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Thermodynamic characterization of polyanetholesulfonic acid and its alkaline salts.
MedLine Citation:
PMID:  17685647     Owner:  NLM     Status:  PubMed-not-MEDLINE    
Abstract/OtherAbstract:
Experimental and theoretical results for the thermodynamic properties of polyanetholesulfonic acid and its lithium, sodium, and cesium salts in aqueous solution at 298 K are presented. The osmotic pressure was measured using membrane and vapor pressure apparatus in the concentration range c(m) = 0.001-0.30 monomoles/dm(3). The osmotic coefficients obtained from these measurements were low, from 0.2 to 0.45 in this concentration range, indicating a strong interaction between counterions and polyions. The osmotic coefficients of the polyacid and its lithium and sodium salts appeared to be equal within experimental error, but the results for the cesium salt were lower. This indicates a somewhat stronger binding of cesium ions to the polyanion. In addition, enthalpies of dilution, DeltaH(D), from a certain concentration, m(m), to m(m) = 0.0044 monomoles/kg were measured. The measured heats of dilution were exothermic, with the acid producing the strongest and the cesium salt the weakest effect. These results were compared with previously published data for polyelectrolytes of similar structure, namely, polystyrenesulfonic acid and its alkaline salts. The osmotic pressure results indicate that polystyrenesulfonates bind the counterions more strongly than polyanetholesulfonic acid and its salts. Consistent with this finding, the enthalpies of dilution reveal that more heat is released upon dilution of polyanetholesulfonates (stronger exothermic effect) in comparison with the corresponding solutions of polystyrenesulfonic acid in its alkaline salts. These findings can be explained in terms of the structural differences between the two polyions. The experimental results were analyzed in relation to popular electrostatic theories such as the Manning condensation theory and the Poisson-Boltzmann cell model approach, where the polyion is pictured as a uniformly charged line or cylinder. In addition, we performed Monte Carlo simulations for a model polyanetholesulfonic anion having discrete charges. In all of the calculations, the solvent was treated as a continuum with the dielectric constant of pure water under the conditions of measurement. The theoretical considerations mentioned above yield results in semiquantitative agreement with the measured quantities.
Authors:
Irena Lipar; Petra Zalar; Ciril Pohar; Vojko Vlachy
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Publication Detail:
Type:  Journal Article     Date:  2007-08-09
Journal Detail:
Title:  The journal of physical chemistry. B     Volume:  111     ISSN:  1520-6106     ISO Abbreviation:  J Phys Chem B     Publication Date:  2007 Aug 
Date Detail:
Created Date:  2007-08-23     Completed Date:  2007-11-08     Revised Date:  -    
Medline Journal Info:
Nlm Unique ID:  101157530     Medline TA:  J Phys Chem B     Country:  United States    
Other Details:
Languages:  eng     Pagination:  10130-6     Citation Subset:  -    
Affiliation:
Faculty of Chemistry and Chemical Technology, University of Ljubljana, Askerceva 5, P.O.B. 537, 1001 Ljubljana, Slovenia.
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