Ion Exchange and Surface Charge on Montmorillonite Clay

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Abstract
An ion‐exchange model originally developed for pure oxides prepared in the laboratory is extended to study of ion exchange and surface charge on a naturally occurring montmorillonite clay. The range of surface charges (−2.0 × 10−6 to 0 mol/m2) measured for montmorillonite with various electrolyte solutions and clay pretreatments is within the range of those measured for a wide variety of oxides prepared in the laboratory (−6.0 × 10−6 to 1.0 × 10−7 mol/m2), including MnO2‐IC1, MnO2‐IC12, MnO2‐IC22, titanium dioxide, ferric oxide, and aluminum oxide. In addition, fitted parameter values for lateral interaction constants and equilibrium constants for the acid sites that characterize ion exchange on montmorillonite are on the same order of magnitude as those obtained for pure oxides. Surface charge of montmorillonite in sodium nitrate solution is measured to be approximately 15 to 25% greater than that measured between a pH of 4 and 9 in calcium chloride solution. This difference is attributed to the greater charge on the calcium (2+) ion; thus, its stronger electrostatic attraction to the acid hydroxyl site. An order of magnitude change in solids concentration (Cp) can lead to a difference in measured net surface charge density of the same oxide sample of several orders of magnitude. This difference increases at higher pH, indicating the importance of reporting the corresponding Cp at which experiments are conducted.

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