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Radiolysis of poly(acrylic acid) in aqueous solution

Abstract

Poly(acrylic acid), PAA, reacts with OH-radicals yielding -CH-CH(CO{sub 2}H)- ({beta}-radicals) and -CH{sub 2}-C(CO{sub 2}H)-({alpha}-radicals) in a ratio of approximately 2:1. This estimate is based on pulse radiolysis data where the absorption spectrum of the PAA-radicals was compared with the spectra of {alpha}-radicals from model systems. The {beta}-radicals convert slowly into {alpha}-radicals (k = 0.7s {sup -1} at pH 10). This process has also been observed by ESR. At PAA-concentrations of 10{sup -2} mol dm{sup -3} chain scission dominates over other competing reactions except at low pH. The rate of chain scission was followed by pulse conductometry and in the pH range 7-9 k = 4 x 10{sup -2}s{sup -1} was observed. Oxygen reacts with PAA-radicals with k = 3.1 x 10{sup 8} dm{sup 3} mol{sup -1} s{sup -1} at pH 3.5 and k = 1.0 x 10{sup 8} dm{sup 3} mol{sup -1} s{sup -1} at pH 10. The corresponding peroxyl radicals undergo slow intramolecular H-transfer yielding a UV-absorbing product whose properties are that of 1,3-diketones. (Author).
Authors:
Ulanski, P; [1]  Bothe, E; Hildenbrand, K; Sonntag, C von; [1]  Rosiak, J M [2] 
  1. Max-Planck-Institut fuer Strahlenchemie, Muelheim an der Ruhr (Germany)
  2. Politechnika Lodzka, Lodz (Poland)
Publication Date:
Oct 01, 1995
Product Type:
Journal Article
Report Number:
CONF-940908-
Reference Number:
SCA: 400600; PA: AIX-27:064894; EDB-96:144429; SN: 96001665386
Resource Relation:
Journal Name: Radiation Physics and Chemistry; Journal Volume: 46; Journal Issue: 4-6; Conference: 9. international meeting on radiation processing: dedicated to the dissemination and advancement of the technology of industrial radiation processing, Istanbul (Turkey), 11-16 Sep 1994; Other Information: DN: Published in two parts.; PBD: Oct-Dec 1995
Subject:
40 CHEMISTRY; POLYACRYLATES; RADIOLYSIS; ABSORPTION SPECTRA; AQUEOUS SOLUTIONS; CHEMICAL REACTION KINETICS; CROSS-LINKING; HYDROXYL RADICALS; PEROXY RADICALS; PH VALUE; PULSED IRRADIATION
OSTI ID:
369066
Country of Origin:
United Kingdom
Language:
English
Other Identifying Numbers:
Journal ID: RPCHDM; ISSN 0969-806X; TRN: GB9601349064894
Submitting Site:
GBN
Size:
pp. 909-912
Announcement Date:

Citation Formats

Ulanski, P, Bothe, E, Hildenbrand, K, Sonntag, C von, and Rosiak, J M. Radiolysis of poly(acrylic acid) in aqueous solution. United Kingdom: N. p., 1995. Web. doi:10.1016/0969-806X(95)00290-E.
Ulanski, P, Bothe, E, Hildenbrand, K, Sonntag, C von, & Rosiak, J M. Radiolysis of poly(acrylic acid) in aqueous solution. United Kingdom. doi:10.1016/0969-806X(95)00290-E.
Ulanski, P, Bothe, E, Hildenbrand, K, Sonntag, C von, and Rosiak, J M. 1995. "Radiolysis of poly(acrylic acid) in aqueous solution." United Kingdom. doi:10.1016/0969-806X(95)00290-E. https://www.osti.gov/servlets/purl/10.1016/0969-806X(95)00290-E.
@misc{etde_369066,
title = {Radiolysis of poly(acrylic acid) in aqueous solution}
author = {Ulanski, P, Bothe, E, Hildenbrand, K, Sonntag, C von, and Rosiak, J M}
abstractNote = {Poly(acrylic acid), PAA, reacts with OH-radicals yielding -CH-CH(CO{sub 2}H)- ({beta}-radicals) and -CH{sub 2}-C(CO{sub 2}H)-({alpha}-radicals) in a ratio of approximately 2:1. This estimate is based on pulse radiolysis data where the absorption spectrum of the PAA-radicals was compared with the spectra of {alpha}-radicals from model systems. The {beta}-radicals convert slowly into {alpha}-radicals (k = 0.7s {sup -1} at pH 10). This process has also been observed by ESR. At PAA-concentrations of 10{sup -2} mol dm{sup -3} chain scission dominates over other competing reactions except at low pH. The rate of chain scission was followed by pulse conductometry and in the pH range 7-9 k = 4 x 10{sup -2}s{sup -1} was observed. Oxygen reacts with PAA-radicals with k = 3.1 x 10{sup 8} dm{sup 3} mol{sup -1} s{sup -1} at pH 3.5 and k = 1.0 x 10{sup 8} dm{sup 3} mol{sup -1} s{sup -1} at pH 10. The corresponding peroxyl radicals undergo slow intramolecular H-transfer yielding a UV-absorbing product whose properties are that of 1,3-diketones. (Author).}
doi = {10.1016/0969-806X(95)00290-E}
journal = {Radiation Physics and Chemistry}
issue = {4-6}
volume = {46}
journal type = {AC}
place = {United Kingdom}
year = {1995}
month = {Oct}
}