Adsorption of Aerosol-OT at the calcite/water interface--comparison of the sodium and calcium salts

Isabella N Stocker; Kathryn L Miller; Rebecca J L Welbourn; Stuart M Clarke; Ian R Collins; Christian Kinane; Philipp Gutfreund

doi:10.1016/j.jcis.2013.11.046

Adsorption of Aerosol-OT at the calcite/water interface--comparison of the sodium and calcium salts

J Colloid Interface Sci. 2014 Mar 15:418:140-6. doi: 10.1016/j.jcis.2013.11.046. Epub 2013 Dec 4.

Authors

Isabella N Stocker¹, Kathryn L Miller¹, Rebecca J L Welbourn¹, Stuart M Clarke², Ian R Collins³, Christian Kinane⁴, Philipp Gutfreund⁵

Affiliations

¹ BP Institute and Department of Chemistry, University of Cambridge, Madingley Rise, Madingley Road, Cambridge CB3 0EZ, UK.
² BP Institute and Department of Chemistry, University of Cambridge, Madingley Rise, Madingley Road, Cambridge CB3 0EZ, UK. Electronic address: stuart@bpi.cam.ac.uk.
³ BP Exploration Operating Company Ltd., Chertsey Road, Sunbury on Thames TW16 7LN, UK.
⁴ ISIS, Rutherford Appleton Laboratory, Harwell Science and Innovation Campus, Didcot, UK.
⁵ Institut Laue-Langevin, 6 rue Jules Horowitz, BP 156, 38042 Grenoble Cedex 9, France.

PMID: 24461829
DOI: 10.1016/j.jcis.2013.11.046

Abstract

The adsorption of the surfactant Aerosol-OT (AOT) at the calcite-water interface has been investigated using batch adsorption isotherms and neutron reflection. The adsorption isotherms showed that NaAOT adsorption followed S-type adsorption behaviour with a maximum surface excess of 2.5 mg m(-2) but the method could not be used for the investigation of Ca(AOT)2 adsorption owing to the changes in the bulk phase behaviour of the solution. The surface excess, determined by neutron reflection at the critical micelle concentration (CMC), was 2.5 mg m(-2) for Ca(AOT)2 and 1.8 mg m(-2) for NaAOT. The time dependence of the NaAOT adsorption suggests a slow conversion from the sodium to the calcium salt of AOT at the calcite-water interface by binding calcium ions released from the slightly soluble calcite. The layer thickness in both cases was 35 Å which indicates adsorption as bilayers or distorted micelles. At higher concentrations of NaAOT (~10× CMC) adsorption of an AOT lamellar phase was evident from Bragg peaks in the specular reflection. To our knowledge, this is the first time that adsorption of a surfactant at the calcite-water interface has been investigated by neutron reflection. The technique provided significant new insight into the adsorption behaviour of AOT which would not have been accessible using traditional techniques.

Keywords: AOT; AOT calcium salt; AOT sodium salt; Aerosol-OT; CMC; Ca(AOT)(2); Calcite; Calcium carbonate; NRW; NaAOT; Neutron reflection; PCC; TOC; critical micelle concentration; null-reflecting water; precipitated calcium carbonate; total organic carbon analysis.