4.8 Article

Gas-phase water-mediated equilibrium between methylglyoxal and its geminal diol

Publisher

NATL ACAD SCIENCES
DOI: 10.1073/pnas.0912121107

Keywords

hydration; equilibrium constant; water clusters

Funding

  1. National Science Foundation
  2. Cooperative Institute for Research in Environmental Sciences
  3. NASA
  4. Direct For Mathematical & Physical Scien
  5. Division Of Chemistry [1011770] Funding Source: National Science Foundation
  6. Div Atmospheric & Geospace Sciences
  7. Directorate For Geosciences [0749145] Funding Source: National Science Foundation

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In aqueous solution, aldehydes, and to a lesser extent ketones, hydrate to form geminal diols. We investigate the hydration of methylglyoxal (MG) in the gas phase, a process not previously considered to occur in water-restricted environments. In this study, we spectroscopically identified methylglyoxal diol (MGD) and obtained the gas-phase partial pressures of MG and MGD. These results, in conjunction with the relative humidity, were used to obtain the equilibrium constant, K-P, for the water-mediated hydration of MG in the gas phase. The Gibbs free energy for this process, Delta G degrees, obtained as a result, suggests a larger than expected gas-phase diol concentration. This may have significant implications for understanding the role of organics in atmospheric chemistry.

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