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At least 181 records · Page 10

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.↗

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 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.↗

Fluorescence from VUV excitation of formaldehyde

The 105-180-nm photoabsorption and fluorescence cross sections of H2CO are determined experimentally using a synchrotron-radiation light source and the apparatus described by Lee (1980). The results are presented in tables and graphs and discussed. VUV emission with threshold wavelength 140.3 nm is detected and attributed to the A 1Pi - X 1Sigma(+) system of CO, and UV emission from the HCO (B-X) system is found below a 147.5-nm threshold, the H-HCO dissociation energy having an upper limit of 3.61 + or - 0.03 eV. At 116 nm, the maximum quantum yields of the VUV and UV fluorescences are about 1.6 and 0.23 percent, respectively.

Suto, Masako↗

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↗

The V3, V4 and V6 bands of formaldehyde: A spectral catalog from 900 cm(-1) to 1580 cm(-1)

The results of a complete high resolution study of the three vibration-rotation bands v sub 3, v sub 4, and V sub 6 using both TDLs and FT-IR spectroscopy are presented. The reults are given in terms of a table of over 8000 predicted transition frequencies and strengths. A plot of the predicted and calculated spectra is shown. Over 3000 transitions were assigned and used in the simultaneous analysis of the three bands. The simultaneous fit permitted a rigorous study of Coriolis and other type iterations among bands yielding improved molecular constants. Line intensities of 28 transitions measured by a TDL and 20 transitions from FTS data were used, along with the eigenvectors from the frequency fitting, in a least squares analysis to evaluate the band strengths.

Nadler, Shachar↗

Radio detection of formaldehyde emission from Comet Halley

The J(K-1 K1) = -1(11) -10(10) transition of H2CO was detected in emission at 4829.659 MHz from Comet Halley. The H2CO emission line had a peak intensity of 2.66 + or - 0.78 mJy/beam with a small blueshift of -0.76 + or - 0.40 km/s, which is consistent with the anisotropic outgassing of the nucleus in the solar direction found for other cometary species. Data analysis suggests that cometary H2CO was produced from an extended source in the coma as well as directly from the nucleus and that it was not refrigerated as in interstellar dark nebulae. The derived H2CO production rate of 1.5 x 10 to the 28th molecules/s is obtained which is consistent with observational and theoretical findings.

Snyder, Lewis E.↗

Uptake of formaldehyde by sulfuric acid solutions - Impact on stratospheric ozone

The study investigates the uptake of CH2O by low temperature sulfuric acid solutions representative of global stratospheric particulate. It is argued that if similar uptake occurs under stratospheric pressures of CH2O, i.e., 1000 times lower than used in the present study, then the removal of CH2O from the gas phase can take away a significant source of odd hydrogen in the mid- and high-latitude lower stratosphere. It is shown that with the inclusion of this reaction, concentrations of OH and H2O are reduced by as much as 4 percent under background levels of aerosols and more than 15 percent under elevated (volcanic) conditions. The accumulation of CH2O in stratospheric aerosols over a season, reaching about 1 M solutions, will alter the composition and may even change the reactivity of these sulfuric acid-water mixtures.

Tolbert, Margaret A.↗

Isotopic Measurements of Sulphonates and Phosphonates and Investigations of Possible Formaldehyde Products from the Murchison Meteorite

Intramolecular carbon, hydrogen, and sulfur isotope measurements have been made on a homologous series of organic sulfonates discovered in the Murchison meteorite. Mass independent sulfur isotope fractionations were observed along with D/H ratios clearly larger than terrestrial. The sulfur fractionations may be produced chemically and due to molecular symmetry factors. The deuterium enrichments indicate formation of the hydrocarbon portion of these compounds in a low temperature astrophysical environment consistent with that of molecular clouds. The source of the sulfonate precursors may have been the reactive interstellar molecule, CS. Low temperature CS reactions also produce other sulfur containing compounds as well as a solid phase. Isotopic measurements on bulk phosphonates were also made.

Cooper, George↗

Field intercomparison of a novel optical sensor for formaldehyde quantification

A one-week in situ intercomparison campaign was completed on the Rice University campus for measuring HCHO using three different techniques, including a novel optical sensor based on difference frequency generation (DFG) operating at room temperature. Two chemical derivatization methods, 2,4-dinitrophenylhydrazine (DNPH) and o-(2,3,4,5,6-pentafluorobenzyl) hydroxylamine (PFBHA), were deployed during the daylight hours for three- to four-hour time-integrated samples. A real-time optical sensor based on laser absorption spectroscopy was operated simultaneously, including nighttime hours. This tunable spectroscopic source based on difference frequency mixing of two fiber-amplified diode lasers in periodically poled LiNb03 (PPLN) was operated at 3.5315 micrometers (2831.64 cm 1) to access a strong HCHO ro-vibrational transition free of interferences from other species. The results showed a bias of -1.7 and -1.2 ppbv and a gross error of 2.6 and 1.5 ppbv for DNPH and PFBHA measurements, respectively, compared with DFG measurements. These results validate the DFG sensor for time-resolved measurements of HCHO in urban areas.

NASA Discipline Life Sciences Technologies↗

Phenol-formaldehyde intumescent coating composition and coating prepared therefrom

Intumescent coatings which form a thick, uniform, fine celled, low density foam upon exposure to a high intensity heat flux or flame are disclosed, the invention coatings comprise phenolic resin prepolymer containing a blowing agent and a nucleating agent; in the preferred embodiments the coatings also contains a silicone surfactant, the coatings are useful in thermal and fire protection systems.

Salyer, Ival O.↗

The Role of Convection in Redistributing Formaldehyde to the Upper Troposphere Over North America and the North Atlantic during the Summer 2004 INTEX Campaign

Measurements of CH2O from a tunable diode laser absorption spectrometer (TDLAS) were acquired onboard the NASA DC-8 during the summer 2004 INTEX-NA (Intercontinental Chemical Transport Experiment - North America) campaign to test our understanding of convection and production mechanisms in the upper troposphere (UT, 6-12-km) over continental North America and the North Atlantic Ocean. Point-by-point comparisons with box model calculations, when MHP (CH3OOH) measurements were available for model constraint, resulted in a median CH2O measurement/model ratio of 0.91 in the UT. Multiple tracers were used to arrive at a set of UT CH2O background and perturbed air mass periods, and 46% of the TDLAS measurements fell within the latter category. At least 66% to 73% of these elevated UT observations were caused by enhanced production from CH2O precursors rather than direct transport of CH2O from the boundary layer. This distinction is important, since the effects from the former can last for over a week or more compared to one day or less in the case of convective transport of CH2O itself. In general, production of CH2O from CH4 was found to be the dominant source term, even in perturbed air masses. This was followed by production from MHP, methanol, PAN type compounds, and ketones, in descending order of their contribution. In the presence of elevated NO from lightning and potentially from the stratosphere, there was a definite trend in the CH2O discrepancy, which for the highest NO mixing ratios produced a median CH2O measurement/model ratio of 3.9 in the 10-12-km range. Discrepancies in CH2O and HO2 in the UT with NO were highly correlated and this provided further information as to the possible mechanism(s) responsible. These discrepancies with NO are consistent with additional production sources of both gases involving CH3O2 + NO reactions, most likely caused by unmeasured hydrocarbons.

Fried, Alan↗

Homochirality: an Origin in the Formaldehyde Chemistry?

Chirality is commonly defined as compounds that are composed of two non-superimposable mirror images (enantiomers). Each enantiomer is labeled “L” or “D”: a common analogy is a left and right hand. Many decades of non-biological laboratory synthesis have shown that each enantiomer is produced in equal (racemic) amounts: this was also expected in the early solar system from presumed non-biased physical and chemical synthetic processes. However, as far back as can be traced, biological polymers such as nucleic acids and proteins have been composed of only one of the two possible enantiomers, for example, D sugars and L amino acids. For nearly 200 years, scientists have tried to understand the origin of this complete excess of one enantiomer or “homochirality”. The answer to this question may be essential for understanding the origins of early life forms: apparently, bio-polymers cannot form if both enantiomers are present in nearly equal amounts. This study aims to create enantiomeric excesses in a laboratory setting using prebiotic conditions to simulate phenomena that may have happened billions of years ago. Although much more work must be done, preliminary results indicate that a similar process may have played a role in the origins of early enantiomers excesses.

Enantiomers↗