화학공학소재연구정보센터
Journal of Physical Chemistry, Vol.100, No.39, 15695-15703, 1996
Vibrational Analysis of the Van-der-Waals Complexes Between Vinyl Fluoride and Hydrogen-Chloride in Liquefied Argon
The mid-infrared spectra (4000-400 cm(-1)) of vinyl fluoride/HCl and vinyl fluoride/DCl mixtures, dissolved in liquefied argon at 105 K, were examined. In both cases, evidence was found for the occurrence of a 1:1 van der Waals complex between CH2 = CHF and HCl (DCl). At higher concentrations of hydrogen chloride, absorption bands of a 1:2 species were also observed. By using spectra recorded at several temperatures between 95 and 115 K, the complexation enthalpies of CH2 = CHF . HCl and CH2 = CHF .(HCl)2 were determined to be -5.78 +/- 0.13 and -9.85 +/- 0.34 kJ mol(-1), respectively. A structural study, using nb initio calculations at the MP2/6-31 + G** level, indicates that the complexation can occur either via the fluorine atom or via the pi bond. From a comparison of the experimental with the ab initio vibrational frequencies, it was concluded that all observed bands of the 1:1 complex are due to a species complexed via the fluorine atom.