Measurements and analysis of rototranslational absorption spectra of low density H2–Ar mixtures

1988 ◽  
Vol 66 (9) ◽  
pp. 803-809 ◽  
Author(s):  
P. Dore ◽  
A. Filabozzi ◽  
G. Birnbaum

We present new measurements of the rototranslational absorption of H2–Ar mixtures at 195 and 298 K. Measurements were made at densities as low as possible. The first accurate (5% error) rototranslational spectrum of the H2–Ar pair was thus derived. We performed a line-shape analysis of these spectra; as a result, we found a low-frequency component associated with an isotropic overlap induced dipole. We also found an important anisotropic overlap contribution associated with the dominant quadrupolar induction. Through a spectral-moment analysis we determined the intensity of isotropic (λ0 = 2.35 ± 0.15 × 10−3ea0) and anisotropic (λ1 = 0.9 ± 0.1 × 10−3ea0) overlap induced dipoles. The range of the isotropic overlap induced dipole was found to be ρ0 = (0.105 ± 0.010)σ, in very good agreement with the value 0.11 σ frequently assumed in the literature for the range of overlap induced dipoles. Our measurements and the results of our analysis were in good agreement with results of recent computations.

1987 ◽  
Vol 52 (2) ◽  
pp. 541-546 ◽  
Author(s):  
Vladimír Mlynárik

Carbon-13 relaxation times in the rotating frame were used to study the exchange between unequally populated rotamers of 2-furaldehyde. Calculated free activation energy and activation enthalpy are in good agreement with the results of 1H line shape analysis. Accuracy and reliability of this method in comparison with the line shape analysis is discussed.


1998 ◽  
Vol 63 (7) ◽  
pp. 955-966
Author(s):  
Eva Přibylová ◽  
Miroslav Holík

Four programs for the 1H NMR line shape analysis: two commercial - Winkubo (Bruker) and DNMR5 (QCPE 165) and two written in our laboratory - Newton (in Microsoft Excel) and Simtex (in Matlab) have been tested in order to get highly accurate rate constants of the hindered rotation about a single bond. For this purpose four testing criteria were used, two of them were also developed by us. As supplementary determinations the rate constants obtained for the coalescence temperature and for the thermal racemization of chromatographically separated enantiomers were used which fitted well the temperature dependence of the rate constants determined by the line shape analysis. As a test compound adamantan-1-yl 3-bromo-2,4,6-trimethylphenyl ketone was prepared and studied. It was shown that supermodified simplex method used in our algorithm (Simtex), though time consuming, gives the most accurate values of the rate constants and consequently the calculated thermodynamic parameters Ea, ∆H≠, and ∆S≠ lay in relatively narrow confidence intervals.


1973 ◽  
Vol 38 (6) ◽  
pp. 1210-1215 ◽  
Author(s):  
Linda G. Greifenstein ◽  
Joseph B. Lambert ◽  
Michael J. Broadhurst ◽  
Leo A. Paquette

Author(s):  
Et-touhami Es-sebbar ◽  
John Mantzaras ◽  
Yves Benilan ◽  
Aamir Farooq

1997 ◽  
Vol 07 (C1) ◽  
pp. C1-443-C1-444
Author(s):  
A. K. Srivastava ◽  
M. J. Patni ◽  
B. K. Chaturvedi

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