Pulse radiolysis of poly(styrenesulfonate) in aqueous solutions

Journal Article · Thu Sep 08 00:00:00 EDT 1988 · J. Phys. Chem.; (United States)

DOI:https://doi.org/10.1021/j100329a044· OSTI ID:6253671

Behar, D; Rabani, J

Various radical species have been identified in the pulse radiolysis of aqueous solutions of poly(styrenesulfonate) (PSS). OH radicals react with PSS (k = (7.5 /plus minus/ 1) /times/ 10/sup 8/ M/sup /minus/1/ s/sup /minus/1/) to produce predominantly a mixture of OH adducts. An intrapolymer biradical decay of the OH adducts (2k/epsilon = (3.0 /plus minus/ 1) /times/ 10/sup 5/ cm s/sup /minus/1/) takes place when several OH radical adducts are produced on the same polymer molecule. This decay reaction competes with a first-order formation of a positive radical ion (k = 160 /plus minus/ 40) s/sup /minus/1/ at pH 5.6. The formation reaction is acid catalyzed. It is slowed down by addition of inert salts. The positive radical ion decays in the time range of hours, obeying a first-order rate law (k = (5.4 /plus minus/ 0.5) /times/ 10/sup /minus/5/ s/sup /minus/1/). This decay is attributed to an intramolecular conversion of the positive radical ion to a benzyl type radical, which subsequently decays to produce stable recombination products. The spectra and kinetics are discussed in light of the known properties of various aromatic and polymer systems. Long-lived polymeric free radicals are useful models for photochemical storage systems.

• Research Organization: Hebrew Univ., Jerusalem (Israel)
• OSTI ID: 6253671
• Journal Information: J. Phys. Chem.; (United States), Journal Name: J. Phys. Chem.; (United States) Vol. 92:18; ISSN JPCHA
• Country of Publication: United States
• Language: English

Related Subjects

38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY
400600* -- Radiation Chemistry
ALKYLATED AROMATICS
AQUEOUS SOLUTIONS
AROMATICS
CHEMICAL RADIATION EFFECTS
CHEMICAL REACTION KINETICS
CHEMICAL REACTIONS
CHEMISTRY
DATA
DECOMPOSITION
DISPERSIONS
EXPERIMENTAL DATA
HYDROCARBONS
INFORMATION
KINETICS
MIXTURES
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC SULFUR COMPOUNDS
PULSE TECHNIQUES
RADIATION CHEMISTRY
RADIATION EFFECTS
RADICALS
RADIOLYSIS
REACTION KINETICS
SOLUTIONS
STYRENE
SULFONATES