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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.
Materials test methods from the 1960's have been used as a starting point in evaluating materials for today's space launch vehicles. These established test methods have been modified to incorporate today's analytical laboratory equipment. The Orbital test objective was to test a wide range of materials to incorporate the revolution in polymer and composite materials that has occurred since the 1960's. Testing is accomplished in 3 stages from rough screening to detailed analytical tests. Several interesting test observations have been made during this testing and are included in the paper. A summary of the set-up, test and evaluation of long-term storage sub-scale tanks is also included. This sub-scale tank test lasted for a 7-month duration prior to being stopped due to a polar boss material breakdown. Chemical evaluations of the hydrogen peroxide and residue left on the polar boss surface identify the material breakdown quite clearly. The paper concludes with recommendations for future testing and a specific effort underway within the industry to standardize the test methods used in evaluating materials.
The compatibility of composite materials with high-test hydrogen peroxide (HTP) was assessed using various chemical and mechanical techniques. Methods included classical schemes combining concentration assay with accelerated aging by means of a heated water bath. Exothermic reactivity was observed using Isothermal Microcalorimetry. Mechanical Properties testing determined degradation of the composite material. Photoacoustic Infrared Spectroscopy was used to monitor chemical alteration of the resin matrix. Other materials were examined including some polymers and metals.
Assessment of the compatibility of high-test hydrogen peroxide (HTP) with materials, in particular new materials such as composites, is critical to the development of new propulsion systems meeting requirements of reduced cost and environmental impact. While compatibility with HTP has been addressed previously, newer materials were not considered. The focus of this project was to develop a scheme for evaluation of HTP with all materials. In the previous summer, methods were developed for production of HTP on site, and preliminary steps were taken to evaluate materials. Methods investigated this summer have included accelerated aging by heating, coupled with assay of concentration and stabilization loss, observation of reactivity by means of Isothermal Microcalorimetry, and evaluation of changes to the materials by Short Beam Shear testing and by Photoacoustic-Fourier Transform Infrared Spectroscopy. Various metals, polymers, and composites were examined in this study.
A specialized rodent food bar diet has been developed and utilized successfully for short-duration shuttle missions. Recent tests conducted in preparation for experiments aboard the International Space Station (ISS) indicated that long-term food bar feeding for three months induced hyperlipidemia in rats. This study examined oxidative stress status in livers of these same animals. Spectrophotometric analysis of 79 Fischer rat livers (40 female and 39 male) for lipid peroxidation (LPO) and superoxide dismutase (SOD) was conducted using Bioxytech LPO-587(TM) assay kit and SOD-525(Tm) assay kit, respectively. The treatment groups consisted of 20 male CHOW and 19 male FOOD BAR rats and 20 female CHOW and 20 female FOOD BAR rats. Statistical analysis to compare differences between groups was performed by standard analysis of variance procedures. The male FOOD BAR group LPO mean (3.6 +/- 0.2 mmol/g) was significantly (p less than or equal to 0.05) greater than that of the male CHOW group (2.1 +/-0.1 mmol/g). Moreover the female FOOD BAR group LPO mean (2.9 +/-0.1 mmol/g) was also significantly greater than the female CHOW group mean (2.2 +/-0.1 mmol/g). The mean values for SOD in both male and female groups showed no significant differences between CHOW and FOOD BAR groups. These results show that LPO levels were significantly higher in both the male and female FOOD BAR groups compared to CHOW groups and that there was no concomitant increase in SOD levels across the group. In addition, males showed a greater difference than females in terms of LPO levels. These findings suggest a need for further investigation into the use of the current food bar formulation for long-term experiments such as those planned for the ISS.
This presentation is to provide the current status of NASA's efforts in the development of hydrogen peroxide in both mono-propellant and bi-propellant applications, consistent with the Space Launch Initiative goals of pursuing low toxicity and operationally simpler propellants for application in the architectures being considered for the 2nd Generation Reusable Launch Vehicle, also known as the Space Launch Initiative, or SLI.
High-Test Hydrogen Peroxide (HTP) propellant (equal to or greater than 70%) offers many advantages in space launch applications. However, materials used in construction of propulsion systems must be shown to be compatible with HTP. Isothermal Microcalorimetry (IMC) was used to determine the compatibility of several metallic and non-metallic materials with 90% HTP. The results of these experiments agreed with those from immersion bath tests when the values were converted to % Active Oxygen Loss per week (%AOL/wk).
An experimental investigation of hypergolicity and ignition delay of fuel mixtures with hydrogen peroxide is presented. Example results of high speed photography and schleiren from drop tests are shown. Also, a discussion of the sensitivity to experimental parameters such as drop size and subsequent uncertainty considerations of ignition delay results is presented. It is shown that using the described setup on the mixtures presented, the precision uncertainty is on the order of 6% of average ignition delay and 5% of average decomposition delay. This represents sufficient repeatability for first order discrimination of ignition delay for propellant development and screening. Two mixtures, each using commonly available amines and transition metal compounds, are presented as examples that result in ignition delays on the order of 10 milliseconds.
Galileo's Near Infrared Mapping Spectrometer (NIMS) detected hydrogen peroxide, carbon dioxide and a hydrated material on Europa's surface, the latter interpreted as hydrated sulfuric acid (H2SO4*nH2O) or hydrated salts. Related compounds are molecular oxygen, sulfur dioxide, and two chromophores, one that is dark in the ultraviolet(UV) and concentrated on the trailing side, the other brighter in the UV and preferentially distributed in the leading hemisphere. The UV-dark material has been suggested to be sulfur.