Solubility and dissolution rate of silica in acid fluoride solutions

We performed 57 batch reactor experiments in acidic fluoride solutions to measure the dissolution rate of quartz. These rate data along with rate data from published studies were fit using multiple linear regression to produce the following non-unique rate law for quartz r(qz) (mol/m(2) s) = 10(-4.53) (e(-18932/RT))a(HF)(1.18)a(H+)(-0.39) where 10(-5.13) < a(HF) < 10(1.60), -0.28 < pH < 7.18, and 298 < T < 373 K. Similarly, 97 amorphous silica dissolution rate data from published studies were fit by multiple linear regression to produce the following non-unique rate law for amorphous silica r(as) (mol/m(2) s) = 10(0.48) (e(-34243/RT))a(HF)(1.50)a(H+)(-0.46) where 10(-2.37) < a(HF) < 10(1.61), -0.32 < pH < 4.76 and 296 < T < 343 K. Regression of the rates versus other combinations of solution species, e. g. HF2- + H+, F- + H+, HF + HF2-, HF + F-, or HF2- + F-, produced equally good fits. Any of these rate laws can be interpreted to mean that the rate-determining step for silica dissolution in fluoride solutions involves a coordinated attack of a Lewis acid, on the bridging O atom and a Lewis base on the Si atom. This allows a redistribution of electrons from the Si-O bond to form a O-H group and a Si-FH group. (C) 2009 Elsevier Ltd. All rights reserved.