Thermodynamics of the salting effect; free energies, enthalpies, entropies, heat capacities, and volumes of the ternary systems electrolyte–alcohol–water at 25 °C

Abstract

MOREL. Can. J. Chem. 56,552 (1978). The thermodynamic pair interaction parameters of the ternary systems electrolyte (alkali halides and tetraalkylammonium bromides) -nonelectrolyte (12-alcohols and rerr-butylalcohol) -water were measured at 25°C through enthalpies of solution, of mixing and of dilution, densities and heat capacities per unit volume. Some freezing point and electromotive force data were also combined with previously published data to obtain free energies. From these pair parameters the complete thermodynamics of the salting in and salting out of alcohols can be derived and were used to test various theoretical approaches. Most results are consistent with the cosphere overlap structural model, and the various trends can also be correlated through the scaledparticle theory. Chem. 56,552 (1978).Des mesures, effectutes a 2S°C, d'enthalpie de dissolution, de melange et de dilution, de densitt et de capacite calorifique permettent le calcul des parametres thermodynamiques d'interaction par paire dans les systttmes ternaires: electrolyte (halogenures alcalins, bromure de tetraalkylamnionium) -non-tlectrolyte (alcools norniaux et alcool fert-butylique) -eau. Certaines Inesures d'abaissement du point de fusion et de force electroniotrice conduisent, en utilisant des rtsultats deja publits, aux valeurs des enthalpies libres. Des parametres d'interaction par paire, on peut deduire la thermodynamique coniplete du relargage des alcools et verifier diverses theories. Les rtsultats proposes sont en accord avec ceux prtvus par le modele structural de recouvrenient des cospheres d'hydratation. L'allure des variations des differentes grandeurs peut aussi itre prtdite par la thtorie des particules calibrees (scaled particle).

Salting-out of triethylphosphate by inorganic electrolytes

“…The salting coefficient for KBr was calculated from those of KCl, NH4Cl, and NH4Br, assuming additivity. Also shown are results of Perron et al (17) for t-butanol solutions at 25OC. For t-butanol, salting-out is less efficient for the larger cations, but for TEP, salting-out by these larger cations remains higher than for sodium ions.…”

Interactions between cations and sugars. II. Enthalpies, heat capacities, and volumes of aqueous solutions of Ca2+–D-ribose and Ca2+–D-arabinose at 25 °C

“…It is possible to evaluate these parameters through the determination of transfer functions. We shall only give here the relations which are necessary to the understanding of the present work; the details of the theoretical analysis have been given in a previous paper (13) and in the references cited therein. In these expressions, we shall designate the components of the ternary system water-nonelectrolyte-electrolyte Can.…”

“…Studies of this kind have already been performed on various solutes involving either nonelectrolyte-nonelectrolyte or electrolyte-nonelectrolyte pairs. Our previous work regarding the interactions between electrolytes and alcohols (13) in aqueous solutions will serve as a basis for the method and the formalism used in the present paper. We shall determine enthalpies of solution, volumes, and heat capacities which give access to the corresponding sugar-electrolyte (SE) pair interaction parameters hsE , U S E , C S E .…”

Dissolution enthalpy of NaI in water–alcohol mixtures at 288.15 and 308.15 K. Enthalpy of interaction in electrolyte–alcohol–water systems

“…For the sake of con~parison CEN values for NaC1-alcohol pairs in water adopted from Perron et al (20) are also included. As can be seen from the results above, the CEN coefficients for the investigated electrolyte-alcohol pairs in water have negative values.…”