Ionic association in low-dielectric media. II. Electrical conductance of nitrate salts in tetrahydrofuran. Conductance equation for quadrupole formation

1973 ◽  
Vol 95 (16) ◽  
pp. 5119-5121 ◽  
Author(s):  
Hsien-Chang. Wang ◽  
Paul. Hemmes
Keyword(s):  
Electrical Conductance ◽  
Ionic Association ◽  
Low Dielectric ◽  
Dielectric Media ◽  
Nitrate Salts

Importance of Polarization for Dipolar Solutes in Low-Dielectric Media: 1,2-Dichloroethane and Water in Cyclohexane

1995 ◽  
Vol 117 (47) ◽  
pp. 11809-11810 ◽  
Author(s):  
William L. Jorgensen ◽  
Nora A. McDonald ◽  
Massimo Selmi ◽  
Paul R. Rablen
Keyword(s):  
Low Dielectric ◽  
Dielectric Media

Corresponding states for electrolyte solutions

2001 ◽  
Vol 73 (11) ◽  
pp. 1733-1748 ◽  
Author(s):  
Hermann Weingärtner
Keyword(s):  
Dielectric Constant ◽  
Electrical Conductance ◽  
Electrolyte Solutions ◽  
Corresponding States ◽  
Phase Separations ◽  
Ion Clusters ◽  
Low Dielectric ◽  
Singly Charged ◽  
Charged Ions ◽  
Fused Salt

The equilibrium properties of electrolyte solutions over wide ranges of concentration, temperature, and solvent dielectric constant are discussed on a corresponding-states basis. If low-melting salts are used, these properties can be studied up to the pure fused salt. We mainly focus on systems at low reduced temperature, where the depth of the interaction potential is large compared with the thermal energy. Examples are singly charged ions in solvents of low dielectric constant and of highly charged ions in water. The state of the ions is discussed on the basis of thermodynamic, electrical conductance and dielectric constant data. Special attention is given to the transition to the fused salt, where ion clusters have to redissociate to form the dissociated structure of the salt. This transition can lead to liquid­liquid phase separations. The resulting critical points serve as important targets for testing theories. Examples are given for large deviations from corresponding-states behavior caused by specific short-range interactions.

Unusual behavior of the conductivity of LiNO3 in tert-butanol: ion clustering or ion-pair aggregation

1995 ◽  
Vol 73 (12) ◽  
pp. 2131-2136 ◽  
Author(s):  
Yixing Zhao ◽  
Gordon R. Freeman
Keyword(s):  
Pure Water ◽  
Mixed Solvents ◽  
Electrical Conductance ◽  
Ion Pair ◽  
Negative Ion ◽  
Lithium Nitrate ◽  
Measured Temperature ◽  
Kinetics Parameters ◽  
Tert Butanol ◽  
Nitrate Salts

The electrical conductance of LiNO3 in tert-butanol–water mixed solvents changes gradually from "normal" in pure water to "abnormal" in pure tert-butanol. In water the measured specific conductance increases with increase of temperature, and in tert-butanol the conductance decreases with increase of temperature. In pure tert-butanol, the electrical conductances of NH4ClO4 and LiClO4 increase with the salt concentration and temperature at lower temperatures, but decrease at higher temperatures. The molar conductivity Λ0(10−4 S m2 mol−1) in tert-butanol at 300 K is 5.0 for NH4ClO4 and 4.0 for LiClO4. Both activation energies EΛ0 are 17 kJ mol−1, which gives an unusual correlation between Λ0 and viscosity η(mPa s): [Formula: see text] The values of Λ0 for NH4NO3 and LiNO3 in tert-butanol could not be measured, because ion aggregation is significant even at the lowest concentrations required to obtain conductances sufficiently above that of the solvent. The measured temperature coefficient of LiNO3 conductance in tert-butanol is negative. Ion clustering of nitrate salts is attributed to poor solvation of the planar NO3− ions by the globular tert-butanol molecules. Ion aggregation in tert-butanol increases with increasing T, due to the relatively rapid decrease of the value of εT. Corrections are listed for reaction kinetics parameters for nitrate salts in pure tert-butanol solvent reported in Can. J. Chem. 73, 392 (1995). Keywords: tert-butanol, ion-pair aggregation, lithium nitrate, electrical conductance, solvent effects.

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