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Effect of Oligomerization of Counterions on Water Activity in Aqueous Cationic Surfactant Systems
Malmö högskola, Faculty of Health and Society (HS), Department of Biomedical Science (BMV). Malmö högskola, Biofilms Research Center for Biointerfaces.ORCID iD: 0000-0002-9852-5440
Physical Chemistry, Center for Chemistry and Chemical Engineering, Lund University , P.O. Box 124, SE-22100 Lund, Sweden.
2016 (English)In: Journal of Physical Chemistry B, ISSN 1520-6106, E-ISSN 1520-5207, Vol. 120, no 28, p. 6961-6968Article in journal (Refereed)
Abstract [en]

A sorption calorimetry study of cationic cetyltrimethyl ammonium surfactants with four different counterions was performed. The counterions were acetate, succinate, citrate, and butyl tetracarboxylate with formal charges ranging from 1 to 4, respectively. The counterions with 2–4 charges can be considered as oligomers. In all the cases, hydration experiments started with dry solid phases that upon water uptake went through solid-state phase transitions and hexagonal to micellar cubic phase transitions. It was found that in liquid-crystalline phases the activity of water increased with the degree of oligomerization or, equivalently, the formal charge of the counterions. The results are discussed in terms of the forces acting between the colloidal aggregates. It is argued that under the conditions investigated, the so-called strong-coupling theory can be used to describe the electrostatic forces between the charged colloidal objects. Therefore, we suggest that the observed dependence of water activity on the degree of polymerization is due to the entropy of mixing of the counterions in the water volume, which we describe using Flory–Huggins theory.

Place, publisher, year, edition, pages
American Chemical Society (ACS), 2016. Vol. 120, no 28, p. 6961-6968
National Category
Natural Sciences
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URN: urn:nbn:se:mau:diva-14837DOI: 10.1021/acs.jpcb.6b03104ISI: 000380590900006PubMedID: 27340840Scopus ID: 2-s2.0-84978629996Local ID: 21940OAI: oai:DiVA.org:mau-14837DiVA, id: diva2:1418358
Available from: 2020-03-30 Created: 2020-03-30 Last updated: 2024-06-17Bibliographically approved

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Kocherbitov, Vitaly

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