Thermochemistry of cyclic acetone peroxides

• Old data on DADP and TATP enthalpies of formation have been revised.
• Combining Gaussian-4 (G4) theory with an isodesmic reaction scheme allowed calculated enthalpies of formation of TATP and DADP.
• Oxygen bomb calorimetry measurements allowed experimental enthalpies of formation of the peroxides.
• Both experimental and calculated values show a satisfactory agreement between each other.
• The newly obtained enthalpies reasonably account for the observed derivative parameters: heats of decomposition, combustion, and explosion.

Two potentially initiating explosive peroxides, diacetonediperoxide (DADP) and triacetonetriperoxide (TATP), were studied in respect to their thermochemical properties. To get the internally self-consistent estimations of gas-phase enthalpy of formation of DADP and TATP, their values were calculated by combining Gaussian-4 (G4) theory with an isodesmic reaction scheme. The energies of combustion (ΔcU  ) were measured and the standard enthalpies of formation (ΔfH298°) of DADP and TATP were derived using the standard enthalpies of formation of the combustion products. The heat of explosion was measured for small low-pressed charges of the peroxides. The obtained enthalpies of formation of DADP and TATP were found to agree well with quantum chemical calculations and reasonably account for the observed derivative parameters: heats of decomposition, combustion, and detonation.