Effect of Counterions and Temperature on the Association and Partition Balances of Hexadecylpyridinium Halides in Aqueous Solutions

J. Oremusová; O. Greksáková

doi:10.3139/113.100270

Article

Effect of Counterions and Temperature on the Association and Partition Balances of Hexadecylpyridinium Halides in Aqueous Solutions

J. Oremusová and O. Greksáková

Published/Copyright: May 8, 2013

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From the journal Tenside Surfactants Detergents Volume 42 Issue 5

Abstract

The effect of counterions and temperature on the association (critical micelle concentration, thermodynamics of micellization) and partition balances (experimental partition coefficient) of three quarternary ammonium surfactants (CPX) having a common hexadecylpyridinium cation and different anions (chloride, bromide, iodide) were studied in aqueous solutions at the temperature range 20–50°C, using conductometry, potentiometry, UV spectroscopy and measurement of surface tension. All methods used gave closely similar values for critical micelle concentration. From calculated thermodynamics parameters the process of micellization was found to be spontaneous and exothermic. Experimental partition coefficient of hexadecylpyridinium halides increased from chloride to iodide.

The objective of this work was to check whether surfactant counterions can affect the micellization and partition processes. From the results obtained it seems that the differences found in micellization and partitioning of all compounds studied, may be attributed to the different physicochemical properties of chloride, bromide and iodide anions as their differences in mobility etc.

Kurzfassung

Der Einfluss von Gegenionen und Temperatur auf die Assoziation (kritische Mizellbildungskonzentration, Thermodynamik der Mizellenbildung) und Verteilungsgleichgewichte (experimenteller Verteilungskoeffizient) von drei quaternären Ammoniumtensiden (CPX), mit einem herkömmlichem Hexadecylpyridinium-Kation und verschiedenen Anionen (Chloride, Bromide, Jodide), wurde in wässrigen Lösungen in einem Temperaturbereich von 20–50°C mittels Konduktometrie, Potentiometrie, UV-Spektroskopie und Messung der Oberflächenspannung untersucht. Alle verwendeten Methoden ergaben nahezu ähnliche Werte für die kritische Mizellbildungskonzentration. Aus den berechneten thermodynamischen Parametern wurde ein spontaner und exothermer Prozess der Mizellenbildung gefunden. Der experimentelle Verteilungskoeffizient von Hexadecylpyridiniumhalogeniden steigt vom Chlorid zum Jodid hin an.

Das Ziel dieser Arbeit war es zu überprüfen, ob Tensidgegenionen die Mizellenbildung und den Verteilungsprozeß beeinflussen können. Anhand der erhaltenen Ergebnisse sieht es so aus, als ob die gefundenen Unterschiede in der Mizellenbildung und Partitionierung aller untersuchten Verbindungen den verschiedenen physikalisch chemischen Eigenschaften von Chlorid-, Bro-mid- und Jodidanion, wie ihre Unterschiede in der Beweglichkeit etc., zugeordnet werden können.

Keywords:: Surfactants; hexadecylpyridinium halides; micellization; effect of temperature; counterions; critical micelle concentration; thermodynamic parameters; experimental partition coefficient

Schlüsselwörter: Tenside; Hexadecylpyridiniumhalogenide; Mizellbildung; Temperatureinfluss; Gegenionen; kritische Mizellbildungskonzentration; thermodynamische Parameter; experimenteller Verteilungskoeffizient

¹Jarmila Oremusová, Department of Physical Chemistry of Drugs Faculty of Pharmacy, Comenius University Odbojárov 10, 83232 Bratislava, Slovak Republic Fax: +42 12 50 11 71 00 E-mail: oremusova@fpharm.uniba.sk

Doc. Dr. Olga Greksáková, PhD. was born in 1937 and obtained her MSc./PhD in chemistry from Comenius University in Bratislava. She works in the Department of the Physical Chemistry of Drugs, Faculty Pharmacy, Comenius University in Bratislava.

Dr. Jarmila Oremusová, PhD. was born in 1959 and obtained her MSc./PhD in Physical and Analytical Chemistry at Slovak Techical University in Bratislava. Now she works in the Department of the Physical Chemistry of Drugs, Faculty of Pharmacy, Comenius University in Bratislava.

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Received: 2005-4-5

Published Online: 2013-05-08

Published in Print: 2005-11-01

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Articles in the same Issue

https://doi.org/10.3139/113.100270

Keywords for this article

Surfactants; hexadecylpyridinium halides; micellization; effect of temperature; counterions; critical micelle concentration; thermodynamic parameters; experimental partition coefficient