Engineering topics
Publications and source records attributed to Huntress, W. T., Jr..
Product distributions and rate constants for the reaction of ground state C(+) ions with O2, NO, HCl, CO2, H2S, H2O, HCN, NH3, CH4, H2CO, CH3OH, and CH3NH2 have been measured. Rate constants were obtained using ion cyclotron resonance trapped ion methods, and product distributions were obtained using a tandem mass spectrometer. Rapid carbon isotope exchange has also been observed in C(+)-CO collisions.
Laboratory measurements using the ion-cyclotron resonance technique yield a rate constant of 2 by 10 to the -10th power cu cm/sec at 300 K for the isotope exchange C-13(+) + (C-12)O yields C-12(+) + (C-13)O. According to the usual ideas about ion-molecule reactions, this rate constant should also be appropriate at temperatures not exceeding about 100 K. Then the observed C-13/C-12 ratio obtained from radio observation of interstellar molecules may be either larger or smaller than the actual value in the interstellar medium by factors of 2 or so. If the ratio is altered from the actual interstellar value, it will not be the same in all molecules, and CO will tend to have the highest value. The chief astronomical uncertainty for the occurrence of this isotope fractionation is the abundance of 'unobservable' molecules which can react rapidly with C(+): e.g., O2, H2O, CO2, and CH4. If their abundance is greater than about one-tenth that of CO, the isotope fractionation will be inhibited.
Present knowledge concerning the chemistry of planetary atmospheres is reviewed along with the theories which attempt to explain observational data. The known gross atmospheric compositions of the terrestrial and giant planets are listed, differences between the atmospheres of earth and Venus are discussed, and the atmospheres of the giant planets are described. The origin and evolution of the atmospheres of earth, Venus, Mars, Jupiter, Saturn, and Uranus are outlined, and chemical processes in the atmospheres are examined, particularly cloud formation. The question of organic synthesis and evolution in the reducing atmospheres of the giant planets is considered. It is noted that laboratory work on the individual chemical processes and reactions involved in the evolution of organic compounds in planetary atmospheres, comets, and interstellar space points to the inevitability of organic-compound synthesis in all these situations and to the pervasiveness of organic chemistry throughout the universe.
The rate constants for proton transfer from H3(+) ions to N2, O2, and CO have been measured as function of hydrogen-buffer-gas partial pressure. The rate constant for proton transfer from H3(+) to N2 shows a very large pressure dependence, increasing from 1.0 by 10 to the -9th power cu cm/s at low H2 partial pressures to 1.7 by 10 to the -9th power cu cm/s at high H2 partial pressures. The rate constants for proton transfer from H3(+) to O2 and CO are constant with partial pressure of H2. The roles of excess vibrational energy in H3(+) ions and of equilibrium between forward and back reactions are discussed. Back reaction is observed only for the reaction of H3(+) ions with O2, and an equilibrium constant of 2.0 (plus or minus 0.4) at 298 K has been determined. From these data, the proton affinity of O2 is deduced to be 0.47 (plus or minus 0.11) kcal/mole higher than that of H2.
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Use of ion cyclotron resonance methods to measure the thermal energy rate constants for a number of ion-molecule reactions involving hydrogen and hydrogen-helium mixtures. Assuming that the distribution of initial vibrational states in the H2(+) ion is a near-Franck-Condon distribution, the occurrence of collisional deactivation of vibrationally excited H2(+) ions by He atoms is identified, and an approximate rate constant for the deactivation process and its dependence on vibrational energy are given.
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The thermal energy, bimolecular ion-molecule reactions occurring in gaseous water, hydrogen sulfide, ammonia, and methane have been identified and their rate constants determined using ion cyclotron resonance methods. Absolute rate constants were determined for the disappearance of the primary ions by using the trapped ion method, and product distributions were determined for these reactions by using the cyclotron ejection method. Previous measurements are reviewed and compared with the results using the present methods. The relative rate constants for hydrogen-atom abstraction, proton transfer, and charge transfer are also determined for reactions of the parent ions.
A new detector using an extremelly driven tuned circuit has been developed for use in ion cyclotron resonance spectroscopy experiments. Based on the Q-meter circuit, this detector will operate at frequencies greater than 1 MHz at rf levels less than 1 mV. Operation in the frequency range 1-15 MHz allows the use of higher magnetic fields for more efficient storage of low mass ions in the trapping mode of operation. In the frequency range 2-6 MHz electrons can be detected in the ion cyclotron resonance cell by their resonant motion in the trapping plane.
The extent of hydrogen atom exchange in the reaction, CH3(+) + CH4 yields C2H5(+) + H2, is determined by examining the product distribution for the reactions CH3(+) + CD4 and CD3(+) + CH4 as a function of relative kinetic energy from thermal energies to 10 eV. It is found that the reaction of CH4(+) with the parent neutral proceeds both via proton transfer and hydrogen abstraction accompanied by approximately 10% hydrogen atom exchange during the reaction.
The technique of electron spectroscopy for chemical analysis (ESCA) is used to obtain rapid, nondestructive elemental analyses of selected lunar samples, and the chemical shift of the Fe(2p) line in lunar materials is found characteristic of iron in the Fe(2+) state. A difference in binding energy of approximately 0.5 eV is observed between the 0(1s) levels of the terrestrial minerals fayalite and quartz, and effects due to surface oxidation and absorption are also observed in terrestrial materials. The new ESCA technique is based on energy analysis at high resolution of electrons emitted from the surface of a sample on irradiation with X rays and is valuable for the study of the electronic structure of atoms and molecules.
Ion cyclotron resonance power absorption, deriving expression for average ion kinetic energy at saturation in steady state limit