| Abstract: | It is widely accepted that the fixation of oxyanions is due to diffusion of the ions into the pores and interdomains of iron oxides. Most studies have used batch techniques, which do not allow to clearly differentiate chemisorption from mass transport phenomena. Thus, it is not yet clear, whether strengthening of chemical Mo bonding occurs along with residence time, in addition to diffusion processes. In this study we used pressure jump relaxation (p‐jump), a very fast kinetic technique, to (1) elucidate the Mo/goethite interaction and to (2) analyze the effects of aging the Mo/goethite complex on Mo chemisorption. A synthetic goethite was incubated with Mo solution (1 mM Mo) for 12, 24, and 72 hours at pH 4. At the end of the incubations p‐jump experiments were performed on the suspensions at temperatures ranging from 283 to 303 K. Relaxation kinetics were modelled using a combination of two first order terms. In addition, the amount of Mo sorbed to the goethite after different incubation times was determined by graphite furnace atomic absorption spectroscopy. The MoO4/goethite systems revealed a fast relaxation time (= reciprocal of rate constant, about 4 ms), that decreased with increasing temperature and a slow one (about 60 ms) that did not depend on temperature. Activation energy of the fast process was 76 kJ mol—1. We did not observe any effects of incubation time on the fast process. However, the amount of Mo sorbed to the iron oxide increased with increasing incubation time. We conclude that the fast relaxation represents Mo chemisorption to the goethite. Slow relaxation seems to be due to Mo transport within the suspension. The pressure jump results indicate, that the dominant surface species of Mo sorbed to goethite do not change along with residence time. |
