Journal of Physical Chemistry p. 265 - 272 (1992)
Update date:2022-08-11
Topics:
Zhou, Xianliang
Lee, Yin-Nan
The aqueous-phase equilibria and kinetics of the formation of hydroxymethyl hydroperoxide (HMP) and of bis(hydroxymethyl) peroxide (BHMP) from formaldehyde and hydrogen peroxide, i.e., H2CO + H2O2 <*> HOCH2O2H (1, -1), and HOCH2O2H + H2CO <*> HOCH2O2CH2OH (2) were studied using an amperometric technique which is highly sensitive and selective for H2O2.The equilibrium constants of reactions 1 and 2 between 5 and 35 deg C were determined to be K1 = 2.35*10-2 exp(2610/T) M-1 and K2 = 1.04*10-3 exp(2780/T) M-1, respectively, both independent of pH between 4.0 and 8.4.The rate coefficients of (1) and (-1) determined at pH 7.07 +/- 0.02 between 5 and 35 deg C are k1 = 6.0*1013 exp(-9450/T) M-1 s-1 and k-1 = 1.0*1015 exp(-11800/T) s-1.Both k1 and k-1 are base-catalyzed and are linearly dependent on pH between 4.0 and 8.2, namely, k-1 = (5.0 +/- 0.3)*10-10/
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