Alkali metal species in liquid amines, ammonia, and ethers. Formation by pulse radiolysis

Journal Article · Thu Dec 18 04:00:00 EST 1975 · J. Phys. Chem., v. 79, no. 26, pp. 3055-3064

DOI:https://doi.org/10.1021/j100593a054· OSTI ID:4096877

Fletcher, J W; Seddon, W A

Pulsed electron radiolysis of solutions of alkali metal cations in methylamine, ethylamine, liquid ammonia, tetrahydrofuran, and diethyl ether demonstrates the formation of solvated electrons, e/sub s//sup -/, ion pairs (M$sup +$, e/sub s//sup -/), and alkali metal anions M$sup -$. Previous work is correlated and kinetic evidence presented for the formation of a triple ion intermediate (Na$sub 2$$sup 2+$, e/sub s//sup -/) in the formation of Na$sup -$ in methylamine. Studies on the formation of Na$sup -$ in metal--ethylamine or-- methylamine solutions containing trace amounts of Na$sup +$ show a marked difference in the rate depending on the metal in excess. Evidence is presented which suggests the formation of a complex with sodium in Li, Mg, or Ca solutions, whereas in K, Cs, or Rb solutions, the reaction proceeds via the corresponding K$sup -$, Cs$sup -$, or Rb$sup -$ species. The spectrum of (Na$sup +$, e sub s// sup -/) was investigated in binary mixtures of THF--ethylamine and ethylamine-- ammonia. In each case, a single absorption was observed; it showed a shift in the band maximum to a wavelength intermediate to that obtained in pure solvents. The effects of ammonia on the formation of, and equilibrium between, (M$sup -$, e/ sub s//sup -/) and M$sup -$ in ethylamine are also discussed. (auth)

• Research Organization: Atomic Energy of Canada, Chalk River, Ont.
• NSA Number: NSA-33-019715
• OSTI ID: 4096877
• Journal Information: J. Phys. Chem., v. 79, no. 26, pp. 3055-3064, Journal Name: J. Phys. Chem., v. 79, no. 26, pp. 3055-3064; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

*AMINES-- RADIOLYSIS
*AMMONIA-- RADIOLYSIS
*ETHERS-- RADIOLYSIS
*FURANS-- RADIOLYSIS
*SODIUM COMPOUNDS-- RADIOLYSIS
400600* --Chemistry--Radiation Chemistry
ANIONS
CALCIUM COMPLEXES
CATIONS
CESIUM COMPOUNDS
ELECTRON BEAMS
LITHIUM COMPLEXES
MAGNESIUM COMPLEXES
N40300* --Chemistry--Radiation Chemistry
POTASSIUM COMPOUNDS
PULSED IRRADIATION
RUBIDIUM COMPOUNDS
SOLVATED ELECTRONS