Determination of the adsorption mechanism of imidazolium-type ionic liquids onto kaolinite: implications for their fate and transport in the soil environment

Wojciech Mrozik; Christian Jungnickel; Michał Skup; Piotr Urbaszek; Piotr Stepnowski

doi:10.1071/EN08015

RESEARCH ARTICLE

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Determination of the adsorption mechanism of imidazolium-type ionic liquids onto kaolinite: implications for their fate and transport in the soil environment

Wojciech Mrozik ^A ^B , Christian Jungnickel ^C , Michał Skup ^A , Piotr Urbaszek ^A and Piotr Stepnowski ^A ^D

+ Author Affiliations

- Author Affiliations

^A Faculty of Chemistry, University of Gdansk, Sobieskiego 18, PL-80-952 Gdańsk, Poland.

^B Faculty of Pharmacy, Medical University of Gdańsk, Gen. J. Hallera 107, PL-80-416 Gdańsk, Poland.

^C Chemical Faculty, Gdańsk University of Technology, ul. Narutowicza 11/12, PL-80-952 Gdańsk, Poland.

^D Corresponding author. Email: sox@chem.univ.gda.pl

Environmental Chemistry 5(4) 299-306 https://doi.org/10.1071/EN08015
Submitted: 19 February 2008 Accepted: 6 June 2008 Published: 19 August 2008

Environmental context. The present paper looks at the possible spreading of a new class of chemicals, namely, ionic liquids in soils. These ionic liquids have gained increasing attention, and their environmental impact and fate needs to be determined before accidental release. The paper specifically focusses on the adhesion mechanisms of these chemicals onto a type of clay, kaolinite. It was found that a multilayer adhesion mechanism occurs. Sorption of ionic liquids on kaolinite indicates that these chemicals can modify the clay surfaces, which may lead to changes in its natural geochemical cycles.

Abstract. In the present study, the mechanism of sorption of ionic liquids onto kaolinite clay mineral has been investigated in detail. Results obtained indicate a multilayer type of adsorption. At final saturations, the highest distribution coefficients were found for the long alkyl chain molecules. The mean free energy values obtained are below values of a typical ion-exchange process, which thus suggests that the adsorption mechanism is a combination of electrostatic interaction and physical sorption. At the beginning of the binding process (formation of a monolayer), ion-exchange and van der Waals interactions are predominantly responsible for the process, whereas at higher concentrations of ionic liquids, dispersive interactions become dominant.

Thermodynamic parameters were also calculated from graphical interpretation of experimental data. Negative values of ΔG indicate a spontaneous sorption process for ionic liquids. Standard heats of adsorption were found to be exothermic and entropy contributions were negative in all cases studied.

Additional keywords: alternative solvents, clay minerals, sorption isotherm, sorption mechanism, thermodynamics of sorption.

Acknowledgement

Financial support was provided by the Polish Ministry of Education and Research under grants: 2P04G 083 29, 2P04G 118 29, N205 041 32/2340 and DS 8200–4-0085–7.

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Determination of the adsorption mechanism of imidazolium-type ionic liquids onto kaolinite: implications for their fate and transport in the soil environment

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