Regioselectivity of the photochemical addition of phosphine to unsaturated hydrocarbons in the atmospheres of Jupiter and Saturn.

Phosphine (PH3) has been observed in the atmospheres of Jupiter and Saturn. We have studied the regioselectivity in the gaseous phase of the photochemical addition of PH3 to propene 1, propadiene 2, propyne 3, 1,3-butadiene 4 and 1,3-butadiyne 5. The photolysis were performed at 185 and 254 nm. The volatile products formed in these reactions were characterized by 1H and 31P NMR. The n-propylphosphine 6 and the isopropylphosphine 7 were the major products observed in the photolysis of PH3 with propene. The allylphosphine 8 was obtained when most of the light was absorbed by propene. This allylphosphine was the main product formed in the photolysis of PH3 in the presence of propadiene; the methylvinylphosphine 10 being not detected in these experiments, the reaction presents a very high regioselectivity. When most of the light was absorbed by propadiene, the propargylphosphine 9 was also observed. The photolysis of PH3 in the presence of propyne led to the E- and Z-1-propenylphosphines 12a,b and small amounts of methylvinylphosphine 10. Even when most of the light was absorbed by propyne, the propargylphosphine 9 was not observed. The Z-1-butene-3-ynylphosphine 13a and a mixture of primary phosphines containing the E-and Z-2-butenylphosphines 14a,b were obtained as major products when 1,3-butadiyne and 1,3-butadiene respectively where photolyzed with PH3. A high regioselectivity was thus observed in the photolysis of PH3 with an alkyne or an allene but alkenes led to mixtures of products.     

Partial pressures and nature of products. Application to the photolysis of PH3 and NH3 in the atmosphere of Jupiter and Saturn.

The photolysis of mixtures of gases containing NH3 or PH3 presents important differences mainly due to the strength of the X-H bond. On some examples, these differences are evidenced and the consequences for mixtures of gases containing these two compounds are shown: the photolysis of ammonia and ethylene mainly gives ethyl-, butyl- and hexylamine whereas the photolysis of phosphine and ethylene leads to ethyl- and vinylphosphine. When gaseous mixtures of NH3, PH3 and ethylene are photolyzed together, the presence of phosphine dramatically decreases the formation of nitrogen derivatives. The relevance of such lab studies to the atmospheres of Jupiter and Saturn is discussed.     

Complex organics in laboratory simulations of interstellar/cometary ices.

We present the photochemical and thermal evolution of both non-polar and polar ices representative of interstellar and pre-cometary grains. Ultraviolet photolysis of the non-polar ices comprised of O2, N2, and CO produces CO2, N2O, O3, CO3, HCO, H2CO, and possibly NO and NO2. When polar ice analogs (comprised of H2O, CH3OH, CO, and NH3) are exposed to UV radiation, simple molecules are formed including: H2, H2CO, CO2, CO, CH4, and HCO (the formyl radical). Warming produces moderately complex species such as CH3CH2OH (ethanol), HC(=O)NH2 (formamide), CH3C(=O)NH2 (acetamide), R-CN and/or R-NC (nitriles and/or isonitriles). Several of these are already known to be in the interstellar medium, and their presence indicates the importance of grain processing. Infrared spectroscopy, 1H and 13C nuclear magnetic resonance (NMR) spectroscopy, and gas chromatography-mass spectrometry demonstrate that after warming to room temperature what remains is an organic residue composed primarily of hexamethylenetetramine (HMT, C6H12N4) and other complex organics including the amides above and polyoxymethylene (POM) and its derivatives. The formation of these organic species from simple starting mixtures under conditions germane to astrochemistry may have important implications for the organic chemistry of interstellar ice grains, comets and the origins of life.     

Organic chemistry in Titan's atmosphere: new data from laboratory simulations at low temperature.

Many experiments have already been carried out to simulate organic chemistry on Titan, the largest satellite of Saturn. They can provide fruitful information on the nature of minor organic constituents likely to be present in Titan's atmosphere, both in gas and aerosol phases. Indeed, all the organic compounds but one already detected in Titan's atmosphere have been identified in simulation experiments. The exception, C4N2, as well as other compounds expected in Titan from theoretical modeling, such as other N-organics, and polyynes, first of all C6H2, have never been detected in experimental simulation thus far. All these compounds are thermally unstable, and the temperature conditions used during the simulation experiments were not appropriate. We have recently started a new program of simulation experiments with temperature conditions close to that of Titan's environment. It also uses dedicated analytical techniques and procedures compatible with the analysis of organics only stable at low temperatures, as well solid products of low stability in the presence of O2 and H2O. Spark discharge of N2-CH4 gas mixtures was carried out at low temperature in the range 100-150 K. Products were analysed by FTIR, GC and GC-MS techniques. GC-peaks were identified by their mass spectrum, and, in most cases, by comparison of the retention time and mass spectrum with standard ones. We report here the first detection in Titan simulation experiments of C6H2 and HC5N. Their abundance is a few percent relative to C4H2 and HC3N, respectively. Preliminary data on the solid products indicate an elemental composition corresponding to (H11C11N)n. These results open new prospects in the modeling of Titan's haze making.     

Neutral upper atmospheres of the outer planets

Several recent papers have reviewed the upper atmospheres and ionospheres of Jupiter and Saturn in the post Voyager era (see, e.g., /1/ and references therein). Therefore, this paper will review only the most salient characteristics, as far as Jupiter and Saturn are concerned. The emphasis here, however, is placed on the Uranus upper atmosphere that was probed in January, 1986, by Voyager 2 spacecraft. In particular comparative aspects of atmospheric composition, thermal structure, photochemistry and the vertical mixing are discussed.     

The atmosphere of the primitive earth and the prebiotic synthesis of organic compounds.

The prebiotic synthesis of organic compounds using a spark discharge on various simulated prebiotic atmospheres at 25 degrees has been studied. Methane mixtures contained H2 + CH4 + H2O + N2 + NH3 with H2/CH4 molar ratios from 0 to 4 and pNH3 = 0.1 torr. A similar set of experiments without added NH3 was performed. The yields of amino acids (1.2 to 4.7% based on the carbon) are approximately independent of the H2/CH4 ratio and the presence of added NH3, and a wide variety of amino acids are obtained. Mixtures of H2 + CO + H2O + N2 and H2 + CO2 + H2O + N2, with and without added NH3, all give about 2% yields of amino acids at H2/CO and H2/CO2 ratios of 2 to 4. For the H2/CO and H2/CO2 ratios less than 1, the yields fall off drastically to as low as 10(-3)%. Glycine is almost the only amino acid produced from CO and CO2 atmospheres. These results show that the maximum yield is about the same for the three carbon sources at high H2/carbon ratios, but that CH4 is superior at low H2/carbon ratios. In addition, CH4 gives a much greater variety of amino acids than either CO or CO2. If it is assumed that amino acids more complex than glycine were required for the origin of life, then these results indicate the need for CH4 in the primitive atmosphere. The yields of cyanide and formaldehyde parallel the amino acid results, with yields of HCN and H2CO as high as 13% based on the carbon. Ammonia is also produced from N2 in experiments with no added NH3 in yields as high as 4.9%. These results show that large amounts of NH3 would have been synthesized on the primitive earth by electric discharges. The amount of ammonia formed by hydrolysis of HCN and various nitriles may have exceeded that formed directly in electric discharges.     

Isotopic ratios in planetary atmospheres.

Recent progress on measurements of isotopic ratios in planetary or satellite atmospheres include measurements of the D/H ratio in the methane of Uranus, Neptune and Titan and in the water of Mars and Venus. Implications of these measurements on our understanding of the formation and evolution of the planets and satellite are discussed. Our current knowledge of the carbon, nitrogen and oxygen isotopic ratios in the atmospheres of these planets, as well as on Jupiter and Saturn, is also reviewed. We finally show what progress can be expected in the very near future due to some new ground-based instrumentation particularly well suited to such studies, and to forthcoming space missions.     

Chemical interactions of solar wind with cometary nuclei and comae

Solar wind particles, especially H, C, N, O, S, and P-ions, may undergo specific chemical reactions with gaseous or solid matter of comets when in the energy region of a few 10 to some eV. Each component of the solar wind, even if not chemically reactive itself, creates a multiplicity of energetic secondary particles by knock-on processes with the cometary matter. These are responsible for the majority of the so called “hot” chemical processes. Endothermic reactions with high activation energy and atom molecule interactions are possible and may add to the classical exothermic ion-molecule or radical reactions. Other sources of hot atoms or ions in comets are: cosmic rays, acceleration or pick-up processes and turbulences in comae and gas or dust tails, and photon absorption induced dissociation. The products of hot chemical reactions, short period comets experience on their orbits, add to those formed in the individual component ice or dust grains by strong fluxes of energetic particles in times prior to the accretion to a comet.     

Characterization of complex organic compounds formed in simulated planetary atmospheres by the action of high energy particles.

A wide variety of organic compounds, which are not simple organics but also complex organics, have been found in planets and comets. We reported that complex organics was formed in simulated planetary atmospheres by the action of high energy particles. Here we characterized the experimental products by using chromatographic and mass spectrometric techniques. A gaseous mixture of CO, N2 and H2O was irradiated with high energy protons (major components of cosmic rays). Water-soluble non-volatile substances, which gave amino acids after acid-hydrolysis, were characterized by HPLC and mass spectrometry. Major part of the products were complex compounds with molecular weight of several hundreds. Amino acid precursors were produced even when no water was incorporated with the starting materials. It was suggested that complex molecules including amino acid precursors were formed not in solution from simple molecules like HCN, but directly in gaseous phase.     

A study of chemical systems using signal flow graph theory.

Photochemistry of giant planets and their satellites is characterized by numerous reactions involving a lot of chemical species. In the present paper, chemical systems are modeled by signal flow graphs. Such a technique evaluates the transmission of any input into the system (solar flux, electrons ... ) and gives access to the identification of the most important mechanisms in the chemical system. This method is applied to the production of hydrocarbons in the atmospheres of giant planets. In particular, the production of C2H6 in the atmosphere of Neptune from the photodissociation of CH4 is investigated. Different pathways of dissociation of CH4 are possible from L alpha radiation. A chemical system containing 14 species and 30 reactions including these different pathways of dissociation is integrated. The main mechanism of production of C2H6 is identified and evaluated for each model of dissociation. The importance of various reaction pathways as a function of time is presented.     

Hydrogen cyanide polymers on comets.

The original presence on cometary nuclei of frozen volatiles such as methane, ammonia and water makes them ideal sites for the formation and condensed-phase polymerization of hydrogen cyanide. We propose that the non-volatile black crust of comet Halley consists largely of such polymers. Dust emanating from Halley's nucleus, contributing to the coma and tail, would also arise partly from these solids. Indeed, secondary species such as CN have been widely detected, as well as HCN itself and particles consisting only of H, C and N. Our continuing investigations suggest that the yellow-orange-brown-black polymers are of two types: ladder structures with conjugated -C=N- bonds, and polyamidines readily converted by water to polypeptides. These easily formed macromolecules could be major components of the dark matter observed on the giant planets Jupiter and Saturn, as well as on outer solar system bodies such as asteroids, moons and other comets. Implications for prebiotic chemistry are profound. Primitive Earth may have been covered by HCN polymers either through cometary bombardment or by terrestrial happenings of the kind that brought about the black crust of Halley. The resulting proteinaceous matrix could have promoted the molecular interactions leading to the emergence of life.     

Numerical simulation of organic compounds formation in planetary atmospheres: comparison with laboratory experiments.

A numerical model of CH4 and CH4-NH3 photochemistry at 147 nm has been developed and results are directly compared with experimental simulations carried out for the same mixtures. Simulations with varying quantities of ammonia and hydrogen show how amines and nitriles can be produce in planetary atmospheres. These comparisons allow one to test schemes of reactions used in photochemical models. In particular, it is shown that the scheme of reactions of CH4 is fairly well consistent with experimental data. On the other hand, the photochemistry of NH3 should be improved.     

Past and future of radio occultation studies of planetary atmospheres

Measurements of radio waves that have propagated through planetary atmospheres have provided exploratory results on atmospheric constituents, structure, dynamics, and ionization for Venus, Mars, Titan, Jupiter, Saturn, and Uranus. Highlights of past results are reviewed in order to define and illustrate the potential of occultation and related radio studies in future planetary missions.     

Space telescope studies of Jupiter and Saturn simulated by Voyager observations

Space Telescope (ST) observations of Jupiter and Saturn will offer a unique opportunity for monitoring their changing meteorological characteristics. They will provide higher spatial and temporal resolution for composition and vertical structure studies than have been available to date. We have simulated the planetary camera observations of Jupiter and Saturn by Voyager images of the appropriate spatial scale. With this data set we have investigated the meteorological properties of these atmospheres which can be studied at these scales. In addition we have considered the advances obtainable with the high resolution spectrometer on ST compared with observations from ground-based and other Earth-orbiting satellites. These studies will provide insight into the scientific gain and possible problems in the use of ST for planetary studies.     

The chemical conditions on the parent body of the murchison meteorite: Some conclusions based on amino, hydroxy and dicarboxylic acids

Amino and hydroxy acids have been identified in the Murchison meteorite. Their presence is consistent with a synthetic pathway involving aldehydes, hydrogen cyanide and ammonia in an aqueous environment (Strecker-cyanohydrin synthesis). From the various equilibrium and rate constants involved in this synthesis, four independent estimates of the ammonium ion concentrations on the parent body at the time of compound synthesis are obtained; all values are about 2 × 10^?3 M. Succinic acid and β-alanine have also been detected in the Murchison meteorite. Their presence is consistent with a synthesis from acrylonitrile, hydrogen cyanide and ammonia. Using the equilibrium and rate constants for this synthetic pathway, and the succinic acid/β-alanine ratio measured in the Murchison meteorite, an estimate of the hydrogen cyanide concentration of 10^?3 to 10^?2 M is obtained. Since hydrogen cyanide hydrolyzes relatively rapidly in an aqueous environment ($\text{t}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{< 10}{}^4\text{yrs}$) this high concentration implies a period of synthesis of organic compounds as short as 10⁴ years on the Murchison meteorite parent body.     

Radiation-induced syntheses in cometary simulated models.

The behavior of an aqueous-dominant multicomponent cometary model is examined at high doses of ionizing radiation. The system is composed of a water mixture of HCN (0.2 mol dm-3), CH3CN (0.04 mol dm-3), C2H5CN (0.02 mol dm-3), CH3OH (0.12 mol dm-3) and HCO2H (0.01 mol dm-3. It was exposed to gamma rays at doses up to 18.5 MGy. The chemical kinetic database used in the computer treatment of experimental data consists of 79 reactions. A complex mixture of products has been synthesized: gases, amino acids, carboxylic acids and polymeric material. The results suggest that the pristine material in cometary nuclei may have been chemically altered by the action of cosmic rays and embedded radionuclides.     

The magnetic fields of Jupiter and Saturn

Jupiter and Saturn are two of the more “exotic” planets in our solar system. The former possesses its own system with 15 satellites in orbit about the parent planet. Saturn has a uniquely well developed and distinctive ring system of particulate matter and also at least 11 satellites, including the largest one amongst all the planets, Titan, with a radius of 2900 km ± 100 km. In the decade of the 70's, the USA launched 4 unmanned spacecraft to probe these giant planets in-situ with a suite of highly advanced instrumentation. Four separate encounters have occurred at Jupiter: 1. Pioneer 10 in December 1973 2. Pioner 11 in December 1974 3. Voyager 1 in March 1979 4. Voyager 2 in July 1979 The characteristics of these trajectories is shown in Table I. Thus far, only a single encounter of Saturn has occurred, that by Pioneer 11 in September 1979. Future encounters of Saturn by Voyager spacecraft will occur in mid-November 1980 and late-August 1981. It is the purpose of this talk to summarize what is presently known about the magnetic fields of these planets and the characteristics of their magnetospheres, which are formed by interaction with the solar wind.     

A differential measurement of the Lyman alpha emission from the giant planets using IUE

The intensity of the resonantly scattered Ly-α line of the gian planets depends on the scattering column length of atomic hydrogen above the methane layer and on the incident solar flux. We have obtained measurements of the Ly-α brightness of Jupiter and Saturn on December 19, 1979, with a time difference of 111 minutes, which is only slightly longer than the additional travel time for solar photons scattered at Saturn compared to those from Jupiter. This observational technique eliminates two major uncertainties — the use of different instruments and solar variability — affecting previous determinations of the relative brightness of the planets. The measured ratio of the brightness of the subsolar points is 3.0 ± 0.4 which agrees well with the ratio of the incident solar flux of 3.4. This implies approximately equal scattering column lengths of H on both planets.     

Hydrogen cyanide polymers from the impact of comet P/Shoemaker-Levy 9 on Jupiter.

Hydrogen cyanide polymers--heterogeneous solids ranging in color from yellow to orange to brown to black--may be among the organic macromolecules most readily formed within the Solar System. The non-volatile black crust of comet Halley, for example, as well as the extensive orange-brown streaks in the atmosphere of Jupiter, might consist largely of such polymers synthesized from HCN formed by photolysis of methane and ammonia. Laboratory studies of these ubiquitous compounds point to the presence of polyamidine structures synthesized directly from hydrogen cyanide. These would be converted by water to polypeptides which can be further hydrolyzed to alpha-amino acids. Other polymers and multimers with ladder structures derived from HCN would also be present and might well be the source of the many nitrogen heterocycles, adenine included, detected by thermochemolytic analysis. The dark brown color arising from the impacts of comet P/Shoemaker-Levy 9 on Jupiter could therefore be mainly caused by the presence of HCN polymers, whether originally present, deposited by the impactor or synthesized from freshly formed HCN. Spectroscopic detection of these predicted macromolecules and their hydrolytic and pyrolytic by-products would strengthen significantly the hypothesis that cyanide polymerization is a preferred pathway for prebiotic and extraterrestrial chemistry.     

Organic molecules in the gas phase of dense interstellar clouds.

Since a previous COSPAR review on this subject, the number of molecular species identified by astronomers in dense interstellar clouds or in the envelopes expelled by evolved stars has grown from about eighty to approximately one hundred. Recent detections in stellar envelopes include the radical CP, the second phosphorus-containing astronomical molecule; SiN, the first astronomical molecule with a Si-N bond; and the HCCN radical. In the dense interstellar clouds recent detections or verifications of previous possible identifications include the H3O+ ion, which is a critical intermediary in the production of H2O and O2; the CCO radical, which is isoelectronic with HCCN; the SO+ ion, which appears to be diagnostic of shock chemistry; two new isomers of cyanoacetylene, HCCNC and CCCNH; and the two cumulenes H2C3 and H2C4. Some recent work is also described on the mapping of interstellar clouds in multiple molecular transitions in order to separate variations in chemical abundance from gradients in physical parameters.