1112-02-3Relevant articles and documents
Rotational isomerism of acetic acid isolated in rare-gas matrices: Effect of medium and isotopic substitution on IR-induced isomerization quantum yield and cis→ trans tunneling rate
Macoas,Khriachtchev,Pettersson,Fausto,Raesaenen
, p. 1331 - 1338 (2004)
The rotational isomerization of acetic acid was studied in Ar, Kr, and Xe matrices. Using resonant excitation of a number of modes in the 3500-7000 cm-1 region, the light induced trans→cis reaction was promoted. The quantum yields for this process were also measured for various acetic acid isotopologues and matrix materials. For excitation of acetic acid at energies above the predicted isomerization energy barrier, it was found that the measured quantum yields were in average 2%-3%, one order of magnitude smaller that the corresponding values known for formic acid.
Halford, J. O.,Anderson, L. C.
, p. 736 - 740 (1936)
-
Burr
, p. 1481 (1957)
-
Secondary deuterium isotope effects on the acidity of carboxylic acids and phenols
Perrin, Charles L.,Dong, Yanmei
, p. 4490 - 4497 (2008/02/04)
Secondary deuterium isotope effects (IEs) on acidities have been accurately measured by an NMR titration method applicable to a mixture of isotopologues. Deuteration definitely decreases the acidity of carboxylic acids and phenols, by up to 0.031 in the ΔpK per D. For aliphatic acids, the IEs decrease as the site of deuteration becomes more distant from the OH, as expected, but a surprising result is that IEs in both phenol and benzoic acid do not decrease as the site of deuteration moves from ortho to meta to para. The experimental data are supported by ab initio computations, which, however, substantially overestimate the IEs. The discrepancy does not seem to be due to solvation. The IEs originate in isotope-sensitive vibrations whose frequencies and zero-point energies are lowered upon deprotonation. In the simplest case, formate, the key vibration can be recognized as the C-H stretch, which is weakened by delocalization of the oxygen lone pairs. For the aromatic acids, delocalization cannot account for the near constancy of IEs from ortho, meta, and para deuteriums, but the observed IEs are consistent with calculated vibrational frequencies and electron densities. Moreover, the ability of the frequency analysis to account for the IEs is evidence against an inductive origin.