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Kinetic study of the isotope exchange reactions of malonic acid and its derivatives in various acidic D 2 O media using 1 H NMR spectroscopy. Implication in the Belousov‐Zhabotinsky reaction
Author(s) -
Hsu M.C.,
Jwo J.J.
Publication year - 1999
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/(sici)1097-4601(1999)31:6<455::aid-kin7>3.0.co;2-0
Subject(s) - chemistry , kinetic isotope effect , deuterium , malonic acid , catalysis , hydrogen–deuterium exchange , nuclear magnetic resonance spectroscopy , spectroscopy , kinetics , isotope , medicinal chemistry , chemical kinetics , ion exchange , inorganic chemistry , ion , organic chemistry , hydrogen , physics , quantum mechanics
The kinetics of the isotope exchange reactions of RCH(COOH) 2 (RH, D, Me, Et, Bu, and Ph) in D 2 O solution were studied by using 1 H NMR spectroscopy. It was observed that the rate of isotope exchange reaction was inhibited by the presence of 1 M of DNO 3 , DCl, DBr or D 2 SO 4 and catalyzed by the presence of 4 M of D 2 SO 4 . No inhibition effect was observed in the case of D 3 PO 4 . The effect of inorganic acids follows the order of D 3 PO 4 >D 2 SO 4 ≫ (DNO 3 , DCl, DBr). The conjugated base (RCH(COOD)(COO − )) of RCH(COOD) 2 plays an important role in the isotope exchange reaction. The presence of deuterium ion suppresses the generation of RCH(COOD)(COO − ) ion from RCH(COOD) 2 and inhibits the rate of isotope exchange. In general, the order of reactivity of RCH(COOH) 2 toward isotope exchange with deuterium atom is RPh>(H, Br)>Me>(Et, Bu). © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 455–461, 1999