Iron-Catalyzed Reaction between Nitrosyl Disulfonate and Hydroxylamine Monosulfonate Ions

Abstract

An investigation of the kinetics of the iron-catalyzed reaction between the purple-colored, paramagnetic nitrosyl disulfonate (ON(SO3)₂ ⁼ ) ions and hydroxylamine monosulfonate (HONHSO₃^---) ions has been made. [W. J. Ramsey and D. M. Yost, J. Chem. Phys. 21, 957 (1953)]. At a temperature of 20°C, an ionic strength of 0.026, and total added iron concentrations less than 3.5×10^—7 VF, the initial rate of disappearance of ON(SO3)₂ ⁼ is well represented by the equation: [dformula -((d(ON(SO[sub 3])[sub 2] [equals sign] ))/dt) [equals sign] 2{((k[sub 2]h[sub 1](H[sup +]) + k[sub 3]h[sub 1]h[sub 2])/((H[sup +])[sup 2] + h[sub 1](H[sup +]) + h[sub 1]h[sub 2]))}(Sigma Fe[sup +3])(HONHSO[sub 3][sup -]),] where h1 and h2 are the first and second hydrolysis constants for ferric iron and where k2 and k3 are the specific second-order rate constants for the reactions of HONHSO₃^--- with Fe(OH) + + and Fe(OH)₂ ⁺ , respectively. Under the above conditions, and if a value of 3×10^—3 is assumed for h1; h2, k2, and k3 have the values, 7×10^—4 l·mole^—1, 13.7±1.0×10^4 l·mole^—1·min^—1, and 1.5±0.5×10^4 l·mole^—1·min^—1, respectively.

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