B63
Stadlbauer,
J.M., Barnabas, M.V. and Walker, D.C.
J.
Phys. Chem.A,
1997, 101, 2442.
Reaction:
HOOC-COOH
+ Mu ®
HOOCC(OMu)OH
Type
of reaction: addition to C=O of carboxylate group with Mu attached to an O
atom
kMobs
=
(4.8 ± 0.4) x 108 dm3mol-1s-1 at pH = 0.52 (ca. 83% H2C2O4 and 17 % HC2O4-)
kMobs
=
(3.4
± 0.3) x 108 dm3mol-1s-1
at pH = 1.0 (ca. 50 %) H2C2O4 and 50 %
HC2O4-)
a)
Barnabas, M.V. and Walker, D.C. Can. J. Chem., 1991, 69,
1252.
kM(obs)
= 2 x 109 dm3mol-1s-1
pH = 1.0
kM
=
(5.6
± 0.6) x 108 dm3mol-1s-1
for H2C2O4 (value deduced)
KIE = kMobs
/ kHobs = 3.4 x 108 / 3.4 x 105 =
1000
KIE value indicate different routes for Mu and H atoms
kH(obs)
= 3.4 x 105 dm3mol-1s-1 average of
2 values
at pH=1.0
from:
www.rcdc.nd.edu/compilations/HAtom/H.htm
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