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

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Clays and Clay Minerals

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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Authors and Affiliations

  1. Institute of Geological Sciences, Polish Academy of Sciences, ul. Senacka 1, 31-002, Krakow, Poland

    Artur Kuligiewicz & Arkadiusz Derkowski

  2. 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

    Katja Emmerich

  3. School of Mineral Resources Engineering, Technical University of Crete, Chania, Greece, 73100

    George E. Christidis

  4. Theoretical and Physical Chemistry Institute, National Hellenic Research Foundation, 48 Vass. Constantinou Ave., Athens, Greece, 11635

    Constantinos Tsiantos, Vassilis Gionis & Georgios D. Chryssikos

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  1. Artur Kuligiewicz
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  2. Arkadiusz Derkowski
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  3. Katja Emmerich
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  4. George E. Christidis
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  5. Constantinos Tsiantos
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Correspondence to Arkadiusz Derkowski or Georgios D. Chryssikos.

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Kuligiewicz, A., Derkowski, A., Emmerich, K. et al. Measuring the Layer Charge of Dioctahedral Smectite by O—D Vibrational Spectroscopy. Clays Clay Miner. 63, 443–456 (2015). https://doi.org/10.1346/CCMN.2015.0630603

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  • DOI: https://doi.org/10.1346/CCMN.2015.0630603

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