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

被引:80
|
作者
Axson, Jessica L. [1 ,2 ]
Takahashi, Kaito [3 ]
De Haan, David O. [4 ]
Vaida, Veronica [1 ,2 ]
机构
[1] Univ Colorado, Dept Chem & Biochem, Boulder, CO 80309 USA
[2] Univ Colorado, Cooperat Inst Res Environm Sci, Boulder, CO 80309 USA
[3] Inst Atom & Mol Sci, Taipei 10617, Taiwan
[4] Univ San Diego, Dept Chem & Biochem, San Diego, CA 92110 USA
基金
美国国家科学基金会;
关键词
hydration; equilibrium constant; water clusters; VISIBLE ABSORPTION-SPECTRUM; OXALIC-ACID; SPECTROSCOPY; PHOTOLYSIS; CHEMISTRY; VAPOR;
D O I
10.1073/pnas.0912121107
中图分类号
O [数理科学和化学]; P [天文学、地球科学]; Q [生物科学]; N [自然科学总论];
学科分类号
07 ; 0710 ; 09 ;
摘要
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.
引用
收藏
页码:6687 / 6692
页数:6
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