Reactions of nitriles in ices relevant to Titan, comets, and the interstellar medium: formation of cyanate ion, ketenimines, and isonitriles

Science.gov (United States)

Hudson, R. L.; Moore, M. H.

2004-12-01

Motivated by detections of nitriles in Titan's atmosphere, cometary comae, and the interstellar medium, we report laboratory investigations of the low-temperature chemistry of acetonitrile, propionitrile, acrylonitrile, cyanoacetylene, and cyanogen (CH 3CN, CH 3CH 2CN, CH 2CHCN, HCCCN, and NCCN, respectively). A few experiments were also done on isobutyronitrile and trimethylacetonitrile ((CH 3) 2CHCN and (CH 3) 3CCN, respectively). Trends were sought, and found, in the photo- and radiation chemical products of these molecules at 12-25 K. In the absence of water, all of these molecules isomerized to isonitriles, and CH 3CN, CH 3CH 2CN, and (CH 3) 2CHCN also formed ketenimines. In the presence of H 2O, no isonitriles were detected but rather the cyanate ion (OCN -) was seen in all cases. Although isonitriles, ketenimines, and OCN - were the main focus of our work, we also describe cases of hydrogen loss, to make smaller nitriles, and hydrogen addition (reduction), to make larger nitriles. HCN formation also was seen in most experiments. The results are presented in terms of nitrile ice chemistry on Titan, in cometary ice, and in the interstellar medium. Possible connections to prebiotic chemistry are briefly discussed.

Research investigation directed toward extending the useful range of the electromagnetic spectrum

Science.gov (United States)

Hartmann, S. R.

1971-01-01

The lifetimes and fine structure of He(-) were studied using time-of-flight techniques and quenching by a static axial magnetic field. Using level-crossing spectroscopy the hyperfine constants A and B and the lifetime of the 3 2P3/2 state of Li-7 were measured. Polarization of the Ru 7S level was created as a first step in determining the hyperfine structure of the alkali excited S state. The parametric interaction between light and microwaves in optically pumped Rb-87 vapor were investigated. Measurements and analyses of transitions in formaldehyde and its isotopic species and in the lowest two excited vibrational states of H2CO were also made, as well as of transitions in furan, pyrrole, formic acid, and cyanoacetylene. The Hanle effect was studied in the NO molecule, and RF oscillators were developed with flat, wideband output to observe excited state hyperfine transitions at zero field. Data was generated on the time-dependent behavior of photon echoes in ruby. Stimulated Raman scattering was studied in atomic Tl vapor. A Q switched, temperature-tuned ruby laser was developed which operates between 6934 and 6938 A. The frequency shift due to resonant interaction between identical radiating atoms was calculated.

Carbon Chemistry in IRC+10216: Infrared Detection of Diacetylene

Science.gov (United States)

Fonfría, J. P.; Agúndez, M.; Cernicharo, J.; Richter, M. J.; Lacy, J. H.

2018-01-01

We present the detection of C4H2 for first time in the envelope of the C-rich AGB star IRC+10216, based on high spectral resolution mid-infrared observations carried out with the Texas Echelon-cross-Echelle Spectrograph mounted on the Infrared Telescope Facility. The obtained spectrum contains 24 narrow absorption features above the detection limit, identified as lines of the ro-vibrational C4H2 band {ν }6+{ν }8({σ }u+). The analysis of these lines through a ro-vibrational diagram indicates that the column density of C4H2 is (2.4 ± 1.5) × 1016 cm‑2. Diacetylene is distributed in two excitation populations accounting for 20% and 80% of the total column density and with rotational temperatures of 47 ± 7 and 420 ± 120 K, respectively. This two-folded rotational temperature suggests that the absorbing gas is located beyond ≃0.″4 ≃ 20 R ⋆ from the star, with a noticeable cold contribution outwards from ≃10″ ≃ 500 R ⋆. This outer shell matches up with the place where cyanoacetylenes and carbon chains are known to form due to the action of the Galactic dissociating radiation field on the neutral gas coming from the inner layers of the envelope.

INFRARED SPECTRA AND OPTICAL CONSTANTS OF NITRILE ICES RELEVANT TO TITAN's ATMOSPHERE

International Nuclear Information System (INIS)

Moore, Marla H.; Hudson, Reggie; Ferrante, Robert F.; James Moore, W.

2010-01-01

Spectra and optical constants of nitrile ices known or suspected to be in Titan's atmosphere are presented from 2.0 to 333.3 μm (∼5000-30 cm -1 ). These results are relevant to the ongoing modeling of Cassini CIRS observations of Titan's winter pole. Ices studied are: HCN, hydrogen cyanide; C 2 N 2 , cyanogen; CH 3 CN, acetonitrile; C 2 H 5 CN, propionitrile; and HC 3 N, cyanoacetylene. For each of these molecules, we also report new cryogenic measurements of the real refractive index, n, determined in both the amorphous and crystalline phases at 670 nm. These new values have been incorporated into our optical constant calculations. Spectra were measured and optical constants were calculated for each nitrile at a variety of temperatures, including, but not limited to, 20, 35, 50, 75, 95, and 110 K, in both the amorphous phase and the crystalline phase. This laboratory effort used a dedicated FTIR spectrometer to record transmission spectra of thin-film ice samples. Laser interference was used to measure film thickness during condensation onto a transparent cold window attached to the tail section of a closed-cycle helium cryostat. Optical constants, real (n) and imaginary (k) refractive indices, were determined using Kramers-Kronig analysis. Our calculation reproduces the complete spectrum, including all interference effects.

Behaviour of solid phase ethyl cyanide in simulated conditions of Titan

Science.gov (United States)

Couturier-Tamburelli, I.; Toumi, A.; Piétri, N.; Chiavassa, T.

2018-01-01

In order to simulate different altitudes in the atmosphere of Titan, we investigated using infrared spectrometry and mass spectrometry the photochemistry of ethyl cyanide (CH3CH2CN) ices at different temperatures. Heating experiments of the solid phase until complete desorption showed up three phase transitions with a first one appearing to be approximately at the temperature of Titan's surface (94 K), measured by the Huygens probe. Ethyl cyanide, whose presence has been suggested in solid phase in Titan, can be considered as another nitrile for photochemical models of the Titan atmosphere after our first study (Toumi et al., 2016) concerning vinyl cyanide (CH2CHCN). The desorption energy of ethyl cyanide has been calculated to be 36.75 ( ± 0.55) kJ mol-1 using IRTF and mass spectroscopical techniques. High energetic photolysis (λ > 120 nm) have been performed and we identified ethyl isocyanide, vinyl cyanide, cyanoacetylene, ethylene, acetylene, cyanhydric acid and a methylketenimine form as photoproducts from ethyl cyanide. The branching ratios of the primary products were determined at characteristic temperatures of Titan thanks to the value of the νCN stretching band strength of ethyl cyanide that has been calculated to be 4.12 × 10-18 cm molecule-1. We also report here for the first time the values of the photodissociation cross sections of C2H5CN for different temperatures.

Formation of Nitriles in the Interstellar Medium via Reactions of Cyano Radicals, CN(X2Σ+), with Unsaturated Hydrocarbons

Science.gov (United States)

Balucani, N.; Asvany, O.; Huang, L. C. L.; Lee, Y. T.; Kaiser, R. I.; Osamura, Y.; Bettinger, H. F.

2000-12-01

Crossed molecular beam experiments of cyano radicals, CN(X2Σ+, ν=0), in their electronic and vibrational ground state reacting with unsaturated hydrocarbons acetylene, C2H2(X1Σ+g), ethylene, C2H4(X1Ag), methylacetylene, CH3CCH(X1A1), allene, H2CCCH2(X1A1), dimethylacetylene, CH3CCCH3(X1A1'), and benzene, C6H6 (X1A1g), were performed at relative collision energies between 13.3 and 36.4 kJ mol-1 to unravel the formation of unsaturated nitriles in the outflows of late-type AGB carbon stars and molecular clouds. In all reactions, the CN radical was found to attack the π electron density of the hydrocarbon molecule with the radical center located at the carbon atom; the formation of an initial addition complex is a prevalent pathway on all the involved potential energy surfaces. A subsequent carbon-hydrogen bond rupture yields the nitriles cyanoacetylene, HCCCN (X1Σ+), vinylcyanide, C2H3CN (X1A'), 1-methylcyanoacetylene, CH3CCCN (X1A1), cyanoallene, H2CCCH(CN) (X1A'), 3-methylcyanoacetylene, HCCCH2CN(X1A'), 1,1-cyanomethylallene, H2CCC(CN)(CH3) (X1A'), and cyanobenzene, C6H5CN (X1A1). In case of acetylene and ethylene, a second reaction channel involves a [1, 2]-H atom shift in the initial HCCHCN and H2CCH2CN collision complexes prior to a hydrogen atom release to form cyanoacetylene, HCCCN (X1Σ+), and vinylcyanide, C2H3CN (X1A'). Since all these radical-neutral reactions show no entrance barriers, have exit barriers well below the energy of the reactant molecules, and are exothermic, the explicit identification of this CN versus H atom exchange pathway under single collision conditions makes this reaction class a compelling candidate to synthesize unsaturated nitriles in interstellar environments holding temperatures as low as 10 K. This general concept makes it even feasible to predict the formation of nitriles once the corresponding unsaturated hydrocarbons are identified in the interstellar medium. Here HCCCN, C2H3CN, and CH3CCCN have been already observed

Infrared Spectra, Index of Refraction, and Optical Constants of Nitrile Ices Relevant to Titan's Atmosphere

Science.gov (United States)

Moore, Marla; Ferrante, Robert; Moore, William; Hudson, Reggie

2010-01-01

Spectra and optical constants of nitrite ices known or suspected to be in Titan's atmosphere are presented from 2.5 to 200 microns (4000 to 50 per cm ). These results are relevant to the ongoing modeling of Cassini CIRS observations of Titan's winter pole. Ices studied include: HCN, hydrogen cyanide; C2N2, cyanogen; CH3CN, acetonitrile; C 2H5CN, propionitrile; and HC3N, cyanoacetylene. For each of these molecules we report new measurements of the index of refraction, n, determined in both the amorphous- and crystallinephase at 670 nm. Spectra were measured and optical constants were calculated for each nitrite at a variety of temperatures including 20, 35, 50, 75, 95, and 110 K, in the amorphous- and crystalline-phase. This laboratory effort uses a dedicated FTIR spectrometer to record transmission spectra of thin-film ice samples. Laser interference is used to measure film thickness during condensation onto a transparent cold window attached to the tail section of a closed-cycle helium cryostat. Optical constants, real (n) and imaginary (k) refractive indices, are determined using Kramers-Kronig (K-K) analysis. Our calculation reproduces the complete spectrum, including all interference effects. Index of refraction measurements are made in a separate dedicated FTIR spectrometer where interference deposit fringes are measured using two 670 nm lasers at different angles to the ice substrate. A survey of these new measurements will be presented along with a discussion of their validation, errors, and application to Titan data.

Observed ices in the Solar System

Science.gov (United States)

Clark, Roger N.; Grundy, Will; Carlson, Robert R.; Noll, Keith; Gudipati, Murthy; Castillo-Rogez, Julie C.

2013-01-01

Ices have been detected and mapped on the Earth and all planets and/or their satellites further from the sun. Water ice is the most common frozen volatile observed and is also unambiguously detected or inferred in every planet and/or their moon(s) except Venus. Carbon dioxide is also extensively found in all systems beyond the Earth except Pluto although it sometimes appears to be trapped rather than as an ice on some objects. The largest deposits of carbon dioxide ice is on Mars. Sulfur dioxide ice is found in the Jupiter system. Nitrogen and methane ices are common beyond the Uranian system. Saturn’s moon Titan probably has the most complex active chemistry involving ices, with benzene (C6H6) and many tentative or inferred compounds including ices of Cyanoacetylene (HC3N), Toluene (C7H8), Cyanogen (C2N2), Acetonitrile (CH3CN), H2O, CO2, and NH3. Confirming compounds on Titan is hampered by its thick smoggy atmosphere. Ammonia was predicted on many icy moons but is notably absent among the definitively detected ices with the possible exception of Enceladus. Comets, storehouses of many compounds that could exist as ices in their nuclei, have only had small amounts of water ice definitively detected on their surfaces. Only one asteroid has had a direct detection of surface water ice, although its presence can be inferred in others. This chapter reviews some of the properties of ices that lead to their detection, and surveys the ices that have been observed on solid surfaces throughout the Solar System.

Low temperature measurement of the vapor pressures of planetary molecules

Science.gov (United States)

Kraus, George F.

1989-01-01

Interpretation of planetary observations and proper modeling of planetary atmospheres are critically upon accurate laboratory data for the chemical and physical properties of the constitutes of the atmospheres. It is important that these data are taken over the appropriate range of parameters such as temperature, pressure, and composition. Availability of accurate, laboratory data for vapor pressures and equilibrium constants of condensed species at low temperatures is essential for photochemical and cloud models of the atmospheres of the outer planets. In the absence of such data, modelers have no choice but to assume values based on an educated guess. In those cases where higher temperature data are available, a standard procedure is to extrapolate these points to the lower temperatures using the Clausius-Clapeyron equation. Last summer the vapor pressures of acetylene (C2H2) hydrogen cyanide (HCN), and cyanoacetylene (HC3N) was measured using two different methods. At the higher temperatures 1 torr and 10 torr capacitance manometers were used. To measure very low pressures, a technique was used which is based on the infrared absorption of thin film (TFIR). This summer the vapor pressure of acetylene was measured the TFIR method. The vapor pressure of hydrogen sulfide (H2S) was measured using capacitance manometers. Results for H2O agree with literature data over the common range of temperature. At the lower temperatures the data lie slightly below the values predicted by extrapolation of the Clausius-Clapeyron equation. Thin film infrared (TFIR) data for acetylene lie significantly below the values predicted by extrapolation. It is hoped to bridge the gap between the low end of the CM data and the upper end of the TFIR data in the future using a new spinning rotor gauge.

Monstrous Ice Cloud System in Titan's Present South Polar Stratosphere

Science.gov (United States)

Anderson, Carrie; Samuelson, Robert; McLain, Jason; Achterberg, Richard; Flasar, F. Michael; Milam, Stefanie

2015-11-01

During southern autumn when sunlight was still available, Cassini's Imaging Science Subsystem discovered a cloud around 300 km near Titan's south pole (West, R. A. et al., AAS/DPS Abstracts, 45, #305.03, 2013); the cloud was later determined by Cassini's Visible and InfraRed Mapping Spectrometer to contain HCN ice (de Kok et al., Nature, 514, pp 65-67, 2014). This cloud has proven to be only the tip of an extensive ice cloud system contained in Titan's south polar stratosphere, as seen through the night-vision goggles of Cassini's Composite InfraRed Spectrometer (CIRS). As the sun sets and the gloom of southern winter approaches, evidence is beginning to accumulate from CIRS far-IR spectra that a massive system of nitrile ice clouds is developing in Titan's south polar stratosphere. Even during the depths of northern winter, nothing like the strength of this southern system was evident in corresponding north polar regions.From the long slant paths that are available from limb-viewing CIRS far-IR spectra, we have the first definitive detection of the ν6 band of cyanoacetylene (HC3N) ice in Titan’s south polar stratosphere. In addition, we also see a strong blend of nitrile ice lattice vibration features around 160 cm-1. From these data we are able to derive ice abundances. The most prominent (and still chemically unidentified) ice emission feature, the Haystack, (at 220 cm-1) is also observed. We establish the vertical distributions of the ice cloud systems associated with both the 160 cm-1 feature and the Haystack. The ultimate aim is to refine the physical and possibly the chemical relationships between the two. Transmittance thin film spectra of nitrile ice mixtures obtained in our Spectroscopy for Planetary ICes Environments (SPICE) laboratory are used to support these analyses.

Observations of CO in Titan's Atmosphere Using ALMA

Science.gov (United States)

Serigano, Joseph; Nixon, Conor A.; Cordiner, Martin; Irwin, Patrick G. J.; Teanby, Nicholas; Charnley, Steven B.; Lindberg, Johan E.; Remijan, Anthony J.

2015-11-01

The advent of the Atacama Large Millimeter/submillimeter Array (ALMA) has provided a powerful facility for probing the atmospheres of solar system targets at long wavelengths (84-720 GHz) where the rotational lines of small, polar molecules are prominent. In the dense, nitrogen-dominated atmosphere of Titan, photodissociation of molecular nitrogen and methane leads to a wealth of complex hydrocarbons and nitriles in small abundances. Past millimeter/submillimeter observations, including ground-based observations as well as those by the Composite Infrared Spectrometer (CIRS) aboard the Cassini spacecraft, have proven the significance of this wavelength region for the derivation of vertical mixing profiles, latitudinal and seasonal variations, and molecular detections. Previous ALMA studies of Titan have presented mapping and vertical column densities of hydrogen isocyanide (HNC) and cyanoacetylene (HC3N) (Cordiner et al. 2014) as well as the first spectroscopic detection of ethyl cyanide (C2H5CN) in Titan’s atmosphere (Cordiner et al. 2015).Here, we report several submillimetric observations of carbon monoxide (CO) and its isotopologues 13CO, C18O, and C17O in Titan’s atmosphere obtained with flux calibration data from the ALMA Science Archive. We employ NEMESIS, a line-by-line radiative transfer code, to determine the stratospheric abundances of these molecules. The abundance of CO in Titan's atmosphere is determined to be approximately 50±1 ppm, constant with altitude, and isotopic ratios are determined to be approximately 12C/13C = 90, 16O/18O = 470, and 16O/17O = 2800. This report presents the first spectroscopic detection of C17O in the outer solar system, detected at >11σ confidence. This talk will focus on isotopic ratios in CO in Titan's atmosphere and will compare our results to previously measured values for Titan and other bodies in the Solar System. General implications for the history of Titan from measurements of CO and its isotopologues will be

Study of irradiation of flash lightning type in a Titan simulated atmosphere

International Nuclear Information System (INIS)

Rosa C, J.G. De la

2001-01-01

Titan is the greatest satellite of the Saturn planet and the unique moon of the Solar System which presents a dense atmosphere constituted by nitrogen, methane and traces of hydrocarbons and nitriles. Constantly it is bombarded by different energy sources which interacting with the atmosphere cause countless of chemical reactions which have giving origin to the synthesis of organic molecules from its formation since 4.5 thousand millions of years ago. The electric activity was not detected in the satellite when the space probe Voyager I had its nearest match with Titan in November 1980, however, due to the presence of methane clouds rain and of convective activity in the troposphere of the satellite, it is thought in the possible existence of electrical activity in this. In this work it is studied the production of gaseous compounds generated by irradiations type flash lightning in the Titan simulated atmosphere constituted by nitrogen and methane. The lightning are imitated by laser induced plasma (LIP) with similar physical properties to the naturals produced in the Earth. The separation and identification of the organic compounds generated by simulated lightning s were carried out by attached methods of analysis such as the Gas chromatography, Infrared spectroscopy with Fourier transform (FTIR-S) and Mass spectroscopy (MS). The compounds which were identified are: hydrocarbons and nitriles, some of them already have been identified in Titan as well as the hydrogen cyanide (HCN), acetylene, etilene and cyanoacetylene. Moreover we studied the influence that different parameters of irradiation have in the production of organic molecules generated submitting to discharges type lightning the simulated atmosphere of Titan. It was realized an estimation of the available energy in the satellite which could be vanished as discharges type lightning. By means of a model based on conditions of thermodynamic equilibria it was calculated the temperature to which are freeze

Study of irradiation of flash lightning type in a Titan simulated atmosphere; Estudio de irradiaciones tipo relampago en una atmosfera simulada de Titan

Energy Technology Data Exchange (ETDEWEB)

Rosa C, J.G. De la

2001-07-01

Titan is the greatest satellite of the Saturn planet and the unique moon of the Solar System which presents a dense atmosphere constituted by nitrogen, methane and traces of hydrocarbons and nitriles. Constantly it is bombarded by different energy sources which interacting with the atmosphere cause countless of chemical reactions which have giving origin to the synthesis of organic molecules from its formation since 4.5 thousand millions of years ago. The electric activity was not detected in the satellite when the space probe Voyager I had its nearest match with Titan in November 1980, however, due to the presence of methane clouds rain and of convective activity in the troposphere of the satellite, it is thought in the possible existence of electrical activity in this. In this work it is studied the production of gaseous compounds generated by irradiations type flash lightning in the Titan simulated atmosphere constituted by nitrogen and methane. The lightning are imitated by laser induced plasma (LIP) with similar physical properties to the naturals produced in the Earth. The separation and identification of the organic compounds generated by simulated lightning s were carried out by attached methods of analysis such as the Gas chromatography, Infrared spectroscopy with Fourier transform (FTIR-S) and Mass spectroscopy (MS). The compounds which were identified are: hydrocarbons and nitriles, some of them already have been identified in Titan as well as the hydrogen cyanide (HCN), acetylene, etilene and cyanoacetylene. Moreover we studied the influence that different parameters of irradiation have in the production of organic molecules generated submitting to discharges type lightning the simulated atmosphere of Titan. It was realized an estimation of the available energy in the satellite which could be vanished as discharges type lightning. By means of a model based on conditions of thermodynamic equilibria it was calculated the temperature to which are freeze

The complexity of Orion: an ALMA view. I. Data and first results

Science.gov (United States)

Pagani, L.; Favre, C.; Goldsmith, P. F.; Bergin, E. A.; Snell, R.; Melnick, G.

2017-07-01

Context. We wish to improve our understanding of the Orion central star formation region (Orion-KL) and disentangle its complexity. Aims: We collected data with ALMA during cycle 2 in 16 GHz of total bandwidth spread between 215.1 and 252.0 GHz with a typical sensitivity of 5 mJy/beam (2.3 mJy/beam from 233.4 to 234.4 GHz) and a typical beam size of 1.̋7 × 1.̋0 (average position angle of 89°). We produced a continuum map and studied the emission lines in nine remarkable infrared spots in the region including the hot core and the compact ridge, plus the recently discovered ethylene glycol peak. Methods: We present the data, and report the detection of several species not previously seen in Orion, including n- and I-propyl cyanide (C3H7CN), and the tentative detection of a number of other species including glycolaldehyde (CH2(OH)CHO). The first detections of gGg' ethylene glycol (gGg' (CH2OH)2) and of acetic acid (CH3COOH) in Orion are presented in a companion paper. We also report the possible detection of several vibrationally excited states of cyanoacetylene (HC3N), and of its 13C isotopologues. We were not able to detect the 16O18O line predicted by our detection of O2 with Herschel, due to blending with a nearby line of vibrationally excited ethyl cyanide. We do not confirm the tentative detection of hexatriynyl (C6H) and cyanohexatriyne (HC7N) reported previously, or of hydrogen peroxide (H2O2) emission. Results: We report a complex velocity structure only partially revealed before. Components as extreme as -7 and +19 km s-1 are detected inside the hot region. Thanks to different opacities of various velocity components, in some cases we can position these components along the line of sight. We propose that the systematically redshifted and blueshifted wings of several species observed in the northern part of the region are linked to the explosion that occurred 500 yr ago. The compact ridge, noticeably farther south displays extremely narrow lines ( 1 km s

Complex organic molecules in the interstellar medium: IRAM 30 m line survey of Sagittarius B2(N) and (M)

Science.gov (United States)

Belloche, A.; Müller, H. S. P.; Menten, K. M.; Schilke, P.; Comito, C.

2013-11-01

isotopologues of vinyl cyanide, cyanoacetylene, and hydrogen cyanide. We also report the detection of transitions from within twelve new vibrationally or torsionally excited states of known molecules. Absorption features produced by diffuse clouds along the line of sight are detected in transitions with low rotation quantum numbers of many simple molecules and are modeled with ~30-40 velocity components with typical linewidths of ~3-5 km s-1. Conclusions: Although the large number of unidentified lines may still allow future identification of new molecules, we expect most of these lines to belong to vibrationally or torsionally excited states or to rare isotopologues of known molecules for which spectroscopic predictions are currently missing. Significant progress in extending the inventory of complex organic molecules in Sgr B2(N) and deriving tighter constraints on their location, origin, and abundance is expected in the near future thanks to an ongoing spectral line survey at 3 mm with ALMA in its cycles 0 and 1. The present single-dish survey will serve as a solid basis for the line identification and analysis of such an interferometric survey. Based on observations carried out with the IRAM 30 m telescope. IRAM is supported by INSU/CNRS (France), MPG (Germany), and IGN (Spain).Figures 2-7 and Tables 6-107 are available in electronic form at http://www.aanda.orgThe observed and synthetic 3 mm spectra of Sgr B2(N) and (M), as well as the lists of line identifications corresponding to the blue lab- els in Figs. 2-7, are only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (ftp://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/559/A47