The speciation of CO
2 in dacite, phonolite, basaltic andesite, and alkali silicate melt was studied by synchrotron infrared spectroscopy in diamond anvil cells to 1,000 °C and more than 200 kbar. Upon compression to 110 kbar at room temperature, a conversion of molecular CO
2 into a metastable carbonate species was observed for dacite and phonolite glass. Upon heating under high pressure, molecular CO
2 re-appeared. Infrared extinction coefficients of both carbonate and molecular CO
2 decrease with temperature. This effect can be quantitatively modeled as the result of a reduced occupancy of the vibrational ground state. In alkali silicate (NBO/
t = 0.98) and basaltic andesite (NBO/
t = 0.42) melt, only carbonate was detected up to the highest temperatures studied. For dacite (NBO/
t = 0.09) and phonolite melts (NBO/
t = 0.14), the equilibrium CO
2 + O
2? = CO
3 2? in the melt shifts toward CO
2 with increasing temperature, with ln
K = ?4.57 (±1.68) + 5.05 (±1.44) 10
3 T ?1 for dacite melt (Δ
H = ?42 kJ mol
?1) and ln
K = ?6.13 (±2.41) + 7.82 (±2.41) 10
3 T ?1 for phonolite melt (Δ
H = ?65 kJ mol
?1), where
K is the molar ratio of carbonate over molecular CO
2 and
T is temperature in Kelvin. Together with published data from annealing experiments, these results suggest that Δ
S and Δ
H are linear functions of NBO/
t. Based on this relationship, a general model for CO
2 speciation in silicate melts is developed, with ln
K =
a +
b/
T, where
T is temperature in Kelvin and
a = ?2.69 ? 21.38 (NBO/
t),
b = 1,480 + 38,810 (NBO/
t). The model shows that at temperatures around 1,500 °C, even depolymerized melts such as basalt contain appreciable amounts of molecular CO
2, and therefore, the diffusion coefficient of CO
2 is only slightly dependent on composition at such high temperatures. However, at temperatures close to 1,000 °C, the model predicts a much stronger dependence of CO
2 solubility and speciation on melt composition, in accordance with available solubility data.
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