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At least 73 records · Page 4

Rate constant for the reaction of hydroxyl radical with formaldehyde over the temperature range 228-362 K

Absolute rate constants for the reaction OH ? H2CO measured over the temperature range 228-362 K using the flash photolysis-resonance fluorescence technique are given. The results are independent of variations in H2CO concentration, total pressure Ar concentration, and flash intensity (i.e., initial OH concentration). The rate constant is found to be invariant with temperature in this range, the best representation being k sub 1 = (1.05 ? or - 0.11) x 10 to the 11th power cu cm molecule(-1) s(-1) where the error is two standard deviations. This result is compared with previous absolute and relative determinations of k sub 1. The reaction is also discussed from a theoretical point of view.

Stief, L. J.↗

Rate constant for the reaction of hydroxyl radical with formaldehyde over the temperature range 228-362 K

Absolute rate constants for the reaction OH + H2CO have been measured over the temperature range 228-362 K using the flash photolysis-resonance fluorescence technique. The results were independent of variations in forbidden H2CO, total pressure of forbidden Ar and flash intensity (i.e., initial forbidden OH). The rate constant was found to be invariant with temperature in this range, the best representation being k1 = (1.05 + or - 0.11) x 10 to the -11th cu cm/molecule sec where the error is two standard deviations. This result is compared with previous absolute and relative determinations of k1. The reaction is also discussed from a theoretical point of view.

Stief, L. J.↗

The extinction toward the galactic center from observations of interstellar lines

H2CO absorption observations against Sgr A are used to select the molecular material lying in front of the galactic center, and an analysis similar to that of Blitz and Shu (1980) is carried out. The ratio of visual extinction to equivalent width of the 6 cm line of H2CO is found to be similar for several nearby interstellar clouds. By considering only the molecular components in front of the infrared cluster, the estimate for the extinction is decreased to 15-46 mag. These results are consistent with those from infrared observations toward the galactic center. Extinction estimates based on other interstellar species are also considered. Atomic gas is seen as contributing less than 10 mag of extinction.

Federman, S. R.↗

Model calculations of the molecular composition of interstellar grain mantles

A chemical reaction scheme comprising gas phase as well as grain surface reactions is used for the numerical calculation of the chemical composition of mantles accreting on interstellar grains. The composition of the growing grain mantle is determined on the basis of the relative accretion rates of the gas phase molecules and diffusion-controlled surface reactions. Results show that grain mantles generally consist of the molecules H2O, H2CO, N2, O2, CO, CO2, H2O2, and NH3. A detailed examination of the formation of H2 on grain surfaces leads to the conclusion that it proceeds through hydrogen abstraction from such molecules as H2CO, H2S, N2H2, and N2H4. The IR characteristics of the calculated grain mantles are discussed with emphasis on the observed ice band at the 3250/cm wavelength.

Tielens, A. G. G. M.↗

Prebiotic synthesis in atmospheres containing CH4, CO, and CO2. I - Amino acids

The prebiotic synthesis of amino acids, HCN, H2CO, and NH3 using a spark discharge on various simulated primitive earth atmospheres at 25 C is investigated. Various mixtures of CH4, CO, CO2, N2, NH3, H2O, and H2 were utilized in different experiments. The yields of amino acids (1.2-4.7 percent based on the carbon) are found to be approximately independent of the H2/CH4 ratio and the presence of NH3, and a wide variety of amino acids are obtained. Glycine is found to be almost the only amino acid produced from CO and CO2 model atmospheres, with the maximum yield being about the same for the three carbon sources at high H2/carbon ratios,whereas CH4 is superior at low H2/carbon ratios. In addition, it is found that the directly synthesized NH3 together with the NH3 obtained from the hydrolysis of HCN, nitriles, and urea could have been a major source of ammonia in the atmosphere and oceans of the primitive earth. It is determined that prebiotic syntheses from HCN and H2CO to give products such as purines and sugars and some amino acids could have occurred in primitive atmospheres containing CO and CO2 provided the H2/CO and H2/CO2 ratios were greater than about 1.0.

Schlesinger, G.↗

The morphology and kinematics of the Cep IV star formation region

Rossano et al. (1980) have discussed the morphology and kinematics of Cep IV star formation region. The present investigation is concerned with H2CO observations which have been conducted to examine the relationship between the neutral and ionized gas in the Cep IV star formation region and to study the origin of the unusual kinematics and morphology of the stars, gas, and dust in this region. Six-cm H2CO observations were undertaken throughout a one half degree square area centered on the H II region W1. In addition, VLA observations of the Cep IV region at 6 and 20 cm were also performed. The neutral gas in the vicinity of W1 is found to be located in clouds having velocities of -13, -7, and 1 km/s. The gas at - 7 km/s appears to be undisturbed gas from the original dark cloud complex.

Grayzeck, E. J.↗

Carbon and energy yields in prebiotic syntheses using atmospheres containing CH4, CO and CO2

Yields based on carbon are usually reported in prebiotic experiments, while energy yields (moles/cal) are more useful in estimating the yields of products that would have been obtained from the primitive atmosphere of the earth. Energy yields for the synthesis of HCN and H2CO from a spark discharge were determined for various mixtures of CH4, CO, CO2, H2, H2O, N2 an NH3. The maximum yields of HCN and H2CO from CH4, CO, and CO2 as carbon sources are about 4 x 10 to the -8th moles/cal.

Miller, S. L.↗

Measurement of the formaldehyde ortho to para ratio in three molecular clouds

Observations of ortho and para H2CO in two types of clouds, a warm cloud (Orion A) and two cold clouds (L183 and TMC1), are presented. The ortho to para ratio in Orion deduced from the H2(C-13)O data is about three, while that for TMC1 is about one and that for L183 is 1-2. The former value is in agreement with the value calculated from chemical models of ortho and para H2CO production. The values for the cold clouds are consistent with thermal equilibrium at a temperature slightly smaller than 10 K.

Kahane, C.↗

NGC 2024: Multi-wavelength Infrared and Radio Observations

A series of far-infrared maps obtained on the KAO find the total IR luminosity of NGC 2024 is to the 4th power L, and show a peak in flux density and optical depth about 1' south of IRS 2. High resolution spectra of IRS 2 in Brackett alfa and Pfund gamma indicate the presence of an optically thick wind with M approx. 7 x 10 to the minus 7 power M sub yr to minus 1 power, from which we infer that IRS 2 is unable to supply the luminosity observed. A six centimeter continuum map peaks near the location of the far-infrared peak and confirms it as a likely site for a source to provide this luminosity. Maps in HCN, CS, and H2CO show the gas is dense in the direction of the far IR peak. Velocity analysis shows the H2 region created by the far IR source and IRS 2 forms an expanding bubble in front of which the H2CO is seen in absorption, and which is bounded in the south and behind by dense material.

Smith, H. A.↗

Laboratory identification of the emission features near 3.5 microns in the pre-main sequence star HD 97048

This paper presents the results of a laboratory study of formaldehyde (H2CO) suspended in low temperature molecular matrices with compositions similar to what may be found in the 'dirty ice' mantles of grains. It is shown that the emission features near 3.5 microns in the pre-main-sequence star HD 97048 can be matched by a mixture of chemical complexes of H2CO with surrounding molecules in the grain. Furthermore, a discussion is presented of various possible excitation mechanisms for this emission. The conclusion is, that for the features near 3.5 microns in HD 97048, UV pumped IR fluorescence is the most likely mechanism.

Van Der Zwet, G. P.↗

Energy yields in the prebiotic synthesis of hydrogen cyanide and formaldehyde

Prebiotic experiments are usually reported in terms of carbon yields, i.e., the yield of product based on the total carbon in the system. These experiments usually involve a large input of energy and are designed to maximize the yields of product. However, large inputs of energy result in multiple activation of the reactants and products. A more realistic prebiotic experiment is to remove the products of the activation step so they are not exposed a second time to the energy source. This is equivalent to transporting the products synthesized in the primitive atmosphere to the ocean, and thereby protecting them from destruction by atmospheric energy sources. Experiments of this type, using lower inputs of energy, give energy yields (moles of products/joule) which can be used to estimate the relative importance of the different energy sources on the primitive earth. Simulated prebiotic atmospheres containing either CH4, CO or CO2 with N2, H2O and variable amounts of H2 were subjected to a high frequency Tesla coil. Samples of the aqueous phase were taken at various time intervals from 1 hr to 7 days, and the energy yields were obtained by extrapolation to zero time. The samples were analyzed for HCN with the cyanide electrode and for H2CO by chromotropic acid. The spark energy was estimated by calorimetry. The temperature rise in an insulated discharge flask was compared with the temperature rise from a resistance heater in the same flask. These results will be compared with calculated production rates of HCN and H2CO from lightning and a number of photochemical processes on the primitive Earth.

Stribling, R.↗

The photochemistry of the early atmosphere

The composition of the earth's present atmosphere is described. The formation of the earth from the coalescence and accretion of the refractory elements of the solar nebula is examined. Two possible compositions of the prebiological paleoatmosphere, which are a reducing atmosphere of CH4, NH3, and H2 or a mildly reducing atmosphere of H2O, CO2, and N2, and their photochemistry are analyzed. General photochemical and chemical processes are reviewed. The use of the coupled continuity-transport equation to calculate the vertical distribution of each species is discussed. A study of the photochemical process of CH4 and NH3 reveals that the reducing atmosphere could not possibly exist. An analysis of the photochemistry and chemistry of the H2O, CO2, and N2 atmosphere reveals that the photodissociation of H2O and CO2 results in a prebiotic source of O2, H2CO, and HCN, which are the components for the evolution of photosynthetic organisms and a strongly oxidizing atmosphere. The reactions which produce O2 and H2CO from H2O and CO2, and the relation between H2O and CO2 concentrations and O2 levels are investigated. The formation of O3 photochemically from O2 is explained.

Levine, J. S.↗

Photochemical consequences of enhanced CO2 levels in earth's early atmosphere

Greatly enhanced atmospheric CO2 concentrations are the most likely mechanism for offsetting the effects of reduced solar luminosity early in the earth's history. CO2 levels of 80 to 600 times the present value could have maintained a mean surface temperature of 0 C to 15 C, given a 25 percent decrease in solar output. Such high CO2 levels are at least qualitatively consistent with the present understanding of the carbonate-silicate geochemical cycle. The presence of large amounts of CO2 has important implications for the composition of the earth's prebiotic atmosphere. The hydrogen budget of a high-CO2 primitive atmosphere would have been strongly influenced by rainout of H2O2 and H2CO. The reaction of H2O2 with dissolved ferrous iron in the early oceans could have been a major sink for atmospheric oxygen. The requirement that this loss of oxygen be balanced by a corresponding loss of hydrogen (by escape to space and rainout of H2CO) implies that the atmospheric H2 mixing ratio was greater than 2 x 10 to the -5th and the ground level O2 mixing ratio was below 10 to the -12th, even if other surface sources of H2 were small. These results are only weakly dependent on changes in solar UV flux, rainout rates, and vertical mixing rates in the primitive atmosphere.

Kasting, J. F.↗

The young sun, the early earth and the photochemistry of oxygen, ozone and formaldehyde in the early atmosphere

Recent work on the evolution of the solar nebula and the subsequent formation of planets is reviewed, and the stages of star formation thought to lead to a protosun and an accompanying solar nebula are considered. Photochemical results suggest that concentrations of O2, O3, and H2CO, and the ratio of CO/CO2 in the prebiological paleoatmosphere are very sensitive to atmospheric levels of H2O and CO2 and to the flux of incident solar ultraviolet. For enhanced levels of CO2 and solar UV, surface levels of O2 may have approached the parts per billion level in the prebiological paleoatmosphere. It is suggested that 10 percent or more of the enhanced H2CO production could have been rained out of the atmosphere into the early oceans where synthesis into more complex organic molecules could have taken place. CO/CO2 values of greater than unity could have been possible for enhanced levels of solar UV flux.

Canuto, V. M.↗

Tunable diode laser measurements of formaldehyde foreign-gas broadening parameters and line strengths in the 9-11-micron region

A tunable diode laser spectrometer has been used to determine pressure broadening coefficients due to collision with the foreign gases air, H2, O2, and N2 in the nu4 and nu6 bands of H2CO between 9 and 11 microns. Absolute line strengths for twenty-eight transitions have also been determined. The broadening coefficients are very similar to theoretical literature values in the cases of air, N2, and O2. The H2-H2CO values are in good agreement with earlier experimental millimeter-wave results.

Nadler, Shachar↗

Energy yields for hydrogen cyanide and formaldehyde syntheses - The HCN and amino acid concentrations in the primitive ocean

Simulated prebiotic atmospheres containing either CH4, CO, or CO2, in addition to N2, H2O, and variable amounts of H2, were subjected to the spark from a high-frequency Tesla coil, and the energy yields for the syntheses of HCN and H2CO were estimated from periodic (every two days) measurements of the compound concentrations. The mixtures with CH4 were found to yield the highest amounts of HCN, whereas the CO mixtures produced the highest yields of H2CO. These results model atmospheric corona discharges. From the yearly energy yields calculated and the corona discharge available on the earth, the yearly production rate of HCN was estimated; using data on the HCN production rates and the experimental rates of decomposition of amino acids through the submarine vents, the steady state amino acid production rate in the primitive ocean was calculated to be about 10 nmoles/sq cm per year.

Stribling, Roscoe↗

VLA searches for formaldehyde and cyanoacetylene emission from comet P/Brorsen-Metcalf (1989o)

In Sep. 1989, Very Large Array (VLA) searches were conducted for both formaldehyde (H2CO) and cyanoacetylene (HC3N) emission from Comet P/Brorsen-Metcalf (1989o). In early July, this comet was outgassing strongly at a brighter than average preperihelion rate, and the hope was that it would continue to do so through perihelion. By observing the 1 sub 11 to 1 sub 10 transition of H2CO at 4,829.659 MHz (6 cm lambda) during the phase of maximum outgassing, it was expected that spectra would be collected with a high signal to noise ratio which would show the temporal behavior of formaldehyde relative to other molecules. During this same observation period, a search was also made for the J-1-0, F-2-1 rotational transition of cyanoacetylene at 9098.3321 MHz (3.3 cm lambda).

Snyder, Lewis E.↗

Distributed coma sources and the CH4/CO ratio in Comet Halley

Early analyses of the Ion Mass Spectrometer (IMS) data from the Giotto flyby of Comet P/Halley indicated significant abundances of CH(+) sub n (n = 1 to 4). The source of these ions was assumed to be frozen CH4 in the nucleus. An abundance of about 2 percent CH4 was consistent with this interpretation, resulting in a ratio of CH4/CO that is greater than the predicted limits for interstellar clouds or the solar nebula. However, subsequent analyses of data from the Giotto Neutral Mass Spectrometer indicate distributed sources of CO and H2CO in the coma that are most likely associated with organic (CHON) particles, rich in CH-bearing compounds that decay and produce CH(+) sub n species. A model is presented that qualitatively accounts for the measured spatial distribution of CO and H2CO, and indicates that most of the CH(+) sub n deduced from the Giotto IMS data may originate from organic compounds in the coma dust and not from volatiles released directly from the nucleus. As a consequence, the absence of CH4 in the icy phase of the nucleus is consistent with the observations with an upper limit of about 0.5 percent to the ratio CH4/CO. This is an important criterion for theories of comet formation.

Boice, D. C.↗