone of the free energy density, bifurcations from such configurations are shown to occur as oscillatory perturbations of the in-plane displacement. Experimental observations [2] show a power-law in-pl…
Thermodynamic properties of a liquid–vapor interface in a two-component system
2010
Abstract We report a complete set of thermodynamic properties of the interface layer between liquid and vapor two-component mixtures, using molecular dynamics. The mixtures consist of particles which have identical masses and diameters and interact with a long-range Lennard-Jones spline potential. The potential depths in dimensionless units for like interactions is 1 (for component 1) and 0.8 (for component 2). The surface excess entropy decreases when the temperature increases, so the surface has a negative excess heat capacity. This is a consequence of the fact that the surface tension decreases to zero at the critical point, proportional to ( T C , i − T ) 2 ν . The surface entropy decre…
Thermodynamic Behavior of Non-Ionic Tri-block Copolymers in Water at Three Temperatures
2006
Apparent molar volumes (V Φ) of aqueous solutions of some copolymers, based on ethylene oxide (EO) and propylene oxide (PO) units, were determined as functions of concentration at three temperatures. Viscosity measurements were also carried out on some of these systems. The effects studied include how the molecular architecture and the molecular weight affect the aggregation of the copolymer, keeping constant the EO/PO ratio. Modeling of the volumetric data yielded the partial molar volume of the copolymer in the standard (V°) and the aggregated (V M) states, as well as the equilibrium constant for micellization and the aggregation number. Analysis of the viscosity data supported the insigh…
Adaptive rational interpolation for point values
2019
Abstract G. Ramponi et al. introduced in Carrato et al. (1997,1998), Castagno and Ramponi (1996) and Ramponi (1995) a non linear rational interpolator of order two. In this paper we extend this result to get order four. We observe the Gibbs phenomenon that is obtained near discontinuities with its weights. With the weights we propose we obtain approximations of order four in smooth regions and three near discontinuities. We also introduce a rational nonlinear extrapolation which is also of order four in the smooth region of the given function. In the experiments we calculate numerically approximation orders for the different methods described in this paper and see that they coincide with th…
Enthalpies of transfer of pentanol from water to sodium dodecylsulfate-dodecyl-dimethylamine oxide-water mixtures
1994
At a given surfactant-surfactant ratio, the enthalpies of transfer ΔH (W→W+S) of pentanol 0.03m from water to sodium dodecylsulfate (NaDS)-dodecyldimethylamine oxide-water mixtures as functions of the surfactants mixture concentration (m t) were determined. ForX NaDS=0.9, ΔH (W→W+S) increases monotonically withm t such as observed for pure surfactants. ForX NaDS=0.12 and 0.3, ΔH (W→W+S) increases withm t up to 0.12m beyond which it decreases withm t. AtX NaDS=0.6, two monotonic curves can be distinguished in the ΔH (W→W+S)vs. m t trend. Experimental data were fitted through an equation previously reported for additives in pure surfactants derived by assuming the pseudo-phase transition mode…
Effect of Large Changes in Temperature and Pressure on the Thermodynamic Properties of Micellization and on the Distribution Constant of a Polar Solu…
1996
Density measurements of pentanol (PentOH)−dodecyltrimethylammonium bromide (DTAB)−water mixtures as functions of both alcohol and surfactant (mS) concentrations were carried out at 0.1 MPa from 45 to 75 °C and at 19 MPa from 25 to 130 °C. The standard (infinite dilution) partial molar volumes and expansibilities of DTAB in water and the corresponding properties in the micellar phase were calculated from the experimental data. As far as PentOH in DTAB micellar solutions is concerned, with the exception of the standard partial molar volume (V°R) data at 130 °C and 19 MPa, all the V°R vs mS trends are monotonic curves with mS. The data of V°R as a function of mS were treated by means of an equ…
A thermodynamic study to evidence the alpha,omega-dichloroalkane/ block copolymer mixed aggregates formation: effect of the copolymer architecture.
2006
Abstract The thermodynamics of α , ω -dichloroalkanes in aqueous solutions of (ethylene oxide)11(propylene oxide)16(ethylene oxide)11 (L35) and (propylene oxide)8(ethylene oxide)23(propylene oxide)8 (10R5) was determined at 298 and 305 K. Modeling the experimental data allowed to calculate the standard free energy ( Δ G D o / w ) and the volume ( Δ V D / w ) for the additive–copolymer mixed aggregates formation per additive molecule. Δ G D o / w for Cl2CH2 and Cl2(CH2)2 evidenced that the process is controlled by the forces exercising between the chlorine atoms and the OH groups of the copolymer micelles protruded into the aqueous phase. Cl2(CH2)3 experiences both the hydrophilic and hydrop…