ON THE GRAVIMETRIC DETERMINATION OF TETRAMETHYL AMMONIUM
Gravimetric determination of tetramethyl ammonium
GRAVIMETRY↗
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Ultraviolet-photoproduced organic solids synthesized under simulated Jovian conditions - Molecular analysis
In an earlier paper, Khare and Sagan reported the production of a brownish polymeric material from the near-ultraviolet irradiation of simulated jovian atmospheres with a low hydrogen abundance. Examination of this product indicates that hydrogen sulfide is the initial photon acceptor; the powder resulting after extraction with benzene is 84 percent sulfur, largely S8. In results reported here, the remaining 16 percent was pyrolyzed and then examined by gas chromatography-mass spectrometry. Pyrolysis at 450 C yielded a series of alkanes, alkenes, C3-alkylbenzenes, aromatics, thiophenes, alkylthiophenes, alkylmercaptans, alkyldisulfides, together with the nitrogenous compounds hydrogen cyanide, methyl cyanide, alkylisothiocyanates, acrylonitrile, and allylisothiocyanates. Some of these compounds might be sought on Jupiter and Saturn and their satellites by remote infrared and ultraviolet spectroscopy and directly by entry probes.
Khare, B. N.↗
A Simulation of Bromoform's Contribution to Stratospheric Bromine
Many chlorinated and brominated compounds that are inert in the troposphere are destroyed in the stratosphere and act as an in-situ source of stratospheric reactive chlorine and bromine. Other halogenated compounds that are reactive in the troposphere might contribute to the stratosphere's halogen budget in two ways. First, like their unreactive companions, rapid convective transport might carry them to the upper troposphere and make them available for subsequent advection by the mean circulation into the stratosphere before they are oxidized or photolyzed. Second, it is more likely that they are destroyed in the troposphere, and the chlorine and bromine that is released might then be transported to the stratosphere. We evaluate the relative influence of these processes on stratospheric bromine in a three-dimensional chemistry and transport model which simulates the distribution of bromoform (CHBr3). CHBr3 is parameterized as a short-lived, ocean-surface source gas whose destruction by photolysis and reaction with hydroxyl (OH) in the troposphere and stratosphere yields inorganic bromine (Br(sub y)). Many of the observed features of CHBr3 are simulated well, and comparisons with observations are used to show that the model represents aspects of transport in the upper troposphere and lower stratosphere that are critical to the evaluation. In particular, the model maintains the observed troposphere-stratosphere distinctness in transport pathways and reproduces the observed seasonal dependence of the mixture of air in the middle- and high-latitude lowermost stratosphere. We estimate that adding CHBr3 to models which already include the long-lived organic brominated compounds (halons and methyl bromide) will increase the simulated stratospheric mass of Br(sub y) by about 15 percent. In-situ stratospheric destruction of CHBr3 produces Br(sub y) in amounts which are comparable to that transported into the stratosphere after photolysis and oxidation of CHBr3 in the troposphere. In our simulations the mass of Br(sub y) produced from the destruction of CHBr3 does not exceed the mass of Br(sub y) produced from the destruction of the long-lived compounds at any level in the stratosphere. However, Br(sub y) from the loss of CHBr3 accounts for approximately one-third of the total Br(sub y) in the lowest kilometer of the stratosphere.
Nielsen, J. Eric↗
Possible role of phosphine in chemical evolution
Experiments simulating the formation of organic molecules in model reducing atmospheres including phosphine show that a variety of organic molecules can be synthesized. From the experiments using UV light as an energy source, it appears that the presence of phosphine drastically increases the yield of photolysis of methane and, thus, the yield of the formation of organic matter. The presence of phosphine enhances the formation of organophosphorous compounds, such as methyl and dimethylphosphine.
Raulin, F.↗
Optical spectroscopy of a highly fluorescent aggregate of bacteriochlorophyll c
Bacteriochlorophyll (BChl) c and a similar model compound, Mg-methyl bacteriopheophorbide d, form several types of aggregates in nonpolar solvents. One of these aggregates is highly fluorescent, with a quantum yield higher than that of the monomer. This aggregate is also unusual in that it shows a rise time in its fluorescence emission decay at certain wavelengths, which is ascribed to a change in conformation of the aggregate. An analysis of fluorescence depolarization data is consistent with either a linear aggregate of four or five monomers or preferably a cyclic arrangement of three dimers.
NASA Discipline Exobiology↗
Dimethylsilanediol (DMSD) Source Assessment and Mitigation on ISS: Estimated Contributions from Personal Hygiene Products Containing Volatile Methyl Siloxanes (VMS)
Dimethylsilanediol (DMSD) is a small organosilicon compound present in humidity condensate on the International Space Station. Aqueous DMSD originates from volatile methyl siloxane (VMS) compounds in the ISS cabin atmosphere. DMSD is not effectively removed by the WPA (Water Processor Assembly), requiring removal and replacement of both WPA Multifiltration (MF) Beds for an estimated resupply penalty of approximately 70 kg/year. Analyses indicate that WPA can handle DMSD if the concentration in the condensate can by reduced by fifty percent. Personal Hygiene Products (PHPs) used by crew are suspected to be a significant source of VMS. Source removal of VMS will be required to achieve a measurable impact to the DMSD concentration in the condensate. The inventory of total crew provisions for ISS was analyzed to identify silicon containing materials and products used for personal hygiene that emit VMS. Accounting for the wide range in mass of hygiene product applied to skin or hair, the frequency of application, the product selection, the number of crew using a given product, the range in silicon mass fraction of different products, and the potential vaporization of the product, the potential total VMS emissions from personal hygiene products for a crew of six on ISS were estimated. The total daily VMS emissions from PHPs estimate ranges from 261 to 1145 mg-Si per day, compared to total estimated VMS generation rates on ISS of 800 to 1500 mg-Si per day. The main sources of VMS were determined to be antiperspirants (173 to 696 mg-Si per day), skin lotions (63 to 248 mg-Si per day), wipes (25 to 124 mg-Si per day) and hair conditioner (0 to 69 mg-Si per day). Several siloxanes-free options are available for deodorants, wet wipes, lotions, and leave-in conditioners. These products are now being assessed for crew member use in future increments.
Muirhead, Dean L.↗
The decomposition of oxy-containing organic compounds in a microwave discharge.
Methyl alcohol, ether and acetone vapors decomposition in microwave discharge, obtaining H and CO in addition to solid polymeric films
Lin, S. W.↗
Effects of various additives on physical properties and performance of monomethylhydrazine
Effects of various additives on physical properties of monomethyl hydrazine liquid propellant - nitrogen compounds and water
NITROGEN COMPOUND↗
Some Sources of Contaminants in the Shuttle Bay Measured with Temperature-Controlled Quartz Crystal Microbalances (TQCM)
The sources of molecular deposits on a Temperature-Controlled Quartz Crystal Microbalance (TQCM) attached to the shuttle bay wall at some distance from the payload and pointing out of the bay have been investigated. Explored as possible sources are: (1) the outgassing of the shuttle tiles treated with the water proofing di-methyl-ethoxy-silane (DMES) compound, scattered back by the ambient molecules into the bay; (2) The ambient scattered return flux of the outgassing, from the RTV 560 silicone which is used as the adhesive for the tiles; (3) the ambient scattered return flux of the payload outgassing; (4) the return C, flux from outgassing source originating near, below, or adjacent to the package containing the TQCM; and (5) the self-scattering of venting plumes and outgassing above the monitor package depositing on the TQCM. In all of these sources, the magnitudes of the outgassing, of the leakage rates, and venting had to be estimated in the absence of data. The resulting analyses which can be useful for similar investigations, indicates that the outgassin- from the tiles, the RTV, the payloads, or the shuttle may not have been the sources of the deposit (about 1 micro g/cm(sup 2) during a the period from bay door opening and payload release from the bay). It appears more probable that the origin is the self- and/or ambient-scattered return fluxes originating near, below, or internal to the monitor package.
Scialdone, John J.↗
Infrared Band Strengths for Amorphous and Crystalline Methyl Propionate, a Candidate Interstellar Molecule
Mid-infrared spectra of amorphous and crystalline methyl propionate, CH3CH2COOCH3, are presented for the first time from a single laboratory, along with measurements of the refractive index of each solid form. Density estimates are made and IR band strengths and absorption coefficients are calculated. Vapor pressures of crystalline methyl propionate at 140-150 K are reported along with an enthalpy of sublimation. Spectroscopic results are compared to a recent study of this compound, and the phase of methyl propionate in that work is identified. Several applications are described.
Astrochemistry↗
The Incidence and Fate of Volatile Methyl Siloxanes in a Crewed Spacecraft Cabin
Volatile methyl siloxanes (VMS) arise from diverse, pervasive sources aboard crewed spacecraft ranging from materials offgassing to volatilization from personal care products. These sources lead to a persistent VMS compound presence in the cabin environment that must be considered for robust life support system design. Volatile methyl siloxane compound stability in the cabin environment presents an additional technical issue because degradation products such as dimethylsilanediol (DMSD) are highly soluble in water leading to a unique load challenge for water purification processes. The incidence and fate of VMS compounds as observed in the terrestrial atmosphere, water, and surface (soil) environmental compartments have been evaluated as an analogy for a crewed cabin environment. Volatile methyl siloxane removal pathways aboard crewed spacecraft are discussed and a material balance accounting for a DMSD production mechanism consistent with in-flight observations is presented.
Perry, Jay L.↗
Infrared spectra of molecules and materials of astrophysical interest
The Raman spectra of gaseous, liquid and solid, and infrared spectra of gaseous and solid isopropylamine-d sub 0 and -d sub 2 was investigated between 4000 and 50 cm superscript -1. Differences between the spectrum of the solid phase and that of the fluid phases were interpreted in terms of an equilibrium between low energy s-trans and high energy gauche conformers, and a complete vibrational assignment was proposed for the s-trans conformer. The far infrared spectra of the gaseous compounds contained bands due to the asymmetric amino and coupled methyl torsions; the assignment of these bands was aided by observation of a number of two quantum transitions for each vibrational mode. The asymmetric potential functions were calculated, which resulted in values for the enthalpy differences between conformers in the gaseous phase of 446 and 523 callmole for the sub 0 -d and -d sub 2 compounds, respectively. The methyl torsional potential function of isopropylamine-d sub 0 was calculated which led to a value for the barrier height to internal rotation of the methyl rotors of 4.23 + or - 0.06 kcal/mole. Values for the ideal gas thermodynamic functions were calculated over a range of temperatures.
Durig, J. R.↗
Alkyl phosphonic acids and sulfonic acids in the Murchison meteorite
Homologous series of alkyl phosphonic acids and alkyl sulfonic acids, along with inorganic orthophosphate and sulfate, are identified in water extracts of the Murchison meteorite after conversion to their t-butyl dimethylsilyl derivatives. The methyl, ethyl, propyl, and butyl compounds are observed in both series. Five of the eight possible alkyl phosphonic acids and seven of the eight possible alkyl sulfonic acids through C4 are identified. Abundances decrease with increasing carbon number as observed of other homologous series indigenous to Murchison. Concentrations range downward from approximately 380 nmol/gram in the alkyl sulfonic acid series, and from 9 nmol/gram in the alkyl phosphonic acid series.
Cooper, George W.↗
Detection and Quantification of Nitrogen Compounds in the First Drilled Martian Solid Samples by the Sample Analysis at Mars (SAM) Instrument Suite on the Mars Science Laboratory (MSL)
The Sample Analysis at Mars (SAM) instrument suite on the Mars Science Laboratory (MSL) Curiosity Rover detected both reduced and oxidized nitrogen-bearing compounds during the pyrolysis of surface materials at Yellowknife Bay in Gale Crater. Preliminary detections of nitrogen species include NO, HCN, ClCN, CH3CN, and TFMA (trifluoro-N-methyl-acetamide). Confirmation of indigenous Martian N-bearing compounds requires quantifying N contribution from the terrestrial derivatization reagents (e.g. N-methyl-N-tertbutyldimethylsilyltrifluoroacetamide, MTBSTFA and dimethylformamide, DMF) carried for SAM's wet chemistry experiment that contribute to the SAM background. Nitrogen species detected in the SAM solid sample analyses can also be produced during laboratory pyrolysis experiments where these reagents are heated in the presence of perchlorate, a compound that has also been identified by SAM in Mars solid samples.
Curiosity rover↗
The 1-((diorganooxy phosphonyl) methyl)-2,4- and -2,6-diamino benzenes and their derivatives
The 1-((diorganooxy phosphonyl) methyl)-2,4- and -2,6-dinitro- and diamino benzenes are prepared by nitrating an (organo phosphenyl) methyl benzene to produce the dinitro compounds which are then reduced to the diamino compounds. The organo groups (alkyl, haloalkyl, aryl) on the phosphorus may be removed to give the free acids (HO)2P(=0)-. The diamino compounds may be polymerized with dianhydrides or diacyl halides to produce fire and flame resistant polymers which are useful in the manufacture of aircraft structures.
Mikroyannidis, John A.↗
The 1-((diorganooxyphosphonyl)-methyl)-2,4- and -2,6-diamido benzenes
1-((Diorgano oxyphosphonyl) methyl)-2,4- and -2,6-dinitro and diamino benzenes are prepared by nitrating an (organophosphonyl) methyl benzene to produce the dinitro compounds which are then reduced to the diamino compounds. The organo grounds (alkyl, haloalkyl, aryl) on the phosphorus may be removed to give the free acids (HO)2P(double bond O)single bond. The diamino compounds may be polymerized with dianhydrides or diacyl halides to produce fire and flame resistant polymers which are useful in the manufacture of aircraft structures.
Mikroyannidis, John A.↗
QFD analysis of RSRM aqueous cleaners
This paper presents a Quality Function Deployment (QFD) analysis of the final down-selected aqueous cleaners to be used on the Redesigned Solid Rocket Motor (RSRM) program. The new cleaner will replace solvent vapor degreasing. The RSRM Ozone Depleting Compound Elimination program is discontinuing the methyl chloroform vapor degreasing process and replacing it with a spray-in-air aqueous cleaning process. Previously, 15 cleaners were down-selected to two candidates by passing screening tests involving toxicity, flammability, cleaning efficiency, contaminant solubility, corrosion potential, cost, and bond strength. The two down-selected cleaners were further evaluated with more intensive testing and evaluated using QFD techniques to assess suitability for cleaning RSRM case and nozzle surfaces in preparation for adhesive bonding.
Marrs, Roy D.↗
New reactions of paraformaldehyde and formaldehyde with inorganic compounds
Both paraformaldehyde and formaldehyde undergo reactions in the presence of several inorganic compounds to generate a variety of interesting organic products that can be important in chemical evolutionary processes. Some examples are acrolein, acetaldehyde, methyl formate, methanol, glycolaldehyde and formic acid. The organic compounds are produced at temperatures as low as 56 C and in high yield (up to 75%). The quantity produced depends principally on the nature of the inorganic compound, the ratio of the inorganic compound to paraformaldehyde, temperature and reaction time. The percent distribution of product depends on some of the foregoing factors.
Becker, R. S.↗