Hydrodynamic Interpretation on the Rotational Diffusion of Peroxylamine Disulfonate Solute Dissolved in Room Temperature Ionic Liquids As Studied by Electron Paramagnetic Resonance Spectroscopy

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• 作者：Yusuke Miyake ; Nobuyuki Akai ; Akio Kawai ; Kazuhiko Shibuya
• 刊名：Journal of Physical Chemistry A
• 出版年：2011
• 出版时间：June 23, 2011
• 年：2011
• 卷：115
• 期：24
• 页码：6347-6356
• 全文大小：968K
• 年卷期：v.115,no.24(June 23, 2011)
• ISSN：1520-5215

文摘

Rotational motion of a nitroxide radical, peroxylamine disulfonate (PADS), dissolved in room temperature ionic liquids (RTILs) was studied by analyzing electron paramagnetic resonance spectra of PADS in various RTILs. We determined physical properties of PADS such as the hyperfine coupling constant (A), the temperature dependence of anisotropic rotational correlation times (蟿 and 蟿), and rotational anisotropy (N). We observed that the A values remain unchanged for various RTILs, which indicates negligible interaction between the N鈥揙 PADS group and the cation of RTIL. Large N values suggest strong interaction of the negative sulfonyl parts of PADS with the cations of RTILs. Most of the 蟿, 蟿, and (蟿蟿)^1/2 values are within the range calculated on the basis of a hydrodynamic theory with stick and slip boundary conditions. It was deduced that this theory could not adequately explain the measured results in some RTILs with smaller BF₄ and PF₆ anions.