Bolaform Electrolytes. IV. Conductance of α,ι-Bispyridinium Polymethylene Bromides and β,β'-Bisquaternary Substituted Diethyl Ethers in Methanol

Nichol, James C.; Fuoss, Raymond M.

doi:10.1021/ja01606a075

Cited by 8 publications

(6 citation statements)

References 2 publications

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“…The ionic association and the reaction of the ions with the solvent in water-ethanol mixtures were investigated for N-ethyl-4-cyanopyridinium iodide [46] as a function of the concentration of the dissolved salt, and the data were analyzed with regard to the existence of solvent-separated ion pairs. The temperature variations of the association constants were established.…”

Section: Salts Containing Aromatic Cations (Without Heteroatoms In Thmentioning

confidence: 99%

“…In [46] the dependence of the limiting solubility and the dissociation constants of bolaform electrolytes (a type of electrolyte in which the charges are separated by the chain of atoms in a polyion) was discussed: 1,2-ethane-, 1,4-butane-, and 1,10-decane-N,N′-bispyridinium dibromides, and also the diethyl ether of bis-β-pyridinium dichloride.…”

Section: Salts Containing Aromatic Cations (Without Heteroatoms In Thmentioning

confidence: 99%

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Structure and characteristics of the ionic forms of heteroarenium salts in organic solvents (review)

Shvaika

Kovach

2009

Chem Heterocycl Comp

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The results of investigations into the formation of the various ionic forms of heteroarenium salts, their characteristics, and their reactivity are summarized. Salts containing (4n+2)π-electron aromatic cations (n = 0-3), including chalcogenopyrylium (O, S, Se), azinium, benzo-and dibenzoazinium, and chalcogenoazolium (O, S, Se, NR) ions are examined. In this system of compounds the relationships between the structure and the macroscopic characteristics of the heteroarenium salts (ionization constants, association/dissociation constants, distances of closest interionic approach) and the effect of the nature of the ionic forms in the solutions on their reactivity in heterolytic reactions are analyzed.Salt forms and in particular heteroarenium salts occupy an extremely important position in the chemistry of heterocyclic compounds, being of interest both in structural respects and in their high reactivity in nucleophilic reactions, recyclization reactions [1-3], and more recently at the applied level as ionic liquids [4]. It is on the basis of heteroarenium salts that the modern chemistry of stable carbenes -the organic chemistry of the divalent carbon atom -has developed [5][6][7][8][9].In spite of numerous investigations into the structure of the salts, carried out by various physicochemical methods (spectral, polarographic, X-ray crystallographic, etc.) direct information about their properties as salts, i.e., their capacity for dissociation/association and the formation of various ionic forms (free ions, various ionic associates -ion pairs and ion triplets), has remained almost in the dark. Among the characteristics directly describing the state of heteroarenium salts in solutions the most important are clearly the thermodynamic characteristics (which can be regarded as macroscopic in contrast to the microscopic characteristics relating, for example, to the spectral characteristics) -the ionic association (K a )/dissociation (K d ) constants, the distance of closest approach of the ions, and theories about the dependence of these quantities on the structure of the salts. Information on the ionic association of heteroarenium salts is of considerable interest for assessing their reactivity. It is also important for understanding the processes that give rise to the effectiveness of organic electrolytes containing heteroaromatic cations in physical systems (e.g., as luminophores [10]).

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Section: Salts Containing Aromatic Cations (Without Heteroatoms In Thmentioning

confidence: 99%

Section: Salts Containing Aromatic Cations (Without Heteroatoms In Thmentioning

confidence: 99%

Structure and characteristics of the ionic forms of heteroarenium salts in organic solvents (review)

Shvaika

Kovach

2009

Chem Heterocycl Comp

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“…Often the form of the frequency dispersion was not f-1/2. Nichol and Fuoss (43) observed ]-1 frequency dependence in methanol solutions, while De Nooijer (44) reported that in molten nitrate melts plots of measured resistance vs. 1-1/2 were not linear, but approached linearity as the frequency approached infinity. His values of measured resistance at 20 kHz only differed from values extrapolated to infinite frequency by about 0.1%.…”

Section: Frequency Response--as Seen In Tablementioning

confidence: 99%

“…Rm: Rs +Rz [5] Frequency dispersion of the measured resistance has been observed in organic solvents (43) and in molten salts. Often the form of the frequency dispersion was not f-1/2.…”

Section: Frequency Response--as Seen In Tablementioning

confidence: 99%

Measurement of Electrical Conductivity in Molten Fluorides. A Survey

Robbins¹

1969

J. Electrochem. Soc.

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“…With a conductance cell that Is not. a pure series RC combination, some frequency dependence of measured or calculated Rs still may be observed, and extrapolation to infinite frequency as a function of w or a more appropriate empirical function of frequency still may be required (15,24) This extrapolation should not, however be based on an incorrect equivalent circuit of the cell. The fact that one does not know the exact equivalent circuit of the cell does not eliminate the necessity of a choice if a resistance is to be calculated from the measurable impedance and phase angle, and the series RC combination is the best approximation in many cases.…”

Section: Balance Of Pure Resistancesmentioning

confidence: 99%

Electrolytic conductance measurements and capacitive balance

Braunstein¹,

Robbing²

1971

J. Chem. Educ.

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Paper No. 110. 1 The term ionic constituent refers to the ion-forming portion of an electrolyte, without specification of the extent of dissociation, association, solvation, etc. See, e.g., reference (4), p. 60. Thus the ionic constituents in an aqueous solution of CdR are Cd! + and I-, regardless of the fact that, the actual species in solution may include hydrated cadmium ions, anionic complexes such as Cdl4!_, etc. Measurements of macroscopic properties yield information only on the components (Cdl-j and water) or the ionic constituents. Unusual values of these properties may suggest the microscopic nature of the species (e.g., ions). More detailed information on the nature of the species requires measurements sensitive to the species properties and distribution (e.g., spectra).Alternative methods of conductance measurement are pointed out, as are some aspects pertinent to the measurement of dielectric constant. The extent of coverage can easily be modified to suit the level of the course and the time available.Phenomenology: Ohm's Law Applied to Electrolytes rent occurs whether the system be liquid, solid, or gaseous, single component or multicomponent. (See reference (47)).

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Bolaform Electrolytes. IV. Conductance of α,ι-Bispyridinium Polymethylene Bromides and β,β'-Bisquaternary Substituted Diethyl Ethers in Methanol

Cited by 8 publications

References 2 publications

Structure and characteristics of the ionic forms of heteroarenium salts in organic solvents (review)

Structure and characteristics of the ionic forms of heteroarenium salts in organic solvents (review)

Measurement of Electrical Conductivity in Molten Fluorides. A Survey

Electrolytic conductance measurements and capacitive balance

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