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Measuring the Layer Charge of Dioctahedral Smectite by O—D Vibrational Spectroscopy

Published online by Cambridge University Press:  01 January 2024

Artur Kuligiewicz
Affiliation:
Institute of Geological Sciences, Polish Academy of Sciences, ul. Senacka 1, 31-002, Krakow, Poland
Arkadiusz Derkowski*
Affiliation:
Institute of Geological Sciences, Polish Academy of Sciences, ul. Senacka 1, 31-002, Krakow, Poland
Katja Emmerich
Affiliation:
Competence Center for Material Moisture (CMM) and Institute of Functional Interfaces (IFG), Karlsruhe Institute of Technology, Hermann-von-Helmholtz-Platz 1, D-76344, Eggenstein-Leopoldshafen, Germany
George E. Christidis
Affiliation:
School of Mineral Resources Engineering, Technical University of Crete, Chania, Greece 73100
Constantinos Tsiantos
Affiliation:
Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vass. Constantinou Ave. Athens, Greece 11635
Vassilis Gionis
Affiliation:
Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vass. Constantinou Ave. Athens, Greece 11635
Georgios D. Chryssikos*
Affiliation:
Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vass. Constantinou Ave. Athens, Greece 11635
*
*E-mail address of corresponding author: ndderkow@cyf-kr.edu.pl
*E-mail address of corresponding author: gdchryss@eie.gr

Abstract

Layer charge (LC) is a fundamental property of smectite but its measurement remains challenging and tedious to apply on a high-throughput basis. The present study demonstrates that the position of a sharp, high-energy O—D stretching band of adsorbed D2O (νO—D, at ~2686–2700 cm−1), determined by infrared spectroscopy, correlates with LC and provides a simple method for its measurement. Twenty nine natural dioctahedral smectites and 14 reduced-charge montmorillonites with LC determined previously by different methodologies were saturated with D2O and examined by attenuated total reflectance infrared spectroscopy (ATR-IR). The samples included smectites in Mg, Ca, Na, Li, K, and Cs forms and covered the full range of the smectite LC (0.2 to 0.6 e per formula unit). Statistically significant correlations were found between νO—D and LC values determined with each of the two main methods of LC determination: the structural formula method (R2 = 0.96, σ = 0.02, ~0.2 < LC < 0.6) and the alkylammonium method (R2 = 0.92, σ = 0.01, 0.27 < LC < 0.37). These correlations were based on Li- and Na-saturated smectites, respectively, but other cationic forms can be employed provided that the exchangeable cations are of sufficiently high hydration enthalpy (e.g. Mg2+ or Ca2+, but not K+ or Cs+). The new method is fast, low-cost, implemented easily in laboratories equipped with ATR-FTIR, and applicable to samples as small as ~5 mg.

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Article
Copyright
Copyright © The Clay Minerals Society 2015

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