Amino acid hydration in aqueous magnesium and sodium sulfate solutions

We study the partial volumes of amino acids in aqueous magnesium and sodium sulfate solutions, which have a different effect on the structure of water, and calculate the structural parameters of hydrated complexes of NH ₃ ⁺ and COO^? groups: hydration numbers and water volumes inside and outside the hydration shell. The hydration numbers are given as a sum of the contributions of the interactions in the ternary (water-salt-amino acid) and binary (water-salt) systems.     

Activity coefficient of hydrochloric acid in aqueous solutions of sodium chloride

Electromotive-force measurements of the cell $$Pt;H_2 \left( {g,1{\text{ }}atm} \right)|HCl\left( {{\text{m}}_A } \right),NaCl\left( {{\text{m}}_B } \right)|AgCl;Ag$$ have been made at temperatures between 5 and 45°C at values ofm _A+m _B of 0.1, 0.3809, 0.6729, and 0.8720 mole-kg^?1. The activity coefficients of HCl in HCl/NaCl mixtures and the Harned coefficients α₁₂ have been obtained. The change of α₁₂ with total molality is consistent with the existence of binary interactions between H⁺ and Na⁺ ions. The linear variation of the relative partial molal heat content with the fraction of NaCl in the mixture suggests that an analog of the Harned rule exists for this thermodynamic quantity.     

Free energy relationships in aqueous amino acid and peptide solutions containing sodium chloride

Three systems of the type amino acid or peptide-sodium chloride-water have been investigated over wide solute molality ranges using the isopiestic vapor pressure method. The amino acid employed was L--alanine, while the peptides were diglycine and triglycine. Equations were obtained for the activity coefficients of these compounds in the salt solutions in terms of the molalities of the solutes. The trace activity coefficients of the peptides were negative at low salt molality and became positive as the salt molality was increased. The limiting interaction parameters were calculated for the systems using the Kirkwood ion-dipole expression and empirical quantities derived from previous work to obtain the salt effect on the nonpolar and amide portion of the molecule. Good agreement was obtained between the calculated values and the experimental results in the case of diglycine, but they diverged in the case of triglycine. The calculated value for L--alanine is in poorer agreement with the experimental value than for the other amino acids studied previously.Presented in part at the Second International Conference on Calorimetry and Thermodynamics, Orono, Maine, July 1971.     

Aggregation of sodium dodecyl sulfate in aqueous sodium chloride solutions

Summary Aqueous solutions of sodium dodecyl sulfate with added sodium chloride (0–0.3 mol kg^–1) were studied at 298.2 K in order to calculate the molar standard free energy of micelle formationG _m . The following properties were measured: (i) aggregation number by membrane osmometry, (ii) counter-ion binding and sodium ion activities by electromotive force, (iii) critical micelle concentration by electromotive force and fluorescence spectrophotometry. The results indicate thatG _m . is independent of the NaCl concentration.     

Ionization of methyl orange in aqueous sodium chloride solutions

Ionization constants of sodium 4′-dimethylaminoazobenzene-4-sulphonate (methyl orange) were determined by means of spectrophotometric measurements in water and in aqueous sodium chloride solutions with molalities up to 2 mol·kg⁻¹ at temperatures between 278.15 K and 333.15 K. The temperature dependence of the thermodynamic acidity constant shows a slight curvature in accordance with published data. The influence of sodium chloride on the methyl orange deprotonation was assessed by the measurement of stoichiometric acidity constants in this ionic medium. The Pitzer theory, widely used in the evaluation of the excess free energy of non-ideal electrolyte solutions, was applied to the computation of the activity coefficients of the chemical species involved in the equilibria and a good fit of those equations to the experimental data was observed, at all temperatures under consideration.     

Transference numbers of sodium chloride in concentrated aqueous solutions and chloride conductances in several concentrated electrolyte solutions

Stable chlorine electrodes with low bias potentials have been developed by introducing 25% Ir+75% Pt electrodes and an improved gas line. With their use in cells with transference, cation constituent transference numbers have been measured at 25°C in NaCl solutions from 1.7 to 6 modal. These results agree well with four other sets of data in the literature but disagree with two further sets based on emf determinations with Ag/AgCl electrodes. A table of best NaCl transference numbers is proposed. The conductances of the chloride ion-constituent in concentrated NaCl, KCl, and HCl solutions are compared.     

Hydration of α-alanine in aqueous sodium chloride and urea solutions

The hydration number of α-alanine in aqueous urea solutions is greater than in aqueous NaCl solutions; the ratio of the hydration numbers increases from 0.2 (m = 1) to ≈2 (m = 6). Given the same partial volumes of water, the hydration numbers of α-alanine in the two systems are close to each other.     

Hydration numbers of glycine in aqueous sodium chloride and urea solutions

The hydration number of the glycine amino acid in aqueous sodium chloride solution is less than in aqueous urea solution; the difference increases significantly with increasing concentration of the nonaqueous component. Given the same partial volume of water, the hydration numbers of glycine in the two systems are close together (δ ≈ 5%).     

Adiabatic and isothermal compressibility of aqueous solutions of sodium chloride

By the example of aqueous solutions of sodium chloride an approach is developed to obtain the hydration number, molar volume and compressibility of hydrate complexes using the data on adiabatic and isothermal compressibility. It is shown that the results of calculations based on isothermal and adiabatic compressibility are consistent with each other     

Optimization of plasma treatment of aqueous sodium chloride solutions

The effect of pressure in a plasma reactor on the synthesis of mixtures of H₂O₂ and ClO ₂ ^- has been studied. The yield of oxidants, selectivity for chlorites, the rate of the process, and its energy consumption have been treated as optimization parameters. Functional dependences of the optimal time of the plasma treatment of NaCl solutions on the reactor pressure with respect to parameters, such as the process selectivity and chlorite yield, have been determined.     

The phase-separation behaviour of aqueous solutions of polyacrylic acid and its partial sodium salts in the presence of sodium chloride

Phase-separation temperatures have been measured for polyacrylic acid dissolved in aqueous sodium chloride solutions over a range of ionic strengths, degrees of neutralisation, polymer concentrations and molecular weights. The data are used to derive θ-temperatures for this system. The dependence of the θ-points on ionic strength and degree of ionisation is discussed and the results are briefly compared with data for other polyelectrolytes.     

Quantitative characteristics of hydration in solutions of sodium sulfate and sodium chloride at 278.15–323.15 K

The solvation parameters of aqueous solutions of sodium chloride and sodium sulfate were studied on the basis of published density and ultrasound velocity data. Correct thermodynamic relations for temperature variation from 278.15 to 323.15 were used to determine quantitative parameters of solvation, in particular, the hydration numbers h, the molar adiabatic compressibility of hydrate structures β _h V _h , the volume V _1h and compressibility β _1h of water in the hydration shells of ions, and others. h and β _h V _h do not depend on temperature in the range of parameters studied, and electrostriction compression about the ions has a more pronounced effect on the structure than mere pressure change.     

Hydroxide ion hydration in aqueous solutions

Hydroxide ion hydration was studied in aqueous solutions of selected alkali metal hydroxides by means of Fourier transform infrared (FTIR) spectroscopy of HDO isotopically diluted in H2O. The quantitative difference spectra procedure was applied for the first time to investigate such systems. It allowed removal of bulk water contribution and separation of the spectra of solute-affected HDO. The obtained spectral data were confronted with ab initio calculated structures of small gas-phase and polarizable continuum solvation model (PCM) solvated aqueous clusters, OH-(H2O)n, n = 1-7, to establish the structural and energetic states of hydration spheres of the hydrated hydroxide anion. This was achieved by comparison of the calculated optimal geometries with the interatomic distances derived from HDO band positions. The energetic state of water in OH- hydration shells, as revealed by solute-affected HDO spectra, is similar to that of an isoelectronic F- anion. No evidence was found for the existence of stable hydroxide dimer, H3O2-, in an aqueous solution. Spectral data do confirm, however, existence of a weak interaction with a single water molecule at the hydrogen site of OH-.     

Dilute solution properties of poly(dimethyldiallylammonium chloride) in aqueous sodium chloride solutions

MW fractions of poly(dimethyldiallylammonium chloride) (PDMDAAC) were prepared by preparative size-exclusion chromatography and characterized by static and dynamic light scattering, viscometry, size-exclusion chromatography, and electrophoretic light scattering, in 0.50M NaCl solution. The behavior of fractions with MW < 2 × 10⁵ was as expected for a strong polyelectrolyte in a good solvent, with a Mark-Houwink exponent of ca. 0.8, and MW-dependencies of the hydrodynamic radius and the radius of gyration of corresponding magnitude. At higher MW, curvature appears in the MW-dependencies, which can be best explained by the presence of branching. While this notably lowers the intrinsic viscosity at high MW, the electrophoretic mobility is unchanged regardless of molar mass. Thus, the branched polymers display the electrophoretic free-draining behavior characteristic of linear polyelectrolytes. ©1995 John Wiley & Sons, Inc.     

Enthalpic interactions of anti-tumor drug matrine in aqueous sodium chloride solutions

The enthalpies of dilution of matrine (MAT) in pure water and aqueous sodium chloride solutions were determined by isothermal titration microcalorimetry at 298.15 K, and the corresponding homogeneous enthalpic interaction coefficients were calculated according to the modified McMillan–Mayer model. The values of enthalpic pair-wise interaction coefficients, h ₂, are all positive and become more positive with increasing concentration of sodium chloride.     

Low-concentration aqueous solutions of undecenoic acid and sodium undecenoate

The behaviors of low-concentration aqueous solutions of 10-undecenoic acid and its sodium salt were studied by several techniques. The acid does not have a critical micelle concentration, but gives an emulsion of very small droplets at (0.8–1) ×  10⁻⁴ mol dm⁻³. The emulsion was clearly visible by eye at 0.002 mol dm⁻³. The sodium salt has a stepwise aggregation process, giving premicellar aggregates at 0.023 ± 0.008 mol dm⁻³, which grow to form micelles at 0.117 ± 0.007 mol dm⁻³. The compositions of the solution and the micelles were also studied. Received: 25 February 1999 Accepted in revised form: 21 June 1999     

Temperature dependence of fractionation of hydrogen isotopes in aqueous sodium chloride solutions

The D/H ratios of hydrogen gas in equilibrium with aqueous sodium chloride solutions of 2, 4 and 6 molalities were determined within the range 10 to 95°C, using a hydrophobic platinum catalyst. With each of the different sodium chloride concentrations, the hydrogen isotope effect between the solution and pure water changes linearly with the square of the reciprocal temperature. On the basis of the results for hydrogen isotope fractionation observed in this study, and those of hydrogen isotope fractionation between pure water and vapor, it is concluded that the structure of the aqueous sodium chloride solution does not change significantly with temperature. The hydrogen isotope effect is evidently different from the results of vapor pressure isotope effects (VPIE) on sodium chloride solutions measured on separated isotopes. The difference between the present work and the VPIE studies is probably due to a non-ideal behavior in a mixture of isotopic water molecules and/or to a H₂O-D₂O disproportionation reaction in sodium chloride solutions. The distinction between the latter two mechanisms can not be differentiated at present.     

Concentration-dependent aggregation patterns of conjugated bile salts in aqueous sodium chloride solutions

Based on light scattering intensity measurements, a critical concentration for micelle formation can be assigned to sodium taurodeoxycholate in aqueous electrolyte solutions. For sodium taurocholate a progressive aggregation even at very low concentrations of bile salt is indicated. Surface tension and diffusion coefficients are also reported.     

Lanthanide-fluoride ion association in aqueous sodium chloride solutions at 25°C

New results on lanthanide-fluoride ion association constants from potentiometric measurements in 1M NaCl at 25°C are presented for 13 lanthanide elements and compared with literature values. All data have been evaluated by taking two successive association steps into account and difluoro association constants are given where this is justified from the range of ligand numbers that could be reached before precipitation occurred. The lanthanide-monofluoride association constants may be arranged into several series usually referred to as the tetrad effect, and they show a maximum at Dy in the middle of the lanthanide series. Data on the ionic strength dependence of the lanthanide-monofluoride association constants in I=0.1, 0.5, 1.0, and 3.0M NaCl solutions for La, Nd, Tb, Er, and Lu are interpreted applying an extended Debye-Hückel formulation.