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Experimental binary diffusion coefficients for short-chain alcohols in supercritical carbon dioxide were measured using the Taylor dispersion technique in a temperature range of 306.15 K to 331.15 K and along the 10.5 MPa isobar. The obtained diffusion coefficients were in the order of 10-8 m2 s-1. The dependence of D on temperature and solvent density was examined together with the influence of molecular size. Some classic correlation models based on the hydrodynamic and free volume theory were used to estimate the diffusion coefficients in supercritical carbon dioxide. Predicted values were generally overestimated in comparison with experimental ones and correlations were shown to be valid only in high-density regions.
RESUMO
The Taylor dispersion technique has been used for measuring ternary mutual diffusion coefficients for mixtures of cyclohexane-toluene-methanol, corresponding to the mixtures under study on the International Space Station (ISS) within the scope of the project DCMIX2 (second series of the experiment Diffusion Coefficients in Mixtures). Five ternary systems with different composition of cyclohexane-toluene-methanol were investigated in order to accurately obtain the mass diffusion coefficients, contributing to a better understanding of the isothermal molecular diffusion in conjunction with the coupled flows of solutes occurring in such fluid systems. Current standardized protocols for carrying out an experience are also examined to understand if the experimental conditions may be ill conditioning the final results.
RESUMO
Diffusion coefficients, thermodynamic and mobility factors of iron salts in aqueous solutions are estimated from Onsager-Fuoss model. The influence of the ion size parameter a, "mean distance of closest approach of ions", determined from different approaches, on the variation of diffusion coefficients with concentration, is also discussed. The aim of this work is to have a better understanding of the structure of these systems and of the thermodynamic behaviour of iron salts in aqueous media.
RESUMO
This paper presents an analysis of the molecular mechanisms involved in the formation of inclusion complexes together with some structural interpretation of drug-carrier molecule interactions in aqueous multicomponent systems comprising methylxanthines and cyclodextrins. The determination of apparent partial molar volumes (Φv) from experimental density measurements, both for binary and ternary aqueous solutions of cyclodextrins and methylxanthines, was performed at low concentration range to be consistent with their therapeutic uses in the drug-releasing field. The estimation of the equilibrium constant for inclusion complexes of 1:1 stoichiometry was done through the mathematical modelling of this apparent molar property. The examination of the volume changes offered information about the driving forces for the insertion of the xanthine into the cyclodextrin molecule. The analysis on the volumes of transfer, Δ, Φv,c and the viscosity B-coefficients of transfer, ΔB, for the xanthine from water to the different aqueous solutions of cyclodextrin allowed evaluating the possible interactions between aqueous solutes and/or solute-solvent interactions occurring in the solution. Mutual diffusion coefficients for binary, and ternary mixtures composed by xanthine, cyclodextrin, and water were measured with the Taylor dispersion technique. The behavior diffusion of these multicomponent systems and the coupled flows occurring in the solution were analyzed in order to understand the probable interactions between cyclodextrin-xanthine by estimating their association constants and leading to clearer insight of these systems structure. The measurements were performed at the standard (298.15 ± 0.01) K and physiological (310.15 ± 0.01) K temperatures.
Assuntos
Ciclodextrinas/química , Portadores de Fármacos/química , Xantinas/química , Difusão , Termodinâmica , ViscosidadeRESUMO
Binary (D) and ternary (D(11), D(22), D(12) and D(21)) mutual diffusion coefficients determined by the Taylor dispersion method are reported for two aqueous systems, pure hydrocortisone (HC/H(2)O) and HC plus HP-ß-cyclodextrin (HC/HP-ßCD/H(2)O), at T=298.15 K. From these data, some thermodynamic information as well as conclusions about the influence of that carbohydrate in the diffusion of this drug are given.