Supercooling of aqueous NaCl and KCl solutions under acoustic levitation

The supercooling capability of aqueous NaCl and KCl solutions is investigated at containerless state by using acoustic levitation method. The supercooling of water is obviously enhanced by the alkali metal ions and increases linearly with the augmentation of concentrations. Furthermore, the supercooling depends on the nature of ions and is 2-3 K larger for NaCl solution than that for KCl solution in the present concentration range: Molecular dynamics simulations are performed to reveal the intrinsic correlation between supercoolability and microstructure. The translational and orientational order parameters are applied to quantitatively demonstrate the effect of ionic concentration on the hydrogen-bond network and ice melting point. The disrupted hydrogen-bond structure determines essentially the concentration dependence of supercooling. On the other hand, the introduced acoustic pressure suppresses the increase of supercooling by promoting the growth and coalescence of microbubbles, the effective nucleation catalysts, in water. However, the dissolved ions can weaken this effect, and moreover the degree varies with the ion type. This results in the different supercoolability for NaCl and KCl solutions under the acoustic levitation conditions.     

Interactions of DL-serine and L-serine with NaCl and KCl in aqueous solutions

The activity coefficients at 25‡C of DL-serine and L-serine in aqueous solutions of NaCl and KC1 were measured. This study examines the effect of the nature of the cation of the electrolyte on the activity coefficients of the optical-isomers of serine in aqueous solutions for molality of serine up to 0.4 and molality of electrolyte up to 1. An electrochemical cell with two ion-selective electrodes, a cation, and an anion ion selective electrode,vs. a double-junction reference electrode was used to measure the activity coefficients of the electrolyte and the results were converted to the activity coefficients of serine in the aqueous electrolyte solution. The comparison of the results obtained for DL- and L-serine indicates that the two optical isomers have identical interactions with electrolytes in aqueous solutions and that for this amino acid the effect of the cation of the electrolyte is not significant. Comparison of these results with previous measurements for DL-alanine in aqueous solutions of the same electrolytes show the notable effect of the backbone of the amino acid.     

Solvation of a hydrogen isotope in aqueous methanol, NaCl, and KCl solutions

The muon hyperfine coupling constant (hfc) of the light hydrogen isotope muonium (Mu) was measured in aqueous methanol, NaCl, and KCl solutions with varying concentrations, in deuterated water, and in deuterated methanol. The muon hfc is shown to be sensitive to the size and composition of the primary solvation shell, and the three-dimensional harmonic oscillator model of Roduner et al. (J. Chem. Phys. 1995, 102, 5989) has been modified to account for dependence of the muon hfc on the methanol or salt concentration. The muon hfc of Mu in the aqueous methanol solutions decreases with increasing methanol concentration up to a mole fraction (chiMeOH) of approximately 0.4, above which the muon hfc is approximately constant. The concentration dependence of the muon hfc is due to hydrophobic nature of Mu. It is preferentially solvated by the methyl group of methanol, and the proportion of methanol molecules in the primary solvation shell is greater than that in the bulk solution. Above chiMeOH approximately 0.4, Mu is completely surrounded by methanol. The muon hfc decreases with increasing methanol concentration because more unpaired electron spin density is transferred from Mu to methanol than to water. The unpaired electron spin density is transferred from Mu to the solvent by collisions that stretch one of the solvents bonds. The amount of spin density transferred is likely inversely related to the activation barrier for abstraction from the solvent, which accounts for the larger muon hfc in the deuterated solvents. The muon hfc of Mu in electrolyte solution decreases with increasing concentration of NaCl or KCl. We suggest that the decrease of the muon hfc is due to the amount of spin density transferred from Mu to its surroundings being dependent on the average orientation of the water molecules in the primary solvation shell, which is influenced by both Mu and the ions in solution, and spin density transfer to the ions themselves.     

KCl/NaCl DMSO aqueous solutions dielectric spectra and cooperative interactions

The complex permittivity spectra of KCl/NaCl DMSO aqueous solutions were measured using microwave dielectric spectroscopy. Ion–water and dipole–water cooperative interactions are investigated by using a fractional relaxation process. Only about one cooperative relaxation was found during the cut-off relaxation time interval and the relaxation time increases with concentration increasing. Ions’ concentration dependent on effective number of water molecules in the shell around ions was calculated to reveal the interactions between K⁺, Cl^?, Na⁺ ions and DMSO molecules.     

Thermodynamics of saturated aqueous solutions including mixtures of NaCl,KCl, and CsCl

The activity coefficients for saturated aqueous KCl, CsCl and mixtures of NaCl with each of these electrolytes are calculated from solution properties using the ion interaction model as well as from the solubility. The agreement between the two sets of results for both single and mixed electrolytes is, in general, good when it is considered that the saturated solution molatities are often much higher than those whose properties were used in the evaluation of the ion interaction parameters. Also, for pure KCl (aq) the agreement is good up to 300°C, an extrapolation 50°C above the range of data on which the equations were based.     

Thermal properties and interactions of l-proline in aqueous solutions of NaCl or KCl at different temperatures

The enthalpies of solution of l-proline in aqueous electrolyte solutions within the electrolyte molality range up to 4.9 mol kg^?1 of NaCl and up to 4.0 mol kg^?1 of KCl at 288, 298 and 313 K have been measured by the calorimetric method. Enthalpies of transfer of l-proline from water to aqueous electrolyte solutions up to saturation have been derived at 273–348 K. The enthalpic and heat capacity parameters of pair and triplet interaction of l-proline with electrolyte in water have been evaluated. Enthalpic parameters of pair interaction at 298 K have been compared to similar parameters for glycine and l-alanine. The temperature changes of reduced enthalpy, and also the change of entropy and reduced Gibbs energy of transfer of l-proline from water to aqueous electrolyte solution at temperature rise from 273 to 323 K have been determined. It has been shown that the entropy–enthalpy compensation takes place for transfer processes.     

Study on transmembrane electrical potential of nanofiltration membranes in KCl and MgCl2 solutions

The transmembrane electrical potential (TMEP) across two commercial nanofiltration membranes (ESNA1-K and Filmtec NF) was investigated in KCl and MgCl(2) solutions. TMEP was measured in a wide range of salt concentrations (1-60 mol·m(-3)) and pH values (3-10) at the feed side, with pressure differences in the range of 0.1-0.6 MPa. A two-layer model based on the Nernst-Planck equation was proposed to describe the relation between TMEP and permeation flux. From the pattern of these curves, the information of membrane structure could be deduced. In the concentration range investigated, TMEP in KCl solutions was always positive and decreased as the salt concentration increased. The contribution of the membrane potential to the TMEP decreased. TMEP was greatly affected by the feed pH. When the feed pH increased, the mobility of cations increased, which indicated that the charges of NF membranes were more negative. The zero point of TMEP and the minimum of rejection in KCl solution were consistent and occurred at the isoelectric point of NF membranes, while in MgCl(2) solution the zero point of TMEP located at a higher pH value. The TMEP in MgCl(2) solutions changed its sign at a given concentration, and by calculating the transport number the location of the minimum rejection could be determined.     

Stability of nanocrystalline cellulose in aqueous KCl solutions

The electrokinetic properties and aggregation stability of nanocrystalline cellulose sols in aqueous KCl solutions have been studied at pH 5.2. Cellulose nanoparticles have been prepared via controlled degradation in a mixture of phosphotungstic and acetic acids. At electrolyte concentrations of <0.01 mol/dm³, the system is stable to aggregation. The experimentally determined threshold of fast coagulation is 0.08 mol/dm³. It has been noted that the structural component of disjoining pressure must be taken into account when considering the aggregation stability of nanocrystalline cellulose sols in terms of the DLVO theory. It has been shown that the sizes of water boundary layers decrease with an increase in the KCl concentration. The effect of medium pH on the electrokinetic potentials and sizes of aggregates has been studied.     

Specific heats of aqueous solutions of NaCl,NaBr, and KCl: Comparisons with related thermal properties

Earlier unpublished measurements of the specific heat capacities of aqueous NaCl, KCl, and NaBr solutions from 5 to 85°C and from 0.05m to saturation are presented. A twin calorimeter was used. A precision of nearly 1 part in 10⁴ in the specific heat capacity is claimed. The results are compared with literature values (summaries or original data) for heat capacity, heat of dilution, and activity coefficient of these salts in solution by means of a polynomial in half-integer powers of molality and temperature. It is found that our values agree well with the more recent literature values of the heat capacities. Small systematic inconsistencies between the various types of data were found.The experimental results presented here are taken from the postdoctoral work of Dr. F. W. Lamb, 1946–47, and from the master's thesis of Dr. J. E. Tanner, Indiana University (1954), obtainable from University Microfilms, Inc., Ann Arbor, Michigan, order number M-763.     

Electrochemical characterization of an asymmetric nanofiltration membrane with NaCl and KCl solutions: influence of membrane asymmetry on transport parameters

Electrochemical characterization of a nanofiltration asymmetric membrane was carried out by measuring membrane potential, salt diffusion, and electrical parameters (membrane electrical resistance and capacitance) with the membrane in contact with NaCl and KCl solutions at different concentrations (10(-3)< or =c(M)< or =5 x 10(-2)). From these experiments characteristic parameters such as the effective concentration of charge in the membrane, ionic transport numbers, and salt and ionic permeabilities across the membrane were determined. Membrane electrical resistance and capacitance were obtained from impedance spectroscopy (IS) measurements by using equivalent circuits as models. This technique allows the determination of the electrical contribution associated with each sublayer; then, assuming that the dense sublayer behaves as a plane capacitor, its thickness can be estimated from the capacitance value. The influence of membrane asymmetry on transport parameters have been studied by carrying out measurements for the two opposite external conditions. Results show that membrane asymmetry strongly affects membrane potential, which is attributed to the Donnan exclusion when the solutions in contact with the dense layer have concentrations lower than the membrane fixed charge (X(ef) approximately -0.004 M), but for the reversal experimental condition (high concentration in contact with the membrane dense sublayer) the membrane potential is practically similar to the solution diffusion potential. The comparison of results obtained for both electrolytes agrees with the higher conductivity of KCl solutions. On the other hand, the influence of diffusion layers at the membrane/solution interfaces in salt permeation was also studied by measuring salt diffusion at a given NaCl concentration gradient but at five different solutions stirring rates.     

Molal volumes of sucrose in aqueous solutions of NaCl,KCl, or urea at 25°C

The apparent molal volume _v of sucrose in water has been measured at 25°C in the concentration range 0.04–4.4m from precise density measurements. The same property was also determined for dilute solutions of sucrose in mixed aqueous solvents containing NaCl, KCl, or urea. The limiting values _v ^° and the slopesS _v ^* were obtained in each case, and their significance has been discussed briefly. The mean apparent molal volumes _v of the ternary systems were also calculated, and the predictive accuracy of Ward and Millero's modified Young's rule for _v was found to be comparable to that for other electrolyte-nonelectrolyte solutions. For the system H₂O-sucrose-urea, an additivity rule based simply on total molality predicted _v with similar accuracy.Deceased January 15, 1976.     

Anomalies in supercooled NaCl aqueous solutions: a microscopic perspective

In this work we studied the effect of NaCl on the thermodynamic and dynamic properties of supercooled water, for salt concentrations between 0.19 and 1.33 mol?kg(-1), using molecular dynamic simulations for TIP5P∕E water model and ion parameters specially designed to be used in combination with this potential. We studied the isobaric heat capacity (C(p)) temperature dependence and observed a maximum in C(p), occurring at T(m), that moves to lower temperature values with increasing salt concentration. Many characteristic changes were observed at scaled temperature T∕T(m) ～ 0.96, namely a minimum in the density of the system, a reduction of the slope of the number of hydrogen bonds vs. temperature, and a crossover from Vogel-Tamman-Fulcher to Arrhenius dynamics. Finally, at low temperatures we observed that water dynamics become heterogeneous with an apparently common relationship between the fraction of immobile molecules and T/T(m) for all studied systems.     

Zeta potential of microbubbles in aqueous solutions: electrical properties of the gas-water interface

Microbubbles are very fine bubbles and appropriate for the investigation of the gas-water interface electrical charge, because of their long stagnation, due to slow buoyancy, in the electrophoresis cell observation area. This study investigated the zeta potential of microbubbles in aqueous solutions and revealed that the bubbles were negatively charged under a wide range of pH conditions. The potential was positive under strong acidic conditions, and the inorganic electrolytes decrease the potential by increasing the amount of counterions within the slipping plane. OH(-) and H(+) are crucial factors for the charging mechanism of the gas-water interface, while other anions and cations have secondary effects on the zeta potential, because counterions are attracted by the interface charge. The addition of a small amount of propanol and butanol provided significant information for considering the mechanism of the gas-water interface charge. Even though these alcohols did not have any electrical charge, they had a strong effect on the gas-water interface charge and dispersed the zeta potential of the microbubbles in the aqueous solution. These alcohols tended to adsorb to the interface and affect the hydrogen-bonding network at the interface, so that it was concluded that the gas-water interface electrical charge must be related to the difference of the construction of the hydrogen-bonding network between the bulk water and the gas-water interface.     

Diffusion of cyclodextrins in aqueous polymer solutions

Diffusion of α and β cyclodextrin (α-CD and β-CD, respectively) has been studied in aqueous solutions of poly(methacrylic acid), sodium poly(styrene sulfonate), having three different degrees of sulfonation (DS), and copoly(styrene-methacrylic acid) containing three different amounts of styrene. N-Acetylglucosamine and raffinose were included as reference diffusants. It was found that a decrease of the diffusion coefficients of the CD's in these polymer solutions is characteristically dependent on the polymer concentration, DS, Styrene content, and the degree of neutralization. The results were interpreted by assuming a 1:1 complex formation between CD and an appropriate residue in the polymer. The complex diffusion behavior of CD in the copolymer solutions suggested that the ability of the polymer residue to form complexes with the CD is lost when the polymer chain dimensions are reduced with decreasing neutralization.     

Electrical conductivity of aqueous polymer solutions

 Theoretical equations were proposed to adequately simulate the electrical conductivity behavior of aqueous solutions of both charged and uncharged polymers. The theory, based on the mixture equation of Boned and Peyrelasse, was experimentally verified on poly(acrylic acid) (PAA) in water and poly(ethylene oxide) (PEO) in aqueous electrolyte solutions. The data analysis suggested that both the polymer coils may be depicted as oblate ellipsoids. Subsequently, the semiaxes values of the polymer coils were determined, and they were in good agreement with the results reported in the literature. Received: 25 June 1996 Accepted: 2 October 1996     

Electrical conductance of aqueous solutions of KCl solutions at pressures up to 2000 atm

Electrical conductance measurements are reported for aqueous KCl solutions at 25°C as a function of concentration up to 0.02 M and pressure up to 2000 atm. The data from 103 runs were analyzed with the Fuoss-Hsia-Fernandez-Prini (FHFP) equation. The standard error of fit varies from 0.018 at 1 atm to 0.12 at 2000 atm. The increase of with pressure arises from increasing nonrandomness in the distribution of errors about the FHFP equation, suggesting that modifications in the theory are necessary. Departures from the Walden product for KCl as a function of pressure are compared with MgSO₄ and CaSO₄ in aqueous solutions.     

Solubilities of ionic surfactants in aqueous polymer solutions

Summary Solubility of ionic surfactants in water have been found to increase with added amount of nonionic hydrophilic polymers when both are capable of forming watersoluble complexes. Experiments were carried out with sodium hexadecyl sulfate (SHS) and hexadecyl amine hydrochloride (HAC) below theKrafft points of the respective surfactants. The solubility increment of the surfactants brought about by the polymers depends upon the kind of polymers, their molecular weight, concentration and temperature. The results have been interpreted on the basis of the amount of surfactants bound to the polymers and by the properties of the polymer-surfactant complexes formed. It is noteworthy that the anionic surfactant (SHS) can be bound to polymers much more extensively than the cationic surfactant (HAC).

---

Zusammenfassung Die L?slichkeit von ionischen Benetzern in Wasser w?chst mit dem zugefügten Betrag an nicht-ionischen hydrophilen Polymeren, wenn beide zusammen wasserl?sliche Komplexe büden k?nnen. Versuche wurden mit Natrium-hexadecyl-sulfat (SHS) und Hexadecylamin-hydrochlorid (HAC) ausgeführt, und zwar unter denKrafft-Punkten der bezüglichen Benetzer. Das L?slichkeitsinkrement der Benetzer, gegeben durch die Polymeren, h?ngt von der Art des Polymeren, dessen Molekulargewicht, Konzentration und Temperatur ab. Die Ergebnisse werden interpretiert auf der Grundlage des Betrages an Benetzer, der an das Polymere gebunden ist, und durch die Eigenschaften des Komplexes Polymer/Benetzer. Es ist bemerkenswert, da? der anionische Benetzer (SHS) viel st?rker an das Polymere gebunden werden kann als der kationische Benetzer (HAC).

     

Phase separation behavior of aqueous solutions of a thermoresponsive polymer

Cloud‐point and binodal curves of the LCST type were obtained for aqueous solutions of a thermoresponsive polymer, poly [2‐(2‐ethoxy)ethoxyethyl vinyl ether], poly(EOEOVE). The cloud‐point curve obtained was very flat except in a dilute region, that is the cloud‐point temperature was insensitive to the polymer concentration, resembling the cloud‐point curve for aqueous solutions of poly(N‐isopropylacrylamide). On the other hand, the binodal curve obtained was parabolic, and located within the two‐phase region of the cloud‐point curve. Accompanied with the phase separation, a sharp endothermic peak was observed in a region including the cloud‐point and binodal temperatures. The reciprocal of the osmotic compressibility ?Π/?c obtained by sedimentation equilibrium indicated that water changes from a good to poor solvent for poly(EOEOVE) with increasing temperature. Analyzing the ?Π/?c data by a thermodynamic perturbation theory, we determined the interchain interaction parameters, the hard‐core diameter d and the depth ε of the square‐well potential. Theoretical binodal and endothermic curves calculated by the perturbation theory using the estimated interaction parameters reproduced experimental ones semiquantitatively, but the theoretical binodal disagreed with the experimental flat cloud‐point curve. The disagreement at high concentrations was in the opposite direction to that expected from the sample polydispersity in the molecular weight. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 2937–2949, 2005