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NASA NTRS2021

Direct Measurements of Infrared Intensities of HCN and H2O + HCN Ices for Laboratory and Observational Astrochemistry

Hydrogen cyanide (HCN) is found in a wide variety of extraterrestrial environments within and beyond the solar system, and for that reason laboratory spectroscopists have studied this compound in many spectral regions, including the infrared (IR). However, one aspect that remains to be investigated is the intrinsic IR spectral intensities of solid HCN as opposed to relative band strengths, intrinsic intensities being needed to measure HCN abundances. Here we report measurements of IR absorption coefficients and band strengths, along with supporting refractive indices and densities, of both amorphous and crystalline HCN at two temperatures, one for interstellar work and one more relevant to the outer solar system. Spectra are presented at both temperatures, along with optical constants that can be used in numerical models. Despite widespread and longstanding interest in and investigations of solid HCN, this is the first time that the properties we are reporting have been measured in a single laboratory, avoiding the need for estimates or to combine results from various authors. We find that our measured band strength of ~1 × 1017 cm molecule1 for the CN vibration of HCN, in both amorphous HCN and in an H2O-rich ice, is substantially higher than an earlier estimate. Unless errors of 100% can be tolerated then our new value requires a rescaling of earlier work. Our results shed light on why HCN and other nitriles have been so difficult to identify in the solid state, in contrast to their many detections in the gas phase.

astrochemistry – methods: laboratory – solid state↗
NASA NTRS2021

Direct Measurements of Infrared Intensities of HCN and H2O + HCN Ices for Laboratory and Observational Astrochemistry

Hydrogen cyanide (HCN) is found in a wide variety of extraterrestrial environments within and beyond the solar system, and for that reason laboratory spectroscopists have studied this compound in many spectral regions, including the infrared (IR). However, one aspect that remains to be investigated is the intrinsic IR spectral intensities of solid HCN as opposed to relative band strengths, intrinsic intensities being needed to measure HCN abundances. Here we report measurements of IR absorption coefficients and band strengths, along with supporting refractive indices and densities, of both amorphous and crystalline HCN at two temperatures, one for interstellar work and one more relevant to the outer solar system. Spectra are presented at both temperatures, along with optical constants that can be used in numerical models. Despite widespread and longstanding interest in and investigations of solid HCN, this is the first time that the properties we are reporting have been measured in a single laboratory, avoiding the need for estimates or to combine results from various authors. We find that our measured band strength of ~1 × 1017 cm molecule1 for the CN vibration of HCN, in both amorphous HCN and in an H2O-rich ice, is substantially higher than an earlier estimate. Unless errors of 100% can be tolerated then our new value requires a rescaling of earlier work. Our results shed light on why HCN and other nitriles have been so difficult to identify in the solid state, in contrast to their many detections in the gas phase.

astrochemistry – methods: laboratory – solid state↗
NASA NTRS1984

On the abiotic formation of amino acids. I - HCN as a precursor of amino acids detected in extracts of lunar samples. II - Formation of HCN and amino acids from simulated mixtures of gases released from lunar samples

Two studies on the abiotic formation of amino acids are presented. The first study demonstrates the role of hydrogen cyanide as a precursor of amino acids detected in extracts of lunar samples. The formation of several amino acids, including glycine, alanine, aspartic acid, and glutamic acid, under conditions similar to those used for the analysis of lunar samples is demonstrated. The second study investigates the formation of hydrogen cyanide as well as amino acids from lunar-sample gas mixtures under electrical discharge conditions. These results extend the possibility of synthesis of amino acids to planetary bodies with primordial atmospheres less reducing than a mixture of methane, ammonia, hydrogen and water.

Yuasa, S.↗
NASA NTRS2002

In-Situ Measurements of HCN and CH3CN in the Pacific Troposphere: Sources, Sinks, and Comparisons with Spectroscopic Observations

We report the first in-situ measurements of hydrogen cyanide (HCN) and acetonitrile (CH3CN) from the Pacific troposphere (0-12 km) obtained during the NASA/Trace-P mission (Feb.-April, 2001). Mean HCN and CH3CN mixing ratios of 243 (+/-118) ppt and 149 (+/-56) ppt respectively, were measured. The in-situ observations correspond to a total HCN column of 4.4-4.9 x 10(exp 15) molec. cm(exp -2) and a CH3CN column of 2.8-3.0 x 10(exp 15) molec. cm(exp -2). This HCN column is in good agreement with available spectroscopic observations. The atmospheric concentrations of HCN and CH3CN were greatly influenced by outflow of pollution from Asia. There is a linear relationship between the mixing ratios of HCN and CH3CN, and in turn these are well correlated with tracers of biomass combustion (e.g. CH3Cl, CO). Relative enhancements with respect to known tracers of biomass combustion within selected plumes in the free troposphere, and pollution episodes in the boundary layer allow an estimation of a global biomass burning source of 0.8+/-0.4 Tg (N)/y for HCN and 0.4+/-0.1 Tg (N)/y for CH3CN. In comparison, emissions from automobiles and industry are quite small (<0.05 Tg (N)/y). The vertical structure of HCN and CH3CN indicated reduced mixing ratios in the MBL (Marine Boundary Layer). Using, a simple box model, the observed gradients across the top of the MBL are used to derive an oceanic flux of 6.7 x 10(exp -15) g (N) cm(exp -2)/s for HCN and 4.8 x 10(exp -15) g (N) cm(exp -2)/s for CH3CN. An air-sea exchange model is used to conclude that this flux can be maintained if the oceans are under-saturated in HCN and CH3CN by 23% and 17%, respectively. It is inferred that oceanic loss is a dominant sink for these nitrites, and they deposit some 1.3 Tg (N) of nitrogen annually to the oceans. Assuming reaction with OH radicals and loss to the oceans as the major removal processes, a mean atmospheric residence time of 4.7 months for HCN and 5.1 months for CH3CN is calculated. A global budget analysis shows that the sources and sinks of HCN and CH3CN are roughly in balance. There are indications that biogenic sources may also be present. Mechanisms involved in nitrate formation during combustion and removal in the oceans are poorly understood.

Singh, Hanwant B.↗
NASA NTRS2004

Bima Array Detections of HCN in Comets Linear (C/2002 T7) and Neat (C/2001 Q4)

We present interferometric detections of HCN in comets LINEAR (C/2002 T7) and NEAT (C/2001 Q4) with the Berkeley-Illinois-Maryland Association (BIMA) Array in its D-configuration cross-correlation mode. We detected the HCN J = 1 - 0 emission line in both comets. With a 25".4 x 20".3 synthesized beam around Comet LINEAR, we found a total beam averaged HCN column density (assuming a rotation temperature of 146 K) of < N(sub T) > = 2.1(11)x 10(sup 13) cm(exp -2), and a HCN production rate of Q(HCN)=2.8(15)x 10(sup 27) s(exp -1). With a 21".3 x 17".5 synthesized beam around Comet NEAT, we found a total beam averaged HCN column density (assuming a rotation temperature of 107 K) of < N(sub T) > = 5.7(30) x 10(sup l2) cm(exp -2), and a HCN production rate of Q(HCN)=8.3(44) x 10(sup 26) s(exp -l) giving a production rate of HCN relative to H2O of approximately 0.09(5)%. The production rates relative to H2O and spatial extent of HCN are similar to previous comet observations.

Friedel, D. N.↗
NASA NTRS2004

On The Effect of Electron Collisions in the Excitation of Cometary HCN

The electron-HCN collision rate for the excitation of rotational transitions of the HCN molecule is evaluated in comets C/1995 01 (Hale-Bopp) and C/1996 B2 (Hyakutake). Based on theoretical models of the cometary atmosphere, we show that collisions with electrons can provide a significant excitation mechanism for rotational transitions in the HCN molecule. Computed values of the cross section sigma(sub e-HCN) can be as high as 1.3 x cm2, more than 2 orders of magnitude greater than the commonly assumed HCN-H2O cross section. For the ground rotational transitions of HCN, the electron-HCN collision rate is found to exceed the HCN-H2O collision rate at distances greater than 3000 km from the cometary nucleus of Hale-Bopp and 1000 km from that of Hyakutake. Collisional excitation processes dominate over radiative excitation processes up to a distance of 160,000 km from the cometary nucleus of Hale-Bopp and 50,000 km from that of Hyakutake. Excitation models that neglect electron collisions can underestimate the HCN gas production rates by as much as a factor of 2.

Lovell, Amy J.↗
NASA NTRS1986

HCN production from Comet Halley

Observations of the HCN J=1-0 rotational transition at 3.4 mm wavelength in comet P/Halley with a 14m antenna were obtained during 56 individual observing sessions between Nov. 1985 and May 1986. The HCN production rate is well correlated with the total visual magnitude of the comet, indicating that HCN follows the overall gas and dust production. However, comparison of HCN production to the total gas production of the comet indicates that it is a relatively minor consitiuent with 0.1% of the abundance of H2O. Spectra obtained by binning the HCN data with heliocentric distance show that the HCN line width, and thus the parent outflow velocity, increases with decreasing heliocentric distance, and that there is a tendency for the lines to be blue shifted as expected from the observed anisotropic outgassing from the nucleus. There is evidence of day-to-day time variability in the total HCN emission and variations in the HCN hyperfine ratios from their LTE values.

Schloerb, F. Peter↗
NASA NTRS2002

Detection of HCN and C2H2 in ISO Spectra of Oxygen-Rich AGB Stars

Cool oxygen-rich AGB stars were not expected to have organic molecules like HCN in either their photospheres or circumstellar envelopes (CSEs). The discovery of HCN and CS microwave emission from the shallowest CSE layers of these stars was a considerable surprise and much theoretical effort has been expended in explaining the presence of such organics. To further explore this problem, we have undertaken a systematic search of oxygen-rich AGB stellar spectra in the Infrared Space Observatory (ISO) data archive. Our purposes are to find evidence regarding critical molecular species that could be of value in choosing among the proposed theoretical models, to locate spectral features which might give clues to conditions deeper in the CSEs, and to lay the groundwork for future SIRTF (Space Infrared Telescope Facility) and SOFIA (Stratospheric Observatory for Infrared Astronomy) observations. Using carefully reduced observations, we have detected weak absorption features arising from HCN and possibly C2H2 in a small number of oxygen-rich AGB stars. The most compelling case is NML Cyg which shows both HCN (14 microns) and CO2 (15 microns). VY CMa, a similar star, shows evidence for HCN, but not CO2. Two S-type stars show evidence for the C-H bending transitions: W Aql at 14 microns (HCN) and both W Aql and S Cas at 13.7 microns (C2H2). Both W Aql and S Cas as well as S Lyr, a SC-type star, show 3 micron absorption which may arise from the C-H stretch of HCN and C2H2. In the case of NML Cyg, we show that the HCN and CO2 spectral features are formed in the CSE at temperatures well above those of the outermost CSE layers and derive approximate column densities. In the case of the S-stars, we discuss the evidence for the organic features and their photospheric origin.

Carbon, Duane F.↗
NASA NTRSDate not supplied

HCN emissions from the explosive volcanic eruption of Mt. Pinatubo, Philippines, in June 1991

In June 1991, Mt. Pinatubo explosively erupted magma and overlying rock, with ejecta reaching stratospheric altitudes. The sulphate aerosol burden resulting from the 1991 eruption was still measurable in 1992 and its complete removal took 5-6 years. Here we present new analyses of measurements by the ATMOS instrument on the Atlas-1 Space Shuttle mission and the MkIV balloon interferometer in 1992 that show about 40-50 ppt of unexpected excess HCN in the middle stratosphere. HCN has no stratospheric sources and a lifetime of several years. Multi-year runs with the GEOS-Chem Chemistry-Transport model have been performed in order to derive the most plausible HCN injection amounts. The overall structure of the modeled HCN agrees reasonably well with observations by MkIV and ATMOS. The current best estimate is an emission of about 6 kt of HCN into the stratosphere at an altitude of about 23 km. This compares to a total gas emission in the order of 70-700 Mt, based on an emission of 14 Mt SO2 and an SO2/total gas ratio of 2% - 20%. We will discuss possible sources and formation mechanisms of the HCN. These include abiotic formation during or prior to the eruption and may involve HCN accumulated in the subaerial volcanic-hydrothermal system of Mt. Pinatubo. We present results from thermochemical equilibrium calculations as well as photochemical plume modeling in order to provide plausibility constraints on the source of the HCN.

Armin Kleinboehl↗
DOE OSTI2024

Direct HCN synthesis via plasma-assisted conversion of methane and nitrogen

Hydrogen cyanide (HCN) is synthesized from ammonia (NH 3 ) and methane (CH 4 ) at ~1200°C over a Pt catalyst. Ammonia synthesis entails several complex, highly emitting processes. Plasma-assisted HCN synthesis directly from CH 4 and nitrogen (N 2 ) could be pivotal for on-demand HCN production. Here, we evaluate the potential of dielectric barrier discharge (DBD) N 2 /CH 4 plasma for decentralized catalyst-free selective HCN production. We demonstrate a single-step conversion of methane and nitrogen to HCN with a 72% yield at <300°C. HCN is favored at low CH 4 concentrations with ethane (C 2 H 6 ) as the secondary product. We propose a first-principles microkinetic model with few electron impact reactions. The model accurately predicts primary product yields and elucidates that methyl radical (·CH 3 ) is a common intermediate in HCN and C 2 H 6 synthesis. Compared to current industrial processes, N 2 /CH 4 DBD plasma can achieve minimal CO 2 emissions.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
NASA NTRS1994

The vertical distribution and origin of HCN in Neptune's atmosphere

Measurements and modeling of the (3-2) rotational line of hydrogen cyanide at 265.9 GHz in Neptune's atmosphere are presented. High signal-to-noise observations provide information on the HCN vertical distribution in Neptune's stratosphere. The HCN mixing ratio is found to be nearly uniform with height above the condensation level. Best fits occur for HCN distributions that have a slight increase with altitude. A least-squares analysis yields a mixing ratio of (3.2 +/- 0.8)10(exp -10) at 2 mbar and a mean mixing ratio scale height of 250(sup 750)(sub -110) km in the 0.1-3 mbar region. To interpret these results, we developed a photochemical model of HCN. HCN formation is initiated by the reaction between CH3 radicals, produced from methane photochemistry, and N atoms. The primary sink for HCN is condensation, with minor contributions from photolysis and chemical losses. Two possible sources of N atoms are investigated: (1) infall of N escaped from Triton's upper atmosphere, and (2) galactic cosmic ray (GCR) impact on internal N2. Given the uncertainties on (i) the transport and possible ionization of N in Neptune's magnetosphere, and the fate of N(+) reaching Neptune's upper atmosphere and (ii) the N2 mixing ratio in Neptune's deep atmosphere, we suggest that both sources of N atoms may significantly contibute to the formation of HCN.

Lellouch, Emmanuel↗
NASA NTRS1981

Structural studies on HCN oligomers

NMR spectral studies on the HCN oligomers suggest the presence of carboxamide and urea groupings. The release of CO2, H2O, HCN, CH3CN, HCONH2 and pyridine on pyrolysis is consistent with the presence of these groupings as well as carboxylic acid groups. No basic primary amine groupings could be detected with fluorescamine. Hydrazinolysis of the HCN oligomers releases 10% of the amino acids normally released by acid hydrolysis. The oligomers give a positive biuret test but this is not due to the presence of peptide bonds. There is no conclusive evidence for the presence of peptide bonds in the HCN oligomers. No diglycine was detected on partial hydrolysis of the HCN oligomers at pH 8.5 suggesting that HCN oligomers were not a source of prebiotic peptides.

Ferris, J. P.↗
NASA NTRS1987

Clustering reactions of H2CN(+) ions with HCN

The rate coefficients for the first and second steps in the clustering sequence of H2CN(+) ions with HCN, H2CN(+) + HCN + M - H2CN(+) (HCN) + M and H2CN(+) (HCN) + HCN + M - H2CN(+) (HCN)2 + M, have been measured at temperatures from 189 to 296 K for M = He. The three-body association rate coefficients for both reactions are least-squares fitted for a power dependence on gas temperature. The temperature dependences of the three-body association reaction rate coefficients fitted in the range 200 to 300 K are given. The absolute values and temperature dependences are rather similar.

Chatterjee, B. K.↗
NASA NTRS1987

Observations of HCN in Comet Halley

Observations of the HCN J = 1-0 rotational transition at 3.4 mm wavelength in comet P/Halley are discussed. The data were obtained during a total of 56 individual observing sessions between Nov. 18, 1985 and May 11, 1986, and represent the first time that a cometary parent molecule has been so extensively monitored. The HCN production rate is well correlated with the total visual magnitude of the comet, indicating that HCN follows the overall gas production. There is also evidence of time variability and variations in the HCN hyperfine ratios from their LTE values. Spectra obtained by binning the HCN data with heliocentric distance show that the HCN line width, and thus the parent outflow velocity, increases with decreasing heliocentric distance.

Schloerb, F. Peter↗
NASA NTRS1987

Observations of HCN in comet P/Halley

This paper presents observations of the HCN J =1-0 rotational transition at 3.4 mm wavelength in Comet P/Halley, obtained during 56 individual observing sessions between November 1985 and May 1986 carried out at the Five College Radio Astronomy Observatory. A comparison of the HCN production with the total gas production of the comet indicates that HCN is a relatively minor constituent with 0.1 percent the abundance of H2O. A comparison of HCN and CN production suggests that HCN is a major parent molecule of CN, but probably not the sole parent. Evidence is presented of day-to-day time variability in the total HCN emission and in the hyperfine ratios. The time variation of the total emission is consistent with the known time variable behavior of the comet.

Schloerb, F. P.↗
NASA NTRS1991

CN and HCN in the infrared spectrum of IRC + 10216

The abundance of HCN in the inner circumstellar shell of IRC + 10216 has been remeasured using the 12-micron nu2 band. The 12-micron lines are less saturated than HCN 3-micron lines previously detected in the spectrum of IRC + 10216. The observed 12-micron HCN line is formed in the circumstellar shell from about 4 to 12 R sub * in accord with a photospheric origin for HCN. The derived HCN abundance in the 4 to 12 R sub* region is 4 x 10 exp-5 and the column density is 7 x 10 exp 18/sq cm. The 5-micron CN vibration-rotation fundamental band was detected for the first time in an astronomical source. Using four CN lines, the CN column density was determined to be 2.6 x 10 exp 15/sq cm and the rotational temperature to be 8 +/-2 K. The peal radial abundance is 1 x 10 exp -5. The values for the temperature and abundance are in good agreement with microwave results and with the formation of CN from the photolysis of HCN.

Wiedemann, G. R.↗
NASA NTRS2002

In-Situ Measurements of HCN and CH3CN In the Pacific Troposphere: Sources, Sinks, and Comparisons with Satellite Observations

A new capillary gas chromatographic method using a Reduction Gas Detector was developed to measure HCN and CH3CN in the remote troposphere. This instrumental configuration was deployed for the very first time in the Trace-P field mission performed during the spring of 2001. The NASA DC-8 aircraft afforded an opportunity to measure HCN and CH3CN in polluted and pristine environments over the Pacific to a maximum altitude of 12 km. These are some of the first in situ measurements of the distribution of HCN and CH3CN over the Pacific. Large background concentrations of both nitriles were found to be present and significant variability was observed. The abundance of HCN and CH3CN was strongly impacted by outflow of pollution from Asia. In general there appeared to be a direct but nonlinear relationship between the mixing ratios of HCN and CH3CN. The vertical structure of these chemicals shows direct evidence of the presence of a significant oceanic sink. These observations will be compared with the column content HCN data from satellites and other available measurements. A large body of data have been collected and are being analyzed, both statistically and with the help of models, to better understand the sources and sinks of these nitriles. These results will be presented.

Singh, Hanwant B.↗
NASA NTRS1994

(abstract) Neptune: CO and HCN Distributions from Observations at the CSO

We used the Caltech Submillimeter Observatory (CSO ) to make spatially unresolved observations of the 230.538 GHz 2-1 transition of CO and the 265.886 GHz 3-2 transition of HCN at Neptune. All observations used the 10.4 meter antenna with a double sideband SIS junction heterodyne receiver. Spectra were observed with parallel acousto-optic spectrometers simultaneously providing 580 MHz bandwidth at 0.57 MHz resolution and 50 MHz bandwidth at 0.049 MHz resolution. Observed line shapes agree with prior observations by Rosenqvist et al and Marten et al. Analysis of the line shapes and intensities will yield information about the distributions of CO and HCN in the stratosphere of Neptune, and these results will be compared with previous results. The data imply that the mixing ratios of CO and HCN must decrease with altitude somewhere within the pressure range from 1 to 0.001 mbar. HCN data will also address the sharp saturation-induced decrease in the HCN mixing ratio at the lower levels in the stratosphere.

Caltech Submillimeter Observatory SRO CO carbon mo↗