Electron energy-loss spectroscopy study of polyatomic molecular systems under pyrolytic conditions

The technique of variable-angle, electron energy-loss spectroscopy has been used to study the electronic spectroscopy of the diketene molecule. The experiment was performed using incident electron beam energies of 25 eV and 50 eV, and at scattering angles between 10° and 90°. The energy-loss region from 2 eV to 11 eV was examined. One spin-forbidden transition has been observed at 4.36 eV and three others that are spin-allowed have been located at 5.89 eV, 6.88 eV and 7.84 eV. Based on the intensity variation of these transitions with impact energy and scattering angle, and through analogy with simpler molecules, the first three transitions are tentatively assigned to an n → π* transition, a π - σ* (3s) Rydberg transition and a π → π* transition.

Thermal decomposition of chlorodifluoromethane, chloroform, dichloromethane and chloromethane under flash-vacuum pyrolysis conditions (900-1100°C) was investigated by the technique of electron energy-loss spectroscopy, using the impact energy of 50 eV and a scattering angle of 10°. The pyrolytic reaction follows a hydrogen-chloride α-elimination pathway. The difluoromethylene radical was produced from chlorodifluoromethane pyrolysis at 900°C and identified by its X^1 A_1 → A^1B_1 band at 5.04 eV.

Finally, a number of exploratory studies have been performed. The thermal decomposition of diketene was studied under flash vacuum pressures (1-10 mTorr) and temperatures ranging from 500°C to 1000°C. The complete decomposition of the diketene molecule into two ketene molecules was achieved at 900°C. The pyrolysis of trifluoromethyl iodide molecule at 1000°C produced an electron energy-loss spectrum with several iodine-atom, sharp peaks and only a small shoulder at 8.37 eV as a possible trifluoromethyl radical feature. The electron energy-loss spectrum of trichlorobromomethane at 900°C mainly showed features from bromine atom, chlorine molecule and tetrachloroethylene. Hexachloroacetone decomposed partially at 900°C, but showed well-defined features from chlorine, carbon monoxide and tetrachloroethylene molecules. Bromodichloromethane molecule was investigated at 1000°C and produced a congested, electron energy-loss spectrum with bromine-atom, hydrogen-bromide, hydrogen-chloride and tetrachloroethylene features.

Interaction of aqueous inorganic orthophosphate and phosphate rock

An experimental study was made of the interaction of phosphate rock and aqueous inorganic orthophosphate, calcium, and hydroxyl ions. A model of the reaction was developed by observing electron diffraction patterns in conjunction with concentration changes of chemical components. The model was applied in explaining the performance of batch suspensions of powdered phosphate rock and packed columns of granular phosphate rock. In both cases the reaction consisted initially of a rapid nucleation phase that occurred in a time period of minutes. In the batch system the calcium phosphate nuclei then ripened into larger micro-crystals of hydroxyapatite, which eventually became indistinguishable from the original phosphate rock surface. During column operation the high supersaturation ratio that existed after the rapid nucleation phase resulted in a layer of small nuclei that covered a slowly growing hydroxyapatite crystal.

The column steady-state rate constant was found to increase with increasing temperature, pH, and fluoride concentration, and to decrease with increasing concentrations of magnesium sulfate, ammonium chloride, and bicarbonate ion.

An engineering feasibility study indicated that, based on economic considerations, nucleation of apatite on phosphate rock ore has a potential use as a wastewater phosphate removal treatment process.

Structural geology of the region between Pacoima and Little Tujunga Canyons, San Gabriel Mountains, California

An area of about 25 square miles in the western part of the San Gabriel Mountains was mapped on a scale of 1000 feet to the inch. Special attention was given to the structural geology, particularly the relations between the different systems of faults, of which the San Gabriel fault system and the Sierra Madre fault system are the most important ones. The present distribution and relations of the rocks suggests that the southern block has tilted northward against a more stable mass of old rocks which was raised up during a Pliocene or post-Pliocene orogeny. It is suggested that this northward tilting of the block resulted in the group of thrust faults which comprise the Sierra Madre fault system. It is show that this hypothesis fits the present distribution of the rocks and occupies a logical place in the geologic history of the region as well or better than any other hypothesis previously offered to explain the geology of the region.

The energy spectra of uranium atoms sputtered from uranium metal and uranium dioxide targets

The energy spectra of ²³⁵U atoms sputtered from a 93% enriched ²³⁵U metal foil and a hot pressed ²³⁵U0₂ pellet by an 80 keV ⁴⁰Ar⁺ beam have been measured in the range 1 eV to 1 keV. The measurements were made using a mechanical time-of-flight spectrometer in conjunction with the fission track technique for detecting ²³⁵U. The design and construction of this spectrometer are discussed in detail, and its operation is mathematically analyzed.

The results of the experiment are discussed in the context of the random collision cascade model of sputtering. The spectrum obtained by the sputtering of the ²³⁵U metal target was found to be well described by the functional form E(E+E_b)^-2.77, where E_b = 5.4 eV. The ²³⁵U0₂ target produced a spectrum that peaked at a lower energy (~ 2 eV) and decreased somewhat more rapidly for E ≳ 100 eV.

Propagation of cosmic rays through interstellar space

The propagation of cosmic rays through interstellar space has been investigated with the view of determining what particles can traverse astronomical distances without serious loss of energy. The principal method of loss of energy of high energy particles is by interaction with radiation. It is found that high energy (10¹³-10¹⁸ev) electrons drop to one-tenth their energy in 10⁸ light years in the radiation density in the galaxy and that protons are not significantly affected in this distance. The origin of the cosmic rays is not known so that various hypotheses as to their origin are examined. If the source is near a star it is found that the interaction of electrons and photons with the stellar radiation field and the interaction of electrons with the stellar magnetic field limit the amount of energy which these particles can carry away from the star. However, the interaction is not strong enough to affect the energy of protons or light nuclei appreciably. The chief uncertainty in the results is due to the possible existence of general galactic magnetic field. The main conclusion reached is that if there is a general galactic magnetic field, then the primary spectrum has very few photons, only low energy (˂ 10¹³ ev) electrons and the higher energy particles are primarily protons regardless of the source mechanism, and if there is no general galactic magnetic field, then the source of cosmic rays accelerates mainly protons and the present rate of production is much less than that in the past.

A study of T = 2 states in ^(12)B, ^(12)C, ^(20)F and ^(28)Al

The lowest T = 2 states have been identified and studied in the nuclei ¹²C, ¹²B, ²⁰F and and ²⁸Al. The first two of these were produced in the reactions ¹⁴C(p,t)¹²C and ¹⁴C (p,³He)¹²B, at 50.5 and 63.4 MeV incident proton energy respectively, at the Oak Ridge National Laboratory. The T = 2 states in ²⁰F and ²⁸Al were observed in (³He,p) reactions at 12-MeV incident energy, with the Caltech Tandem accelerator.

The results for the four nuclei studied are summarized below:

(1) ¹²C: the lowest T = 2 state was located at an excitation energy of 27595 ± 20 keV, and has a width less than 35 keV.

(2) ¹²B: the lowest T = 2 state was found at an excitation energy of 12710 ± 20 keV. The width was determined to be less than 54 keV and the spin and parity were confirmed to be 0⁺. A second ¹²B state (or doublet) was observed at an excitation energy of 14860 ± 30 keV with a width (if the group corresponds to a single state) of 226 ± 30 keV.

(3) ²⁰F: the lowest T = 2 state was observed at an excitation of 6513 ± 5 keV; the spin and parity were confirmed to be 0⁺. A second state, tentatively identified as T = 2 from the level spacing, was located at 8210 ± 6 keV.

(4) ²⁸Al: the lowest T = 2 state was identified at an excitation of 5997 ± 6 keV; the spin and parity were confirmed to be 0⁺. A second state at an excitation energy of 7491 ± 11 keV is tentatively identified as T = 2, with a corresponding (tentative) spin and parity assignment J^π = 2⁺.

The results of the present work and the other known masses of T = 2 states and nuclei for 8 ≤ A ≤ 28 are summarized, and massequation coefficients have been extracted for these multiplets. These coefficients were compared with those from T = 1 multiplets, and then used to predict the mass and stability of each of the unobserved members of the T = 2 multiplets.

Devil's Gate Reservoir and its effect upon Pasadena's water supply

[Intro.] The Devil’s Gate Dam has been of great benefit to Pasadena’s water supply, in that it prevents a large amount of the flood waters of the Arroyo Seco being wasted into the ocean.

Investigations into electronic stopping regime sputtering of uranium tetrafluoride

Yields were measured for ²³⁵U sputtered from UF₄ by ¹⁶O, ¹⁹F, and ³⁵Cl over the energy range ~.12 to 1.5 MeV/ amu sing a charge equilibrated beam in the stripped beam arrangement for all the incident ions and in the transmission arrangement for ¹⁹F and ³⁵Cl. In addition, yields were measured for ¹⁹F incident in a wide range of discrete charge states. The angular dependence of all the measured yields were consistent with cosʋ. The stripped beam and transmission data were well fit by the form (Az²eqln(BƐ)/Ɛ)⁴ (where Ɛ was the ion energy in MeV/amu and z_eq(Ɛ) was taken from Zeigler(80). The fitted values of B for the various sets of data were consistent with a constant B₀, equal to 36.3 ± 2.7, independent of incident ion. The fitted values of A show no consistent variation with incident ion although a difference can be noted between the stripped beam and transmission values, the transmission values being higher.

The incident charge data were well fit by the assumptions that the sputtering yield depended locally on a power of the incident ion charge and that the sputtering from the surface is exponentially correlated to conditions in the bulk. The equilibrated sputtering yields derived from these data are in agreement with the stripped beam yields.

In addition, to aid in the understanding of these data, the data of Hakansson(80,81a,81b) were examined and contrasted with the UF₄ results. The thermal models of Seiberling(80) and Watson(81) were discussed and compared to the data.