Transients and specific rates of some reactions of the solvated electron with inorganic ions in liquid ammonia investigated by nanosecond pulse radiolysis at 23/sup 0/C

Journal Article · Thu Nov 18 04:00:00 EST 1976 · J. Phys. Chem.; (United States)

OSTI ID:7334340

Cordier, F; Cordier, P

For ammoniacal solutions at 23/sup 0/C, the absorption spectrum of CuCl and the transient absorption spectra of Ni/sup +/, Zn/sup +/, Cd/sup +/, Hg, Tl, and Pb/sup +/ are given. For the solvent liquid ammonia at 23/sup 0/C and in units of M/sup -1/ s/sup -1/, the measured specific rates of reactions of e/sup -//sub am/ with inorganic solutes follow in parentheses after each solute: Cu/sup +/ (2.5 x 10/sup 8/), Hg/sup +/ (2.3 x 10/sup 11/), Tl/sup +/ (1.2 x 10/sup 12/), Fe/sup 2 +/ (1.2 x 10/sup 9/ at zero ionic strength), Co/sup 2 +/ (5.7 x 10/sup 11/), Ni/sup 2 +/ (1.1 x 10/sup 11/), Cu/sup 2 +/ (8.3 x 10/sup 11/), Zn/sup 2 +/ (1.3 x 10/sup 10/), Cd/sup 2 +/ (4.6 x 10/sup 11/), Hg/sup 2 +/ (3.2 x 10/sup 11/), Pb/sup 2 +/ (5.6 x 10/sup 11/), Al/sup 3 +/ (less than 6 x 10/sup 6/), Cr/sup 3 +/ (5.8 x 10/sup 10/), Fe/sup 3 +/ (4.9 x 10/sup 11/ at zero ionic strength), Co/sup 3 +/ (7.7 x 10/sup 11/), Ce/sup 3 +/ (3.1 x 10/sup 11/), Ce/sup 4 +/ (1.5 x 10/sup 11/), No/sub 3//sup -/ (1.2 x 10/sup 8/ at zero ionic strength), ClO/sub 4//sup -/ (no reaction), I/sup -/ (no reaction). Only the reaction of e/sub am//sup -/ with Tl/sup +/ appears to be a diffusion-controlled reaction. For the solvent liquid ammonia at 25/sup 0/C, the standard free energy changes for the reactions of e/sub am//sup -/ with metal cations mentioned above have been computed. The activation-controlled specific rate increases and attains a plateau value with the increasing negative free energy of the reaction. This relationship is consistent with a quantum mechanical description of an exothermic electron transfer reaction, in which the theory is formulated by treating the reaction as the nonradiative decay of a ''supermolecule'' consisting of the electron donor, the electron acceptor, and the polar solvent.

• Research Organization: Univ. of Notre Dame, IN
• OSTI ID: 7334340
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 80:24; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400104 -- Spectral Procedures-- (-1987)
400600* -- Radiation Chemistry
ABSORPTION SPECTRA
ALKALI METALS
ALUMINIUM
AMMONIA
CADMIUM
CERIUM
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
CHROMIUM
COBALT
COPPER
DECOMPOSITION
ELECTRONS
ELEMENTARY PARTICLES
ELEMENTS
FERMIONS
HYDRIDES
HYDROGEN COMPOUNDS
INTERMEDIATE STRUCTURE
IRON
IRRADIATION
KINETICS
LEAD
LEPTONS
MEDIUM TEMPERATURE
MERCURY
METALS
NICKEL
NITROGEN COMPOUNDS
NITROGEN HYDRIDES
PHYSICAL PROPERTIES
POTASSIUM
PULSED IRRADIATION
RADIATION CHEMISTRY
RADIATION EFFECTS
RADIOLYSIS
RARE EARTHS
REACTION KINETICS
SODIUM
SOLVATED ELECTRONS
SOLVENT PROPERTIES
SPECTRA
THALLIUM
THERMODYNAMIC PROPERTIES
TRANSITION ELEMENTS
ZINC