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Relation of Water and Neutral Organic Compounds in the Interlayers of Mixed Ca/Trimethylphenylammonium-Smectites

Published online by Cambridge University Press:  28 February 2024

Guangyao Sheng  and
Stephen A. Boyd
Guangyao Sheng
Affiliation:
Department of Crop and Soil Sciences, Michigan State University, East Lansing, Michigan 48824
Stephen A. Boyd
Affiliation:
Department of Crop and Soil Sciences, Michigan State University, East Lansing, Michigan 48824
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Abstract

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Organoclays were prepared by exchanging Ca2+ in a Ca2+-saturated smectite partially or fully with trimethylphenylammonium (TMPA) cations. The mechanistic function of these organoclays as adsorbents for neutral organic compounds in aqueous solution was examined. TMPA cations were found to take a random distribution on the surfaces of mixed Ca/TMPA-smectites. The presence of TMPA, and its random distribution, resulted in water associated with the clay surfaces being held more weakly. Apparently, the interspersing of TMPA and Ca2+ ions prohibits the formation of a stable network of water molecules around Ca2+. Water molecules associated with the siloxane surface in mixed Ca/TMPA-clays are removed during the adsorption of neutral organic compounds from bulk water, leaving only ∼11 strongly held water molecules around each Ca2+, as opposed to ∼58 water molecules in homoionic Ca2+-smectite. These results demonstrate that the amount of water associated with the clay surfaces and interlayers depends on the nature of the exchange cation(s), and not on the amount of available siloxane surface area by itself. We conclude that in TMPA-smectites the TMPA cations function as nonhydrated pillars, and sorption of organic solutes occurs predominantly on the adjacent siloxane surfaces, which are hydrophobic in nature. The water molecules around Ca2+ in mixed Ca/TMPA-smectites obscures some of the siloxane surfaces. This diminishes sorption capacity, in an amount roughly equivalent to the fraction of the CEC occupied by Ca2+, because organic solutes cannot displace the waters of hydration of Ca2+.

Keywords

AdsorptionOrganoclaySmectiteTMPA
Type
Research Article
Information
Clays and Clay Minerals , Volume 46 , Issue 1 , February 1998 , pp. 10 - 17
Copyright
Copyright © 1998, The Clay Minerals Society

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