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At least 19 records

Comet Shoemaker-Levy 9, Jupiter, and Impact Shock Chemistry

Four years ago this month, a hitherto unknown comet in loose orbit around Jupiter passed so near the giant planet that it was torn apart into 20 fragments by tides. One orbit later, two years ago this month, the fragments of doomed comet P/Shoemaker Levy (SL9) fell into Jupiter. The enormous energies of these impacts (the largest fragments were nearly 1 km across and, hitting at 60 km/s, released some 2-4 x 10(exp 27) ergs) produced enormous explosions. Several of the ejecta plumes were imaged towering 3000 km above Jupiter's limb. The heat released when the plumes fell was considerable and easily observed on Earth. The impacts produced strong shocks, both promptly at the impact site and again, later, and over thousands of kilometers, when the ejecta plume reentered the atmosphere. The focus of this talk will be to discuss what the SL9 impacts taught us about impact shock chemistry - the processes, the ingredients, the results - and what inferences we may draw for impacts on early Earth. Shock chemistry generates a suite of molecules not usually seen on Jupiter. The most surprising report was of a huge amount of diatomic sulfur S2 at the site of the G impact. Other unusual products include CS, CS2, OCS, H2S, SO2, HCN, CO, and H2O; although H2S and H2O are doubtless abundant below the visible clouds. Hot or enhanced CH4 and NH3 were also detected. A general rule of shock chemistry is that CO forms until either C or O is exhausted. If O greater than C, the other products are oxidized, and excess O goes to H2O. If C greater than O, the other products are reduced, and excess C goes to HCN, C2H2, and a wide variety of more complicated organics. Ultimately, given time, the carbon would react all the way to graphite, but in practice the reactions are incomplete. The dark ejecta debris were probably composed in part of carbonaceous particles generated by the shocks. In a sense, the SL9 impacts performed the famous Miller-Urey experiment on a grand scale, with one result being the production of a lot of complex brown organic solids (called "tholins"). We use, a straightforward chemical kinetics model for the H, N, C, O, S system to follow the nonequilibrium chemistry behind the shocks. The model traces the evolving chemical composition of a parcel of gas by directly integrating the web of chemical reactions. Pressure and temperature histories of the parcels are patterned after those calculated by numerical hydrodynamic simulations of the ejecta plume. A given plume parcel is generally shocked twice; t.e a parcel shocked near the impact site is ejected at high velocity and is shocked again when it reenters the atmosphere. The final state of the gas depends mostly on the second shock, provided that the latter is hot enough. The chemical evidence is ambiguous, but most indications are that C greater than O in the shocked, reacting gas. Telltale signatures of abundant oxygen - SO2, SO, CO2, O2 - were not seen, while signatures of abundant carbon - CS, CS2, and HCN - were. On the other hand, abundant H2O would appear to require O greater than C, and two other observed sulfur species, S2 and OCS, appear to form more easily in a somewhat oxidized gas, presumable vaporized from the comet itself. Since on general principles one expects the -comet to have had a more-or-less cosmic composition, i.e. O greater than C, the production of CS, CS2, and HCN probably requires C greater than O in the shocked jovian air. This in turn implies that even the largest fragments released the bulk of their energy above the jovian water table, in all likelihood above 5 bars . There is no evidence in favor of the proposition that a significant amount of wet jovian air was shocked strongly enough to coax water to react; i.e. wet jovian air saw only temperatures significantly below 2000 K.

Zahnle, Kevin↗

Tests of shock chemistry in IC 443G

Eight molecular species, in the hot dense clump IC 443G, believed to be impacted by the shock wave from the SNR IC 443, are investigated. The clump consists of two distinct regions, one relatively cool, and one hotter and denser. Region 1 contains CO, HCO(+), HCN, and CN, whose abundances may be explained either by ion-molecule chemistry, or by a D shock of 60-90 km/s, passing through a clump of about 100,000/cu cm. Region 2 gives rise to SiO, CS, SO, and H2CO, and requires an ND shock of 5-15 km/s passing through a region of about 1,000,000/cu cm. Observed fractional abundances fit ND shock models if L is about 6.6 x 10 exp 15 cm. In general, observed line widths vary inversely with derived excitation density, while centroid velocities of all species are essentially identical.

Turner, B. E.↗

Some new results on shock chemistry in IC 443

New observations have been made of CO, CO-13, SiO, SO, H2CO, HCO(+), N2H(+), CS, OCS, HCN, and OH in the shocked clouds of IC 443. It is found that at position IC 443 B, (1) the shocked CO is optically thin; (2) the HCO(+)/CO abundance ratio is 4-9 x 10 to the -4 th, representing a tenfold enhancement over that of normal interstellar clouds; (3) there is no enhancement of SO or SIO, as occurs in Orion KL; and (4) there is optically thin preshock OH, confirming a hundredfold enhancement of the OH/CO ratio in the shock.

Denoyer, L. K.↗

Shock chemistry in the molecular clouds associated with SNR IC 443

Observations of several interstellar molecules toward the highly perturbed B and G clouds associated with SNR IC 443 are reported. The results suggest that hot and dense material is present in the SNR, and that shocks are present in both regions. The HCO(+) abundance is shown to be a few times greater that found in cold quiescent gas, in contradiction with previous results. The SO, CS, CN, and NH3 abundances are similar to those found in cold dark clouds.

Ziurys, L. M.↗

Nonequilibrium chemistry in shocked molecular clouds

The gas-phase chemistry is studied behind a 10-km/s shock propagating into a dense molecular cloud. The principal conclusions are that: the concentrations of certain molecules (CO, NH3, HCN, N2) are unperturbed by the shock; other molecules (H2CO, CN, HCO(+)) are greatly decreased in abundance; and substantial amounts of H2O, HCO, and CH4 are produced. Approximately 1 million yr (independent of the density) must elapse after shock passage before chemical equilibrium is attained.

Iglesias, E. R.↗

Oxygen chemistry of shocked interstellar clouds. III - Sulfur and oxygen species in dense clouds

The chemical evolution of oxygen and sulfur species in shocked dense clouds is studied. Reaction rate constants for several important neutral reactions are examined, and revised values are suggested. The one-fluid magnetohydrodynamic shock structure and postshock chemical evolution are calculated for shocks of velocity v(s) = 10 km/s through clouds of initial number density n(0) = 100,000/cu cm and of molecule/atom ratios H2/H = 10, 1000, and 100,000 with most sulfur contained initially in molecules SO2 and SO. Abundances of SO2, SO, CS, and OCS remain near their preshock values, except in clouds containing substantial amounts of atomic hydrogen, where significant destruction of sulfur-oxygen species occurs. Abundances of shock-enhanced molecules HS and H2O are sensitive to the molecule/atom ratio. Nonthermal oxygen-hydrogen chemistry has a minor effect on oxygen-sulfur molecules in the case H2/H = 10.

Leen, T. M.↗

Shock-tube chemistry. I - The laminar-to-turbulent boundary layer transition

A model is proposed for calculating laminar-turbulent transition in the boundary layer of flows in chemical shock tubes. It is shown that the time to turbulent transition may be treated as the time required by the shocked gas to move over one shock-tube diameter. The model is shown to provide a means of predicting the turbulent transition time in any shock tube experiment, provided the condition of limiting flow is met. Knowing the transition time, it becomes possible to obtain the density and temperature profiles and, hence, to determine precisely the effect of shock tube boundary layers on the measurement of chemical rate constants.

Bander, J. A.↗

Shock-induced chemistry and high strain-rate viscoelastic behavior of a phenolic polymer

We use impact experiments and a finite element model (up to 1.2 GPa), and molecular dynamics simulations (up to 60 GPa), to examine the behavior of a phenolic polymer under shock compression, spanning both nonreactive and reactive regimes. In the nonreactive regime, relaxation following compression at strain rates of ∼105 s−1 can be explained by viscoelasticity observed at ordinary laboratory rates (≲1 s−1) by accounting for the temperature dependence of the phenolic β-transition. Reasonable agreement is found between the measured shock Hugoniot up to 1.2 GPa and molecular dynamics simulation for cross-linked structures of comparable density. We also observed a first-order mechanical transition near 0.36 GPa shock stress and estimated a spall strength of 0.102 GPa and Hugoniot elastic limit of 1–2 GPa. The shock stress is found to vary up to 24% among phenolics made with different resin and/or cure processes. Finally, molecular dynamics simulations are used to identify a reactive regime at shock pressures ≳20 GPa that is characterized by chemically driven, rate-dependent relaxation processes, including dehydrogenation and dehydration reactions that promote the formation of a dense, highly cross-linked carbonaceous solid and the release of light volatiles.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Shock enhancement of HCO/+/

In the shocked gas associated with the supernova remnant IC 443, it is found that the HCO(+)/CO abundance is approximately 0.004. This is about 100 times greater than in the unshocked gas in this source where the ratio is typical of molecular clouds. This increase contradicts some current models for shock chemistry which predict a decrease of HCO(+) behind shock fronts.

Dickinson, D. F.↗

Organic synthesis in experimental impact shocks

Laboratory simulations of shocks created with a high-energy laser demonstrate that the efficacy of organic production depends on the molecular, not just the elemental composition of the shocked gas. In a methane-rich mixture that simulates a low-temperature equilibrium mixture of cometary material, hydrogen cyanide and acetylene were produced with yields of 5 x 10(17) molecules per joule. Repeated shocking of the methane-rich mixture produced amine groups, suggesting the possible synthesis of amino acids. No organic molecules were produced in a carbon dioxide-rich mixture, which is at odds with thermodynamic equilibrium approaches to shock chemistry and has implications for the modeling of shock-produced organic molecules on early Earth.

NASA Discipline Exobiology↗

Li, B - Behavior in Lunar Basalts During Shock and Thermal Metamorphism: Implications for H2O in Martian Magmas

Introduction: The water-content of Martian magmas is a topic of debate among researchers. Some Martian basalts are characterized with melt inclusions of biotite, apatite and amphibole; phases typically associated with hydration reactions on Earth [1-3]. However, the H-content of melt inclusions from these basalts is low, and bulk-rock H2O-contents range from a meager 0.013 to 0.035 wt. % in Shergotty [4]. Nonetheless, researchers note that low present-day water contents do not preclude a once hydrous past [5]. Since light lithophile elements (LLE), such as Li and B, partition into aqueous fluids at T > 350 C, workers proposed that Li-B depletions in pyroxene rims of Nakhlite and Shergottite basalts reflect the loss of several weight percent water from Martian magmas during crystallization [6]. Since similar depletions were observed in pyroxene rims from completely dry lunar basalts, it is likely that alternative mechanisms also contribute to the distribution of elements such as Li and B [7]. Given that many Martian basalts have experienced considerable shock pressures (15-45 GPa), it is possible that shock and subsequent thermal metamorphism may have influenced the volatile element records of these basalts [8]. In order to better understand the distribution of Li and B, we are studying the effects of crystal chemistry, shock pressure, and thermal metamorphism in pyroxenes from lunar basalts. Below, we discuss results from experimentally shocked and thermally metamorphosed Apollo 11, 10017 (A-11) and Apollo 17, 75035 (A-17) basalts.

Chaklader, Johny↗

Comparison of three-dimensional nonequilibrium PNS codes

A comparison study has been conducted using four recently developed parabolized Navier-Stokes (PNS) codes which have the capability of predicting finite-rate, chemically reacting flows over three-dimensional bodies. These are the (1) UPS code, (2) the STUFF code, (3) the TONIC code, and (4) the VRA-PNS code. All of the codes use the same seven-species, single-temperature air chemistry model, but otherwise they are unique, with different capabilities and characteristics. The differences include upwinding vs central differencing, strongly-coupled vs weakly-coupled chemistry, shock capturing vs shock fitting, finite volume vs finite difference, and full PNS vs thin-layer PNS equations. Three test cases were utilized to compare the codes. The comparisons presented indicate a good agreement among the codes tested.

Buelow, Philip E.↗

Reynolds number influences in aeronautics

Reynolds number, a measure of the ratio of inertia to viscous forces, is a fundamental similarity parameter for fluid flows and therefore, would be expected to have a major influence in aerodynamics and aeronautics. Reynolds number influences are generally large, but monatomic, for attached laminar (continuum) flow; however, laminar flows are easily separated, inducing even stronger, non-monatomic, Reynolds number sensitivities. Probably the strongest Reynolds number influences occur in connection with transitional flow behavior. Transition can take place over a tremendous Reynolds number range, from the order of 20 x 10(exp 3) for 2-D free shear layers up to the order of 100 x 10(exp 6) for hypersonic boundary layers. This variability in transition behavior is especially important for complex configurations where various vehicle and flow field elements can undergo transition at various Reynolds numbers, causing often surprising changes in aerodynamics characteristics over wide ranges in Reynolds number. This is further compounded by the vast parameterization associated with transition, in that any parameter which influences mean viscous flow development (e.g., pressure gradient, flow curvature, wall temperature, Mach number, sweep, roughness, flow chemistry, shock interactions, etc.), and incident disturbance fields (acoustics, vorticity, particulates, temperature spottiness, even electro static discharges) can alter transition locations to first order. The usual method of dealing with the transition problem is to trip the flow in the generally lower Reynolds number wind tunnel to simulate the flight turbulent behavior. However, this is not wholly satisfactory as it results in incorrectly scaled viscous region thicknesses and cannot be utilized at all for applications such as turbine blades and helicopter rotors, nacelles, leading edge and nose regions, and High Altitude Long Endurance and hypersonic airbreathers where the transitional flow is an innately critical portion of the problem.

Bushnell, Dennis M.↗

Organic molecules in the gas phase of dense interstellar clouds

Since a previous Committee on Space Research (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.

Irvine, W. M.↗

Prebiotic Processing induced by Comet and Meteor Impact

In their study of organic synthesis from impact shocks using the laser-induced-plasma (LIP) technique, McKay and Borucki(l) found that organic synthesis preferentially occurred in a reducing gas mixture rich in methane, and not in a mixture rich in carbon dioxide. This result means chemical models based on the thermodynamical equilibrium approach do not apply to shock chemistry. In this study, we employ the technique of reacting flow, i.e., chemical kinetics in a fluid flow, to simulate the chemistry occurring in LIP and in the wake region from comet or meteor impact. Three different air compositions have been used: (1) 1/3 CO2 and 2/3 H2, (2) pure CH4, and (3) 1/4 CH4, 1/4 CO2, and 1/2 H2O. The stoichiometric ratio of gas mixtures (1) and (3) are kept the same. For (1) we obtain equal mole fractions of CO and H2O as the major products and for (2) C2H2 is the major product. In both cases our results are in agreement with Ref. (1). For (3) we find an interesting case where the nature of chemicals produced to be critically dependent on the flowfield temperature. At the higher temperature part of the wake region, CO and H2O are the dominant products, whereas in the cooler region C2H2 is the dominant product. Further studies of these reactions, as well as for the gas mixture including N2, are being pursued.

Dateo, Christopher E.↗

Interactions Between CRs and MCs in the Vicinity of Supernova Remnants

Supernovae are incredibly energetic events which drive the dynamic state of the interstellar medium and accelerate cosmic rays up to energies of a few PeV. I present multi-wavelength observations constraining the shocks, chemistry, dust grain processing, and magnetic fields in a large sample of supernova remnants interacting with dense clouds. These are among the most luminous Galactic sources detected by the Fermi Gamma-Ray Space Telescope. Surprisingly, spectral breaks are seen between GeV and TeV energies. Radio spectral breaks have also been detected for a few remnants, providing clear evidence that supernovae are a significant source of hadronic cosmic rays in the Galaxy. Resolving the origin of these spectral breaks will allow the physics of cosmic ray acceleration and diffusion to be probed.

Hewitt, John W.↗

Molecular diagnostics of interstellar shocks

The chemistry of molecules in shocked regions of the interstellar gas is considered and calculations are carried out for a region subjected to a shock at a velocity of 8 km/sec. Substantial enhancements are predicted in the concentrations of the molecules H2S, SO, and SiO compared to those anticipated in cold interstellar clouds.

Hartquist, T. W.↗

Radiative shocks and nonequilibrium chemistry in the early universe - Galaxy and primordial star formation

The nonequilibrium radiative cooling, recombination, and molecule formation behind steady-state shock waves in primordial composition gas is studied. The hydrodynamical conservation equations are solved as well as equations for nonequilibrium ionization, recombination, and molecule formation and the equation of radiative transfer. The shocked gas is found to cool faster than it can recombine; as a result it is able to form an H2 concentration as high as 0.001 or higher via the formation of H(-) and H2(+) intermediaries due to the enhanced nonequilibrium ionization at 10,000 K. With such an H2 concentration, the gas cools by rotational-vibrational line excitation of H2 molecules to well below the canonical final temperature of 10,000 K for a molecule-free gas without metals. It is shown that, as the level of external ionizing and dissociating radiation flux is increased, the formation of and cooling by H2 molecules can be inhibited and delayed.

Shapiro, Paul R.↗