Ionic aggregates of 1-1 salts in non-aqueous solutions: Structure, thermodynamics and solvation

Chabanel, Martial

doi:10.1351/pac199062010035

Cited by 50 publications

(37 citation statements)

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“…The relatively low level of dissociation is quite surprising, taking into account the strength of the acid and the behaviour of DMF as a dissociating solvent in terms of both its donating power and dielectric constant. 24,25 However, as we have reported previously, 8 lithium triflate (another typical strong electrolyte) is strongly associated in DMF solutions and Burdin et al 9 could find no evidence for HCl dissociation in HCl/DMF solutions.…”

Section: Benzenesulfonic Acidmentioning

confidence: 60%

Hydrogen bonding in benzenesulfonic and 4‐toluenesulfonic acids dissolved in N,N′‐dimethylformamide: an FT‐Raman study

Alía

Edwards

Kiernan

2004

J Raman Spectroscopy

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Solutions of benzenesulfonic acid (BSA) and monohydrated 4-toluenesulfonic acid (PTSA) in dimethylformamide (DMF) were studied by FT-Raman spectroscopy in the concentration range 1.0-5.0 mol dm −3 . Spectra in the region of the acid S -OH and benzenesulfonate anion SO 3 − stretching bands were analysed using band-fitting procedures in order to ascertain the degree of acid dissociation. In BSA solutions, this parameter changes from 0.34 (1.02 M solution) to 0.11 (5.01 M solution) despite the strong character of the acid. Interaction of DMF with undissociated BSA produces a new band in the n(C -N -C ) Raman spectral region near 866 cm −1 , displaced −11.0 cm −1 and assigned to DMF molecules hydrogen-bonded to BSA. In PTSA solutions, hydrogen bonds are formed with the oxonium ion (H 3 O + ) dissociated from the acid. In this case, the displacement observed is only −7.0 cm −1 , indicating a weaker interaction. From the concentration of hydrogen-bonded DMF, the mean number of hydrogen-bonds participating in bonding with each solvent molecule can be calculated. This number changes, in BSA solutions, from ca. 0.5 in the less concentrated solutions up to ca. 1.0 in the most concentrated. This result supports the conclusion that BSA-DMF complexes of fixed stoichiometry are not present in the range of concentrations studied here. On the contrary, the oxonium ions form a stable complex of stoichiometry (DMF) 2 ·H 3 O + which does not change with the acid concentration.

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Section: Benzenesulfonic Acidmentioning

confidence: 60%

Hydrogen bonding in benzenesulfonic and 4‐toluenesulfonic acids dissolved in N,N′‐dimethylformamide: an FT‐Raman study

Alía

Edwards

Kiernan

2004

J Raman Spectroscopy

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“…In aprotic solvents such as tetrahydrofuran, diethyl ether, pyridine, and diethyl carbonate, the salts LiNCS and LiBr form ion pairs that can agglomerate (8,9). For example, the following species have been detected by various spectroscopic methods (8,9): The trimer (LiNCS)3,s was not detected.…”

Section: Comparison Of Molar Conductivities Of Salts In Tert-butanolmentioning

confidence: 99%

“…For example, the following species have been detected by various spectroscopic methods (8,9): The trimer (LiNCS)3,s was not detected. The tetramer has a cubane-like structure.…”

Section: Comparison Of Molar Conductivities Of Salts In Tert-butanolmentioning

confidence: 99%

“…The species LiNCS is strongly polar, but the dimer and tetramer are nonpolar. The pairing and agglomeration reactions are entropy driven; each step involves partial desolvation of the species (9).…”

Section: Comparison Of Molar Conductivities Of Salts In Tert-butanolmentioning

confidence: 99%

“…We suspect that the planar NO3-ions are not well solvated by the globular tert-butanol molecules, and that this makes the nitrate salts susceptible to ion clustering, or aggregation of ion pairs as in aprotic solvents (9). However, for the analysis of reaction rate constants (7) we need values of Ao.…”

Section: Comparison Of Molar Conductivities Of Salts In Tert-butanolmentioning

confidence: 99%

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

Zhao¹,

Freeman²

1995

Can. J. Chem.

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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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Deprotonative Metalation Using Alkali Metal–Nonalkali Metal Combinations

et al. 2015

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Ionic aggregates of 1-1 salts in non-aqueous solutions: Structure, thermodynamics and solvation

Abstract: Abstract

Cited by 50 publications

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Hydrogen bonding in benzenesulfonic and 4‐toluenesulfonic acids dissolved in N,N′‐dimethylformamide: an FT‐Raman study

Hydrogen bonding in benzenesulfonic and 4‐toluenesulfonic acids dissolved in N,N′‐dimethylformamide: an FT‐Raman study

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

Deprotonative Metalation Using Alkali Metal–Nonalkali Metal Combinations

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Ionic aggregates of 1-1 salts in non-aqueous solutions: Structure, thermodynamics and solvation

Abstract: Abstract

Cited by 50 publications

References 0 publications

Hydrogen bonding in benzenesulfonic and 4‐toluenesulfonic acids dissolved in N,N′‐dimethylformamide: an FT‐Raman study

Hydrogen bonding in benzenesulfonic and 4‐toluenesulfonic acids dissolved in N,N′‐dimethylformamide: an FT‐Raman study

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

Deprotonative Metalation Using Alkali Metal–Nonalkali Metal Combinations

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Product

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