The quantity : potential relationships for Ca+K exchange in six soils were evaluated, where potential is defined by ~G K , c~+ M~. Using the percentage K saturation of the CEC as the index of quantity, the Worcester Series soil, rich in hydrous micas, was shown to have the highest concentration of K selective sites, and Newport Series soil, with mainly kaolinitic clay, the lowest. The other soils, containing mainly smectites, had intermediate K selectivities.An algebraic transformation of this relationship to separate the effects of exchangeable K and CEC showed that 0.01 M C~C I , released more K than M ammonium acetate. From the exchangeable K : AG relationship, two regions of K buffering were observed for all but the Newport soil, the transition occurring at a mean A G K , c~+ M~ value of -20.7 kJ mol-1, signifying the K concentration below which K from 'perlpheral' regions of micaceous minerals is released. This may explain why the percentage K saturation of the CEC of a soil cropped exhaustively (without K manuring) in the field does not drop below a minimum value.Based on pot experiments, exhaustion and optimum K potentials (dG,,h and AGop,) were derived from second-degree polynomials fitted to the response curves of plant dry matter yield against ~G K , c~+ M~ for five soils, the Worcester soil showing little response. dG,,h was inversely related to the 2 : 1 layer silicate content of the soil (r*=0.98 and 0.94 for ryegrass and fescue respectively), and similarly, AGO,,, to their CEC values (r2=0.74 and 0.77). Potassium uptake was more closely correlated with exchangeable K than with AGO,,.
Introduclion
Soil K potentialThe thermodynamic potential of K in soil is taken as its partial molar free energy referred to that of calcium+magnesium, and is expressed as the free energy of K -(Ca + Mg) exchange (Woodruff, 1955a, b; Arnold, 1962):It is measured as the difference between the chemical potentials of K+ and (Ca2+ + Mg2+) in a dilute solution in equilibrium with the soil, i.e.