A study of Cr(III)-polyacrylamide reaction kinetics by equilibrium dialysis

A kinetic model was developed to describe the rate of reaction between chromium(III) and polyacrylamide (PAAm) that leads to the crosslinking or gelation of the polymer. Cr(III) was added directly to solutions of polyacrylamide which had a degree of hydrolysis of approximately 4%. The unreacted Cr(III) was separated from that which had reacted with the polymer by equilibrium dialysis and measured by atomic absorption. The rate of the reaction was described by an empirical model based on the assumption of invariant polymer group concentration during the reaction. The order of reaction was determined to be 1.32 for Cr(III), 0.8 for the polymer group, and −1.0 for hydrogen ion. Modifications were made to the model to allow for variation during reaction of the concentration of the polyacrylamide reactive group. The modified model accurately described the reaction rate for Cr(III) concentration ranging from 0.19 to 1.2 mM, polyacrylamide concentrations from 6.9 to 69 mM, and pH values from 4.0 to 5.5.