Quasi-Equilibrium Volume Changes of Polyaniline Films upon Redox Switching. Formal Potential Distribution and Configurational Modeling
The quasi-equilibrium electrochemomechanical behavior of relatively thick polyaniline films in sulfuric acid is investigated through experimental measurements and theoretical modeling. The leucoemeraldine (LE)−emeraldine (EM) conversion, or redox switching, is studied. The dependence of film volume...
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| Veröffentlicht in: | The journal of physical chemistry. B 2005-10, Vol.109 (40), p.18815-18821 |
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| container_title | The journal of physical chemistry. B |
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| creator | Lizarraga, Leonardo Andrade, Estela M Florit, María I Molina, Fernando V |
| description | The quasi-equilibrium electrochemomechanical behavior of relatively thick polyaniline films in sulfuric acid is investigated through experimental measurements and theoretical modeling. The leucoemeraldine (LE)−emeraldine (EM) conversion, or redox switching, is studied. The dependence of film volume and electrochemical charge is determined as a function of applied potential. It is observed that the film volume follows the charge, showing an expansion during the second half of the LE−EM oxidation. The model postulates the existence of a stable intermediate, protoemeraldine (PE), with a formal potential distribution for the PE−EM reaction. The volume change is modeled statistically considering contributions from mixing, polymer deformation, and electrostatic charge. The model shows very good agreement with the experiments, indicating that, in the conditions studied, the deformation contribution dominates the volume changes as a result of the conformational modifications undergone by the polymer in the PE−EM oxidation. |
| doi_str_mv | 10.1021/jp054052s |
| format | Article |
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The volume change is modeled statistically considering contributions from mixing, polymer deformation, and electrostatic charge. The model shows very good agreement with the experiments, indicating that, in the conditions studied, the deformation contribution dominates the volume changes as a result of the conformational modifications undergone by the polymer in the PE−EM oxidation.</description><identifier>ISSN: 1520-6106</identifier><identifier>EISSN: 1520-5207</identifier><identifier>DOI: 10.1021/jp054052s</identifier><identifier>PMID: 16853421</identifier><language>eng</language><publisher>United States: American Chemical Society</publisher><subject>Aniline Compounds - chemistry ; Electrochemistry ; Membranes, Artificial ; Models, Chemical ; Molecular Structure ; Oxidation-Reduction ; Polymers - chemistry ; Sulfuric Acids - chemistry</subject><ispartof>The journal of physical chemistry. 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The model shows very good agreement with the experiments, indicating that, in the conditions studied, the deformation contribution dominates the volume changes as a result of the conformational modifications undergone by the polymer in the PE−EM oxidation.</description><subject>Aniline Compounds - chemistry</subject><subject>Electrochemistry</subject><subject>Membranes, Artificial</subject><subject>Models, Chemical</subject><subject>Molecular Structure</subject><subject>Oxidation-Reduction</subject><subject>Polymers - chemistry</subject><subject>Sulfuric Acids - chemistry</subject><issn>1520-6106</issn><issn>1520-5207</issn><fulltext>true</fulltext><rsrctype>article</rsrctype><creationdate>2005</creationdate><recordtype>article</recordtype><sourceid>EIF</sourceid><recordid>eNpt0E9PFDEYBvDGaASBg1_A9CKJh8H-2U5nj2ZhwWSNwIJ6azqdt0vXmXZppwG-gJ_bkt3gxUPTN-0vz5s8CL2n5IQSRj-vN0RMiGDpFdqngpGqHPl6N9eU1HvoXUprQphgTf0W7dG6EXzC6D76c5V1ctXZfXa9a6PLA_4R-jwAnt1pv4KEg8WXoX_SvgAPeO76IeG8CR5fQxce8fLBjebO-dUJnoc46L7wEfzoynTq0hhdm0dXuPYdngVv3SpH_fxSwLfQQYldHaI3VvcJjnb3Abqdn93MLqrF9_Ovsy-LSnNBx6qRnBPTGkOmU0pry1uwghLdwMQKK2lHawHWTDjQxmgrG1a3GrS0hNOasYYfoONt7iaG-wxpVINLBvpeewg5KUmoLBmywE9baGJIKYJVm-gGHZ8UJeq5dPVSerEfdqG5HaD7J3ctF1BtQakDHl_-dfytasmlUDeXS3Uqlj9_XV1M1aL4j1uvTVLrkGOpKv1n8V_VLppu</recordid><startdate>20051013</startdate><enddate>20051013</enddate><creator>Lizarraga, Leonardo</creator><creator>Andrade, Estela M</creator><creator>Florit, María I</creator><creator>Molina, Fernando V</creator><general>American Chemical Society</general><scope>BSCLL</scope><scope>CGR</scope><scope>CUY</scope><scope>CVF</scope><scope>ECM</scope><scope>EIF</scope><scope>NPM</scope><scope>AAYXX</scope><scope>CITATION</scope><scope>7X8</scope></search><sort><creationdate>20051013</creationdate><title>Quasi-Equilibrium Volume Changes of Polyaniline Films upon Redox Switching. 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The leucoemeraldine (LE)−emeraldine (EM) conversion, or redox switching, is studied. The dependence of film volume and electrochemical charge is determined as a function of applied potential. It is observed that the film volume follows the charge, showing an expansion during the second half of the LE−EM oxidation. The model postulates the existence of a stable intermediate, protoemeraldine (PE), with a formal potential distribution for the PE−EM reaction. The volume change is modeled statistically considering contributions from mixing, polymer deformation, and electrostatic charge. 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| source | ACS Publications; MEDLINE |
| subjects | Aniline Compounds - chemistry Electrochemistry Membranes, Artificial Models, Chemical Molecular Structure Oxidation-Reduction Polymers - chemistry Sulfuric Acids - chemistry |
| title | Quasi-Equilibrium Volume Changes of Polyaniline Films upon Redox Switching. Formal Potential Distribution and Configurational Modeling |
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