Kinetic parameters for two-electron oxidation of hydrogen peroxide by hypochlorous acid have been determined. Reaction with HOCI proceeds according to the rate law d[02]/dz = fc2[HOCl] [H+] [Cl-]; with OC1ion, d[02]/dz = k3[H202]-[OC1-].For the alkaline (k3) pathway, the primary yield of electronically excited oxygen was measured by chemical trapping with 2,5-dimethylfuran (DMFu); results indicate essentially 100% initial formation of ( )02. The rate law for reaction with HOCI is identical with that found for halogenation of DMFu and other reactive organic molecules and, possibly, for conversion of HOCI to Cl2. Kinetic arguments are presented supporting the view that these reactions proceed by rate-limiting formation of a common reactive intermediate whose stoichiometry is H20C12. From consideration of available thermodynamic parameters, molecular mechanisms and activated complex geometries for the various pathways are proposed.
Articles you may be interested inProtonation effect on the electronic properties of 2-pyridone monomer, dimer and its water clusters: A theoretical study J. Chem. Phys. 140, 024315 (2014); 10.1063/1.4859255 Magnetocaloric effect and spin reorientation transition in single-crystal Er 2 ( Co 0.4 Fe 0.6 ) 17 J. Appl. Phys. 105, 07A918 (2009); 10.1063/1.3063669Effect of oxygen adsorption on the structure and spin-reorientation transition of Fe films on Cu (1 1 25) Rotationally resolved ultraviolet spectroscopy of indole, indazole, and benzimidazole: Inertial axis reorientation in the S 1(1 L b )←S 0 transitions Rotationally resolved fluorescence excitation spectra of two vibronic bands in the SI <-So electronic transition of2-hydroxypyridine (2HP), and of the corresponding bands in the hydroxy-deuterated molecule, have been obtained. A comparison of the rotational constants of the two molecules shows that the two bands both originate in the zero-point vibrati6nallevel of the planar keto tautomer of2HP, 2-pyridone (2PY), and terminate in different zero-point levels of 2PY that have different out-of-plane eqUilibrium geometries at nitrogen. Additionally, all four bands exhibit "anomalous" rotational line intensities that are shown to result from an in-plane inertial axis reorientation which occurs on absorption of the photon. Likely atomic displacements that are responsible for this "rotational" Duschinsky effect, which may have significant dynamical consequences in 2PY and other molecules, are discussed.
Rotationally resolved Si •*-So electronic spectra of the hydrogen-bonded complexes of 2-pyridone (2PY) with one and two ammonia molecules have been observed. Both complexes, in both electronic states, exhibit behavior which indicates that the ammonia molecule acts as both an acid and a base. Evidence for this amphoteric behavior in the monosolvated complex (2PY-NH3) is found in the derived, effective, hydrogen-bonded structure and in the barriers to internal rotation of the NH3 group, K3(S0) = 424.3 cm-1 and K3(Si) = 274.4 cm-1. The effective structure derived for the disolvated complex [2PY-(NH3)2] shows strong hydrogen bonding, similar to that found for the dihydrated complex (Held and Pratt, J. Am. Chem. Soc., preceding paper in this issue). The donor and acceptor bonds in 2PY-(NH3)2 are strong enough to completely inhibit any internal rotation of the ammonia molecules. Like the dihydrated complex, 2PY-(NH3)2 exists in a number of different conformational forms. The structural and dynamical properties of these complexes are discussed.
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