Transition state kinetics of Hg(II) adsorption at gibbsite-water interface.

Kinetics of adsorption plays a pivotal factor in determining the bio-availability and mobility of Hg(II) in the environment. The kinetics of Hg(II) adsorption on gibbsite was examined as a function of pH, temperature and electrolyte type. Adsorption of Hg(II) was highly non-linear where the rate of Hg(II) retention was rapid initially and was followed by gradual or somewhat slow retention behavior with increasing contact time. The respective rate constants designated as k(1) (S-1: fast step) and k(2) (S-2: slow step). Always k(1) follows the order: k(1)(CIO)(4) >/= k(1)(NO3)(4) >> k(1)(Cl). Such a relationship was not observed for the S-2 route. A two-step reaction model with pseudo-first order kinetics successfully described the adsorption rates of Hg(II) on gibbsite. Arrhenius and Erying models determined the thermodynamic parameters at activation states, which correspond to S-1 and S-2 routes. In a given system, always the activation energies showed a decrease with the pH. Gibbs free energy (DeltaG(#)), enthalpy (DeltaH(#)), and entropy (DeltaS(#)) values of activation states were almost similar both in NaClO(4) and NaNO(3) which signal a similar Hg(II) adsorptive mechanism on gibbsite. The configurations of different Hg(II)-surface complexes were elucidated by transmission vibration spectroscopy.