The structure and equilibria of a manganese(II) complex of fulvic acid studied by ion exchange and nuclear magnetic resonance

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Abstract
The binding of Mn2+ to a well characterized fulvic acid sample is reported based on the competition with K+ in an ion exchange equilibration. The free energy of binding of [Formula: see text] to fulvic acid is only 1–2 kJ/equivalent more favourable than that for K+. This suggests an outer sphere electrostatic structure for the complex. The suggestion is confirmed by observation of minimal change in the presence of fulvic acid of the effect of paramagnetic Mn2+ on the nmr spectra of water. The interpretation of nmr spectra is supported by comparison with nmr measurements of Mn2+ complexes with simple ligands and contrast with nmr measurements on Fe3+ – fulvic acid complexing. The latter is confirmed as inner sphere.