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Deuteration kinetics of N ‐methylacetamide by means of a stopped‐flow multi‐detector Raman spectrophotometry
Author(s) -
Nishimura Yoshifumi,
Tsuboi Masamichi
Publication year - 1982
Publication title -
journal of raman spectroscopy
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.748
H-Index - 110
eISSN - 1097-4555
pISSN - 0377-0486
DOI - 10.1002/jrs.1250120210
Subject(s) - raman spectroscopy , chemistry , analytical chemistry (journal) , kinetics , amide , excitation , volumetric flow rate , spectrophotometry , reaction rate constant , chromatography , optics , physics , organic chemistry , thermodynamics , quantum mechanics
N ‐methylacetamide dissolved in 1 H 2 O was rapidly mixed with 2 H 2 O by the use of a stopped‐flow device, and Raman spectra of the mixed solution were observed at various times in the course of the deuteration reaction by the use of a multi‐detector system. With continuous wave excitation (Ar + laser), the time‐resolution reached by our present setup was about 50 ms. The molecular association of N ‐methylacetamide in H 2 O was found to cause a low‐frequency shift of the amide III Raman band at 1317 cm −1 by 9 cm −1 . The effect of this association upon the deuteration rate, however, was not found to be appreciable. At 25°C, the rate constants were determined to be 0.067, 0.14, 0.20, 0.41, and 0.63 s −1 at pH = 6.43, 6.87, 7.15, 7.39, and 7.43, respectively.