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Academic literature on the topic 'Ionic equilibrium. Polyelectrolytes. electrolyte solutions'
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Journal articles on the topic "Ionic equilibrium. Polyelectrolytes. electrolyte solutions"
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Munk, Petr, Zdeněk Tuzar, and Karel Procházka. "Donnan Equilibria in Polymeric Micellar Systems with Weak Polyelectrolyte Shells: The Lowering of the pH Value." Collection of Czechoslovak Chemical Communications 62, no. 11 (1997): 1730–36. http://dx.doi.org/10.1135/cccc19971730.
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When two electrolyte solutions are separated and only some of the ions can cross the boundary, the concentrations of these ions are different on both sides of the boundary. This is the well-known Donnan effect. When weak electrolytes are involved, the imbalance includes also hydrogen ions: there is a difference of pH across the boundary and the dissociation of nondiffusible weak electrolytes is suppressed. The effect is very pronounced when the concentration of the weak electrolyte is high and ionic strength is low. The significance of this phenomenon is discussed for polyelectrolyte solutions, and particularly for block copolymer micelles with weak polyelectrolyte shells. The effect is quite dramatic in the latter case.
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Louati, Islem, Fatma Guesmi, Akram Chaabouni, Chiraz Hannachi, and Béchir Hamrouni. "Effect of ionic strength on the ion exchange equilibrium between AMX membrane and electrolyte solutions." Water Quality Research Journal 51, no. 1 (2015): 60–68. http://dx.doi.org/10.2166/wqrjc.2015.006.
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The effect of ionic strength variation on the ion exchange equilibrium between AMX anion exchange membrane and electrolyte solutions containing the most dominant anions on natural waters (Cl−, NO3−, and SO42−) was studied. All experiments were carried out at a constant temperature of 25 °C. Ion exchange isotherms were established, at different ionic strengths from 0.1 to 0.5 M, for the systems (Cl−/NO3−), (Cl−/SO42−) and (NO3−/SO42−). Obtained results showed that for I = 0.1 M the affinity order is SO42 −>NO3−>Cl−. For I = 0.2 M this order is NO3−>SO42−>Cl−. For 0.3 and 0.5 M the AMX membrane becomes more selective for chloride than for nitrate or sulfate. Selectivity coefficients KNO3−Cl−, K2Cl−SO42− and K2NO3−SO42−, thermodynamic constants, and separation factors were calculated and decreased with the increase of ionic strength.
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Sadeghi, Rahmat. "Modification of the NRTL and Wilson models for the representation of phase equilibrium behavior of aqueous amino acid – electrolyte solutions." Canadian Journal of Chemistry 86, no. 12 (2008): 1126–37. http://dx.doi.org/10.1139/v08-166.
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The extended NRTL and Wilson local composition models for amino acid solutions have been modified for the representation of the phase equilibrium behavior of aqueous amino acid – electrolyte solutions by considering cells with random composition for the reference Gibbs energies or enthalpies of local composition cells with a central amino acid molecule and also with a central ion. These new local composition models, which have a molecular thermodynamic framework, have been used to model the vapor–liquid and solid–liquid equilibrium behavior of amino acids and small peptides in aqueous solutions as functions of temperature, ionic strength, and amino acid compositions. The utility of the models is demonstrated with a successful representation of the activity coefficients and the solubility of several amino acids in different aqueous solutions.Key words: amino acid, NRTL, Wilson, activity coefficient, solubility, aqueous solution.
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Chen, Wei L., and Huan J. Keh. "Electroosmosis and Electric Conduction of Electrolyte Solutions in Charge-Regulating Fibrous Media." Colloids and Interfaces 5, no. 1 (2021): 19. http://dx.doi.org/10.3390/colloids5010019.
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An analytical study of the electroosmosis and electric conduction of electrolyte solutions in a fibrous medium composed of parallel charge-regulating cylinders with arbitrary electric double layer thickness is presented. A linearized charge regulation model was adopted for the association and dissociation reactions occurring at the amphoteric functional groups over the surfaces of the cylinders, and a unit cell model was employed to accommodate interactions among the cylinders. The electrokinetic equations governing the ionic concentration, electric potential, and liquid flow fields were solved at low zeta potential for the cylinders. Explicit formulas for the electroosmotic mobility and effective electric conductivity in the fiber matrix were obtained. The results indicate that the charge regulation characteristics, such as the equilibrium constants of the reactions occurring at the cylinders’ surfaces and the bulk concentration of the charge-determining ions, influence the surface charge density and potential, electroosmotic mobility, and effective electric conductivity substantially.
5
Tanganov, B. B. "Applied aspects of acid-base interactions and modelling equilibrium concentrations in two-component acid mixtures." Proceedings of Universities. Applied Chemistry and Biotechnology 10, no. 3 (2020): 393–400. http://dx.doi.org/10.21285/2227-2925-2020-10-3-393-400.
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Fundamental and applied research into aqueous and non-aqueous solutions of strong and weak electrolytes remains to be highly relevant, which fact is confirmed by a large number of Russian and foreign publications. In almost all such publications, acid-base interactions are considered exclusively with regard to changes in hydrogen ion concentrations. However, the ionic strength of solutions is determined by all ions present in the system, the concentration of which varies during interactions. This is particularly true for potentiometric titration of strong and weak electrolytes not only in aqueous, but also in more complex non-aqueous solutions, which differ significantly in their basic properties (dielectric constant, ionic product, dipole moment, viscosity, etc.). In the study of equilibria, it is more feasible to develop model representations that would greatly simplify and facilitate the computation and evaluation of certain properties of the system under consideration. In this work, acid-base interactions are presented in the form of equations based on mass action laws and those describing equilibrium processes, solvent ionic product, electroneutrality and material balance in electrolyte systems. The proposed equations consider the effect of the concentrations of all charged particles in the system (not only of hydrogen ions – pH) on the ionic strength of the solution, activity coefficients and, as a consequence, the thermodynamic dissociation constant. In addition, these equations allow the dependence between the equilibrium concentrations of all charged particles and the solution acidity determined by the potentiometric method to be expressed in convenient and objective logarithmic coordinates, thus facilitating estimation of the concentration of all particles at any moment of titration.
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Tanganov, B. B. "The application of logarithmic charts when evaluating the equilibrium concentrations of all particles in acid-base systems." Proceedings of Universities. Applied Chemistry and Biotechnology 11, no. 1 (2021): 26–33. http://dx.doi.org/10.21285/2227-2925-2021-11-1-26-33.
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Until recently, due to the absence of other suitable approaches, equilibrium concentrations in acid-base systems have been studied exclusively by measuring the pH of a solution. However, this method can not be used for organic (non-aqueous) solvent solutions. It is known that the ionic strength of a solution, which is a fundamental component in assessing the activity coefficient and the thermodynamic dissociation constant of an electrolyte, is influenced by the ions present in the system. The concentration of these ions is variable during interactions in aqueous and more complex non-aqueous solutions, which differ significantly in their physicochemical properties (boiling temperature, structure, permittivity, autoprotolysis constant, solvating ability, dipole moment, viscosity, etc.). Meanwhile, in order to obtain more objective and valid estimates of acid-base interactions, in addition to the activity of hydrogen ions, appropriate account should be taken of the equilibrium concentrations of all particles in the solution, which affect its ionic strength. In this article, on the basis of the law of mass action and equations describing equilibrium processes, the ionic product of a solvent, electrical neutrality and material balance in a solution, the corresponding equations were derived and a method was proposed for considering the effect of the concentrations of all particles in the system (not only hydrogen ions – pH), significantly affecting the properties of acid-base equilibrium systems. The proposed method can also be used to obtain the dependence of the equilibrium concentrations of all process substances on the state of the medium (test solution), determined by various chemical and instrumental methods in logarithmic coordinates, which makes it pos-sible to directly assess the equilibrium concentra- tions of all particles present in the system.
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Popov, Konstantin, Hannu Rönkkömäki, and Lauri H. J. Lajunen. "Guidelines for NMR measurements for determination of high and low pKa values (IUPAC Technical Report)." Pure and Applied Chemistry 78, no. 3 (2006): 663–75. http://dx.doi.org/10.1351/pac200678030663.
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Factors affecting the NMR titration procedures for the determination of pKa values in strongly basic and strongly acidic aqueous solutions (2 > pH > 0 and 14 > pH > 12) are analyzed. Guidelines for experimental procedure and publication protocols are formulated. These include: calculation of the equilibrium H+ concentration in a sample; avoidance of measurement with glass electrode in highly acidic (basic) solutions; exclusion of D2O as a solvent; use of an individual sample isolated from air for each pH value; use of external reference and lock compounds; use of a medium of constant ionic strength with clear indication of the supporting electrolyte and of the way the contribution of any ligand to the ionic strength of the medium is accounted for; use of the NMR technique in a way that eliminates sample heating to facilitate better sample temperature control (e.g., 1H-coupled NMR for nuclei other than protons, GD-mode, CPD-mode, etc.); use of Me4NCl/Me4NOH or KCl/KOH as a supporting electrolyte in basic solution rather than sodium salts in order to eliminate errors arising from NaOH association; verification of the independence of the NMR chemical shift from background electrolyte composition and concentration; use of extrapolation procedures.
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Calderón, Silvia M., Jussi Malila, and Nønne L. Prisle. "Model for estimating activity coefficients in binary and ternary ionic surfactant solutions." Journal of Atmospheric Chemistry 77, no. 4 (2020): 141–68. http://dx.doi.org/10.1007/s10874-020-09407-4.
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AbstractWe introduce the CMC based Ionic Surfactant Activity model (CISA) to calculate activity coefficients in ternary aqueous solutions of an ionic surfactant and an inorganic salt. The surfactant can be either anionic or cationic and in the present development, the surfactant and inorganic salts share a common counterion. CISA incorporates micellization into the Pitzer–Debye–Hückel (PDH) framework for activities of mixed electrolyte solutions. To reduce computing requirements, a parametrization of the critical micelle concentration (CMC) is used to estimate the degree of micellization instead of explicit equilibrium calculations. For both binary and ternary systems, CISA only requires binary experimentally-based parameters to describe water–ion interactions and temperature–composition dependency of the CMC. The CISA model is intended in particular for atmospheric applications, where higher-order solution interaction parameters are typically not constrained by experiments and the description must be reliable across a wide range of compositions. We evaluate the model against experimental activity data for binary aqueous solutions of ionic surfactants sodium octanoate and sodium decanoate, as common components of atmospheric aerosols, and sodium dodecylsulfate, the most commonly used model compound for atmospheric surfactants. Capabilities of the CISA model to describe ternary systems are tested for the water–sodium decanoate–sodium chloride system, a common surrogate for marine background cloud condensation nuclei and to our knowledge the only atmospherically relevant system for which ternary activity data is available. For these systems, CISA is able to provide continuous predictions of activity coefficients both below and above CMC and in all cases gives an improved description of the water activity above the CMC, compared to the alternative model of Burchfield and Wolley [J. Phys. Chem., 88(10), 2149–2155 (1984)]. The water activity is a key parameter governing the formation and equilibrium growth of cloud droplets. The CISA model can be extended from the current form to include the effect of other inorganic salts with the existing database of binary PDH parameters and using appropriate mixing rules to account for ion specificity in the micellization process.
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De Corato, Marco, and Marino Arroyo. "A theory for the flow of chemically responsive polymer solutions: Equilibrium and shear-induced phase separation." Journal of Rheology 66, no. 5 (2022): 813–35. http://dx.doi.org/10.1122/8.0000475.
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Chemically responsive polymers are macromolecules that respond to local variations of the chemical composition of the solution by changing their conformation, with notable examples including polyelectrolytes, proteins, and DNA. The polymer conformation changes can occur in response to changes in the pH, the ionic strength, or the concentration of a generic solute that interacts with the polymer. These chemical stimuli can lead to drastic variations of the polymer flexibility and even trigger a transition from a coil to a globule polymer conformation. In many situations, the spatial distribution of the chemical stimuli can be highly inhomogeneous, which can lead to large spatial variations of polymer conformation and of the rheological properties of the mixture. In this paper, we develop a theory for the flow of a mixture of solute and chemically responsive polymers. The approach is valid for generic flows and inhomogeneous distributions of polymers and solutes. To model the polymer conformation changes introduced by the interactions with the solute, we consider the polymers as linear elastic dumbbells whose spring stiffness depends on the solute concentration. We use Onsager’s variational formalism to derive the equations governing the evolution of the variables, which unveils novel couplings between the distribution of dumbbells and that of the solute. Finally, we use a linear stability analysis to show that the governing equations predict an equilibrium phase separation and a distinct shear-induced phase separation whereby a homogeneous distribution of solute and dumbbells spontaneously demix. Similar phase transitions have been observed in previous experiments using stimuli-responsive polymers and may play an important role in living systems.
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Smirnova, Natalia N., and Kirill V. Smirnov. "Peculiarities of thermal aggregation of bovine serum albumin in the presence of strong polyelectrolytes." Butlerov Communications 63, no. 9 (2020): 35–42. http://dx.doi.org/10.37952/roi-jbc-01/20-63-9-35.
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The influence of temperature on bovine serum albumin (BSA) aggregation in aqueous solutions in the presence of poly-N,N-dimethyl-N,N-diallylammonium chloride (PDMDAAC) and the sodium salt of carboxymethylcellulose (CMC) was studied. It was shown that protein-polyelectrolyte complexes (PPC) form because of macromolecular reactions that are stabilized mainly by electrostatic forces. To characterize the PPC composition the φ parameter was used. This parameter is defined as the ratio of the concentration of ionic groups of polyelectrolyte per protein molecules. It was studied that when in an interpolyelectrolyte reaction, a sufficiently high degree of transformation occurs the polymer electrolyte initiates aggregation of protein molecules. As the temperature increases, the initiating role of the polymer electrolyte increases due to an increase in the intensity of hydrophobic interactions. Using the method of spectrophotometry, it was found that, depending on the nature of the polymer electrolyte, insoluble complexes of bovine serum albumin are formed when the pH parameter is above or below the isoelectric point of the protein, when its macromolecules are negatively or positively charged. In the presence of poly-N,N-dimethyl-N,N-diallylammonium chloride, the intensive formation of aggregates and their rapid precipitation in the form of flakes at pH > 7.0 was observed when the temperature increased to 60 °C. The maximum yield of the product of the interpolyelectrolyte reaction bovine serum albumin – sodium salt of carboxymethylcellulose was detected at pH ≤ 4.0. A temperature increase up to 60 °C, in this case, was not accompanied by intensive flocculation. Under optimal composition and interaction conditions, the degree of transformation in the BSA – PDMDAAX and BSA – CMC reactions is ~0.93 and 0.9, respectively, and decreases by ~5-7% with an increase in temperature to 60 °C. It was shown that for the same BOD composition (the ratio of components in the [CMC]/[BSA] complex = 0.1 g/g), an increase in temperature from 25 to 60 °C leads to the formation of particles that increase in size from 1 mcm to 5 mcm. The temperature increase leads to a change in composition of BOD, corresponding to its maximum output as a interpolyelectrolyte reactions product: for complex with PDMDAAC at T = 25, 40 and 60 °C, the φ value is 70, 60, 15; for the complex with the CMC – 60, 50, 20.
Book chapters on the topic "Ionic equilibrium. Polyelectrolytes. electrolyte solutions"
1
Hubbard, Joseph B. "Non-Equilibrium Theories of Electrolyte Solutions." In The Physics and Chemistry of Aqueous Ionic Solutions. Springer Netherlands, 1987. http://dx.doi.org/10.1007/978-94-009-3911-0_3.
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Kakiuchi, Takashi. "Partition Equilibrium of Ionic Components in Two Immiscible Electrolyte Solutions." In Liquid-Liquid Interfaces. CRC Press, 2020. http://dx.doi.org/10.1201/9781003068778-1.
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Fawcett, W. Ronald. "The Electrical Double Layer." In Liquids, Solutions, and Interfaces. Oxford University Press, 2004. http://dx.doi.org/10.1093/oso/9780195094329.003.0014.
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In examining the properties of the metal | solution interface, two limiting types of behavior are found, namely, the ideal polarizable interface and the ideally nonpolarizable interface. In the former case, the interface behaves as a capacitor so that charge can be placed on the metal using an external voltage source. This leads to the establishment of an equal and opposite charge on the solution side. The total system in which charge is separated in space is called the electrical double layer and its properties are characterized by electrostatic equilibrium. An electrical double layer exists in general at any interface at which there is a change in dielectric properties. It has an important influence on the structure of the interface and on the kinetics of processes occurring there. The classical example of an ideally polarizable interface is a mercury electrode in an electrolyte solution which does not contain mercury ions, for example, aqueous KCl. The charge on the mercury surface is altered using an external voltage source placed between the polarizable electrode and non-polarizable electrode, for example, a silver | silver chloride electrode in contact with the same solution. Within well-defined limits, the charge can be changed in both the negative and positive directions. When the mercury electrode is positively charged, there is an excess of anions in the solution close to the electrode. The opposite situation occurs when the electrode is negatively charged. An important point of reference is the point of zero charge (PZC), which occurs when the charge on the electrode is exactly zero. The properties of the electrical double layer in solution depend on the nature of the electrolyte and its concentration. In many electrolytes, one or more of the constituent ions are specifically adsorbed at the interface. Specific adsorption implies that the local ionic concentration is determined not just by electrostatic forces but also by specific chemical forces. For example, the larger halide ions are chemisorbed on mercury due to the covalent nature of the interaction between a mercury atom and the anion. Specific adsorption can also result from the hydrophobic nature of an ion.