Sodium chloride ion pair formation in aqueous methanol and aqueous dimethyl sulfoxide

Silber, Herbert B.

doi:10.1016/0022-1902(77)80415-6

Cited by 6 publications

(2 citation statements)

References 11 publications

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“…As a result, the ionic association in DMSO becomes stronger than that in water. 36,37 It should be noted that the association of Li + and Na + with alkoxide anions in pure DMSO is extremely strong: equilibrium constants for the association of tert-butoxides of these cations equal 10 8 and 10 6 M -1 , respectively. 37 By analogy, one should expect also a very strong association of these cations with highly basic hydroxide anions.…”

Section: Bnpp -+ Ohmentioning

confidence: 99%

Solvent Effects and Alkali Metal Ion Catalysis in Phosphodiester Hydrolysis

et al. 2006

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The kinetics of the alkaline hydrolysis of bis(p-nitrophenyl) phosphate (BNPP) have been studied in aqueous DMSO, dioxane, and MeCN. In all solvent mixtures the reaction rate steadily decreases to half of its value in pure water in the range of 0-70 vol % of organic cosolvent and sharply increases in mixtures with lower water content. Correlations based on different scales of solvent empirical parameters failed to describe the solvent effect in this system, but it can be satisfactorily treated in terms of a simplified stepwise solvent-exchange model. Alkali metal ions catalyze the BNPP hydrolysis but do not affect the rate of hydrolysis of neutral phosphotriester p-nitrophenyl diphenyl phosphate in DMSO-rich mixtures. The catalytic activity decreases in the order Li+ > Na+ > K+ > Rb+ > Cs+. For all cations except Na+, the reaction rate is first-order in metal ion. With Na+, both first- and second-order kinetics in metal ions are observed. Binding constants of cations to the dianionic transition state of BNPP alkaline hydrolysis are of the same order of magnitude and show a similar trend as their binding constants to p-nitrophenyl phosphate dianion employed as a transition-state model. The appearance of alkali metal ion catalysis in a medium, which solvates metal ions stronger than water, is attributed to the increased affinity of cations to dianions, which undergo a strong destabilization in the presence of an aprotic dipolar cosolvent.

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Section: Bnpp -+ Ohmentioning

confidence: 99%

Solvent Effects and Alkali Metal Ion Catalysis in Phosphodiester Hydrolysis

et al. 2006

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“…Recent measurements on aqueous methanol have established the existence of a small maximum in sound absorption with water mole fraction.18,24 However, the addition of a nonassociating salt such as NaCI does not significantly alter the shape of the solvent absorption with water mole fraction curve. 18 The only significant difference between the aqueous methanol solutions with and without NaCI is a small increase in a/f below Xh2o = 0.65, explained in terms of the formation of small concentrations of outer-sphere complex. No strong salt-solvent interactions could be detected at any solvent composition for 0.200 M NaCI solutions.…”

Section: Discussionmentioning

confidence: 99%

An ultrasonic absorption investigation of lanthanide chloride complexation in aqueous methanol

Silber¹,

Bouler²,

White³

1978

J. Phys. Chem.

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Publication costs assisted by the Robert A. Welch Foundation and the Petroleum Research Fund Ultrasonic absorption measurements on 0.200 M solutions of NdCl3 and GdCl3 as a function of water mole fraction in aqueous methanol solutions indicate that the complexation reactions are coupled to a solvation number change as the solvent composition varies, which results in a complex of different coordination number. This change does not occur in ErCls solutions, indicating that lanthanide solvation changes are predominantly steric in nature. The Complex formation rate constants, kSi, are determined to be 4.5 X 108 s"1 for NdCl2+ and 2.4 X 107 s'1 for GdCl2+.

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Solvent Effects on Erbium Chloride Complexation Reactions

Silber

1980

The Rare Earths in Modern Science and Technology

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Sodium chloride ion pair formation in aqueous methanol and aqueous dimethyl sulfoxide

Cited by 6 publications

References 11 publications

Solvent Effects and Alkali Metal Ion Catalysis in Phosphodiester Hydrolysis

Solvent Effects and Alkali Metal Ion Catalysis in Phosphodiester Hydrolysis

An ultrasonic absorption investigation of lanthanide chloride complexation in aqueous methanol

Solvent Effects on Erbium Chloride Complexation Reactions

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