Development of bacterial sensing instrumentation for spacecraft water systems Final report
Monitoring water sterility in spacecraft water storage and supply systems using porphyrin initiated chemiluminescence technique
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Energy distribution among reaction products - H plus SC12 yielding HC1 plus SC1
IR chemiluminescence from HCl formed in atomic hydrogen reaction with sulfur dichloride, noting energy distribution among reaction products
Heydtmann, H.↗
Kinetics of the O plus O3 reaction
The gas phase reaction O + O3 yields 2 O2 was studied directly in a flow system under conditions of excess ozone, with O-atoms produced by thermal decomposition of Ar-O3 mixtures on a Nernst Glower, and measurement of the spatial O-atom decay by O + NO chemiluminescence with small, variable NO additions. The rate constant was found to be (9.6 + or - 0.7) x 10 to the minus 15th power cu/cm/molecule/sec at 298 K. Over the temperature range 269 to 409 K a rate expression (1.78 + or - 0.28) x 10 to the 11th power exp((-4.46 + or - 0.10 kcal/mole)/RT) is reported. The effects of interference by O2 (delta sub g) and product excitation are discussed, and the present results are compared with earlier investigations.
Mccrumb, J. L.↗
Energy distribution among reaction products. IV.
Use of an infrared chemiluminescence technique, called 'Method II,' or the 'method of arrested relaxation' to measure the distribution of energy among products of the Cl + HI and Cl + DI reactions. Preliminary results are also given for the Br + HI and Cl + HBr reactions. Instead of measuring vibrational relaxation, Method II attempts to arrest vibrational and rotational relaxation by the rapid removal of excited products at a cold surface.
Maylotte, D. H.↗
Energy distribution among reaction products. VI - F + H2, D2.
Study of the F + H2 reaction, which is of special theoretical interest since it is one of the simplest examples of an exothermic chemical reaction. The FH2 system involves only 11 electrons, and the computation of a potential-energy hypersurface to chemical accuracy may now be within the reach of ab initio calculations. The 'arrested relaxation' variant of the infrared chemiluminescence method is used to obtain the initial vibrational, rotational and translational energy distributions in the products of exothermic reactions.
Polanyi, J. C.↗
The air afterglow revisited
The air afterglow, 0 + NO2 chemiluminescence, is discussed in terms of fluorescence, photodissociation, and quantum theoretical calculations of NO2. The experimental results presented include pressure dependence, M-dependence, spectral dependence of P and M, temperature dependence, and infrared measurements. The NO2 energy transfer model is also discussed.
Kaufman, F.↗
Tape Cassette Bacteria Detection System
The design, fabrication, and testing of an automatic bacteria detection system with a zero-g capability and based on the filter-capsule approach is described. This system is intended for monitoring the sterility of regenerated water in a spacecraft. The principle of detection is based on measuring the increase in chemiluminescence produced by the action of bacterial porphyrins (i.e., catalase, cytochromes, etc.) on a luminol-hydrogen peroxide mixture. Since viable as well as nonviable organisms initiate this luminescence, viable organisms are detected by comparing the signal of an incubated water sample with an unincubated control. Higher signals for the former indicate the presence of viable organisms. System features include disposable sealed sterile capsules, each containing a filter membrane, for processing discrete water samples and a tape transport for moving these capsules through a processing sequence which involves sample concentration, nutrient addition, incubation, a 4 Molar Urea wash and reaction with luminol-hydrogen peroxide in front of a photomultiplier tube. Liquids are introduced by means of a syringe needle which pierces a rubber septum contained in the wall of the capsule. Detection thresholds obtained with this unit towards E. coli and S. marcescens assuming a 400 ml water sample are indicated.
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Energy distribution among reaction products. VII - H + F2.
The 'arrested relaxation' variant of the IR chemiluminescence technique is used in a study of the distribution of vibrational, rotational and translational energies between the products of the reaction by which H + F2 yields HF + F. Diagrams are plotted and numerical values are obtained for the energy distribution rate constants.
Polanyi, J. C.↗
Instrumentation for air quality measurements.
Comparison of the new generation of air quality monitoring instruments with some more traditional methods. The first generation of air quality measurement instruments, based on the use of oxidant coulometric cells, nitrogen oxide colorimetry, carbon monoxide infrared analyzers, and other types of detectors, is compared with new techniques now coming into wide use in the air monitoring field and involving the use of chemiluminescent reactions, optical absorption detectors, a refinement of the carbon monoxide infrared analyzer, electrochemical cells based on solid electrolytes, and laser detectors.
Loewenstein, M.↗
Cassette bacteria detection system
The design, fabrication, and testing of an automatic bacteria detection system, with a zero-g capability, based on the filter-capable approach, and intended for monitoring the sterility of regenerated water in spacecraft is discussed. The principle of detection is based on measuring the increase in chemiluminescence produced by the action of bacterial porphyrins on a luminol-hydrogen peroxide mixture. Viable organisms are detected by comparing the signal of an incubated water sample with an unincubated control. High signals for the incubated water sample indicate the presence of viable organisms.
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The molecular dynamics of atmospheric reaction
Detailed information about the chemistry of the upper atmosphere took the form of quantitative data concerning the rate of reaction into specified states of product vibration, rotation and translation for exothermic reaction, as well as concerning the rate of reaction from specified states of reagent vibration, rotation and translation for endothermic reaction. The techniques used were variants on the infrared chemiluminescence method. Emphasis was placed on reactions that formed, and that removed, vibrationally-excited hydroxyl radicals. Fundamental studies were also performed on exothermic reactions involving hydrogen halides.
Polanyi, J. C.↗
NO and O3 measurements in the lower stratosphere from a U-2 aircraft
In situ measurements of nitric oxide and ozone were carried out at altitudes up to 21 km during two flights of a U-2 aircraft on Dec. 6 and 18, 1973, over the west coast of the United States. A chemiluminescent detector based on the luminescent reaction of nitric acid with excess ozone was used in nitric acid measurements. Ozone concentration measurements were based on the absorption of the Hg line at 2,537 A in the Hartley continuum. The results are compared with available data.
Loewenstein, M.↗
Nitric oxide gamma and delta band emission at twilight
Nitric oxide twilight emission above 140 km in the gamma- and delta-bands was observed with a rocket-borne spectrophotometer. The relative intensity of the two band systems indicates that the emission is produced predominantly by the chemiluminescent preassociation of oxygen and nitrogen atoms.
Feldman, P. D.↗
Nitric oxide, water vapor, and ozone in the atmosphere as measured in SITU from an aircraft
As part of the instrument evaluation plan for the NASA Global Atmospheric Sampling Program, prototype instruments were tested aboard the NASA Convair 990 during four flights in January and February of 1974. All the data were taken in maritime air between Hawaii and San Francisco and between Hawaii and 155 deg W, 35 deg N. A chemiluminescent instrument was used to measure nitric oxide. Water vapor, which was measured by using an aluminum oxide hygrometer, ranged from 5.2 micro g/g to saturation. Ozone was measured by an instrument using the ultraviolet absorption technique and ranged up to 235 ppbv. Typical temporal plots of the concentrations of the three constituents are presented. All the constituents showed considerable spatial and day-to-day variation in concentration at each altitude flown. Measurements of the three constituents were made simultaneously at various altitudes between 7.6 and 12.5 km.
Briehl, D.↗
Study of the reaction of atomic oxygen with aerosols
The rate of disappearance of atomic oxygen was measured at several pressures in a fast flow pyrex reactor system with its walls treated with (NH4)2SO4 (s), H2SO4 (l), and NH4CL (s). Atomic oxygen, P-3 was generated by dissociation of pure, low pressure oxygen in a microwave discharge. Concentrations of atomic oxygen were measured at several stations in the reactor system using chemiluminescent titration with NO2. Recombination efficiencies calculated from experimentally determined wall recombination rate constants are in good agreement with reported values for clean Pyrex and an H2SO4 coated wall. The recombination efficiency for (NH4)2SO4, results in a slightly lower value than for H2S04. A rapid exothermic reaction between atomic oxygen and the NH4Cl wall coating prevented recombination efficiency determination for this coating. The results show that the technique is highly useful for wall recombination measurements and as a means of extrapolating to the case of free stream aerosol-gas interactions.
Akers, F. I.↗
In situ measurements of nitric oxide, water vapour and ozone from an aircraft
This paper describes flight tests of prototype instruments for the NASA global atmospheric sampling program (GASP). Three gas sampling instruments were included in the installation: (1) a chemiluminescent nitric oxide monitor; (2) an ultraviolet absorption ozone monitor; and (3) an aluminum oxide water vapor hygrometer. Results indicate the range and kind of variability in NO, H2O, and O3 that can be expected in routine tropospheric air sampling. They have also demonstrated the need for increasing instrument sensitivities, particularly in NO measurement.
Briehl, D. C.↗
NOx production in lightning
The rate of odd nitrogen (NOx) production by electrical discharge through air was theoretically and experimentally estimated to be about 60,000 trillion NOx molecules per joule. The theoretical treatment employed a cylindrical shock-wave solution to calculate the rate of NOx production in high temperature reactions. The limits obtained were experimentally verified by subjecting a regulated air flow to electrical discharges followed by a measurement of NOx production using chemiluminescence. These measurements also indicated that water vapor content has no detectable effect on the NOx production rate. The results imply that lightning is a significant source of NOx, producing about 30-40 megatons NOx-N per year and possibly accounting for as much as 50% of the total atmospheric NOx source.
Chameides, W. L.↗
Spatially localized, shock-wave-induced continuous and very fast mixing between gases and liquid in parallel flow /An experimental study/
Shock-wave-induced patterns and turbulent supersonic shear flows over a stagnant bubble were determined for cases where recirculation and final mixing occurred within a very short time and within a distance of about 1 cm. The effect of a shock wave upon stratified laminas of gases in a shock tube was studied for a series of gases of different densities and molecular weights. Steady-state mixing of gas streams were investigated in wind tunnel experiments by means of a chemiluminescent reaction. Shock-wave-induced mixing which involves the introduction of a liquid jet into a supersonic gas stream is also described.
Devis, E.↗