ALBERT

Description: The results of a study of ion-molecule reactions occurring in pure methane, acetylene, ethylene, ethane, propyne, propene, propane, and diacetylene at pressures up to 40 microns of pressure are reported. A variety of experimental methods are used: The standard double resonance in an ICR, for determination of the precursor ions and the modulated double resonance ejection in an ICR, for the determination of the daughter ions. The FA-SIFT technique was used for validation and examination of termolecular reactions with rate coefficients that are less than 10(-26) cm(6) s(-1). An extensive database of reaction kinetics already exists for many of these reactions. The main point of this study was the determination of the accuracy of this database and to search for any missing reactions and reaction channels that may have been omitted from earlier investigations. A specific objective of this work was to extend the study to the highest pressures possible to find out if there were any important termolecular reaction channels occurring. A new approach was used here. In the pure hydrocarbon gases the mass spectra were followed as a function of the pressure changes of the gas. An initial guess was first made using the current literature as a source of the reaction kinetics that were expected. A model of the ion abundances was produced from the solution of the partial differential equations in terms of reaction rate coefficients and initial abundances. The experimental data was fitted to the model for all of the pressures by a least squares minimization to the reaction rate coefficients and initial abundances. The reaction rate coefficients obtained from the model were then compared to the literature values. Several new channels and reactions were discovered when the modeled fits were compared to the actual data. This is all explained in the text and the implications of these results are discussed for the Titan atmosphere.

Description: The results of a study of the ion-molecule reactions of N(+), N(2)(+), and HCN(+) with methane, acetylene, and ethylene are reported. These studies were performed using the FA-SIFT at the University of Canterbury. The reactions studied here are important to understanding the ion chemistry in Titan's atmosphere. N(+) and N(2)(+) are the primary ions formed by photo-ionization and electron impact in Titan's ionosphere and drive Titan's ion chemistry. It is therefore very important to know how these ions react with the principal trace neutral species in Titan's atmosphere: Methane, acetylene, and ethylene. While these reactions have been studied before the product channels have been difficult to define as several potential isobaric products make a definitive answer difficult. Mass overlap causes difficulties in making unambiguous species assignments in these systems. Two discriminators have been used in this study to resolve the mass overlap problem. They are deuterium labeling and also the differences in reactivities of each isobar with various neutral reactants. Several differences have been found from the products in previous work. The HCN(+) ion is important in both Titan's atmosphere and in the laboratory.

Description: In the ion-molecule reaction between HC3N(+) and HC3N, the lifetime of the collision complex (H2C6N2+)-asterisk was long enough that ion cyclotron double-resonance techniques could be used to probe the distribution of the lifetimes of the collision complex. The mean lifetime of the collision complex at room temperature was measured as 180 microsec with a distribution ranging from 60 to 260 microsec as measured at the half-heights in the distribution. Lifetimes of this magnitude with respect to unimolecular dissociation allow for some stabilization of the collision complex by the slower process of infrared photon emission.

Description: An ion cyclotron resonance mass spectrometer is used to examine the association reactions, C4H2(+) + C2H2 and C4H3(+) + C2H2, at pressures in the range of 8 x 10 to the -8 to 1 x 10 to the -4 Torr at 298 K. The association of C4H2(+) and C4H3(+) with C2H2 was found to exhibit classical behavior in the pressure range of 5 x 10 to the -8 Torr to 0.4 Torr. It is found that an efficient route via radiative association exists for unsaturated hydrocarbon cations to convert to aromatic structures in the presence of acetylene.

Description: Ion cyclotron mass spectrometry is used here to study the reactions between HC3N(+) and HC3N and between HC5N(+) and HC3N at pressures from 1 x 10 to the -7th to 0.001 Torr. The former reaction has both a bimolecular reaction path and a termolecular reaction path. The overall bimolecular reaction rate coefficient is 1.3 x 10 to the -19 cu cm/s. The primary product HC5N(+) represents 90 percent of the product ions, while HC6N2(+) and H2C6N2(+) each represent 5 percent. The termolecular association rate coefficient is 3.7 x 10 to the -24th cm exp 6/s, with He as the third body. The mean lifetime of the collision is 180 microsec. HC5N(+) reacts with HC3N to form the adduct ion H2C8N2(+) through both bimolecular and termolecular reactions. The bimolecular rate coefficient is 5.0 x 10 to the -10th cu cm/s and the termolecular one is 1.2 x 10 to the -22nd cm exp 6/s, with HC3N as the third body.

Description: The model of Titan at present has the surface temperature, pressure, and composition such that there is a possibility of a binary ethane-methane ocean. Proposed experiments for future Titan flybys include microwave mappers. Very little has been measured of the dielectric properties of the small hydrocarbons at these radar frequencies. An experiment was conducted utilizing a slotted line to measure the dielectric properties of the hydrocarbons, methane to heptane, from room temperature to -180 C. Measurements of the real part of the dielectric constants are accurate to + or - 0.006 and the imaginary part (the loss tangent) of the liquids studied is less than or equal to 0.001. In order to verify this low loss tangent, the real part of the dielectric constant of hexane at 25 C was studied as a function of the frequency range of the slotted line system used. The dielectric constant of hexane at room temperature, between 500 MHz and 3 MHz, is constant within experimental error.

Description: The association reaction of the ions CH(sub 2)CHCN+ and CH(sub 2)CHCN have been examined using ion cyclotron resonance (ICR) and selected ion flow tube (SIFT) techniques at room temperature.

Description: Twenty-four new ion-molecule reactions are presented for inclusion in the modeling of the ionosphere of Saturn's satellite Titan. Sixteen reactions were re-examined to reduce uncertainties in the previous literature results. The ions selected for this study were derived either from nitrogen, appropriate hydrocarbons on nitriles.

Description: The reaction between CH3(+) and CH3CN is examined at pressures between 8 x 10 to the -8th and 1 x 10 to the -3rd Torr in an ion cyclotron resonance mass spectrometer. At pressures below 3 x 10 to the -5th Torr the reaction is bimolecular and proceeds through exothermic channels with a rate coefficient of 1.8 x 10 to the -9th cu cm/s. Competing with the exothermic bimolecular process is a bimolecular association which, it is suggested, results from radiative stabilization of (CH3CNCH3+)-asterisk. At pressures above 3 x 10 to the -5th Torr the reaction becomes termolecular with a rate coefficient 1.9 x 10 to the -22nd cm exp 6/s. The change to termolecular kinetics is due to an increasing fraction of the (CH3CNCH3+)-asterisk complexes being stabilized by collision. At still higher pressures the reaction becomes bimolecular again, corresponding to the onset of saturation when almost every complex is stabilized by collision and the rate coefficient approaches the collision rate.

Description: Experiments simulating the codeposition of molecular hydrogen and water ice on interstellar grains demonstrate that amorphous water ice at 12 K can incorporate a substantial amount of H2, up to a mole ratio of H2/H2O = 0.53. We find that the physical behavior of approximately 80% of the hydrogen can be explained satisfactorily in terms of an equilibrium population, thermodynamically governed by a wide distribution of binding site energies. Such a description predicts that gas phase accretion could lead to mole fractions of H2 in interstellar grain mantles of nearly 0.3; for the probable conditions of WL5 in the rho Ophiuchi cloud, an H2 mole fraction of between 0.05 and 0.3 is predicted, in possible agreement with the observed abundance reported by Sandford, Allamandola, & Geballe. Accretion of gas phase H2 onto grain mantles, rather than photochemical production of H2 within the ice, could be a general explanation for frozen H2 in interstellar ices. We speculate on the implications of such a composition for grain mantle chemistry and physics.