The kinetics of homogeneous reactions are important in understanding the cooling history of rocks and in understanding experimental speciation data. We have experimentally studied the kinetics of the interconversion reaction between H_2O molecules and OH groups in natural rhyolitic glasses (0.5-2.3% total water) and a synthetic albitic glass (l% total water) at 400-600°C. The reaction rate increases with temperature and total water content.\ud Equilibrium is not always approached monotonically; the speciation may first depart from equilibrium and then come back to equilibrium. Experimental reaction rates agree with those inferred from previous speciation data of rhyolitic glasses quenched from 850°C.\ud The experimental data are modeled successfully by considering both the reaction and the diffusion of OH that brings OH groups together to react. This study shows that species concentrations in glasses quenched from ≤ 600°C reflect those at experimental temperatures unless the water content is higher than that used in the present study. Species concentrations in glasses with total water contents ≥0.8 wt% and which were rapidly quenched\ud in water from 850°C do not represent their equilibrium concentrations in the melt at 850°C, but record a lower apparent equilibrium temperature that depends on water content\ud and quench rate. Natural rhyolitic glasses and glass inclusions do not record preeruptive melt speciation, though total water content may be conserved. The experimental data are used to infer cooling rates for natural obsidian glasses. Pyroclastic glass fragments from the bb site of Mono Craters have cooling rates similar to air-cooled experimental charges\ud (~3°C/s). Different types of glasses from the Mono Craters have different cooling rates, which cover four orders of magnitude. Some natural obsidians appear to have had complex cooling histories. The wide range of cooling rates and thermal histories is consistent with previous inferences that some obsidian clasts at the Mono Craters formed as glass selvages lining volcanic conduits or dikes that were subsequently caught up in the explosive eruption,\ud which led to variable degrees of transient heating followed by rapid cooling and deposition. These experimental data reveal surprisingly rich detail in water speciation in volcanic glasses and show how, at least in principle, quantitative constraints on thermal histories can be extracted by experimentation and application of kinetic models
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