Rotational State Change of Acetonitrile Vapor on MCM-41 upon Capillary Condensation with the aid of Time-Correlation Function Analysis of IR Spectroscopy

The infrared spectra of adsorbed acetonitrile on MCM-41 (porewidth = 3.2 nm) were measured at 303 K. In the CN stretching ν2 region, two bands were observed at 2265 cm− 1 and 2254 cm− 1, assigned to hydrogen-bonded molecules on surface hydroxyls of MCM-41, and physisorbed molecules in mesopores, respectively. We designate here the 2265 cm− 1 band as the ν2α band and the 2254 cm− 1 band as the ν2β band. The bandwidth of the fundamental transition ν2fβ, was obtained by removing the overlap with hot band transitions of the same mode, ν2α band, and other modes by least-squares fitting. Before capillary condensation, the relaxation time τ obtained from the bandwidth of the ν2fβ band was smaller …

Molecular mechanism of capillary condensation of acetonitrile vapor on MCM-41 with the aid of a time-correlation function analysis of IR spectroscopy

Abstract The adsorption isotherm and IR spectra of acetonitrile adsorbed on MCM-41 (pore-width=3.2 nm) were measured at 303 K. The adsorption isotherm had a sharp jump at P / P 0 =0.3 without adsorption hysteresis. The CN stretching ν 2 -band of adsorbed acetonitrile had two-component α- and β-bands at 2263 and 2254 cm −1 , respectively, assigned to hydrogen-bonded molecules on surface hydroxyls of MCM-41 and physisorbed molecules in mesopores whose walls are coated with hydrogen-bonded molecules, respectively. The β-band was analyzed with a time correlation function, giving a reorientation time τ . The τ value of the adsorbed molecule before capillary condensation was smaller than that of …

Relationship between intrinsic pore-wall corrugation and adsorption hysteresis of N-2, O-2, and Ar on regular mesopores