Pulse Radiolytic Formation of Solvated Electrons, Ion-pairs, and Alkali Metal Anions in Tetrahydrofuran

1974 ◽  
Vol 52 (18) ◽  
pp. 3259-3268 ◽  
Author(s):  
G. A. Salmon ◽  
W. A. Seddon ◽  
J. W. Fletcher
Keyword(s):  
Alkali Metal ◽  
Alkali Metals ◽  
Dissociation Constants ◽  
Alkali Metal Cation ◽  
Ion Pairs ◽  
Alkali Metal Cations ◽  
Solvated Electrons ◽  
Sodium Potassium ◽  
Sodium And Potassium ◽  
Metal Anions

Pulse radiolysis of solutions of alkali metal cations in tetrahydrofuran (THF) demonstrates the formation of solvated electrons es−, alkali metal cation-ion pairs (M+, es−), and alkali metal anions M−. This paper describes the spectra, extinction coefficients, and radiolytic yields of es−, lithium, sodium, potassium, and cesium species in THF. The reaction kinetics are complex but largely involve reactions A and B[Formula: see text]with the concomitant disappearance of all three species by reaction with radiolytically produced radicals. Rate constants and ion-pair dissociation constants for es− and the sodium and potassium species are presented and compared with data established from studies of blue solutions of alkali metals dissolved in THF.

Solution Properties of Tetraalkylammonium Halide and Alkali-Metal Halide Ion Pairs. The Relationship Between Dissociation Constants and Solubility Products

1987 ◽  
Vol 40 (7) ◽  
pp. 1201 ◽  
Author(s):  
W Mizerski ◽  
MK Kalinowski
Keyword(s):  
Alkali Metal ◽  
Solubility Product ◽  
Dissociation Constants ◽  
Ion Pairs ◽  
Empirical Relation ◽  
Alkali Metal Halide ◽  
Alkali Metal Cations ◽  
Solubility Products ◽  
The Relationship ◽  
Dissociation Constant Kd

An empirical relation describing the effect of solvent on the dissociation constant ( Kd ) of ion pairs is described. An equation of the form pKd = apKso + bD-1 + c ( Kso and D stand for the solubility product of a given salt and for the electric permittivity of a solvent, respectively) has been tested with 13 sets of experimental data for salts containing tetraalkylammonium and alkali-metal cations. A successful correlation was obtained in 100% of the cases considered.

Solvated electrons and the effect of coordination on the optical spectra of alkali metal cation – electron pairs in ethers

1977 ◽  
Vol 55 (19) ◽  
pp. 3356-3363 ◽  
Author(s):  
William Arthur Seddon ◽  
John Wallace Fletcher ◽  
Fred Charles Sopchyshyn ◽  
Ron Catterall
Keyword(s):  
Alkali Metal ◽  
Alkali Metal Cation ◽  
Ion Pairs ◽  
Alkali Metal Salts ◽  
Solvated Electrons ◽  
Electron Pairs ◽  
Monomeric Species ◽  
Spin Resonance ◽  
Resonance Data ◽  
Electron Spin Resonance Data

Pulse radiolysis of tetrahydrofuran (THF), dimethoxyethane (DME), diglyme (DG), and triglyme (TG), results in the formation of solvated electrons, es−, with optical band maxima λmax ≥ 1840 nm. In the presence of alkali metal salts transient optical bands are observed with λmax at ∼900 and ≥1600 nm. The latter bands are assigned to the formation of 'monomeric' species of stoichiometry M considered to be 'tight' and 'loose' ion-pairs, respectively. The proportion of 'loose' ion-pairs increases with decreasing temperature and increasing coordination of the solvent in the order [Formula: see text] These results demonstrate a good correlation with established electron spin resonance data in alkali metal solutions and substantiate the coexistence of at least two 'monomeric' species in DME and the glymes.

Pulse Radiolysis of Alkali Metal Solutions in Methylamine

1975 ◽  
Vol 53 (23) ◽  
pp. 3571-3579 ◽  
Author(s):  
John Wallace Fletcher ◽  
William Arthur Seddon ◽  
John Joseph Jevcak ◽  
Fred Charles Sopchyshyn
Keyword(s):  
Reaction Mechanism ◽  
Alkali Metal ◽  
Reaction Kinetics ◽  
Pulse Radiolysis ◽  
Ion Pairs ◽  
Solvated Electrons ◽  
Extinction Coefficients ◽  
Ion Species ◽  
Triple Ion ◽  
Metal Anions

Pulse radiolysis studies of solutions of alkali metal methylamides (CH3NHM) in methylamine indicate the formation of solvated electrons, es−, ion-pairs (M+, es−), and alkali metal anions M−. This paper compares the spectra, extinction coefficients, and yields of es−, Li, Na, K, and Cs species, with those observed previously in other solvents. The overall reaction kinetics are complex and, in CH3NHNa/NaI solutions, suggest the formation of a higher aggregate or triple ion species (Na22+, es−). A reaction mechanism, quantitatively consistent with experiment, is presented and discussed in detail for solutions containing Na+.

Association of radical anions with alkali metal cations; I. Modified π(PPP-like) method for the investigation of ion pairs

1980 ◽  
Vol 45 (2) ◽  
pp. 339-350 ◽  
Author(s):  
Stanislav Miertuš ◽  
Ondrej Kyseľ ◽  
Pavol Mach
Keyword(s):  
Alkali Metal ◽  
Alkali Metals ◽  
Ion Pairs ◽  
Metal Cations ◽  
Radical Anions ◽  
Alkali Metal Cations

A simple π-approximation (PPP-like) method was modified to enable study of the association of radical anions with alkali metals. The possible uses of the method are demonstrated by the calculations of the different properties of the pyrazine-Me (Me = Li, Na, Cs) system.

Axle component separated ion-pair recognition by a neutral heteroditopic [2]rotaxane

2014 ◽  
Vol 50 (13) ◽  
pp. 1540-1542 ◽  
Author(s):  
Richard C. Knighton ◽  
Paul D. Beer
Keyword(s):  
Alkali Metal ◽  
Metal Cation ◽  
Alkali Metal Cation ◽  
Ion Pairs ◽  
Ion Pair ◽  
Sodium Cation ◽  
Halide Anion ◽  
Cooperative Recognition

A neutral heteroditopic pyridine N-oxide axle containing [2]rotaxane, synthesised via sodium cation templation, displays cooperative recognition of alkali metal cation-halide anion ion-pairs in an unprecedented axle component separated ion-pair binding fashion.

Shaping the cavity of calix[4]arene using transition metals and binding alkali-metal cations inside the cavity: the relevance of the alkali-metal cation–arene interaction

1997 ◽  
pp. 183-184 ◽  
Author(s):  
Antonio Zanotti-Gerosa ◽  
Euro Solari ◽  
Luca Giannini ◽  
Carlo Floriani ◽  
Angiola Chiesi-Villa ◽  
...  
Keyword(s):  
Transition Metals ◽  
Alkali Metal ◽  
Metal Cation ◽  
Alkali Metal Cation ◽  
Metal Cations ◽  
Alkali Metal Cations

Reaction between alkali metal ferrocyanides and persulfates in aqueous solution

1967 ◽  
Vol 45 (20) ◽  
pp. 2411-2418 ◽  
Author(s):  
R. W. Chlebek ◽  
M. W. Lister
Keyword(s):  
Aqueous Solution ◽  
Alkali Metal ◽  
Rate Constants ◽  
Ion Pairs ◽  
Metal Cations ◽  
Activation Energies ◽  
Alkali Metal Cations ◽  
Potassium Salts ◽  
Apparent Activation Energies

The rates of the reaction of ferrocyanide and persulfate ions, in the presence of various concentrations of different alkali metal cations, have been measured at various temperatures and ionic strengths. The results are interpreted in terms of ion pairs and support the view that the actual reacting species are MFe(CN)6−3 and MS2O8−, where M is an alkali metal. This is similar to the situation found earlier for potassium salts of these ions. The rate constants obtained on this assumption increase gradually from lithium to cesium. Values are also obtained for the apparent activation energies of these reactions.

Ion pairs formed by alkali metals. Part 1.—Complexes of lithium, sodium and potassium with 4-nitropyridine

1975 ◽  
Vol 71 (0) ◽  
pp. 1829-1838 ◽  
Author(s):  
Pietro Cremaschi ◽  
Aldo Gamba ◽  
Gabriele Morosi ◽  
Cesare Oliva ◽  
Massimo Simonetta
Keyword(s):  
Alkali Metals ◽  
Ion Pairs ◽  
Sodium And Potassium

scholarly journals ESR Studies of the Ion-pairs of the Acenaphthylene Radical Anion and Alkali Metal Cations

1967 ◽  
Vol 40 (6) ◽  
pp. 1325-1332 ◽  
Author(s):  
Masamoto Iwaizumi ◽  
Masayasu Suzuki ◽  
Taro Isobe ◽  
Hiroshi Azumi
Keyword(s):  
Alkali Metal ◽  
Radical Anion ◽  
Ion Pairs ◽  
Metal Cations ◽  
Alkali Metal Cations
Sign in / Sign up

Export Citation Format

Share Document