Thermal decomposition of formaldehyde diperoxide in aqueous solution |
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| Authors: | S. A. I. Cazut E. H. Ramírez Maisuls M. R. Delfino J. M. Romero N. L. Jorge E. A. Castro |
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| Affiliation: | 1. área Fisicoquímica, Facultad de Ciencias Exactas y Naturales y Agrimensura, UNNE, Campus Universitario, Av. Libertad 5400, Corrientes, 3400, Argentina
2. INIFTA, División Química Teórica, Departamento de Química, Facultad de Ciencias Exactas, Diagonal 113 y 64, Suc. 4, C.C. 16, La Plata, Buenos Aires, 1900, Argentina
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| Abstract: | Thermal decomposition of formaldehyde diperoxide (1,2,4,5-tetraoxane) in aqueous solution with an initial concentration of 6.22 × 10?3 M was studied in the temperatures range from 403 to 439 K. The reaction was found to follow first-order kinetic law, and formaldehyde was the major decomposition product. The activation parameters of the initial step of the reaction (ΔH ≠ = 15.25 ± 0.5 kcal mol?1, ΔS ≠ = ?47.78 ± 0.4 cal mol?1K?1, E a = 16.09 ± 0.5 kcal mol?1) support a mechanism involving homolytic rupture of one peroxide bond in the 1,2,4,5-tetraoxane molecule with participation of the solvent and formation of a diradical intermediate. |
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