Engineering topics
Publications and source records attributed to Stief, L. J..
The rate parameters for the reaction of O(3P) with carbonyl sulfide, O(3P) + OCS yields CO + SO have been determined directly by monitoring O(3P) using the flash photolysis-resonance fluorescence technique. The value for k sub 1 was measured over a temperature range of 263 - 502 K and the data were fitted to an Arrhenuis expression with good linearity.
The atmospheric composition of Mars is presented, and the applicability of laboratory data on CO2 absorption cross sections and quantum yields of dissociation is discussed. A summary and critical evaluation are presented on the various mechanisms proposed for converting the photodissociation products CO and O2 back to CO2.
Discussion of laboratory measurements which indicate that the reaction of the thermalized HO(2) radical with CO is exceedingly slow and that this reaction should not, therefore, be of any significance in atmospheric chemistry. The large discrepancy between the new results and data obtained earlier by Westenberg and de Haas (1972) is explained in terms of the reacting hydroperoxyl radical being in a non-Boltzmann distribution in the former study. It appears that the most important reactions of thermalized HO(2) in the atmosphere are those involving the trace gases of NO and sulfur dioxide.
Attention is given to chemical processes which could determine the molecular composition of the cloud during the several stages of its evolution, taking into account thermal reactions at the relatively high interstellar densities expected during the processes. The origin of the observed molecules is discussed together with questions of molecular evolution during collapse of the cloud and the role of organic molecules in planetary chemical evolution. A number of experiments are also considered along with the application of the experimental results to cloud equilibrium problems.
The role of photochemistry in determining the lifetime of interstellar molecules is considered. The probability of photodecomposition depends on three factors, including the absorption cross section, the quantum yield or probability of dissociation following photon absorption, and the interstellar radiation field. A more detailed discussion of the photochemistry of five molecules is presented, giving attention to carbonyl sulfide, methyl acetylene, nitric oxide, acetylene, and benzene. Lifetimes of interstellar molecules in unobscured regions are in the range from 5 to 100 years. It is concluded that polyatomic molecules can exist only in dense clouds which protect them from the full interstellar radiation field.
Chemical processes that could determine the molecular composition of the cloud during the several stages of its evolution are considered. Reactions at the relatively interstellar densities are emphasized.
It is suggested that a potential source of C3 observed in comets is the photodissociation of propyne by solar radiation, most probably in the region of the strong 1216-A Lyman-alpha line. The possibility of a strong correlation between interstellar molecules and the stable parent cometary molecules is also considered.
A Kr resonance lamp was used in the investigations. All experiments were performed at 25 C and 0.2 torr of propyne. Between 5% and 25% of the propyne was decomposed in any one experiment. It was found that the addition of 25% C2D4 had no effect on the quantum yield of molecular hydrogen. This suggests that hydrogen formation in the photolysis of propyne at 1236 A occurs exclusively via a molecular process. Pressure effects on the distribution of isotopic hydrogen formed in the photolysis were also investigated.
A quantitative discussion is presented of the lifetime against photodecomposition, or the probability of photodecomposition, of interstellar molecules. In addition to photodissociation, molecules can also be destroyed by interaction with high energy radiation and energetic particles. These processes are much less effective than destruction by ultraviolet radiation. However, when the ultraviolet is highly attenuated in clouds, the energetic radiation and particles will persist and will become relatively more important and the ultimate lifetimes in clouds may depend upon these processes.
Quantitative discussion of the photochemistry and lifetime against photodecomposition of five interstellar molecules: H2CO, NH3, H2O, CH4, and CO. For the first four molecules, primary photochemical decomposition processes yielding atomic and molecular hydrogen are considered in addition to photoionization. The quantum yield for decomposition of these molecules is unity. For CO, only decomposition to ground-state carbon and oxygen atoms occur, but the quantum yield is not known and may be considerably less than unity. The radiation field in obscuring clouds is estimated, using an interstellar extinction curve for the Perseus region.
The photochemistry of two diatomic and eight polyatomic molecules is discussed quantitatively. For an interstellar molecule, the lifetime against photodecomposition depends upon the absorption cross section, the quantum yield or probability of dissociation following photon absorption, and the interstellar radiation field. The constant energy density of Habing is used for the unobserved regions of interstellar radiation field, and the field in obscuring clouds is estimated by combining the constant flux with the observed interstellar extinction curve covering the visible and ultraviolet regions. Lifetimes against photodecomposition in the unobscured regions and as a function of increasing optical thickness in obscuring clouds are calculated for the ten species. The results show that, except for CO, all the molecules have comparable lifetimes of less than one hundred years. Thus they can exist only in dense clouds and can never have been exposed to the unobscured radiation. The calculations further show that the lifetimes in clouds of moderate opacity are of the order of one million years.
Formaldehyde vapor photodecomposition modes by end product analysis, utilizing mixed isotope, radical scavenger, inert gas pressurization and lamp intensity attenuation
Atomic and molecular hydrogen yields of propyne photolysis at 1470 A Xe resonance line
Disproportionation to combination ratio of hydrazyl radicals generated in absence of hydrazine direct decomposition
Xenon sensitized photolysis of carbon dioxide compared with direct photolysis at 1470 A resonance line
Primary processes leading to atomic and molecular hydrogen formation in hydrogen peroxide photolysis at 1236 A, noting OH formation