Determinação experimental e modelagem termodinâmica do ponto de turbidez de sistemas aquosos com tensoativos nonilfenolpolietoxilados

The nonionic surfactants are composed of substances whose molecules in solution, does not ionize. The solubility of these surfactants in water due to the presence of functional groups that have strong affinity for water. When these surfactants are heated is the formation of two liquid phases, evidenced by the phenomenon of turbidity. This study was aimed to determine the experimental temperature and turbidity nonilfenolpoliethoxyled subsequently perform a thermodynamic modeling, considering the models of Flory-Huggins and the empirical solid-liquid equilibrium (SLE). The method used for determining the turbidity point was the visual method (Inoue et al., 2008). The experimental methodology consisted of preparing synthetic solutions of 0,25%, 0,5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12,5%, 15%, 17% and 20% by weight of surfactant. The nonionic surfactants used according to their degree of ethoxylation (9.5, 10, 11, 12 and 13). During the experiments the solutions were homogenized and the bath temperature was gradually increased while the turbidity of the solution temperature was checked visually Inoue et al. (2003). These temperature data of turbidity were used to feed the models evaluated and obtain thermodynamic parameters for systems of surfactants nonilfenolpoliethoxyled. Then the models can be used in phase separation processes, facilitating the extraction of organic solvents, therefore serve as quantitative and qualitative parameters. It was observed that the solidliquid equilibrium model (ESL) was best represented the experimental data.

Determinação de Dados de Equilíbrio Líquido-Vapor para Sistemas Hidrocarbonetos e Desenvolvimento de uma Nova Célula Dinâmica

In the present work are established initially the fundamental relationships of thermodynamics that govern the equilibrium between phases, the models used for the description of the behavior non ideal of the liquid and vapor phases in conditions of low pressures. This work seeks the determination of vapor-liquid equilibrium (VLE) data for a series of multicomponents mixtures of saturated aliphatic hydrocarbons, prepared synthetically starting from substances with analytical degree and the development of a new dynamic cell with circulation of the vapor phase. The apparatus and experimental procedures developed are described and applied for the determination of VLE data. VLE isobarics data were obtained through a Fischer's ebulliometer of circulation of both phases, for the systems pentane + dodecane, heptane + dodecane and decane + dodecane. Using the two new dynamic cells especially projected, of easy operation and low cost, with circulation of the vapor phase, data for the systems heptane + decane + dodecane, acetone + water, tween 20 + dodecane, phenol + water and distillation curves of a gasoline without addictive were measured. Compositions of the equilibrium phases were found by densimetry, chromatography, and total organic carbon analyzer. Calibration curves of density versus composition were prepared from synthetic mixtures and the behavior excess volumes were evaluated. The VLE data obtained experimentally for the hydrocarbon and aqueous systems were submitted to the test of thermodynamic consistency, as well as the obtained from the literature data for another binary systems, mainly in the bank DDB (Dortmund Data Bank), where the Gibbs-Duhem equation is used obtaining a satisfactory data base. The results of the thermodynamic consistency tests for the binary and ternary systems were evaluated in terms of deviations for applications such as model development. Later, those groups of data (tested and approved) were used in the KijPoly program for the determination of the binary kij parameters of the cubic equations of state original Peng-Robinson and with the expanded alpha function. These obtained parameters can be applied for simulation of the reservoirs petroleum conditions and of the several distillation processes found in the petrochemistry industry, through simulators. The two designed dynamic cells used equipments of national technology for the determination Humberto Neves Maia de Oliveira Tese de Doutorado PPGEQ/PRH-ANP 14/UFRN of VLE data were well succeed, demonstrating efficiency and low cost. Multicomponents systems, mixtures of components of different molecular weights and also diluted solutions may be studied in these developed VLE cells

Caracterização físico-química de sistemas micelares

The process of adsorption and micellization of the surfactants sodium dodecyl sulfate, dodecylammonium chloride and hexaethylene glycol mono-n-dodecyl ether in water-air interface has been studied using measurements of surface tension in aqueous media and NaCl 0.1 mol/L in temperatures of 25, 33 and 40 °C. From these data, critical micelle concentrations and thermodynamic parameters of micellization and adsorption were determined in order to elucidate the behaviors of micellization and adsorption for these surfactants in the proposed medium. For the determination of the thermodynamic parameters of adsorption we utilized the equations of isotherms of Langmuir and Gibbs. Γmáx values determined by the different equations were correlated to the explanation of results. Temperature and salinity were analyzed in terms of their influence on the micellization and adsorption process, and the results were explained based on intermolecular interactions. The values of Gmic have confirmed that the micelle formation for the surfactants studied occurs spontaneously