Low-temperature ozonation (-78degreesC) of 1,3-dioxolanes 1a-1f and 1,3-dioxanes 1g and h in acetone-d(6), methyl acetate, and tert-butyl methyl ether produced both the corresponding hemiortho esters (2a-h, ROH) and acetal hydrotrioxides (3a-h, ROOOH) in molar ratios ROH/ROOOH ranging from 0.5 to 23. Both types of intermediates were fully characterized by H-1, C-13, and O-17 NMR spectroscopy. DFT calculations suggest that ozone abstracts a hydride ion from 1 to form an ion pair, R+ -OOOH, which subsequently collapses to either the corresponding hemiortho ester (ROH) or the acetal hydrotrioxide (ROOOH). Hemiortho esters decomposed quantitatively into the corresponding hydroxy esters. Experimentally obtained activation parameters for the decomposition of 2a (E-a = 13.5 +/- 1.0 kcal/mol, log A = 8.3 +/- 1.0) are in accord with a highly oriented transition state involving, according to B3LYP calculations (DeltaH(a)(298) = 13.2 kcal/mol), two molecules of water as a bifunctional catalyst. This mechanism is also supported by the magnitude of the solvent isotope effect for the decomposition of 2e, i.e., kH(2)O/kD(2)O = 4.6 +/- 1.2. Besides the hydroxy esters and oxygen (O-3(2)/O-1(2)), dihydrogen trioxide (HOOOH) was formed in the decomposition of most of the acetal hydrotrioxicles (ROOOH) investigated. The activation parameters for the decomposition of the hydrotrioxicles 3a-e in various solvents were E-a = 20 +/- 2 kcal/mol, log A = 13.5 +/- 1.5. Several mechanistic possibilities for the decomposition of ROOOH were tested by experiment and theory. The formation of the hydroxy esters and oxygen could be explained by the intramolecular transfer of the proton to form the hydroxy ester. The assistance of water in the decomposition of ROOOH to form the hydroxy esters, either directly or via hemiortho esters, was also investigated. According to DFT calculations, the formation of a hydroxy ester via hemiortho ester is energetically more favorable (DeltaHa(298) = 14.5 kcal/mol), again due to the catalytic effect of two water molecules. HOOOH generation requires the involvement of water in the decomposition of ROOOH where the direct formation out of ROOOH is energetically preferred. The energy for a reaction between two molecules of water and singlet oxygen (Delta(1)O(2)) is too high to occur in solution.