Engineering topics
Publications and source records attributed to Huntress, W. T., Jr..
Using the ICR technique, rate constants are obtained for the reaction of C2H2(+) with HCN and of HCN(+) with C2H2. They are, respectively, 3.6 x 10 to the -10 cu cm/molecule-s and 6.9 x 10 to the -10 cu cm/molecule-s. Discrepancies between these results and other measurements of the first reaction are discussed. The relevance of this reaction to the formation of HC3N in interstellar clouds is considered.
The reactions of the gaseous ion CH3+ with HCN are investigated, using the ion cyclotron resonance technique. The pressure range of the experiment was 1 x 10 to the -6 to 3 x 10 to the -4 Torr with a rate coefficient of 2 x 10 to the -10 cu cm/sec. Good agreement was found between rate coefficients determined in the trapping mode at the low end of the pressure range and the drift mode at the high end of the pressure range. It is shown that the association reaction of CH3 with HCN follows second order kinetics throughout the entire pressure range of the experiment. The reaction is interpreted in terms of both a saturated three-body and a radiative association mechanism. Some explanations for the disagreement of the rate coefficient with that reported previously are also given.
A chemical evolutionary model with a large number of species and a large chemical library is used to examine the principal chemical processes in interstellar clouds. Simple chemical equilibrium arguments show the potential for synthesis of very complex organic species by ion-molecule radiative association reactions.
The cyanopolyynes HC2CN, HC4CN, HC6CN, and HC8CN, and the molecules CH3CHCN and CH3CH2CN, have recently been detected in the interstellar medium. It is shown that the observed abundances of these molecules can be obtained by gas-phase formation pathways if the reaction of H2CN(+) with C2H2 is rapid at low interstellar temperatures. The molecules CH2CHCN and C3N may be formed also by the reactions of H2CN(+) with C2H2, and CH3CH2CN may be formed by reaction of H2CN(+) with C2H4.
The abundances of polyatomic molecules that may be formed by CH3(+) radiative association reactions in dense interstellar molecular clouds are reevaluated. The formation of a number of complex interstellar molecules via radiative association reactions involving ionic precursors other than CH3(+) is also investigated; these additional precursors include CH3O(+), CH3CO(+), CH5(+), HCO(+), NO(+), H2CN(+), C2H2(+), and NH3(+). The results indicate that the postulated gas-phase ion-molecule radiative association reactions could potentially explain the synthesis of most of the more complex species observed in dense molecular clouds such as Sgr B2. It is concluded, however, that in order to be conclusive, laboratory data are needed to show whether or not these reactions proceed at the required rates at low temperatures.
An estimate of the abundances of chain hydrocarbon molecules expected in dense interstellar clouds as a result of gas-phase chemistry alone supports the hypothesis that the long chain molecules are responsible for the diffuse interstellar lines seen in the optical spectra of stars lying behind fairly low-density interstellar clouds. In particular, it is shown that the equilibrium abundances of the long chain carbon molecules may remain quite high even for molecules with as many as 11 carbon atoms.
The possibility is considered that the reaction CO + OH yields CO2 + H may lead to a significant concentration of CO2 in dense clouds where both CO and OH have been found to be present. Experimental measurements and observational data are discussed which indicate a formation rate of 8 x 10 to the -15th per cu cm/s for CO2 by the cited reaction under conditions typical of dense interstellar clouds. Other CO2 formation mechanisms and some loss processes for CO2 are examined. It is concluded that an appreciable concentration of CO2 produced by the cited reaction is possible in dense clouds.
The rate constants and product distributions of the reactions of OH(+) and H2O(+) with some diatomic and simple polyatomic molecules were studied by ion cyclotron resonance (ICR) mass spectrometric techniques. Reaction rates with CO, NO, O2, N2, CO2, H2S, N2O, H2CO, CH4 and CD4 were measured. Charge transfer and proton transfer were generally observed in cases for which the reaction channel is exothermic, but processes involving rearrangement were not found.
Reactions of various positive ions with water vapor were studied by ion cyclotron resonance mass spectrometric techniques. Rate constants and product distributions were determined for reactions of the ions: Ar(+), Co(+), N2(+), and CO2(+), CH2(+), and CH4(+), CH2Cl(+), HCO(+), H2CO(+), H2COH(+), H2S(+) and HS(+). The results obtained in this work are compared with earlier reported data where available.
A satellite program to conduct research on the chemistry, energetics, and dynamics of the upper atmosphere was developed. The scientific goals of the Upper Atmospheric Research Program, the program requirements, and the approach toward meeting those requirements are outlined. An initial series of two overlapping spacecraft missions is described. Both spacecraft are launched and recovered by the STS, one in the winter of 1983 at a 56 deg inclination, and the other a year later at a 70 deg inclination. The duration of each mission is 18 months, and each carries instruments to make global measurements of the temperature, winds, composition, irradation, and radiance in the stratosphere, mesosphere, and lower thermosphere between the tropopause and 120 km altitude. The program requires a dedicated ground-based data system and a science team organization that leads to a strong interaction between the experiments and theory. The program includes supportive observations from other platforms such as rockets, balloons, and the Spacelab.
Ion cyclotron resonance methods were used to measure the product distributions for thermal-energy charge-transfer reactions of He(+), Ne(+), and Ar(+) ions with N2, O2, CO, NO, CO2, and N2O. Except for the He(+)-N2 reaction, no molecular ions were formed by thermal-energy charge transfer from He(+) and Ne(+) with these target molecules. The propensity for dissociative ionization channels in these highly exothermic charge-transfer reactions at thermal energies contrasts with the propensity for formation of parent molecular ions observed in photoionization experiments and in high-energy charge-transfer processes. This difference is explained in terms of more stringent requirements for energy resonance and favorable Franck-Condon factors at thermal ion velocities.
Product distributions and rate constants for the reactions of ground-state N(+) ions with CO, NO, CO2, and CH4 were measured. Rate constants were obtained using ion-cyclotron-resonance trapped-ion methods, and product distributions were obtained using a tandem (Dempster-ICR) mass spectrometer. Rapid nitrogen isotope exchange was also observed in N(+)-N2 collisions.
A constant-reference load is utilized as Q-spoiler in calibrations of relative sensitivity variations of a marginal oscillator with frequency. Frequency-dependent effects troublesome in earlier Q-spoilers are compensated by employing a pure resistive calibration load with compensation for the small distributed capacitance of large resistors. The validity of the approach is demonstrated for a 2:1 mass ratio range, and validity for a mass ratio range greater than 10:1 is claimed. The circuit and technique were developed for use in ion cyclotron resonance (ICR) spectrometric practice.
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Ionization of the atmosphere of Titan by galactic cosmic rays is a very significant process throughout the altitude range from 100 to 400 km. An approximate form of the Boltzmann equation for cosmic-ray transport has been used to obtain local ionization rates. Models of both ion and neutral chemistry have been employed to compute electron and ion density profiles for three different values of the H2/CH4 abundance ratio. The peak electron density is of the order of 1000 per cu cm. The most abundant positive ions are C2/H9(+) and C3H9(+), while the predicted densities of the negative ions H(-) and CH3(-) are very small (less than one ten-thousandth that of the positive ions). It is suggested that inclusion of the ion chemistry is important in the computation of the H and CH3 density profiles in the lower ionosphere.
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The reaction of atomic nitrogen ions with molecular oxygen is a major loss mechanism for N(+) ions in the ionosphere and is a source of NO(+) ions and atomic nitrogen at certain altitudes. Ion cyclotron resonance methods are used to measure the product distribution of thermal energy N(+) ions reacting with O2. Three product channels are identified with the following fractional distributions: O2(+) + N, 0.65 plus or minus 0.04; NO(+) + O, 0.31 plus or minus 0.04; O(+) + NO, 0.04 plus or minus 0.02.