Thermodynamics of electrolytes. Binary mixtures formed from aqueous NaCl,Na2SO4, CuCl2, and CuSO4, at 25°C

Osmotic coefficients to high ionic strengths are reported for five of the binary mixtures formed from NaCl, Na₂SO₄, CuCl₂, and CuSO₄; the sixth system studied, NaCl–Na₂SO₄, is one studied by Wu, Rush, and Scatchard. The equations recently developed by Pitzer are used successfully in the interpretation of the experimental results. Revised values are given for the activity and osmotic coefficients for pure CuSO₄ and CuCl₂ solutions.     

Quaternary diffusion coefficients of NaCl−MgCl2−Na2SO4 −H2O synthetic seawaters by least-squares analysis of taylor dispersion profiles

Equations are developed to calculate the nine inter diffusion coefficients of four-component solutions by least-squares analysis of the refractive index profiles across Taylor dispersion peaks. The pre-exponential weighting factors and the eigenvalues of the diffusion coefficient matrix are used as the fitting parameters instead of the diffusion coefficients. This simplifies the fitting equations and speeds up the convergence. The analysis is tested on dilute aqueous solutions of sucrose + glycine + urea, and then used to determine the interdiffusion coefficients of aqueous NaCl+MgCl₂+Na₂SO₄ solutions at compositions corresponding to synthetic seawaters of salinities 5, 15, 25 and 35. The results are used to predict the concentration profiles that develop when seawater interdiffuses with fresh water.     

Thermodynamics of multicomponent electrolyte solutions: Aqueous mixtures of two salts from among NaCl,KCl, NaH2PO4, and KH2PO4 at 25° C

Five of the six possible aqueous two-salt mixtures from among NaCl, KCl, NaH₂PO₄,and KH₂PO₄ have been studied by the isopiestic method at 25°C. The sixth mixture, NaCl–KCl, has been studied previously. The deviations from ideal mixing behavior are described by a series of coefficients which were found by regression analysis. The coefficients were used to calculate the excess Gibbs energies of mixing for equal ionic strength fractions of each salt and the trace activity coefficient of each salt at an ionic strength of 2 mode-kg^–1. The cross-square mixing rule is obeyed within experimental uncertainty for the excess Gibbs energies of mixing.     

Study on the non-isothermal kinetics of decomposition of 4Na<Subscript>2</Subscript>SO<Subscript>4</Subscript>·2H<Subscript>2</Subscript>O<Subscript>2</Subscript>·NaCl

The non-isothermal decomposition kinetics of 4Na₂SO₄·2H₂O₂·NaCl have been investigated by simultaneous TG-DSC in nitrogen atmosphere and in air. The decomposition processes undergo a single step reaction. The multivariate nonlinear regression technique is used to distinguish kinetic model of 4Na₂SO₄·2H₂O₂·NaCl. Results indicate that the reaction type Cn can well describe the decomposition process, the decomposition mechanism is n-dimensional autocatalysis. The kinetic parameters, n, A and E are obtained via multivariate nonlinear regression. The n ^th-order with autocatalysis model is used to simulate the thermal decomposition of 4Na₂SO₄·2H₂O₂·NaCl under isothermal conditions at various temperatures. The flow rate of gas has little effect on the decomposition of 4Na₂SO₄·2H₂O₂·NaCl.     

Ionic interactions in aqueous electrolyte-polyelectrolyte mixtures: Comparisons with mixtures of sodium chloride and the model electrolyte benzyltrimethyl-ammonium chloride at 25°C

Osmotic coefficients for aqueous mixtures of sodium chloride with benzyltrimethylammonium chloride, BzMe₃NCl, obtained by the gravimetric isopiestic vapor pressure comparison method are interpreted with the McKay-Perring transform, with the Scatchard neutral electrolyte treatment, and with the Pitzer ion-component equations. Molal ionic and mean ionic activity coefficients for Na⁺ and Cl^– ions and for NaCl, respectively, in these mixtures at unit total ionic strength also were determined with an electrochemical cell. The excess free energy chenges G^ex on mixing NaCl with BzMe₃NCl were estimated and employed to gain an insight into the relative importance of like and unlike cation-cation interactions.     

Activity coefficients and pitzer parameters in the systems Na+/Cs+/Cl-/TcO 4 - or ClO 4 - /H2O at 25°C

Isopiestic vapor pressure experiments are performed at 25°C with aqueous NaTcO₄, mixed NaTcO₄-NaCl, and NaCl reference solutions. The solubility of CsTcO₄ is determined in 0–7.4m CsCl and in 0–5.6m NaCl solutions. The osmotic coefficients of the binary and ternary solutions are used to evaluate the binary Pitzer parameters Β⁰, Β^l, and C^Φ for NaTcO₄ and the mixing parameters θ_{TcO 4} ^- /cl^- and ψ_Na ⁺/TcO ₄ ^- /cl^-. The binary Pitzer parameters for the sparingly soluble CsTcO₄ and CsC1O₄ are calculated together with ψ_Cs ⁺/mo ₄ ^- /cl^- from their solubilities in CsCl solution. The solubilities of CsTcO₄ in NaCl and CsClO₄ in NaClO₄ solution are also included in the parametrization of the reciprocal salt systems Na⁺/Cs⁺/Cl^-/MO ₄ ^- . The parameters Β⁰ and Β^l of pertechnetate and perchlorate salts correlate well with the ionic radii.     

Thermodynamics of the system H2O−NaCl−Na2SO4−MgSO4 to the saturation limit of NaCl at 25°C

Isopiestic results are reported for the quaternary system H₂O–NaCl–Na₂SO₄–MgSO₄. The excess free energies for mixing the double salt Na₂ Mg(SO₄)₂ with NaCl are fairly large and negative, as also are the free energies for mixing the three salts to form the quaternary aqueous system.     

Thermodynamic representation of the NaCl + Na2SO4 + H2O system with electrolyte NRTL model

A comprehensive thermodynamic model based on the electrolyte NRTL (eNRTL) activity coefficient equation is developed for the NaCl + H₂O binary, the Na₂SO₄ + H₂O binary and the NaCl + Na₂SO₄ + H₂O ternary. The NRTL binary parameters for pairs H₂O-(Na⁺, Cl⁻) and H₂O-(Na⁺, SO₄²⁻), and the aqueous phase infinite dilution heat capacity parameters for ions Cl⁻ and SO₄²⁻ are regressed from fitting experimental data on mean ionic activity coefficient, heat capacity, liquid enthalpy and dissolution enthalpy for the NaCl + H₂O binary and the Na₂SO₄ + H₂O binary with electrolyte concentrations up to saturation and temperature up to 473.15 K. The Gibbs energy of formation, enthalpy of formation and heat capacity parameters for solids NaCl_(s), NaCl·2H₂O_(s), Na₂SO_4(s) and Na₂SO₄·10H₂O_(s) are obtained by fitting experimental data on solubilities of NaCl and Na₂SO₄ in water. The NRTL binary parameters for the (Na⁺, Cl⁻)-(Na⁺, SO₄²⁻) pair are regressed from fitting experimental data on dissolution enthalpies and solubilities for the NaCl + Na₂SO₄ + H₂O ternary.     

Hygrometric Determination of the Water Activities of the Aqueous Solutions of the Mixed Electrolyte NaCl–CaCl2–H2O at 25°C

The mixture {yNaCl + (1 – y)CaCl₂}(aq) has been studied with the hygrometric method at the temperature 25°C. The water activities were measured at total molalities from 0.25 mol-kg^–1 to near saturation for different ionic-strength fractions y of NaCl with y = 0.33, 0.50, and 0.67. The obtained data allow the calculation of osmotic coefficients. The experimental results are compared with the predictions of the Zdanovskii–Stokes–Robinson (ZSR), Kusik and Meissner (KM), Robinson and Stokes (RS), Lietzke and Stoughton (LS II), Reilly–Wood–Robinson (RWR), and Pitzer models. From the measured osmotic coefficients, the Pitzer ionic mixing parameters _{Na Ca} and _{Na Ca} Cl are determined and are used to predict the solute activity coefficients in the mixtures. The excess Gibbs energy is also determined. These results are compared with those given in the literature.     

Water activity,osmotic and activity coefficients of aqueous solutions of Li2SO4, Na2SO4, K2SO4, (NH4)2SO4, MgSO4, MnSO4, NiSO4, CuSO4, and ZnSO4 at T=298.15 K

The water activities for aqueous solutions of Li₂SO₄(aq), Na₂SO₄(aq), K₂SO₄(aq), (NH₄)₂SO₄(aq), and sulphates MgSO₄(aq), MnSO₄(aq), NiSO₄(aq), CuSO₄(aq), and ZnSO₄(aq) were determined experimentally at a temperature of 298.15 K with a hygrometric method, at molalities in the range from 0.1 mol·kg⁻¹ to saturation. The osmotic coefficients are calculated from these results. The coefficients of Pitzer’s model was used to fit the osmotic coefficients for each salt solution. These parameters were used to predict solute activity coefficients for the salts studied.     

Enthalpies of mixing of some aqueous electrolytes at 373.15 K

The enthalpies of mixing of a variety of aqueous electrolytes at an ionic strength of 1.000 mol·kg^?1 have been measured at 373.15 K. The mixtures studied were LiBr + KBr, NaBr + KBr, KBr + (C₄H₉)₄NBr, NaCl + Na₂SO₄, NaCl + MgCl₂, MgSO₄ + Na₂SO₄, MgCl₂ + MgSO₄, NaCl + MgSO₄, and MgCl₂ + Na₂SO₄. In contrast to most previous enthalpies of mixing of alkali halides, the mixtures with multivalent ions studied here often have large temperature dependences. The results for the mixtures involving MgSO₄ are consistent with a higher degree of ion pairing as the temperature increases. The present measurements, together with Gibbs energies of mixing at 298.15 K, allow the calculation of Gibbs energies of mixing at the higher temperature. This appears to be the most accurate and convenient method available for determining Gibbs energies of mixing at high temperatures.     

Activity Coefficients of Potassium Chloride and Sodium Chloride in the Quaternary System KCl-NaCl-Water-Ethanol

Activity coefficients of KCl and NaCl were determined in the quaternary system KCl-NaCl-water-ethanol, for 10 and 20% (w/w) ethanol in the solvent, from experimental electromotive force data. The molalities varied from 0.1 mol kg^–1 to near saturation and measurements were taken in the temperature range 20 to 50°C. The Pitzer-Simonson equations were used to describe the nonideal behavior of both electrolytes and the corresponding activity coefficients were determined for each solvent and temperature.     

The Cloud Point Behaviors and the Liquid–Liquid Equilibrium of L31—Inorganic Sodium Salt Aqueous Two-Phase Systems

The cloud point (CP) of triblock-copolymer L31 aqueous solution was determined with salting-out salts (Na₂SO₄/Na₂CO₃/NaF/NaCl/NaBr). The results show that all these salts can decrease the CP of L31 aqueous solution and form aqueous two-phase system (ATPS). With increasing concentrations of Na₂SO₄ and Na₂CO₃, an obvious phase inversion could be observed and phase inversion points were found. This was mainly due to the change in density, the salt-rich phase shifted from the top phase to the bottom phase. Meanwhile, the liquid-liquid equilibrium (LLE) data for L31-Na₂SO₄/Na₂CO₃/NaF/NaCl/NaBr ATPSs were measured at 288.15 K. The salt ability to decrease the CP and to induce the phase separation is as follows: Na₂SO₄?>?Na₂CO₃, NaF?>?NaCl?>?NaBr. Finally, the order of anions that reduced the CP and caused phase separation was obtained as follows: SO₄^2? >CO₃^2?, F^??>?Cl^??>?Br^?.     

Thermodynamic Study of the NaCl + Na2SO4 + H2O System by Emf Measurements at Four Temperatures

Activity coefficients for sodium chloride in the NaCl + Na₂SO₄ + H₂O ternary system were determined from emf measurements of the cell

Excess Gibbs energies of mixing in the system H2O−NaCl−Na2SO4−MgSO4 at 298.15°K

Isoptestic results are reported for aqueous mixtures of Na₂SO₄ with solutions of NaCl+MgSO₄ at constant mole ratio of NaCl:MgSO₄. The Gibbs energies of mixing obtained from these measurements are combined with earlier results on the same system to derive diagrams giving Gibbs energies of mixing in the quaternary system at constant ionic strengths of 1 and 6. The osmotic coefficients of the mixture are compared with those predicted from the theory of Reilly and Wood.     

Activity coefficients in aqueous NaCl−CsCl2 mixtures from solubility data up to 75°C: A supplement to Pitzer's work

Activity coefficients of NaCl in aqueous NaCl-CsCl₂ mixtures in the CaCl₂ rich region at 25, 50 and 75°C were calculated from recent solubility data of Chou and his group. The results are compared with those obtained from ion-interaction equations using solution data of de Lima and Pitzer, who had also reported similar comparisons but using the inconsistent solubility data of Plyushchev et al. The agreement obtained between the Chou solubility data and the Pitzer equation is excellent.     

Transference numbers of aqueous NaCl and Na2SO4 at 25°C from EMF measurements with sodium-selective glass electrodes

Transference numbers in aqueous solutions of NaCl and Na ₂ SO ₄ were obtained by measuring the emf of cells with liquid junction using sodium-selective glass electrodes. Transference numbers in the NaCl–H₂O system from about 0.1 to 4 mol-kg ^–1 (m) are in good agreement with literature data obtained by various experimental techniques, but are markedly lower than recent data obtained from emf measurements with Ag,AgCl-electrodes. Transference numbers in the Na ₂ SO ₄ –H ₂ O system from about 0.03 to 1.9 m show a small decrease with increasing salt concentration, which is near the limit of experimental uncertainty. Sodium-selective electrodes are well suited to perform determinations of transference numbers and may provide an alternative to amalgam electrodes.     

Calculation of the osmotic and activity coefficients of seawater at 25°C

The equation of Reilly, Wood, and Robinson was used to predict the osmotic coefficient of seawater and of its concentrates at molal ionic strengths of 0.5 to 6.0 at 25°C. The results agree closely with experimental data at ionic strengths below 5. The average difference in osmotic coefficients over the entire concentration range is 0.0014. The only serious discrepancy is at an ionic strength of 6, where a difference of 0.0068 is found. The accuracy of the predictions of osmotic coefficients prompted the calculation of the activity coefficients of NaCl, Na₂SO₄, MgCl₂, MgSO₄, KCl, and K₂SO₄ in the mixture. The calculated activity coefficients of NaCl and Na₂SO₄ agree within experimental error with previous measurements. This agreement demonstrates the prediction of activity and osmotic coefficients for complex mixtures.     

Ozone solubility in concentrated aqueous solutions of salts

The effect exerted by the concentration of salts (NaCl, Na₂SO₄, and NaNO₃) on the ozone solubility in aqueous solution at 20, 30, and 40°C was studied. The solubility coefficients of ozone were calculated. The Henry constants and the Sechenov coefficients were determined.     

Activity Coefficients of Electrolytes from Liquid Membrane Cells. XI. The Nonsulfate 1:2 Salts,Potassium Oxalate,and Sodium 1,5-Naphthalenedisulfonate

Activity coefficients of K₂C₂O₄ and Na₂ds, ds^2– = 1,5-naphthalenedisulfonate anion, which were previously unavailable, are examined at 25.0°C using liquid membrane cells. The results for both salts are approximated satisfactorily by the primitive model in spite of the fact that ds^2–, a planar ion with electric charges distant from one another, does not resemble a charged hard sphere. Data are compared with those of K₂SO₄ and bivalent metal perchlorates. The Pitzer ion-interaction parameters are reported.