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Perhydroxyl radical electron spin resonance spectrum in solution of hydrogen peroxide and water at 77 K, noting g factor, hyperfine splitting and molecular structure
Primary processes leading to atomic and molecular hydrogen formation in hydrogen peroxide photolysis at 1236 A, noting OH formation
Lithium peroxide utilization feasibility for oxygen supply and carbon dioxide control in extravehicular portable life support systems
Temperature measurement on thin steel shield subjected to hydrogen peroxide motor exhaust heating at cryogenic temperatures in space
Effects of chemical catalysts, bed cooling, chemical manufacturing techniques, operating conditions, and chemical handling procedures on lithium peroxide
The reactions were studied with the aid of a mass spectrometer. A pinhole bleed system provided continuous sampling of the gas mixture in the cell during the reaction. It was found that the homogeneous reactions of nitric oxide and nitrogen dioxide with hydrogen peroxide are too slow to be of any significance in the upper atmosphere. However, the heterogeneous reactions may be important in the conversion of nitric oxide to nitrogen dioxide in the case of polluted urban atmospheres.
Rate constants for the reaction of atomic chlorine with hydrogen peroxide were measured from 265-400 K using the flash photolysis-resonance fluorescence technique. Analytical techniques were developed to measure H2O2 under reaction conditions. Due to ambiguity in the interpretation of the analytical results, the data combine to give two equally acceptable representations of the temperature dependence. The results are compared to previous work at 298 K and are theoretically discussed in terms of the mechanism of the reaction. Additional experiments on the H + H2O2 reaction at 298 and 359 K are compared with earlier results from this laboratory and give a slightly revised bimolecular rate constant.
There is interest in solid materials containing a high percentage of stored oxygen for use in emergency breathing apparatus for miners and as auxiliary oxygen sources for astronauts. In theory, the amount of available oxygen in calcium superoxide, Ca(O2)2 is higher than in potassium superoxide, KO2, and its availability during use should be unhindered by the formation of a low melting and hydrous coating. The decomposition of solid calcium peroxide diperoxyhydrate, CaO2.2H2O2 has been studied, using an apparatus which allows good control of the critical reaction parameters. Samples have been prepared showing apparent superoxide contents in excess of those previously reported and higher than the theoretical 58.4% expected from a disproportionation reaction.
The ultraviolet absorption cross sections of hydrogen peroxide vapor have been determined over the wavelength range 210 to 350 nm at 296 K. At the longer wavelengths, the gas phase absorptivities are significantly larger than the corresponding values in condensed phase. The atmospheric H2O2 photodissociation rate for overhead sun at the earth's surface is estimated to be about 1.3 x 10 to the -5th/sec.
A hydrogen peroxide fueled rocket system, which is to be used as a research tool in flight studies of stall and spin maneuvers, was installed on a light, four place general aviation airplane. The pilot controlled rocket system produces moments about either the roll or the yaw body axis to augment or oppose the aerodynamic forces and inertial moments acting on the airplane during various flight maneuvers, including the spin. These controlled moments of a known magnitude can be used in various ways to help analyze and interpret the importance of the various factors which influence airplane maneuvers. The rocket system and its installation in the airplane are described, and the results of flight rests used to measure rudder and aileron effectiveness at airspeeds above the stall are presented. These tests also serve to demonstrate the operational readiness of the rocket system for future research operations.
Profiles of stratospheric ozone and chlorine monoxide radical (ClO) have been obtained from balloon measurements of atmospheric limb thermal emission at millimeter wavelengths. The ClO measurements, important for assessing the predicted depletion of stratospheric ozone by chlorine from industrial sources, are in close agreement with present theory. The predicted decrease of ClO at sunset was measured. A tentative value for the stratospheric abundance of hydrogen peroxide was also determined.
Results of an ab initio SCF quantum mechanical study are used to derive estimates for the infrared intensities of the fundamental vibrations of hydrogen peroxide. Atomic polar tensors (APTs) were calculated on the basis of a 4-31G basis set, and used to derive absolute intensities for the vibrational transitions. Comparison of the APTs calculated for H2O2 with those previously obtained for H2O and CH3OH, and of the absolute intensities derived from the H2O2 APTs with those derived from APTs transferred from H2O and CH3OH, reveals the sets of values to differ by no more than a factor of two, supporting the validity of the theoretical calculation. Values of the infrared intensities obtained correspond to A1 = 14.5 km/mol, A2 = 0.91 km/mol, A3 = 0.058 km/mol, A4 = 123 km/mol, A5 = 46.2 km/mol, and A6 = 101 km/mol. Charge, charge flux and overlap contributions to the dipole moment derivatives are also computed.
The fluorometric gas-phase hydrogen peroxide procedure is based on the technique used by Lazrus et. al. for the determination of H2O2 in the liquid phase. The analytical method utilizes the reaction of H2O2 with horseradish peroxidase and p-hydroxphenylacetic acid (POPHA) to form the fluorescent dimer of POPHA. The analytical reaction responds stoichiometrically to both H2O2 and some organic hydroperoxides. To discriminate H2O2 from organic hydroperoxides, catalase is used to preferentially destroy H2O2. Using a dual-channel flow system the H2O2 concentration is determined by difference.
Relative absorption cross sections for hydrogen peroxide vapor were measured over the temperature ranges 285-381 K for lambda = 230 nm-295 nm and 300-381 K for lambda = 193 nm-350 nm. The well established 298 K cross sections at 202.6 and 228.8 nm were used as an absolute calibration. A significant temperature dependence was observed at the important tropospheric photolysis wavelengths lambda over 300 nm. Measured cross sections were extrapolated to lower temperatures, using a simple model which attributes the observed temperature dependence to enhanced absorption by molecules possessing one quantum of O-O stretch vibrational excitation. Upper tropospheric photodissociation rates calculated using the extrapolated cross sections are about 25 percent lower than those calculated using currently recommended 298 K cross sections.
The first unequivocal measurement of hydrogen peroxide in the stratosphere have been made, a concentration profile obtained from a balloon platform using Fourier transform thermal emission spectroscopy in the far infrared. Measurements were made using the 112/cm R-Q5 branch of the rotational-torsional spectrum, with some confirmation from the 94/cm R-Q4 branch. The volume mixing ratio of H2O2 is 1.6 x 10 to the -10th at 38.4 km, decreasing to 0.6 x 10 to the -10th at 23.8 km, with uncertainties of about 16 percent. These measurements are compared to a recent stratospheric model calculation.
Possible pathways for the evolution of oxygenic photosynthesis in the early reducing atmosphere of the earth are discussed. It is suggested that the abiotic production of atmospheric oxidants could have provided a mechanism by which locally oxidizing conditions were sustained within spatially confined habitats thus removing the available reductants and forcing photosynthetic organisms to utilize water (rather than ferrous or sulfide ions) as the electron donor. It is argued that atmospheric H2O2 played the key role in inducing oxygenic photosynthesis, because, as peroxide concentrations local environments increased, primitive organisms would not only be faced with a loss of a reductant, but would be also forced to develop a biochemical apparatus (such as catalase) that would protect them against the products of oxygenic photosynthesis. This scenario allows for the early evolution of oxygenic photosynthesis at the time when global conditions were still anaerobic.
We evaluate the ability of a 3% (8800 micromolar) solution of hydogen peroxide to kill 12 strains of bacteria and 12 strains of fungi. A 1:4 dilution of 3% H2O2 equivalent to 1100 micromolar, was lethal to all the tested strains. If the situation calls for a nonagressive disinfectant without residue or toxic aftereffects, 3% H2O2 seems an ideal choice.
We measured gas phase H2O2, CH3OOH, and CH2O on board the NASA DC-8 during the SONEX field mission, presented preliminary results at three scientific meetings, participated in two data workshops and contributed to joint publications of final results. The observations of peroxides and formaldehyde were instrumental in assessing odd-hydrogen radical chemistry, ozone chemistry, and in tracing meteorological transport paths.