Wh. Casey et Ma. Cheney, BRONSTED REACTIONS ON OXIDE MINERAL SURFACES AND THE TEMPERATURE-DEPENDENCE OF THEIR DISSOLUTION RATES, Aquatic sciences, 55(4), 1993, pp. 304-313
Citations number
23
Categorie Soggetti
Water Resources",Limnology,"Marine & Freshwater Biology
The pH-dependence of oxide dissolution rates is controlled by Bronsted
acid-base reactions at the mineral surface. These reactions are rapid
but depend explicitly on temperature, as do the subsequent slow rates
of bond hydrolysis. The net result is that dissolution rates vary in
a complicated fashion with temperature and solution pH. The enthalpy c
hanges of acid-base reactions on oxide materials are sufficiently simi
lar, however, that general statements can be made about their contribu
tion. The enthalpy changes from proton adsorption to a hydroxyl functi
onal group (solid right-pointing triangle SOH), or to a deprotonated f
unctional group (solid right-pointing triangle SO-), are generally exo
thermic. The enthalpy changes become increasingly endothermic, however
, as charge accumulates on the mineral surface and the charged species
interact electrostatically. The result is that mineral dissolution ra
tes are least sensitive to temperature, as measured with an Arrhenius-
like rate law, at pH conditions near the Point of Zero Net Proton Char
ge.