Ion association of caesium chloride solutions and its effect upon the interionic frictional coefficients of an irreversible thermodynamic analysis

Paterson, Russell; Jalota, S. K.; Dunsmore, H. S.

doi:10.1039/j19710002116

Cited by 16 publications

(12 citation statements)

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“…In the conductance results, the salts do become more dissociated as ion sizes increase; however, the opposing desolvation effect seen in pairs of large ions is less pronounced. This could be partly do to the somewhat arbitrary convention used in choosing what separation distance tolerance ( r max ) defines an ion pair in the conductance data analysis 78–80, 90. It has been shown that the resulting K A values are not independent of the choice of r max in experiments at standard temperature and pressure 61, 91.…”

Section: Resultsmentioning

confidence: 99%

Ion Pairing in Molecular Simulations of Aqueous Alkali Halide Solutions

et al. 2009

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Using classical molecular dynamics simulations, we study ion-ion interactions in water. We study the potentials of mean force (PMF) for the full set of alkali halide ion pairs, and in each case, we test different parameter sets for modeling both the water and the ions. Altogether, we compared 300 different PMFs. We also calculate association equilibrium constants (K A ) and compare them to two types of experiments. Of additional interest here was the proposition of Collins called the 'law of matching water affinities', where the relative affinity of ions in solution depends on the matching of cation and anion sizes. From observations on the relative depths of the free energies of the contact ion pair (CIP) and the solvent-shared ion pair (SIP), along with related solvent structure analyses, we find a good correlation with this proposition: small-small and large-large should associate in water and small-large should be more dissociated.

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Section: Resultsmentioning

confidence: 99%

Ion Pairing in Molecular Simulations of Aqueous Alkali Halide Solutions

et al. 2009

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“…On the basis of their conductivity measurements, Paterson et al . derived a K A value of 0.49 for CsCl(aq). The numerical values of such small association constants are highly dependent on the accuracy of the data and the type of conductance equation adopted for the analysis.…”

Section: Resultsmentioning

confidence: 99%

“…All that can be said confidently about the present data is that there is evidence for weak ion pairing in CsCl(aq) but there is insufficient reliable information to determine its strength or type. In this context, the association constant determined from the high-precision conductivity analyses 41,47 should be regarded as more meaningful than the present estimates.…”

Section: Possible Ion Pairing In Cscl(aq)mentioning

confidence: 90%

Dielectric Spectroscopy of Aqueous Solutions of KCl and CsCl

2003

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Results of a dielectric relaxation study of the aqueous solutions of KCl and CsCl at 25 °C are reported using measurements with a vector network analyzer (0.2 ≤ ν/GHz ≤ 20) and with waveguide interferometers (27 ≤ ν/GHz ≤ 89). Similar to previously reported data for NaCl, the spectra of both salts are well fitted by a Cole−Cole equation, although a double-Debye model is competitive at intermediate CsCl concentrations. The impact of the solute on the water structure, reflected in a decrease in the bulk-water relaxation time with rising electrolyte concentration, decreases in the sequence NaCl > KCl > CsCl and appears to be proportional to the surface-charge density of the cation. The interactions of K+ and Cs+ with their hydration shells are too weak to cause irrotational bonding of H2O molecules. It is argued that CsCl exhibits weak ion pairing, although the data are not sufficiently accurate to determine the extent of association and the nature of the ion pair formed.

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“…1 S m -1 . Throughout this study, therefore, data from a variety of literature sources have been used to match the conductivities of CsCl calibration solutions , with those of LiNO 3 , NaNO 3 , KNO 3 , CsNO 3 , KBr, KCl and KI electrolyte systems. − …”

Section: Methodsmentioning

confidence: 99%

The Binding of Monovalent Electrolyte Ions on α-Alumina. I. Electroacoustic Studies at High Electrolyte Concentrations

1999

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An electroacoustic technique has been used to monitor the binding of various monovalent inorganic ions on α-alumina at different pHs, nondilute solids, and moderate to high (0.01−1.0 mol dm-3) electrolyte concentrations. The ζ potential versus pH data show that NaNO3, KNO3, CsNO3, KBr, KCl, and KI are indifferent electrolytes for the α-alumina surface. However, LiNO3 causes a significant change in the isoelectric point of α-alumina, indicating that Li+ adsorbs in a specific manner to the surface over the range of concentrations investigated. At high (1.0 mol dm-3) electrolyte concentrations, the monovalent cations bind to the negative α-alumina surface in the order Li+ > Na+ > K+ ≈ Cs+. By contrast, the Br-, Cl-, I-, and NO3 - anions adsorb to an almost identical extent over the entire range of concentrations and pH conditions investigated. The cation binding sequence is consistent with the water “structure making−structure breaking” model first proposed by Gierst et al. and Bérubé and de Bruyn, which is based on the hydration enthalpies of the ions and the heat of immersion of the colloidal substrate. The comparable anion adsorption behavior is believed to arise because of the similar and/or low hydration enthalpies of the anions, which lead to a similar anion−surface interaction in each case.

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Ion association of caesium chloride solutions and its effect upon the interionic frictional coefficients of an irreversible thermodynamic analysis

Cited by 16 publications

References 0 publications

Ion Pairing in Molecular Simulations of Aqueous Alkali Halide Solutions

Ion Pairing in Molecular Simulations of Aqueous Alkali Halide Solutions

Dielectric Spectroscopy of Aqueous Solutions of KCl and CsCl

The Binding of Monovalent Electrolyte Ions on α-Alumina. I. Electroacoustic Studies at High Electrolyte Concentrations

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