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1996•Journal of the American Chemical SocietyRequires access

A Reassessment of the Bond Dissociation Energies of Peroxides. An ab Initio Study

Robert D. Bach, Philippe Y. Ayala, H. Bernhard Schlegel

Open publisher page 306 citations

Abstract

The strength of the O−O bond is of fundamental importance in a variety of chemical processes. Traditionally, a value of 34 kcal/mol has been ascribed to a generic O−O bond dissociation energy. The present, high-level ab initio calculations indicate that the average O−O bond energy is significantly higher, ca . 45 kcal/mol, and that the bond energy is sensitive to the bonding environment. Calculations at the G2 level of theory give bond dissociation enthalpies at 298 K of 50 kcal/mol for HOOH, 45 kcal/mol for CH 3 OOH, 39 kcal/mol for CH 3 OOCH 3, and 48 kcal/mol for HC(O)OOH and CH 3 C(O)OOH. The G2(MP2) results are similar and, additionally, give bond dissociation enthalpies of 38 kcal/mol for diacetyl peroxide, 49 kcal/mol for trifluoroperoxyacetic acid, 23 kcal/mol for isopropenyl hydroperoxide, and 22 kcal/mol for peroxynitrous acid.

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What this paper is about

The strength of the O−O bond is of fundamental importance in a variety of chemical processes. Traditionally, a value of 34 kcal/mol has been ascribed to a generic O−O bond dissociation energy. The present, high-level ab initio calculations indicate that the average O−O bond energy is significantly higher, ca . 45 kcal/mol, and that the bond energy is sensitive to the bonding environment. Calculations at the G2 level of theory give bond dissociation enthalpies at 298 K of 50 kcal/mol for HOOH, 45 kcal/mol for CH 3 OOH, 39 kcal/mol for CH 3 OOCH 3, and 48 kcal/mol for HC(O)OOH and CH 3 C(O)OOH. The G2(MP2) results are similar and, additionally, give bond dissociation enthalpies of 38 kcal/mol for diacetyl peroxide, 49 kcal/mol for trifluoroperoxyacetic acid, 23 kcal/mol for isopropenyl hydroperoxide, and 22 kcal/mol for peroxynitrous acid.

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Available abstract

The strength of the O−O bond is of fundamental importance in a variety of chemical processes. Traditionally, a value of 34 kcal/mol has been ascribed to a generic O−O bond dissociation energy. The present, high-level ab initio calculations indicate that the average O−O bond energy is significantly higher, ca . 45 kcal/mol, and that the bond energy is sensitive to the bonding environment. Calculations at the G2 level of theory give bond dissociation enthalpies at 298 K of 50 kcal/mol for HOOH, 45 kcal/mol for CH 3 OOH, 39 kcal/mol for CH 3 OOCH 3, and 48 kcal/mol for HC(O)OOH and CH 3 C(O)OOH. The G2(MP2) results are similar and, additionally, give bond dissociation enthalpies of 38 kcal/mol for diacetyl peroxide, 49 kcal/mol for trifluoroperoxyacetic acid, 23 kcal/mol for isopropenyl hydroperoxide, and 22 kcal/mol for peroxynitrous acid.

Key concepts: Chemistry, Bond-dissociation energy, Bond energy, Ab initio, Dissociation (chemistry), Standard enthalpy of formation, Peroxide, Ab initio quantum chemistry methods

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