Silicates Including Feldspars, Dissolution, and Precipitation

Empirical studies of silicate rock or mineral solution rates at low temperatures, under conditions where the water is far from equilibrium with the solid, obey zero-order kinetics (cf. Apps 1983 Paces 1983, Bodek et al. 1988), also called linear kinetics (White and Claassen 1979). The best example of such behavior is the dissolution of S1O2 polymorphs (see Rimstidt and Barnes 1980 and Section 2.7.8). Linear or zero-order kinetics is observed when the area of reacting mineral exposed to a volume of solution or volume of the water-rock system (also called the specific wetted surface, A, in cm or m /m ) may be considered constant with time. The general form of the empirical rate law is 

Based on laboratory dissolution-rate studies of feldspars, obsidian, and volcanic glass. White and Claassen (1979) observe that the initial solution rate of silicates can either obey linear (zero-order) kinetics as in Eq. (2.99), or parabolic kinetics, where the rate is given by 

Equation (2.101) corresponds to transport-controlled kinetics (cf. Stumm 1990). White and Claassen conclude that after long times in natural water/rock systems parabolic rates tend to become linear. Helgeson et al. (1984) show that feldspar dissolution rates are linear if the feldspar is pretreated to remove ultrafine reactive particles. In other words initial parabolic rates are probably an artifact of sample preparation. It seems likely that, in general, the dissolution or weathering of most silicates in natural water/rock systems obeys zero-order kinetics. 

Silicate mineral dissolution is usually incongruent, with precipitation of relatively amorphous metastable products that may crystallize with time to form minerals such as gibbsite, kaolinite, illite, and montmorillonite (Helgeson et al. 1984). The incongruency means that the net release rates of individual components from a silicate mineral into the water may not be equal (cf. White and Claassen 1979 Helgeson et al. 1984). 

Aagaard and Helgeson (1982) and Murphy and Helgeson (1989) propose general-rate expressions for the dissolution of silicate minerals. They suggest that the solution rate in acid water is determined by the decomposition rate of a critical activated surface complex. The rate is given by 

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