• Mass Spectrometry Letters
• /
• 제5권4호
• /
• pp.120-123
• /
• 2014

The interference of water vapor on the chemical ionization (CI) of hydroxyl radicals (OH) by sulfur hexafluoride ion ($SF_6{^-}$) was investigated using a flow tube system coupled to a high-pressure CI mass spectrometer. Water vapor, which is required to study heterogeneous reactions of OH under real tropospheric conditions, transforms the reagent ion $SF_6{^-}$ into $SF_4O^-$ and $F^-(HF)_n$, resulting in a substantial loss in CI sensitivity. Therefore, under humid conditions, peaks corresponding to OH are drastically diminished, while those corresponding to OH-water complex ions ($[OH(H_2O)_n]^-$) are enhanced. $[OH(H_2O)_3]^-$ was observed as the major OH species. The obsercation of $[OH(H_2O)_n]^-$ by isolating humid conditions to the CI region and preliminary ab initio calculations suggested that $[OH(H_2O)_n]^-$ ions were produced from reactions between OH ions ($OH^-$) and water molecules. An additional helium buffer flow introduced into the CI region reduced loss of the reagent ion and resulted in a partial recovery of OH peak intensities under humid conditions.