Melting curve and high-pressure chemistry of formic acid to 8 GPa and 600 K.

We have determined the melting temperature of formic acid (HCOOH) as a function of pressure to 8.5 GPa using infrared absorption spectroscopy, Raman spectroscopy and visual observation of samples in a resistively heated diamond-anvil cell. The experimentally determined incongruent melting curve compares favorably with a two-phase thermodynamic model. Decomposition reactions were observed above the melting temperature up to a pressure of 6.5 GPa, with principal products being CO2, H2O, and CO. At pressures above 6.5 GPa, decomposition led to reaction products that could be quenched as solids to zero pressure, and infrared and Raman spectra indicate that pressure leads to the presence of sp3 carbon-carbon bonding in these reaction products.