Physico-Chemical Aspects of Metal–Fulvic Complexation

Abstract

The interactions of metal ions with fulvic acids were investigated from the point of view of the thermodynamic aspects of complexation as well as the size and charge of the formed complexes. Thermodynamic aspects were studied by means of isothermal titration calorimetry. Particle size distribution was determined by the method of dynamic light scattering and charge by the measurement of zeta potential. Complexation resulted in changes in particle size and charge. The particle size distribution was trimodal for fulvic acids and bimodal for fulvic complexes with calcium and magnesium, while copper–fulvic complexes had only one size fraction. The compensation of the negative charge of carboxylic and phenolic functional groups by positively charged metal ions resulted in an increase in zeta potential which became closer to zero in the case of copper–fulvic complexes. However, all metal–humic complexes behaved as colloidally unstable, which resulted in visually observable sedimentation. Calorimetric measurements provided positive values for changes in enthalpy, which indicated endothermic processes. In contrast, quantum chemical calculations as well as experiments with model compounds provided negative values indicating exothermic processes. Changes in Gibbs energy were determined as negative and changes in entropy as positive.The interactions of metal ions with fulvic acids were investigated from the point of view of the thermodynamic aspects of complexation as well as the size and charge of the formed complexes. Thermodynamic aspects were studied by means of isothermal titration calorimetry. Particle size distribution was determined by the method of dynamic light scattering and charge by the measurement of zeta potential. Complexation resulted in changes in particle size and charge. The particle size distribution was trimodal for fulvic acids and bimodal for fulvic complexes with calcium and magnesium, while copper–fulvic complexes had only one size fraction. The compensation of the negative charge of carboxylic and phenolic functional groups by positively charged metal ions resulted in an increase in zeta potential which became closer to zero in the case of copper–fulvic complexes. However, all metal–humic complexes behaved as colloidally unstable, which resulted in visually observable sedimentation. Calorimetric measurements provided positive values for changes in enthalpy, which indicated endothermic processes. In contrast, quantum chemical calculations as well as experiments with model compounds provided negative values indicating exothermic processes. Changes in Gibbs energy were determined as negative and changes in entropy as positive.