摘要 :
The suggestion that a pressure-sensitive equilibrium is important to the initiation of detonation in nitroalkanes has been tested. First, considered was the potentially important step NO + NO2 = N2O3 to O2 + N2O and the thermal de...
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The suggestion that a pressure-sensitive equilibrium is important to the initiation of detonation in nitroalkanes has been tested. First, considered was the potentially important step NO + NO2 = N2O3 to O2 + N2O and the thermal decomposition of N2O3 at 130C and about 35 atm. When a small amount of water was added to the system, a violent explosion occurred after about 5 minutes of heating. The reaction between NO and NO2 may be water catalyzed and may offer some insight into the energetics of nitroalkane detonation. Also studied was the oxidizing abilities of NO2/N2O4 systems at 100C and 10-20 atm., using isobutane as the organic substrate. The rate of reaction was determined. The results are consistent with our proposition that under detonation initiation (high pressure-high temperature) conditions N2O4 is the p predominant species and is in some way responsible for the oxidation.
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The second year of work under this contract concentrated on instrument development and field studies to investigate the atmospheric chemistry of the nitrogen oxide family. Available laboratory and field data, in conjunction with m...
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The second year of work under this contract concentrated on instrument development and field studies to investigate the atmospheric chemistry of the nitrogen oxide family. Available laboratory and field data, in conjunction with model calculations, suggest that this family of compounds may impact on air quality in at least three significant ways: (1) produce one of the major atmospheric acidic compounds, HNO3; (2) lead to major increases in the concentration levels of potentially harmful oxidants such as O3 and PAN-type compounds; and (3) control the levels of still other more reactive atmospheric oxidants such as OH and HO2. Specific species for which measurement technology was explored during the second year of work include NO2, NO3, and HNO2. Much of the field sampling effort during the second year focused on the nighttime chemistry of the nitrogen oxides, with special emphasis being placed on observations of NO. In addition to ground-based field studies, additional airborne field studies were conducted.
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Instrument development activity during the third-year study was focused on the detection of NO2, HNO2 and NO3. A third-generation NO2/NO sensor, capable of measuring NO and NO2 simultaneously, was developed and fully tested both f...
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Instrument development activity during the third-year study was focused on the detection of NO2, HNO2 and NO3. A third-generation NO2/NO sensor, capable of measuring NO and NO2 simultaneously, was developed and fully tested both for ground-based and airborne field-sampling operations. An in-situ photofragmentation LIF HNO2 was also successfully developed and was used to collect the first HNO2 data for urban Atlanta. Significant progress was also achieved in the development of a long-path differential absorption (LPDA) NO3 system. Three major field studies and one major laboratory investigation were also completed: (1) additional nighttime NO measurements at a field station outside Atlanta; (2) field measurements of HNO2 in urban Atlanta; (3) airborne measurements of NO/NO2 over marine and continental terrain at both high altitudes and within the boundary layer; and (4) laboratory measurements to establish the potential importance of corona discharge in the generation of NOx within electrified clouds.
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The paper reviews the production of oxides of nitrogen in low-altitude atmospheric thermonuclear explosions. As the air surrounding the explosion is heated above 2500K,producing a fireball,about 1-2% of nitric oxide is formed. The...
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The paper reviews the production of oxides of nitrogen in low-altitude atmospheric thermonuclear explosions. As the air surrounding the explosion is heated above 2500K,producing a fireball,about 1-2% of nitric oxide is formed. The fireball cools rapidly by adiabatic expansion and by entraining cold air,and thus a significant fraction of this nitric oxide freezes in because the chemical reactions destroying it become extremely slow. The total production rate of nitric oxide per megaton yield is estimated. During the late fireball (or nuclear cloud) rise, a significant fraction of the NO is converted to NO2by slow reaction with O2,but the production of other nitrogen oxides,and of nitrous and nitric acid in moist air,is negligible. The variation,with yield or burst altitude,of the NOx produced per megaton is small for yields between 1and 60Mt,and altitudes between sea level and a few kilometers. Estimates are made for the total NOx yield of the U.S. and USSR nuclear tests during 1961-62.
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Nitrogen oxide cations, such as NO2(+) and NO(+), are strong oxidizers and useful components for ionic High Energy Density Materials (HEDM) 1. Their energy content and oxidizing power increase with increasing oxidation state of th...
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Nitrogen oxide cations, such as NO2(+) and NO(+), are strong oxidizers and useful components for ionic High Energy Density Materials (HEDM) 1. Their energy content and oxidizing power increase with increasing oxidation state of the nitrogen atom and the number of oxygen ligands. In our search for related, halogen-free, highly energetic cations we have became interested in the bicyclic NO4(+)(I).
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The kinetics of the reaction O + N2 + 3.3 eV yields NO + N were investigated under conditions where the vibrational temperature of the nitrogen was less than the translational temperature. The formation of NO behind incident shock...
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The kinetics of the reaction O + N2 + 3.3 eV yields NO + N were investigated under conditions where the vibrational temperature of the nitrogen was less than the translational temperature. The formation of NO behind incident shock waves in dilute O3-N2 mixtures was studied over the temperature range 3100-6400K with initial pressures of 2 to 25 torr. In the shock front O3 yields O + O2 and the reaction of the O with N2 is then rate-limiting, followed by the fast reaction N + O2 yields NO + O. The NO was monitored in emission at 5.3 microns and the initial slopes were compared to theoretical calculations which included vibrational relaxation processes. The radiation rose linearly from the shock front with no incubation in accord with the theoretical calculations employing only translational energy to determine the fraction of collisions whose energy was above the endothermicity of reaction. (Author)
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