Abstract:The equivalent conductance of magnesium sulfate was measured at 25.00°, 35.00°, and 45.00°C in pure water and in 20.1, 40.7, 60.2, and 80.1 w/o (weight per cent) ethanol. Viscosity, temperature, and dielectric effects are discussed. Activation energies are calculated for the conductance process. Also the observed data were compared to the theoretical requirements of the Onsager equation.
“…Experimental data were taken from Abraham and Abraham. , The lines were calculated using the model. 8 Specific conductivities of (a) the MgCl 2 + ethanol + H 2 O system at 45 °C 12,14,15 and (b) the MgSO 4 + ethanol + H 2 O system at 25 °C. , The lines were calculated using the model.…”
Section: Effective Ionic Radiimentioning
confidence: 99%
“…Specific conductivities of (a) the MgCl 2 + ethanol + H 2 O system at 45 °C 12,14,15 and (b) the MgSO 4 + ethanol + H 2 O system at 25 °C. , The lines were calculated using the model.…”
A comprehensive model has been developed for calculating electrical conductivities of aqueous
or mixed-solvent electrolyte systems ranging from dilute solutions to fused salts. The model
consists of a correlation for calculating ionic conductivities at infinite dilution as a function of
solvent composition and a method for predicting the effect of finite electrolyte concentration.
The effect of electrolyte concentration is calculated using an extended form of the mean-spherical-approximation (MSA) theory coupled with a mixing rule for predicting the conductivities of
multicomponent systems on the basis of the conductivities of constituent binary cation−anion
subsystems. The MSA theory has been extended to very concentrated and mixed-solvent systems
by introducing effective ionic radii that take into account various interactions between ions,
solvent molecules, and ion pairs. The model has been coupled with thermodynamic equilibrium
computations to provide the necessary concentrations of individual ions in complex, multicomponent systems. The model accurately reproduces experimental conductivity data over wide
ranges of composition with respect to both solvents and electrolytes. In particular, the model is
shown to be accurate for aqueous acids (e.g., H2SO4, HNO3, and H3PO4) up to the pure acid
limit, various nitrates ranging from dilute solutions to fused salts, salts in water + alcohol
mixtures, and LiPF6 solutions in propylene and diethyl carbonate.
“…Experimental data were taken from Abraham and Abraham. , The lines were calculated using the model. 8 Specific conductivities of (a) the MgCl 2 + ethanol + H 2 O system at 45 °C 12,14,15 and (b) the MgSO 4 + ethanol + H 2 O system at 25 °C. , The lines were calculated using the model.…”
Section: Effective Ionic Radiimentioning
confidence: 99%
“…Specific conductivities of (a) the MgCl 2 + ethanol + H 2 O system at 45 °C 12,14,15 and (b) the MgSO 4 + ethanol + H 2 O system at 25 °C. , The lines were calculated using the model.…”
A comprehensive model has been developed for calculating electrical conductivities of aqueous
or mixed-solvent electrolyte systems ranging from dilute solutions to fused salts. The model
consists of a correlation for calculating ionic conductivities at infinite dilution as a function of
solvent composition and a method for predicting the effect of finite electrolyte concentration.
The effect of electrolyte concentration is calculated using an extended form of the mean-spherical-approximation (MSA) theory coupled with a mixing rule for predicting the conductivities of
multicomponent systems on the basis of the conductivities of constituent binary cation−anion
subsystems. The MSA theory has been extended to very concentrated and mixed-solvent systems
by introducing effective ionic radii that take into account various interactions between ions,
solvent molecules, and ion pairs. The model has been coupled with thermodynamic equilibrium
computations to provide the necessary concentrations of individual ions in complex, multicomponent systems. The model accurately reproduces experimental conductivity data over wide
ranges of composition with respect to both solvents and electrolytes. In particular, the model is
shown to be accurate for aqueous acids (e.g., H2SO4, HNO3, and H3PO4) up to the pure acid
limit, various nitrates ranging from dilute solutions to fused salts, salts in water + alcohol
mixtures, and LiPF6 solutions in propylene and diethyl carbonate.
“…To test the significance of Lm and µ as important parameters in the conductance of concentrated solutions of electrolytes, the specific conductance of the bi-bivalent electrolyte, magnesium sulfate, was measured in the water-ethanol system at 25°, 35°, and 45°C. The equivalent conductances of dilute solutions of magnesium sulfate in water-ethanol solvents were reported in an earlier paper (2). EXPERIMENTAL All weights were previously standardized against NBS weights.…”
mentioning
confidence: 99%
“…The cell constant was also checked against two other cells of lower cell constants when measuring solutions of higher resistance. The cell constants of the cells used for intercomparison were 5.3886 and 1.0430 (2).…”
“…En fait, le comportement gtnCral des mClanges eau-HMPT est compatible avec le modble proposC par Franks et Ives (14) pour les mClanges eauCthanol et repris depuis par de nombreux auteurs pour d'autres mtlanges eau-solvant (15)(16)(17)(18)(19)(20). Aux fortes teneurs en eau, les interactions entre les molCcules d'eau se trouveraient renforctes par la prCsence du HMPT, les structures tCtraCdriques seraient stabilisies.…”
Section: Propribtbs Physiques Des Mblanges Eau-hmptunclassified
. On a mesure la conductibiliG klectrique de 19 electrolytes 1-1 MX (M = alcalin, ammonium quaternaire; X = halogenure perchlorate, nitrate) dans les melanges eau-hexamethylphosphotriamide B 25°C. A I'aide de I'hypoth6se de I'dquimobilit6 des ions dam Bu4NBPh4, on a d6duit les conductibilites individuelles pour 17 ions monovalents dans ces melanges. Aprks une critique des m6thodes traditionnellement utilisees, nous montrons que seule la theorie de Zwanzig permet, B partir de ces rksultats, d'aborder objectivement le probl6me des interactions ion-solvant. Cependant, cette theorie ne permet pas, dans 1'6tat actuel de son developpement, d'elucider la totalite des probl6mes puisque Zwanzig considkre le dkplacement de I'ion nu mais elle permet de bien distinguer, selon la mobilite d'un ion, la nature des interactions entre celui-ci et le solvant.
JEAN-YVES GAL, CHRISTINE LAVILLE, FRAN~OISE PERSIN, MICHEL PERSIN, JEAN-CLAUDE BOLLINGER, and TH~OPHILE YVERNAULT. Can. J. Chem. 57, 1127 (1979).The electrical conductibilities of 19 1-1 MX electrolytes (M = alkaline, quaternary ammonium; X = perchlorate, halide, nitrate) in water-hexamethylphosphotriamide mixtures at 25°C has been measured. The individual conductibilities of 17 monovalent ions in these mixtures were calculated using the hypothesis of ion equimobility in Bu4NBPh4. Following a critical review of the traditionally used methods, it has been shown that, from these results, Zwanzig's theory alone allows the objective assessment of ion-solvent interactions. However, this theory at its present state of development cannot be used to elucidate all the problems (because Zwanzig considers the displacement of the free ion) but it does distinguish the nature of the interactions between an ion and the solvent, depending on the mobility of that ion.
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