Determination of Alkalinity and dissociation constants of high salinity waters: use of F5BC titration function

Measurements of parameters expressed in terms of carbonic species such as Alkalinity and Acidity of saline waters do not analyze the influence of external parameters to the titration such as Total free and associated Carbonic Species Concentration, activity coefficient, ion pairing formation and Residual Liquid Junction Potential in pH measurements. This paper shows the development of F5BC titration function based on the titrations developed by Gran (1952) for the carbonate system of natural waters. For practical use, samples of saline waters from Pocinhos reservoir in Paraiba were submitted to titration and linear regression analysis. Results showed that F5BC involves F1x and F2x Gran functions determination, respectively, for Alkalinity and Acidity calculations without knowing "a priori" the endpoint of the titration. F5BC also allows the determination of the First and Second Apparent Dissociation Constant of the carbonate system of saline and high ionic strength waters.

Thermodynamic properties of dilute HBr(aq) and HI(aq)

The theory of electrolyte solutions was described by explaining Debye–Hückel theory and deriving the Debye–Hückel equation for the mean activity coefficient. Simple two-parameter Hückel equation was used for the calculation of the activity coefficients of aqueous hydrobromic and hydriodic acids up to 0.5 mol/kg at temperatures from (0 to 60) °C and from (0 to 50) °C, respectively. The parameters were observed to be independent of the temperature. The Hückel equation for the osmotic coefficients of water in the studied solutions was compared to that of Pitzer model by predicting the vapor pressures up to 1 mol/kg at 25 °C. The experimental vapor pressures over the reference electrolyte solutions were calculated with the Pitzer equation for the osmotic coefficients for isopiestic data in this comparison. The simple Hückel model was found to be equally good as the Pitzer model for both hydrobromic and hydriodic acids up to 0.5 mol/kg at 25 °C but applies also to other temperatures studied.

Comparison of fatty acid composition in nine organs of the sympatric Antarctic teleost fish species Notothenia coriiceps and Notothenia rossii (Perciformes: Nototheniidae)

Fatty acid (FA) composition of nine organs from two closely related Antarctic fish species, Notothenia codiceps and Notothenia rossii, was determined through gas chromatography with flame ionization detection. A data set for each species was obtained using major FA profiles from specimens caught in the sea waters of Admiralty Bay during the summer season. The FA profiles for both species are overall similar, but organ peculiarities have been found, which could reflect metabolic specificities and feeding habits between species. With the exception of liver, the most abundant FA in organs was the n-3 polyunsaturated FA. The total n-6 polyunsaturated FAs were minor components in all evaluated organs. Palmitic acid was identified as the major saturated FA, whereas oleic acid was the most represented of the monounsaturated FA in almost all assessed organs of both species. The n-3/n-6 ratios of all organs were higher than 3.5. Differences in individual FA and FA metabolic profiles of some organs observed between N. coriiceps and N. rossii suggest specific requirements in the mobilization, transport, incorporation, and/or catabolism of lipids that were reinforced by differences on some FA ratios expressing the activity coefficient of enzymes implicated on the FA pathway flux. (C) 2009 Elsevier Inc. All rights reserved.

Estudo do equilíbrio líquido-vapor do sistema água+etanol+líquido iônico visando a separação do álcool anidro

Anhydrous ethanol is used in chemical, pharmaceutical and fuel industries. However, current processes for obtaining it involve high cost, high energy demand and use of toxic and pollutant solvents. This problem occurs due to the formation of an azeotropic mixture of ethanol + water, which does not allow the complete separation by conventional methods such as simple distillation. As an alternative to currently used processes, this study proposes the use of ionic liquids as solvents in extractive distillation. These are organic salts which are liquids at low temperatures (under 373,15 K). They exhibit characteristics such as low volatility (almost zero/ low vapor ), thermal stability and low corrosiveness, which make them interesting for applications such as catalysts and as entrainers. In this work, experimental data for the vapor pressure of pure ethanol and water in the pressure range of 20 to 101 kPa were obtained as well as for vapor-liquid equilibrium (VLE) of the system ethanol + water at atmospheric pressure; and equilibrium data of ethanol + water + 2-HDEAA (2- hydroxydiethanolamine acetate) at strategic points in the diagram. The device used for these experiments was the Fischer ebulliometer, together with density measurements to determine phase compositions. The experimental data were consistent with literature data and presented thermodynamic consistency, thus the methodology was properly validated. The results were favorable, with the increase of ethanol concentration in the vapor phase, but the increase was not shown to be pronounced. The predictive model COSMO-SAC (COnductor-like Screening MOdels Segment Activity Coefficient) proposed by Lin & Sandler (2002) was studied for calculations to predict vapor-liquid equilibrium of systems ethanol + water + ionic liquids at atmospheric pressure. This is an alternative for predicting phase equilibrium, especially for substances of recent interest, such as ionic liquids. This is so because no experimental data nor any parameters of functional groups (as in the UNIFAC method) are needed

A Contribution to the Estimation of Binary Halide and Pseudo-Halide Equilibrium Constants using a Linear Extrapolation Methodology

The molar single ion activity coefficient (y(F)) of fluoride ions was determined at 25 degrees C and ionic strengths between 0.100 and 3.00 mol L(-1) NaClO(4) using an ion-selective electrode. The activity coefficient dependency on ionic strength was determined to be Phi(F) = log y(F) = 0.2315I-0.041I(2). The function Phi(F)(I), combined with functions obtained in previous work for copper (Phi(Cu)) and hydrogen (Phi(H)), allowed us to make the estimation of the stoichiometric and thermodynamic protonation constants of some halides and pseudo-halides as well as the formation constants of some pseudo-halides and fluoride 1:1 bivalent cation complexes. The calculation procedure proposed in this paper is consistent with critically-selected experimental data. It was demonstrated that it is possible to use Phi(F)(I) for predicting the thermodynamic equilibrium parameters independently of Pearson's hardness of acids and bases.

Determinação de parâmetros físico-químicos com um sensor potenciométrico sensível ao íon p-aminobenzoato

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Liquid-Liquid Equilibrium Data for the System Lard plus Oleic Acid plus Ethanol + Water at 318.2 K: Cholesterol Distribution Coefficients

This research reports liquid liquid equilibrium data for the system lard (swine fat), cis-9-octadecenoic acid (oleic acid), ethanol, and water at 318.2 K, as well as their correlation with the nonrandom two-liquid (NRTL) and universal quasichemical activity coefficient (UNIQUAC) thermodynamic equations, which have provided global deviations of 0.41 % and 0.53 %, respectively. Additional equilibrium experiments were also performed to obtain cholesterol partition (or distribution) coefficients to verify the availability of the use of ethanol plus water to reduce the cholesterol content in lard. The partition experiments were performed with concentrations of free fatty acids (commercial oleic acid) that varied from (0 to 20) mass % and of water in the solvent that varied from (0 to 18) mass %. The percentage of free fatty acids initially present in lard had a slight effect on the distribution of cholesterol between the phases. Furthermore, the distribution coefficients decreased by adding water in the ethanol; specifically, it resulted in a diminution of the capability of the solvent to remove the cholesterol.

Impact of antibiotic use on carbapenem resistance in Pseudomonas aeruginosa: is there a role for antibiotic diversity?

In this study, we aimed to evaluate the relationship between the rates of resistance of Pseudomonas aeruginosa to carbapenems and the levels and diversity of antibiotic consumption. Data were retrospectively collected from 20 acute care hospitals across 3 regions of Switzerland between 2006 and 2010. The main outcome of the present study was the rate of resistance to carbapenems among P. aeruginosa. Putative predictors included the total antibiotic consumption and carbapenem consumption in defined daily doses per 100 bed days, the proportion of very broad-spectrum antibiotics used, and the Peterson index. The present study confirmed a correlation between carbapenem use and carbapenem resistance rates at the hospital and regional levels. The impact of diversifying the range of antibiotics used against P. aeruginosa resistance was suggested by (i) a positive correlation in multivariate analysis between the above-mentioned resistance and the proportion of consumed antibiotics having a very broad spectrum of activity (coefficient = 1.77; 95% confidence interval, 0.58 to 2.96; P < 0.01) and (ii) a negative correlation between the resistance and diversity of antibiotic use as measured by the Peterson homogeneity index (coefficient = -0.52; P < 0.05). We conclude that promoting heterogeneity plus parsimony in the use of antibiotics appears to be a valuable strategy for minimizing the spread of carbapenem resistance in P. aeruginosa in hospitals.

Optimización de operaciones unitarias utilizando líquidos iónicos como agentes materiales de separación

En este trabajo se estudia la modelización y optimización de procesos industriales de separación mediante el empleo de mezclas de líquidos iónicos como disolventes. Los disolventes habitualmente empleados en procesos de absorción o extracción suelen ser componentes orgánicos muy volátiles y dañinos para la salud humana. Las innovadoras propiedades que presentan los líquidos iónicos, los convierten en alternativas adecuadas para solucionar estos problemas. La presión de vapor de estos compuestos es muy baja y apenas varía con la temperatura. Por tanto, estos compuestos apenas se evaporan incluso a temperaturas altas. Esto supone una gran ventaja en cuanto al empleo de estos compuestos como disolventes industriales ya que permite el reciclaje continuo del disolvente al final del proceso sin necesidad de introducir disolvente fresco debido a la evaporación del mismo. Además, al no evaporarse, estos compuestos no suponen un peligro para la salud humana por inhalación; al contrario que otros disolventes como el benceno. El único peligro para la salud que tienen estos compuestos es por tanto el de contacto directo o ingesta, aunque de hecho muchos Líquidos Iónicos son inocuos con lo cual no existe peligro para la salud ni siquiera a través de estas vías. Los procesos de separación estudiados en este trabajo, se rigen por la termodinámica de fases, concretamente el equilibrio líquido-vapor. Para la predicción de los equilibrios se ha optado por el empleo de modelos COSMO (COnductor-like Screening MOdel). Estos modelos tienen su origen en el empleo de la termodinámica de solvatación y en la mecánica cuántica. En el desarrollo de procesos y productos, químicos e ingenieros frecuentemente precisan de la realización de cálculos de predicción de equilibrios de fase. Previamente al desarrollo de los modelos COSMO, se usaban métodos de contribución de grupos como UNIFAC o modelos de coeficientes de actividad como NRTL.La desventaja de estos métodos, es que requieren parámetros de interacción binaria que únicamente pueden obtenerse mediante ajustes por regresión a partir de resultados experimentales. Debido a esto, estos métodos apenas tienen aplicabilidad para compuestos con grupos funcionales novedosos debido a que no se dispone de datos experimentales para llevar a cabo los ajustes por regresión correspondientes. Una alternativa a estos métodos, es el empleo de modelos de solvatación basados en la química cuántica para caracterizar las interacciones moleculares y tener en cuenta la no idealidad de la fase líquida. Los modelos COSMO, permiten la predicción de equilibrios sin la necesidad de ajustes por regresión a partir de resultados experimentales. Debido a la falta de resultados experimentales de equilibrios líquido-vapor de mezclas en las que se ven involucrados los líquidos iónicos, el empleo de modelos COSMO es una buena alternativa para la predicción de equilibrios de mezclas con este tipo de materiales. Los modelos COSMO emplean las distribuciones superficiales de carga polarizada (sigma profiles) de los compuestos involucrados en la mezcla estudiada para la predicción de los coeficientes de actividad de la misma, definiéndose el sigma profile de una molécula como la distribución de probabilidad de densidad de carga superficial de dicha molécula. Dos de estos modelos son COSMO-RS (Realistic Solvation) y COSMO-SAC (Segment Activity Coefficient). El modelo COSMO-RS fue la primera extensión de los modelos de solvatación basados en continuos dieléctricos a la termodinámica de fases líquidas mientras que el modelo COSMO-SAC es una variación de este modelo, tal y como se explicará posteriormente. Concretamente en este trabajo se ha empleado el modelo COSMO-SAC para el cálculo de los coeficientes de actividad de las mezclas estudiadas. Los sigma profiles de los líquidos iónicos se han obtenido mediante el empleo del software de química computacional Turbomole y el paquete químico-cuántico COSMOtherm. El software Turbomole permite optimizar la geometría de la molécula para hallar la configuración más estable mientras que el paquete COSMOtherm permite la obtención del perfil sigma del compuesto mediante el empleo de los datos proporcionados por Turbomole. Por otra parte, los sigma profiles del resto de componentes se han obtenido de la base de datos Virginia Tech-2005 Sigma Profile Database. Para la predicción del equilibrio a partir de los coeficientes de actividad se ha empleado la Ley de Raoult modificada. Se ha supuesto por tanto que la fracción de cada componente en el vapor es proporcional a la fracción del mismo componente en el líquido, dónde la constante de proporcionalidad es el coeficiente de actividad del componente en la mezcla multiplicado por la presión de vapor del componente y dividido por la presión del sistema. Las presiones de vapor de los componentes se han obtenido aplicando la Ley de Antoine. Esta ecuación describe la relación entre la temperatura y la presión de vapor y se deduce a partir de la ecuación de Clausius-Clapeyron. Todos estos datos se han empleado para la modelización de una separación flash usando el algoritmo de Rachford-Rice. El valor de este modelo reside en la deducción de una función que relaciona las constantes de equilibrio, composición total y fracción de vapor. Para llevar a cabo la implementación del modelado matemático descrito, se ha programado un código empleando el software MATLAB de análisis numérico. Para comprobar la fiabilidad del código programado, se compararon los resultados obtenidos en la predicción de equilibrios de mezclas mediante el código con los resultados obtenidos mediante el simulador ASPEN PLUS de procesos químicos. Debido a la falta de datos relativos a líquidos iónicos en la base de datos de ASPEN PLUS, se han introducido estos componentes como pseudocomponentes, de manera que se han introducido únicamente los datos necesarios de estos componentes para realizar las simulaciones. El modelo COSMO-SAC se encuentra implementado en ASPEN PLUS, de manera que introduciendo los sigma profiles, los volúmenes de la cavidad y las presiones de vapor de los líquidos iónicos, es posible predecir equilibrios líquido-vapor en los que se ven implicados este tipo de materiales. De esta manera pueden compararse los resultados obtenidos con ASPEN PLUS y como el código programado en MATLAB y comprobar la fiabilidad del mismo. El objetivo principal del presente Trabajo Fin de Máster es la optimización de mezclas multicomponente de líquidos iónicos para maximizar la eficiencia de procesos de separación y minimizar los costes de los mismos. La estructura de este problema es la de un problema de optimización no lineal con variables discretas y continuas, es decir, un problema de optimización MINLP (Mixed Integer Non-Linear Programming). Tal y como se verá posteriormente, el modelo matemático de este problema es no lineal. Por otra parte, las variables del mismo son tanto continuas como binarias. Las variables continuas se corresponden con las fracciones molares de los líquidos iónicos presentes en las mezclas y con el caudal de la mezcla de líquidos iónicos. Por otra parte, también se ha introducido un número de variables binarias igual al número de líquidos iónicos presentes en la mezcla. Cada una de estas variables multiplican a las fracciones molares de sus correspondientes líquidos iónicos, de manera que cuando dicha variable es igual a 1, el líquido se encuentra en la mezcla mientras que cuando dicha variable es igual a 0, el líquido iónico no se encuentra presente en dicha mezcla. El empleo de este tipo de variables obliga por tanto a emplear algoritmos para la resolución de problemas de optimización MINLP ya que si todas las variables fueran continuas, bastaría con el empleo de algoritmos para la resolución de problemas de optimización NLP (Non-Linear Programming). Se han probado por tanto diversos algoritmos presentes en el paquete OPTI Toolbox de MATLAB para comprobar cuál es el más adecuado para abordar este problema. Finalmente, una vez validado el código programado, se han optimizado diversas mezclas de líquidos iónicos para lograr la máxima recuperación de compuestos aromáticos en un proceso de absorción de mezclas orgánicas. También se ha usado este código para la minimización del coste correspondiente a la compra de los líquidos iónicos de la mezcla de disolventes empleada en la operación de absorción. En este caso ha sido necesaria la introducción de restricciones relativas a la recuperación de aromáticos en la fase líquida o a la pureza de la mezcla obtenida una vez separada la mezcla de líquidos iónicos. Se han modelizado los dos problemas descritos previamente (maximización de la recuperación de Benceno y minimización del coste de operación) empleando tanto únicamente variables continuas (correspondientes a las fracciones o cantidades molares de los líquidos iónicos) como variables continuas y binarias (correspondientes a cada uno de los líquidos iónicos implicados en las mezclas).

Modelling liquid–liquid equilibria for island type ternary systems

Closed miscibility gaps in ternary liquid mixtures, at constant temperature and pressure, are obtained if phase separations occur only in the ternary region, whilst all binary mixtures involved in the system are completely miscible. This type of behaviour, although not very frequent, has been observed for a certain number of systems. Nevertheless, we have found no information about the applicability of the common activity coefficient models, as NRTL and UNIQUAC, for these types of ternary systems. Moreover, any of the island type systems published in the most common liquid–liquid equilibrium data collections, are correlated with any model. In this paper, the applicability of the NRTL equation to model the LLE of island type systems is assessed using topological concepts related to the Gibbs stability test. A first attempt to correlate experimental LLE data for two island type ternary systems is also presented.

Solubility, Density, Refractive Index, and Viscosity for the Polyhydric Alcohol + CsBr + H2O Ternary Systems at Different Temperatures

The solubility, density, refractive index, and viscosity data for the ethylene glycol + CsBr + H2O, 1,2-propanediol + CsBr + H2O, and glycerin + CsBr + H2O ternary systems have been determined at (288.15, 298.15, and 308.15) K. In all cases, the solubility of CsBr in aqueous solutions was decreased significantly due to the presence of polyhydric alcohol. The liquid–solid equilibrium experimental data were correlated using the NRTL (nonrandom two-liquid) activity coefficient model, considering nondissociation of the dissolved salt in the liquid phase, and new interaction parameters were estimated. The mean deviations between calculated and experimental compositions were low, showing the good descriptive quality and applicability of the NRTL model. The refractive indices, densities, and viscosities for the unsaturated solutions of the three ternary systems have also been measured at three temperatures. Values for all of the properties were correlated with the salt concentrations and proportions of polyhydric alcohol in the solutions.

Gibbs Energy of Mixing Function: Topological Analysis in Azeotropic Systems

ESAT 2014. 27th European Symposium on Applied Thermodynamics, Eindhoven University of Technology, July 6-9, 2014.

Zastosowanie modelu hantli w badaniach właściwości fizykochemicznych i strukturalnych układów homo- i heterogenicznych metodą Monte Carlo

Wydział Chemii

Probing the interactions between ionic liquids and water: experimental and quantum chemical approach

For an adequate choice or design of ionic liquids, the knowledge of their interaction with other solutes and solvents is an essential feature for predicting the reactivity and selectivity of systems involving these compounds. In this work, the activity coefficient of water in several imidazolium-based ionic liquids with the common cation 1-butyl-3-methylimidazolium was measured at 298.2 K. To contribute to a deeper insight into the interaction between ionic liquids and water, COSMO-RS was used to predict the activity coefficient of water in the studied ionic liquids along with the excess enthalpies. The results showed good agreement between experimental and predicted activity coefficient of water in ionic liquids and that the interaction of water and ionic liquids was strongly influenced by the hydrogen bonding of the anion with water. Accordingly, the intensity of interaction of the anions with water can be ranked as the following: [CF3SO3](-) < [SCN](-) < [TFA](-) < Br(-) < [TOS](-) < Cl(-) < [CH3SO3](-) [DMP](-) < [Ac](-). In addition, fluorination and aromatization of anions are shown to reduce their interaction with water. The effect of temperature on the activity coefficient of water at infinite dilution was measured by inverse gas chromatography and predicted by COSMO-RS. Further analysis based on COSMO-RS provided information on the nature of hydrogen bonding between water and anion as well as the possibility of anion-water complex formation.

Effect of the cation on the interactions between alkyl methyl imidazolium chloride ionic liquids and water

A systematic study of the interactions between water and alkyl methyl imidazolium chloride ionic liquids at 298.2 K, based on activity coefficients estimated from water activity measurements in the entire solubility range, is presented. The results show that the activity coefficients of water in the studied ILs are controlled by the hydrophilicity of the cation and the cation-anion interaction. To achieve a deeper understanding on the interactions between water and the ILs, COSMO-RS and FTIR spectroscopy were also applied. COSMO-RS was used to predict the activity coefficient of water in the studied ionic liquids along with the excess enthalpies, suggesting the formation of complexes between three molecules of water and one IL molecule. On the basis of quantum-chemical calculations, it is found that cation-anion interaction plays an important role upon the ability of the IL anion to interact with water. The changes in the peak positions/band areas of OH vibrational modes of water as a function of IL concentration were investigated, and the impact of the cation on the hydrogen-bonding network of water is identified and discussed.