Adsorption of herbicide-derived anilines in dilute aqueous montmorillonite suspensions

Abstract

Adsorption isotherms of aniline and p-chloroaniline were determined from very dilute solutions on montmorillonite saturated with different cations (i.e. Na⁺, K⁺, Ca²⁺, Mg²⁺, Cu²⁺, Fe³⁺ and Al³⁺).In all cases p-chloroaniline was absorbed to a greater extent than aniline. The shapes of the isotherms depend on the adsorbate and on the exchangeable cation and are interpreted in terms of adsorption mechanisms.For aniline, the solvation of the adsorbate and the electronegativity of the saturating cation seem to be the main factors, whereas for p-chloroaniline the polarizing power of the exchange cation plays an important part. In the case of the Fe³⁺ ion the oxidizing power seems also be involved.The enthalpy changes (ΔH°), calculated from the temperature coefficient of the equilibrium constant are exothermic but less exothermic as the polarizing power of the exchange cation increases. The adsorption of the amines on Na-, K- and Ca-, Mg-montmorillonite gives rise to an entropy loss which is higher for the divalent cations. This result is in good agreement with desorption curves obtained after several washings which indicated for the nature of the organo-clay complexes the decreasing order of stability, viz Mg²⁺ > Ca²⁺ > K⁺ > Na⁺.