Recombination of Poly(Acrylic Acid) Radicals in Acidic Aqueous Solutions: A Pulse Radiolysis Study

Carbon-centered radicals have been randomly generated on the chains of poly(acrylic acid), PAA, the simplest synthetic anionic polyelectrolyte, by pulse-irradiating its dilute, oxygen-free aqueous solutions by 6 MeV electron beam. In some experiments, oligo(acrylic acid), OAA, and propionic acid, PA...

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Autores principales: Małgorzata Matusiak, Sławomir Kadłubowski, Piotr Ulański
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Publicado: MDPI AG 2021
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spelling oai:doaj.org-article:f0ae599785a74713b3e05354ca7faf632021-11-11T15:12:42ZRecombination of Poly(Acrylic Acid) Radicals in Acidic Aqueous Solutions: A Pulse Radiolysis Study10.3390/app1121101422076-3417https://doaj.org/article/f0ae599785a74713b3e05354ca7faf632021-10-01T00:00:00Zhttps://www.mdpi.com/2076-3417/11/21/10142https://doaj.org/toc/2076-3417Carbon-centered radicals have been randomly generated on the chains of poly(acrylic acid), PAA, the simplest synthetic anionic polyelectrolyte, by pulse-irradiating its dilute, oxygen-free aqueous solutions by 6 MeV electron beam. In some experiments, oligo(acrylic acid), OAA, and propionic acid, PA, were used as PAA models. Recombination kinetics of PAA radicals has been followed by fast spectrophotometry. A strong pH dependence of radical lifetime on pH, and thus on the linear charge density due to deprotonated carboxylate groups, has been confirmed, while a weaker amplitude of pH dependence was observed for OAA and PA. Decay kinetics of PAA radicals in the protonated state, at pH 2, have been studied in some detail. At moderate doses of ionizing radiation, resulting in a moderate average initial number of radicals per chain, <i>Z<sub>R</sub></i><sub>0</sub>, the decay can be satisfactorily described by a second-order kinetic model, but a somewhat better fit is obtained by using a dispersive kinetics approach. While for a constant polymer concentration the reciprocal half-lives are proportional to the initial radical concentrations, such a data series for different PAA concentrations do not overlap, indicating that the overall radical concentration is not the decisive factor controlling the kinetics. Arranging all data, in the form of second-order rate constants, as a function of the average initial number of radicals per chain allows one to obtain a common dependence. The latter seems to consist of two parts: a horizontal one at low <i>Z<sub>R</sub></i><sub>0</sub> and another one of positive slope at higher <i>Z<sub>R</sub></i><sub>0</sub>. This is interpreted as two kinetic regimes where two distinct reactions dominate, intermolecular and intramolecular recombination, respectively. Comparison of the low <i>Z<sub>R</sub></i><sub>0</sub> data with calculations based on the translational diffusion model indicate that the latter is not the rate-controlling process in intermolecular recombination of polymer radicals; segmental diffusion is the more likely candidate.Małgorzata MatusiakSławomir KadłubowskiPiotr UlańskiMDPI AGarticlereaction kineticsfree radicalsradiation chemistrypulse radiolysispolyelectrolytespoly(acrylic acid)TechnologyTEngineering (General). Civil engineering (General)TA1-2040Biology (General)QH301-705.5PhysicsQC1-999ChemistryQD1-999ENApplied Sciences, Vol 11, Iss 10142, p 10142 (2021)
institution DOAJ
collection DOAJ
language EN
topic reaction kinetics
free radicals
radiation chemistry
pulse radiolysis
polyelectrolytes
poly(acrylic acid)
Technology
T
Engineering (General). Civil engineering (General)
TA1-2040
Biology (General)
QH301-705.5
Physics
QC1-999
Chemistry
QD1-999
spellingShingle reaction kinetics
free radicals
radiation chemistry
pulse radiolysis
polyelectrolytes
poly(acrylic acid)
Technology
T
Engineering (General). Civil engineering (General)
TA1-2040
Biology (General)
QH301-705.5
Physics
QC1-999
Chemistry
QD1-999
Małgorzata Matusiak
Sławomir Kadłubowski
Piotr Ulański
Recombination of Poly(Acrylic Acid) Radicals in Acidic Aqueous Solutions: A Pulse Radiolysis Study
description Carbon-centered radicals have been randomly generated on the chains of poly(acrylic acid), PAA, the simplest synthetic anionic polyelectrolyte, by pulse-irradiating its dilute, oxygen-free aqueous solutions by 6 MeV electron beam. In some experiments, oligo(acrylic acid), OAA, and propionic acid, PA, were used as PAA models. Recombination kinetics of PAA radicals has been followed by fast spectrophotometry. A strong pH dependence of radical lifetime on pH, and thus on the linear charge density due to deprotonated carboxylate groups, has been confirmed, while a weaker amplitude of pH dependence was observed for OAA and PA. Decay kinetics of PAA radicals in the protonated state, at pH 2, have been studied in some detail. At moderate doses of ionizing radiation, resulting in a moderate average initial number of radicals per chain, <i>Z<sub>R</sub></i><sub>0</sub>, the decay can be satisfactorily described by a second-order kinetic model, but a somewhat better fit is obtained by using a dispersive kinetics approach. While for a constant polymer concentration the reciprocal half-lives are proportional to the initial radical concentrations, such a data series for different PAA concentrations do not overlap, indicating that the overall radical concentration is not the decisive factor controlling the kinetics. Arranging all data, in the form of second-order rate constants, as a function of the average initial number of radicals per chain allows one to obtain a common dependence. The latter seems to consist of two parts: a horizontal one at low <i>Z<sub>R</sub></i><sub>0</sub> and another one of positive slope at higher <i>Z<sub>R</sub></i><sub>0</sub>. This is interpreted as two kinetic regimes where two distinct reactions dominate, intermolecular and intramolecular recombination, respectively. Comparison of the low <i>Z<sub>R</sub></i><sub>0</sub> data with calculations based on the translational diffusion model indicate that the latter is not the rate-controlling process in intermolecular recombination of polymer radicals; segmental diffusion is the more likely candidate.
format article
author Małgorzata Matusiak
Sławomir Kadłubowski
Piotr Ulański
author_facet Małgorzata Matusiak
Sławomir Kadłubowski
Piotr Ulański
author_sort Małgorzata Matusiak
title Recombination of Poly(Acrylic Acid) Radicals in Acidic Aqueous Solutions: A Pulse Radiolysis Study
title_short Recombination of Poly(Acrylic Acid) Radicals in Acidic Aqueous Solutions: A Pulse Radiolysis Study
title_full Recombination of Poly(Acrylic Acid) Radicals in Acidic Aqueous Solutions: A Pulse Radiolysis Study
title_fullStr Recombination of Poly(Acrylic Acid) Radicals in Acidic Aqueous Solutions: A Pulse Radiolysis Study
title_full_unstemmed Recombination of Poly(Acrylic Acid) Radicals in Acidic Aqueous Solutions: A Pulse Radiolysis Study
title_sort recombination of poly(acrylic acid) radicals in acidic aqueous solutions: a pulse radiolysis study
publisher MDPI AG
publishDate 2021
url https://doaj.org/article/f0ae599785a74713b3e05354ca7faf63
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AT sławomirkadłubowski recombinationofpolyacrylicacidradicalsinacidicaqueoussolutionsapulseradiolysisstudy
AT piotrulanski recombinationofpolyacrylicacidradicalsinacidicaqueoussolutionsapulseradiolysisstudy
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