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Photodriven Ammonia Synthesis from N 2 and H 2 : Recycling of a Molecular Molybdenum Nitride

Here, the synthesis of ammonia from its elements, N 2 and H 2 , is the most atom-economical and thermodynamically preferred route but presents a high kinetic barrier and thus is rare using molecular compounds. Irradiation of a molecular molybdenum nitride prepared from N 2 cleavage with visible light in the presence of an iridium photocatalyst and 1–4 atm of H 2 produced high yields of ammonia along with the formation of a cationic, formally molybdenum(VI) pentahydride as the major molybdenum-containing product. Continued irradiation of the molybdenum hydride under an N 2 atmosphere resulted in regeneration of the molybdenum nitride that was recycled and used for additional hydrogenation to generate more ammonia, demonstrating superstoichiometric batch ammonia synthesis using only N 2 and H 2 with molecular compounds under ambient conditions.

Hydrogenation

Size Dependence of the Tetragonal to Orthorhombic Phase Transition of Ammonia Borane in Nanoconfinement

We have investigated the thermodynamic property modification of ammonia borane via nanoconfinement. Two different mesoporous silica scaffolds, SBA-15 and MCM-41, were used to confine ammonia borane. Using in situ Raman spectroscopy, we examined how pore size influences the phase transition temperature from tetragonal (I4mm) to orthorhombic (Pmn21) for ammonia borane. In bulk ammonia borane, the phase transition occurs at around 217 K; however, confinement in SBA-15 (with ~8 nm pore sizes) reduces this temperature to approximately 195 K, while confinement in MCM-41 (with pore sizes of 2.1–2.7 nm) further lowers it to below 90 K. This suppression of the phase transition as a function of pore size has not been previously studied using Raman spectroscopy. The stability of the I4mm phase at a much lower temperature can be interpreted by incorporating the surface energy terms to the overall free energy of the system in a simple thermodynamic model, which leads to a significant increase in the surface energy when transitioning from the tetragonal phase to the orthorhombic phase.

Najiba, Shah

Ammonia - Did it have a role in chemical evolution

The significance of ammonia in the chemical evolution related to the origin of life is evaluated. A computer program was employed to calculate the time needed for the decomposition of ammonia by means of a photochemical reaction. Various possible protection mechanisms for ammonia are discussed, giving attention to hydrogen sulfide, hydrogen, ozone, and CO. It is concluded that in the absence of a sufficiently high pressure of hydrogen, any ammonia present in the primitive atmosphere would have been decomposed by photolysis in a million years.

Ferris, J. P.

The distribution of ammonia and its photochemical products on Jupiter

Altitude profiles of ammonia and its photochemical products are generated in the light of measurements of the Jovian temperature structure, eddy transport coefficient, improved chemical scheme, and rate constants. Realistic limits are placed on the concentration of hydrazine which may participate in the recycling of ammonia on Jupiter. The maximum hydrazine-ice production rate is calculated to be about 1.3 mg/sq m per Jovian day. The distribution of nitrogen gas is presented with and without supersaturation of hydrazine. The nitrogen mixing ratio near the ammonia cloud top is estimated to be in the range between 10 to the -9th and 10 to the -11th power. An appreciable latitudinal variation in the ammonia concentration is expected.

Atreya, S. K.

Removal of ammonia from urine vapor by a dual-catalyst system

The feasibility of removing ammonia from urine vapor by a low-temperature dual-catalyst system has been demonstrated. The process is based on the catalytic oxidation of ammonia to a mixture of nitrogen, nitrous oxide, and water, followed by a catalytic decomposition of the nitrous oxide into its elements. Potential ammonia oxidation and nitrous oxide decomposition catalysts were first screened with artificial gas mixtures, then tested with the actual urine vapor produced by boiling untreated urine. A suitable dual-catalyst bed arrangement was found that achieved the removal of ammonia and also organic carbon, and recovered water of good quality from urine vapor.

Budininkas, P.

Reflectance spectra for sodium and potassium doped ammonia frosts - Implications for Io's surface

This paper reports measurements of the reflection spectra of sodium- and potassium-doped ammonia frosts as a function of alkali metal concentration for the wavelength range 0.35-2.5 microns. The purpose of the measurements was to determine whether or not the reflection spectra for such a solid was compatible with the spectra albedo of Io. The data show that, with a sufficiently large alkali metal concentration, the reflection spectra of the doped ammonia frosts do not display the characteristic ammonia features at 2.0 and 2.25 micron. The high reflectance of the more concentrated samples and the character of the observed reflection spectrum make it difficult to rule out sodium-doped ammonia frost as a surface constituent on Io on the basis of existing data.

Rosen, M. D. A.

Remote infrared heterodyne radiometer measurements of atmospheric ammonia profiles

An infrared heterodyne radiometer has been used to study the seasonal variation of the vertical distribution of atmospheric ammonia. The ammonia profiles are inferred from high-resolution atmospheric solar transmittance measurements around the ammonia absorption feature at 927.32323 kaysers. The transmittance data are obtained from six IF channels with spectral resolutions ranging from .0067 to .033 kaysers. Results from this study show a marked decrease in the tropospheric ammonia level with a decrease at ground level from approximately 10 ppb in March 1979 to 1.3 ppb in August 1979.

Hoell, J. M.

Observation of interstellar ammonia ice

An absorption band probably due to solid ammonia on interstellar grains has been detected in the infrared spectrum at 2.97 microns of the Becklin-Neugebauer object and probably in NGC 2264-IR. An ammonia-water amorphous ice mixture can explain the structure of the new band and of the 3.07 microns interstellar absorption. Laboratory data suggest that a long wavelength wind extending to 3.5 microns in interstellar dust spectra may be absorption by NH3-H2O complexes in the ices. In the molecular cloud obscuring the BN object, about 20 times as much NH3 is frozen in grains as exists in the gas phase, suggesting the gas-grain interactions may be important in the ammonia chemistry of molecular clouds. Arguments are given that interstellar features at 6.0 and 6.8 microns are also ammonia-related absorptions.

Knacke, R. F.

High Pressure Cosmochemistry of Major Planetary Interiors: Laboratory Studies of the Water-rich Region of the System Ammonia-water

The behavior of gas-ice mixtures in major planets at very high pressures was studied. Some relevant pressure-temperature-composition (P-T-X) regions of the hydrogen (H2)-helium (He)-water (H2O-ammonia (NH3)-methane (CH4) phase diagram were determined. The studies, and theoretical model, of the relevant phases, are needed to interpret the compositions of ice-gas systems at conditions of planetary interest. The compositions and structures of a multiphase, multicomponent system at very high pressures care characterized, and the goal is to characterize this system over a wide range of low and high temperatures. The NH3-H2O compositions that are relevant to planetary problems yet are easy to prepare were applied. The P-T surface of water was examined and the corresponding surface for NH3 was determined. The T-X diagram of ammonia-water at atmospheric pressure was studied and two water-rich phases were found, NH3-2H2O (ammonia dihydrate), which melts incongruently, and NH3.H2O (ammonia monohydrate), which is nonstoichiometric and melts at a higher temperature than the dihydrate. It is suggested that a P-T surface at approximately the monohydrate composition and the P-X surface at room temperature is determined.

Nicol, M.

Aircraft measurements of ammonia and nitric acid in the lower troposphere

The first simultaneous measurements of ammonia and nitric acid in the troposphere have been made from an aircraft using a tungsten oxide denuder system. Vertical profiles of NH3 and HNO3 taken over coastal Virginia and Maryland in March and September, 1983, at altitudes from 150 m to 3000 m, show mixing ratios that decrease with altitude. Ammonia profiles show substantial seasonal variation, while nitric acid profiles do not. Using the measured profiles and a one-dimensional photochemical model, lifetimes due to heterogeneous loss of one day for HNO3 and ten days for NH3 are calculated. In contrast, NH3 profiles up to 5300 m over the North Atlantic Ocean during August 1982 show mixing ratios that increase slightly with altitude. These data represent the first ammonia profiles measured over the ocean. It is suggested that the increase in NH3 with altitude is a result of an ammonia-rich continental air mass advected over the ocean, followed by the dissolution of NH3 in the marine boundary layer on water-covered sea salt particles.

Lebel, P. J.

Evolution of non-condensable gas in ammonia heat pipes

Accumulation of noncondensible gas (NCG) has been observed in ammonia heat pipes. NCG has been found to be detrimental to the performance of heat pipes and can result in complete operational failure. A kinetic and thermodynamic analysis has been performed that evaluates the dissociation of ammonia under various conditions and predicts the amount of NCG present in heat pipes. The analysis indicates that the observed NCG in ammonia heat pipes can be attributed to the dissociation of ammonia into its constituents, hydrogen and nitrogen. It shows time and temperature to be the important parameters, in conjunction with the catalytic characteristic of the container material.

Richter, Robert

Compatibility testing with anhydrous ammonia

Anhydrous ammonia has been proposed as the working fluid for a number of two-phase thermal control systems to be used in future space applications, including the Space Station Freedom and the Earth Observing Station (EOS). The compatibility of ammonia with the components in these systems is a major concern due to the corrosive nature of the fluid. Compatibility of ammonia with stainless steel and some aluminum alloys is well documented; however, data on other materials potentially suitable for aerospace use is less common. This paper documents the compatibility testing of nine materials with both gaseous and liquid ammonia. The test procedures are presented along with the resulting measurement data. Tensile strength was the only mechanical property tested that indicated a significant material incompatibility.

Steve M. Benner

Hydrogen bonding in the benzene-ammonia dimer

High-resolution optical and microwave spectra of the gas-phase benzene-ammonia dimer were obtained, showing that the ammonia molecule resides above the benzene plane and undergoes free, or nearly free, internal rotation. To estimate the binding energy (De) and other global properties of the intermolecular potential, theoretical calculations were performed for the benzene-ammonia dimer, using the Gaussian 92 (Fritsch, 1992) program at the MP2/6-31G** level. The predicted De was found to be at the lowest end of the range commonly accepted for hydrogen bonding and considerably below that of C6H6-H2O, consistent with the gas-phase acidities of ammonia and water. The observed geometry greatly resembles the amino-aromatic interaction found naturally in proteins.

Rodham, David A.

Ammonia in comet P/Halley

In comet P/Halley the abundances of ammonia relative to water reported in the literature differ by about one order of magnitude from roughly 0.1% up to 2%. Different observational techniques seem to have inherent systematic errors. Using the ion mass channels m/q = 19 amu/e, 18 amu/e and 17 amu/e of the Neutral Mass Spectrometer experiment aboard the spacecraft Giotto, we derive a production rate of ammonia of (1.5(sub -0.7)(sup +0.5))% relative to water. Inside the contact surface we can explain our data by a nuclear source only. The uncertainty in our abundance of ammonia is primarily a result of uncertainties in some key reaction coefficients. We discuss in detail these reactions and the range of error indicated results from extreme assumptions in the rate coefficients. From our data, even in the worst case, we can exclude the ammonia abundance to be only of the order of a few per mill.

Meier, R.

Ammonia Observations of NGC 6334 I(N)

Coincident with the far-infrared source NGC 6334 I(N) and water maser source E is a massive dense cloud which has the most intense ammonia (1, 1) emission of any known interstellar cloud. We have mapped the (3, 3) emission and find the cloud is extended 0.8 pc in the direction parallel to the Galactic plane, and 0.5 pc perpendicular to it. It has a velocity gradient of 1 km/s.pc perpendicular to the Galactic plane. The gas kinetic temperature is about 30 K and the density is greater than 10(exp 6)/cc. The mass of the cloud is about 3000 solar mass, 3 times greater than previously estimated. The para-ammonia column density is 6 - 8 x 10(exp 15)/sq cm. An ammonia abundance of 0.5 - 1.5 x 10(exp -8) is inferred, where the larger number assumes an early time ortho/para ratio. This suggests either a cloud age of less than approximately 10(exp 6) yr, or substantial depletion of ammonia.

Kuiper, T. B. H.

Ammonia Monitor

Ammonia monitor and method of use are disclosed. A continuous, real-time determination of the concentration of ammonia in an aqueous process stream is possible over a wide dynamic range of concentrations. No reagents are required because pH is controlled by an in-line solid-phase base. Ammonia is selectively transported across a membrane from the process stream to an analytical stream to an analytical stream under pH control. The specific electrical conductance of the analytical stream is measured and used to determine the concentration of ammonia.

Sauer, Richard L.

Application of a Chemiluminescence Detector for the Measurement of Total Oxides of Nitrogen and Ammonia in the Atmosphere

By means of the thermal conversion of nitrogen dioxide to the nitric oxide, the chemiluminescent nitric oxide monitor, based on the nitric oxide plus ozone reaction, may be used for monitoring nitrogen dioxide plus nitric oxide (NO(x)). Under conditions previously described, ammonia is also converted to nitric oxide and therefore interferes. A metal surface, gold wool or stainless steel, operated at two different temperatures has been used to convert only nitrogen dioxide or nitrogen dioxide plus ammonia. Quantitative conversion of nitrogen dioxide to nitric oxide has been obtained at temperatures as low as 200 C. Conversion of ammonia is effected at temperatures of 300 C or higher. By the addition of a converter the basic nitric oxide monitor may be used for measuring NO(x) or NO(x) plus ammonia. As an alternate mode, for a fixed high temperature, a specific scrubber is described for removing NH3 without affecting NO2 concentrations.

Hodgeson, J. A.

Spatial distribution of total, ammonia-oxidizing, and denitrifying bacteria in biological wastewater treatment reactors for bioregenerative life support

Bioregenerative life support systems may be necessary for long-term space missions due to the high cost of lifting supplies and equipment into orbit. In this study, we investigated two biological wastewater treatment reactors designed to recover potable water for a spacefaring crew being tested at Johnson Space Center. The experiment (Lunar-Mars Life Support Test Project-Phase III) consisted of four crew members confined in a test chamber for 91 days. In order to recycle all water during the experiment, an immobilized cell bioreactor (ICB) was employed for organic carbon removal and a trickling filter bioreactor (TFB) was utilized for ammonia removal, followed by physical-chemical treatment. In this study, the spatial distribution of various microorganisms within each bioreactor was analyzed by using biofilm samples taken from four locations in the ICB and three locations in the TFB. Three target genes were used for characterization of bacteria: the 16S rRNA gene for the total bacterial community, the ammonia monooxygenase (amoA) gene for ammonia-oxidizing bacteria, and the nitrous oxide reductase (nosZ) gene for denitrifying bacteria. A combination of terminal restriction fragment length polymorphism (T-RFLP), sequence, and phylogenetic analyses indicated that the microbial community composition in the ICB and the TFB consisted mainly of Proteobacteria, low-G+C gram-positive bacteria, and a Cytophaga-Flexibacter-Bacteroides group. Fifty-seven novel 16S rRNA genes, 8 novel amoA genes, and 12 new nosZ genes were identified in this study. Temporal shifts in the species composition of total bacteria in both the ICB and the TFB and ammonia-oxidizing and denitrifying bacteria in the TFB were also detected when the biofilms were compared with the inocula after 91 days. This result suggests that specific microbial populations were either brought in by the crew or enriched in the reactors during the course of operation.

NASA Discipline Life Support Systems