Formation of Hydrogen Polyoxides As Constituents of Peroxy Radical Condensate upon Low-Temperature Interaction of Hydrogen Atoms with Liquid Ozone

Abstract

The composition of low-temperature condensates obtained by the reaction of hydrogen atoms with liquid ozone has been determined from the Raman spectra and data on the molar ratio of O2 to H2O2 in the decomposition products. The main constituents are hydrogen tetroxide H2O4, trioxide H2O3, and peroxide H2O2 in comparable amounts and also water H2O. The mechanism and quantitative kinetic model of their formation have been proposed. H2O4, H2O3, and H2O2 are formed in the diffusion-controlled reactions between OH and HO2 in the liquid ozone layer and stabilized by transfer to the solid phase. OH and HO2 radicals are generated via a sequence of the reactions initiated by the interaction H + O3(liq). The model adequately reproduces the properties of the real condensates.

Theoretical investigation of the structures and spectroscopic properties of (H2O4)n (n = 1–4) clusters

“…Lee and coworkers obtained H 2 O 4 from the UV photolysis of H 2 CO in O 2 at a low temperature, and they concluded that the structure of H 2 O 4 was that of a HOO radical dimer from the matrix isolated IR spectrum . More recently, Levanov et al confirmed the chainlike structure of H 2 O 4 from the peaks at 449, 589, 624, 827, and 865 cm −1 in the Raman spectrum of H 2 O 4 (prepared in relatively large quantities) and observed the Raman spectra of H 2 O 4 , H 2 O 3 , and H 2 O 2 from the reaction of hydrogen atoms with liquid ozone and from electro‐dissociated water vapor …”

Thermochemistry of HO2 + HO2 → H2O4: Does HO2 Dimerization Affect Laboratory Studies?

“…In the 1980s, Rice–Ramsperger–Kassel–Marcus (RRKM) calculations were compared to pressure-dependent kinetics measurements of HO 2 + HO 2 . ,, These gas-phase studies did not indicate significant H 2 O 4 production. However, hydrogen polyoxides have been detected in the condensed phase. ,,, These experiments trap a microwave discharge of H 2 /O 2 in liquid nitrogen to obtain a mixture of hydrogen polyoxides (HOOH, HO 3 H, HO 4 H), then measure the Raman spectrum of the condensate (0–1500 cm –1 ). Levanov et al assigned peaks to HO 4 H on the basis of quantum mechanical calculations, though the overlap of HOOH, HO 3 H, and HO 4 H spectroscopic peaks makes assignment of the spectrum difficult. , …”

Superconductivity of hydrogen superoxide under high pressure

“…On the other hand, if X is an element included in the group 14 to 16, then X accepts electrons from H 2 , which causes the dissociation of H 2 and the formation of covalent bonds between X and H, e.g., H 3 S. Our predicted HO 2 also follows the trend of the latter case as seen in figure 1, whereas the O 2 bonds still remain strong and the enhancement of the superconductivity is much smaller than that in H 3 S. HO 2 , which is also known as the hydroperoxyl radical, is a key transient intermediate in combustion reaction, atmospheric photolysis cycles, and biochemical processes. HO 2 takes an H-O-O-O-O-H chain structure with covalent bonding [55,56], and its solid condensate is experimentally obtained by the reaction of hydrogen atoms with liquid ozone at low temperature of 77 K [57]. Therefore, following the strategy adopted for the exploration of the superconductivity in H 2 S [2], the superconductivity of HO 2 can be observed via loading the sample in DAC at low temperatures below 77 K and then compressing to 180 GPa.…”