1987 Fiscal Year Final Research Report Summary
Electrostatic spray of liquid : Study on the charged particles in the condensed phase
| Project/Area Number |
60470007
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| Research Category |
Grant-in-Aid for General Scientific Research (B)
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| Allocation Type | Single-year Grants |
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| Research Field |
物理化学一般
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| Research Institution | Yamanashi University |
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Principal Investigator |
HIRAOKA Kenzo Yamanashi University, Associate Professor, 工学部, 助教授 (80107218)
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| Project Period (FY) |
1985 – 1987
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| Keywords | electrostatic spray / cluster ions / ion extraction / クラスターイオン |
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| Research Abstract |
The study on the ion solvation is a rather difficult task because of the lack of suitable methodology. In this work, the extraction of ions dissolved in the liquid into the gas phase by applying a strong electric field to the liquid are studied, and an information on the physicochemical behavior of ions in the condensed phase is investigated in detail. This will lead to the elucidation of the solvent effect, chemical reactivity of ions in the condensed phase, solvated electron, etc.
In order to investigate the mechanism of ion solvation, the thermochemical stabilities, structures, and stabilities were studied using the high-pressure mass spectrometer. It was found that the F^- ion is highly reactive toward the solvent molecules and often forms the covalent bodn with them. In contrast, other halide ions (Cl^-, Br^-, I^-) are solvated only electrostatically by solvent molecules. Water is a superior solvent toward a variety of ions. We pointed out that this is due to the mutual polarizatio
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n of water ligands belonging to the different solvation shells which strengthens the interaction between them (enhancement effect). The alcohol molecules in the first shell experience stronger interaction with ions than watermolecules. However, the enhancement effect for alcohols is weaker than that for water, and thus alcohols are generally poorer solvents than water toward ions.
An approximate linear relationship was found between gas-phase proton affinities of conjugate bases B's and free energies of hydration of conjugate ions BH^+'s for B = alkyl-substituted H_2O and NH_3. This means that if the conjugate base B has a higher proton affinity, its conjugate acid ion BH is easier to be extracted from the condensed phase to the gas phase. Thus the electrospray could be a useful tool for the analysis of solvated ions in the fields of medicine, pharmacy, and agriculture.
The ions in solution were electrosprayed and mass-analysed. All of the detected major ions are found to be pseudo-molecular ions. This indicates that the ion extraction process is very mild. Less
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[Publications] K,Hiraoka, S,Mizuse, and S,Yamabe: "Gas-phase solvation of C1^- with H_2O, CH_3OH, C_2H_5OH, i-C_3H_7OH, n-C_3H_7OH, and t-C_4H_9OH" Chemical Physics. 118. 457-466 (1987)
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