Search results for "Activity coefficient"
showing 10 items of 60 documents
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/).
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…
Hydrolysis and chemical speciation of dioxouranium(VI) ion in aqueous media simulating the major ion composition of seawater
2004
Abstract The hydrolysis and chemical speciation of the dioxouranium(VI) ion at 25 °C was studied in a number of binary electrolytes (LiCl, NaCl, MgCl2, CaCl2, Na2SO4) and some mixtures (NaCl–Na2SO4, NaNO3–Na2SO4, CaCl2–MgCl2) as well as artificial seawater (SSWE) as a function of ionic strength. The results in LiCl, CaCl2 and MgCl2 solutions confirmed the formation of (UO2)2(OH)22+, (UO2)3(OH)42+, (UO2)3(OH)5+ and (UO2)3(OH)7− species (at I=0 mol l−1: log Tβ22=−5.76, log Tβ34=−11.82, log Tβ35=−15.89 and log Tβ37=−29.26). For NaNO3, NaCl and artificial seawater the hydrolysis constant for the formation of the UO2(OH)+ species was also determined (at I=0 mol l−1: log Tβ11=−5.19). The results …
Novel solutions for closed-loop Reverse Electrodialysis: thermodynamic characterisation and perspective analysis
2019
Abstract Closed-loop Reverse Electrodialysis is a novel technology to directly convert low-grade heat into electricity. It consists of a reverse electrodialysis (RED) unit where electricity is produced exploiting the salinity gradient between two salt-water solutions, coupled with a regeneration unit where waste-heat is used to treat the solutions exiting from the RED unit and restore their initial composition. One of the most important advantages of closed-loop systems compared to the open systems is the possibility to select ad-hoc salt solutions to achieve high efficiencies. Therefore, the properties of the salt solutions are essential to assess the performance of the energy generation a…
Effect of the reference solution in the measurement of ion activity coefficients using cells with transference at T=298.15K
2010
Abstract This work reports individual activity coefficients of ions at T = 298.15 K in aqueous solutions obtained from voltage values of the respective half-cell ion-selective-electrode and a single-junction Ag–AgCl reference electrode, filled with different reference solutions at different concentrations. For potassium and chloride ions in KCl aqueous solutions, reference solutions of KCl, NaCl, or CsCl were used. For sodium and chloride ions in aqueous NaCl solutions, reference solutions of CsCl were used. Experimental runs were performed at molalities (1, 2, and 3) m of the reference solution. The concentration of the sample solution was increased, starting from around 1 · 10−3 m, up to …
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…
Thermodynamic properties of N-octyl- and N-dodecylnicotinamide chlorides in water
1990
Densities, heat capacities and enthalpies of dilution at 25°C and osmotic coefficients at 37°C were measured for N-octyl- and N-dodecylnicotinamide chlorides in water over an extended concentration region. Partial molar volumes, heat capacities, relative enthalpies and nonideal free energies and entropies at 25°C were derived as a function of the surfactant concentration. For both surfactants, plots of volumes, enthalpies and free energies vs. concentration are regular whereas those of heat capacities and entropies present anomalies at about 0.8 and 0.1m for the octyl and dodecyl compounds, respectively. Changes in the slope of a plot of osmotic coefficients times molality vs. molality were…
Prediction of Maxwell – Stefan diffusion coefficients in polymer – multicomponent fluid systems
2014
Abstract Calculations of mass fluxes in multicomponent fluids based on the system of generalized Maxwell–Stefan equations (GMSE) is preferably used because Maxwell–Stefan (M–S) diffusion coefficients are symmetrical and have a clear physical meaning, as they reflect the binary friction forces between compounds in the system. For the calculation of the mass transport of a multicomponent fluid in the polymer basing on GMSE, it is necessary to have M–S diffusion coefficients. This paper proposes a method that allows their calculation using widely available self-diffusion coefficients and binary diffusion coefficients for infinitely diluted mixtures. The proposed method was compared with the me…