Gibbs-Donnan and specific ion interaction theory descriptions of the effect of ionic strength on proton dissociation of alginic acid

The apparent proton dissociation constants of a commercial alginic acid have been obtained in KNO3 and NaCl at concentrations ranging between 0.01 and 2 mol·L-1. An analysis of the dependence on the ionic strength at a constant value of the dissociation degree was done by means of empirical functions derived from the Gibbs-Donnan formalism for polyelectrolytes and a specific ion interaction theory (SIT). Both functions were able to fit the experimental data, although SIT yielded rather high errors in the fitted parameters due to a problem of multicollinearity, in contrast to the function derived from the Gibbs-Donnan approach.This work was funded by the projects BQU2002-02133 (from the Ministerio de Ciencia y Tecnología of Spain) and PGDIT02TAM10302PR (from the Xunta de Galicia). C.R.C. benefited from a FPU grant of the Ministerio de Educación, Cultura y Deporte of Spain

Kinetic and Equilibrium Study of the Reaction of Nitroprusside and Hydroxide Ions: Influence of Ionic Strength Using Pitzer Model

[Abstract] A kinetic and equilibrium study of the addition reaction of hydroxide ions to nitroprusside has been carried out in this paper. Rate and equilibrium constants at different salt concentrations (up to 4 mol/kg) were obtained and the influence of ionic strength was studied by means of Pitzer equations. This model is of special interest because it is able to explain the experimental behaviour at high ionic strength, when Debye-Huckel limiting law is no longer valid

Biosorption of phenolic compounds by the brown alga Sargassum muticum

"This is a preprint of an article accepted for publication in Journal of chemical technology and biotechnology copyright 2005"[Abstract] Phenol, 2-chlorophenol (2-CP), and 4-chlorophenol (4-CP) biosorption on Sargassum muticum, an invasive macroalga in Europe, has been investigated. The efficiency of this biosorbent was studied measuring the equilibrium uptake using the batch technique. A chemical pre-treatment with CaCl2 has been employed in this study in order to improve the stability as well as the sorption capacity of the algal biomass. The influence of pH on the equilibrium binding and the effect of the algal dose were evaluated. The experimental data at pH=1 have been analysed using Langmuir and Freundlich isotherms. It was found that the maximum sorption capacity of chlorophenols, qmax=251 mg g-1 for 4-CP and qmax=79 mg g-1 for 2-CP, as well as that of a binary mixture of both chlorophenols, qmax=108 mg g-1, is much higher than that of phenol, qmax=4.6 mg g-1. Moreover, sorption kinetics have been performed and it was observed that the equilibrium was reached in less than 10 h. Kinetic data have been fitted to the first order Lagergren model, from which the rate constant and the sorption capacity were determined. Finally, biosorption of the phenolic compounds examined in the present study on Sargassum muticum biomass was observed to be correlated with the octanol-water partitioning coefficients of the phenols. This result allows us to postulate that hydrophobic interactions are the main responsible for the sorption equilibrium binding.Ministerio de Ciencia y Tecnología; BQU2002-02133Xunta de Galicia; PGDIT02TAM10302P

Removal of Inorganic Mercury From Aqueous Solutions by Biomass of the Marine Macroalga Cystoseira Baccata

[Abstract] The ability of Cystoseira baccata algal biomass to remove Hg(II) from aqueous solutions is investigated. The mercury biosorption process is studied through batch experiments at 25ºC with regard to the influence of contact time, initial mercury concentration, solution pH, salinity and presence of several divalent cations. The acid-base properties of the alga are also studied, since they are related to the affinity for heavy metals. The studies of the pH effect on the metal uptake evidence a sharp increasing sorption up to a pH value around 7.0, which can be ascribed to changes both in the inorganic Hg(II) speciation and in the dissociation state of the acid algal sites. The sorption isotherms at constant pH show uptake values as high as 178 mg.g-1 (at pH 4.5) and 329 mg.g-1 (at pH 6.0). The studies of the salinity influence on the Hg(II) sorption capacity of the alga exhibit two opposite effects depending on the electrolyte added; an increase in concentration of nitrate salts (NaNO3, KNO3) slightly enhances the metal uptake, on the contrary, the addition of NaCl salt leads to a drop in the sorption. The addition of different divalent cations to the mercury solution, namely Ca2+, Mg2+, Zn2+, Cd2+, Pb2+ and Cu2+, reveals that their effect on the uptake process is negligible. Finally, the equilibrium sorption results are compared with predictions 1 obtained from the application of a simple competitive chemical model, which involves a discrete proton binding constant and three additional constants for the binding of main neutral inorganic Hg(II) complexes, Hg(Cl) HgOHCl and Hg(OH)2, to the algal surface sites

The salting coefficient and size of alkylamines in saline media at different temperatures: estimation from Pitzer equations and the mean spherical approximation

The renewed theoretical interest in the proton transfer associated to the amino group together with the scarcity of acid-base studies of amines in moderate to concentrated saline media focussed our attention on the study of the basicities of some alkylamines, namely monomethyl, dimethyl and trimethylamine, in aqueous saline solutions of KCl at various temperatures. A non-conventional analysis of stoichiometric equilibrium constants versus ionic strength data is carried out. On one hand, Pitzer’s model is easily applied to calculate the salting coefficient and the thermodynamic equilibrium constant of the alkylamines. On the other hand, the mean spherical approximation has the advantage over the Debye–Hückel based theories that it can account for effects produced by species of different sizes. Here, it is applied to predict the dependence of the salting behavior on the size of the alkylamines.Xunta de Galicia; XUGA 10310B9

Equilibrium constants of triethanolamine in major seawater salts

Acid–base equilibrium constants of triethanolamine (TEA) have been determined by potentiometric titrations with a glass electrode, at 25 °C. Ionic strength was kept constant with only one electrolyte (using one of these salts: NaCl, KCl, MgCl2 or CaCl2), with binary mixtures of MgCl2 and CaCl2, and finally, in a solution with a composition approximately similar to that of natural seawater without sulfate. Equilibrium constants have been expressed in function of ionic strength by means of Pitzer equations and interaction parameters proposed in this theory have been obtained. It has been found that acid–base behaviour of TEA depends greatly on the salt used: basicity of TEA is decreased by CaCl2, while it is increased by the other electrolytes used in this work

Removal of methylene blue from aqueous solutions using as biosorbent sargassum muticum: an invasive macroalga in Europe

"This is a preprint of an article accepted for publication in Journal of chemical technology and biotechnology copyright 2005"[Abstract] Methylene blue adsorption on Sargassum muticum, an invasive macroalga in Europe, has been investigated using visible absorption spectroscopy. Different pre-treatments, protonation and chemical cross-linking with CaCl2 or H2CO, have been tested in order to improve the stability as well as the adsorption capacity of the algal biomass. The equilibrium binding has been described in terms of Langmuir or Freundlich isotherms depending on the algal pre-treatment; from the maximum adsorption capacity values, an estimation of the algal specific surface area was made. Moreover, it has been found that adsorption kinetics can be described according to the first order Lagergren model, from which the rate constant and the adsorption capacity were determined. Finally, simple empirical equations were obtained to evaluate the amount of methylene blue removed at any initial concentration and reaction time. The results obtained have shown that this type of material has a high adsorption capacity for methylene blue dye, this feature together with the short times needed to reach the equilibrium suggest that Sargassum muticum can be used as a low-cost biosorbent in wastewater treatments.Ministerio de Ciencia y Tecnología; BQU2002-02133Xunta de Galicia; PGDIT02TAM10302P

Computational Aided Acetaminophen – Phthalic Acid Molecularly Imprinted Polymer Design for Analytical Determination of Known and New Developed Recreational Drugs

This is a manuscript version of the article.[Abstract] In recent times, abuse drug consumption rates have been increasing. In addition, authorities have detected a trend in the development of new substances expressly created to avoid legislation. These novel psychoactive substances (NPS) are non-registered formulations, closely chemically related to outlawed ones to maintain the same psychotropic effects while circumventing legal restrictions. This issue arises enormous social, sanitary, and road safety problems since there is no way to detect nor quantify these non-registered substances. The aim of this work is the development of a high selective material able to pre-concentrate and detect NPS. On that account, molecularly imprinted polymers (MIPs) designed with an imprinted cavity that matches the cathinones structural shape were proposed to detect both conventional and new cathinone derived recreational drugs. The increasing number of illicit drug modifications that is being reported requires developing a receptor valid for not only known molecules but also for incoming ones; thus, a virtual procedure must be carried out to take a step forward towards future modifications. Accordingly, a computational MIP design is proposed as the most appropriated method to effectively design this receptor. By means of molecular dynamics and molecular docking, several combinations are studied regarding their pre-polymerization complex stability but also their rebinding capacity against the proposed analytes. Hence, a phthalic acid – acetaminophen MIP is selected as the most well-suited receptor, valid for current and forthcoming cathinone recreational drugs.Authors wish to thank Agencia Estatal de Investigación (AEI, Ministerio de Economía y Competitividad) for the financial support through the research project CTQ2016-80473-P cofinanced with FEDER (UE) programm

Determination of biosorption mechanism in biomass of agave, using spectroscopic and microscopic techniques for the purification of contaminated water

[Abstract] Lead (Pb2+) and copper (Cu2+) are polluting metals due to their toxicity; however, the extraction of these metals is essential for economic development, so it is important to look for efficient and low-cost alternatives that can remove heavy metals from the various bodies of water. One of the alternatives used in this work is biosorption, for which an agroindustrial waste (epidermis from Agave atrovirens) was used to evaluate the affinity of removal of lead and copper in aqueous solutions; in addition, spectroscopy and microscopy techniques were used to elucidate and corroborate the removal and affinity capacity of the agave epidermis for both metals studied. The optimal pH value for the removal of both metals was 3. The adsorption isotherms yielded a qmax of 25.7 and 8.6 mg/g for lead and copper, respectively. Adjusting to the Langmuir-Freundlich model, the adsorption kinetics were pseudo-second order, and it was found that the equilibrium time was at 140 min. The spectroscopy and microscopy analyses corroborated the affinity between metals and functional groups of the agave, as well as with the elemental analysis, which reported 17.38% of lead and 4.25% of copper.[Resumen] El plomo (Pb2+) y el cobre (Cu2+) son metales contaminantes debido a su toxicidad; sin embargo, la extracción de estos metales es indispensable para el desarrollo económico, por lo que es importante buscar alternativas eficientes y de bajo costo que puedan remover metales pesados de los diversos cuerpos de agua. Una de las alternativas utilizadas en este trabajo es la biosorción, para la cual se utilizó un residuo agroindustrial (epidermis de Agave atrovirens), para evaluar la afinidad de remoción del plomo y cobre en soluciones acuosas; adicionalmente, se emplearon técnicas de espesctroscopía y microscopía que permitieron elucidar y corroborar la capacidad de remoción y afinidad que tuvo la epidermis de A. atrovirens para ambos metales estudiados. El valor óptimo de pH para la remoción de ambos metales fue 3. Las isotermas de adsorción arrojaron una qmax de 25.7 y 8.6 mg/g para el plomo y cobre, respectivamente. Ajustando al modelo de Langmuir-Freundlich, las cinéticas de adsorción resultaron de pseudo-segundo orden, se encontró que el tiempo de equilibrio es a los 140 min. El análisis espectroscópico y microscópico, corroboró la afinidad entre metales y grupos funcionales del agave, así como con el análisis elemental, el cual reportó 17.38% de plomo y 4.25% de cobre