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Thermionic emission measurement for palladium filament exposed to molecular and atomic hydrogen beam - hydrogen chemisorption on palladium
Electric field effect on chemisorption of oxygen on zinc oxide, discussing electron transfer mechanism
Chemisorption energies of organics on Pb surface by extended Hueckel molecular orbital technique
Hydrogen recombination and molecule formation by nonactivated chemisorption on iron grains surfaces
Investigation of the irreversible chemisorption of water, formic acid and acetic acid on a thin amorphous aluminum oxide film, using inelastic tunneling spectroscopy. All of the tunnel junctions employed were Al-Al2O3-Pb junctions with the adsorbate on the Al2O3 surface between the Al2O3 and the Pb electrode. The results obtained include the finding that all Al2O3 surfaces prepared by oxidation of Al have free CH groups present on them.
Measurements were made of the isothermal adsorption-desorption kinetics for H2 chemisorbed onto Fe films. The chemisorption process is observed to proceed via a precursor state of adsorbed molecular hydrogen similar to the H2-Ni system. The first measurements of the activation energy for desorption, and estimates of the values of the fast kinetic rates between the precursor and chemisorbed states are reported. Adsorption into the precursor state does not appear to be activated, but the process connecting the precursor state with the chemisorbed state will, under certain circumstances, be a rate limiting step for adsorption. The effects of contamination of the surface are evidenced in the measurements.
A method of measuring concentrations of hydrogen chloride between 1 part per billion and 10 parts per million at standard temperature and pressure is presented. The feasibility of a low-cost device incorporating a chemisorption technique coupled with a quartz crystal microbalance was demonstrated in the field at the Viking B launch using a Titan-Centaur vehicle from Kennedy Space Center on August 20, 1975. Hydrogen chloride is a product of solid rocket combustion. The concentration level of hydrogen chloride for this particular launch was measured as approximately 0.2 parts per million at 4 km from the launch site.
An investigation is conducted of the kinetics of isothermal adsorption-desorption processes involving molecular hydrogen which is chemisorbed onto thin (20 to 50 A) polycrystalline Fe films at temperatures near 300 K. The results of the investigation indicate that chemisorption in the H2-Fe system occurs via a precursor state of molecularly adsorbed hydrogen. Contamination of the surface from unknown impurities in the gas phase is found to affect the number of available adsorption sites and to modify the prefactor for the absolute desorption rate constant for the precursor state.
Self-consistent Hartree-Fock-Slater molecular cluster models for the chemisorption of first-row atoms on Ni(100) surfaces are presented. Energy levels and ground-state charge distributions are given for XNi5 clusters with the adatom X = H, C, N, O located in C4V symmetry at a fixed height of 2.0 au above the surface. The variation of properties with height was studied in detail for the case of oxygen. Theoretical results compare rather well with experimental photoelectron and energy-loss data. Local-densities-of-states diagrams are used to clarify the interaction between adsorbate levels and metal conduction bands.
Self-consistent Hartree-Fock-Slater molecular cluster models for the chemisorption of carbon monoxide on a (100) transition metal surface are presented. Energy levels and charge distribution for the CO:Ni5 cluster in C sub 4v symmetry are obtained, and the variation of binding energies with height of the CO molecule above the surface of nickel is studied in detail. Comparison is made with experimental binding energy spectra and with the multiple-scattering results of Batra and Bagus. The redistribution in energy of free-atom valence levels is studied by means of local-densities-of-states diagrams.
A comparative study of the chemisorption of CO on Ni(001) and Cu(001) surfaces has been performed. The study is based on an analysis of the electronic structure of (M)5CO clusters obtained from self-consistent field X alpha scattered-wave calculations. The electron orbital formed principally by the 5 sigma orbital on CO was found to be mainly responsible for the bonding of the CO molecule to the metal surface for both the CO/Ni and CO/Cu systems. The different occupation of the antibonding 7 a sub 1 orbital in the two clusters is believed to be the major reason for the large difference observed in the measured heats of adsorption of CO on Ni and Cu surfaces. It was found also that metal atoms transfer electronic charge to the antibonding pi(asterisk)-like orbital of CO. A possible correlation between the amount of the charge transfered and the relative ease of dissociation of CO molecules on metal surfaces is discussed.
Morphology and CO chemisorption properties are studied as a function of particle size for the case of particulate Pt films, vapor-deposited onto ultrahigh vacuum-cleaved and heat-treated mica surfaces at a 200 C substrate temperature. The particles were found to be mostly irregular in shape and randomly-oriented, with two desorption peaks after CO absorption at 60 C: (1) an alpha peak, at 120 C, attributed to smooth particle surfaces, and (2) a beta peak, at about 175 C, attributed to particle edges and steps. Transmission electron microscopy showed that major changes occur in particle morphology during absorption-desorption cycling, so that the decrease in CO desorption flux may be interpreted as due to particle restructuring, rather than contamination by CO decomposition as in the cases of Ni or Pd on mica. Auger electron spectroscopy corroborates the lack of CO decomposition, even for the case of very small Pt particles.
Potential-energy relations involving a few parameters in simple analytic forms have been found to represent well the energetics of a wide variety of diatomic molecules. However, such two-atom potential functions are not appropriate for metals. It is well known that, in the case of metals, there exist strong volume-dependent forces which can never be expressed as pairwise interactions. The present investigation has the objective to show that, in spite of the observation concerning metals, a single binding-energy relation can be found which accurately describes diatomic molecules as well as adhesion, cohesion, and chemisorption on metals. This universality reveals a commonality between the molecular and metallic bond.
Measurements have been made of the chemisorption-induced resistance change for H2 adsorbed onto Fe film substrates predosed with fixed coverages of chemisorbed oxygen. The measurements were made at temperatures from 295 to 340 K and for estimated oxygen coverages of less than 0.1 monolayers. Two distinct resistance change components were observed in both the adsorption kinetics and the equilibrium isotherms: a positive component which is associated with the adsorption of H2 onto a clean Fe surface, and a negative component which was correlated with the presence of the chemisorbed oxygen. The resistance change isotherms can be fit with a model which assumes that each of the resistance change components result from dissociative chemisorbed hydrogen. Possible mechanisms for the chemisorbed-oxygen-induced negative resistance change are discussed.
Reversible chemical reaction generates pressurized oxygen for cooling. Concept for cryogenic refrigerator based on chemical absorption of oxygen by praseodymium/cerium oxide (PCO) compound. Refrigerator produces cryogenic liquid for cooling infrared sensors. Also used for liquefying air and separating oxygen from nitrogen in air. In chemisorption refrigerator, PCO alternately absorbs and desorbs oxygen depending on whether cooled or heated. One pair of compressors accepts oxygen while others releases it. Compressed oxygen liquefied when precooked and expanded.
The present invention relates to a chemisorption compressor cryogenic refrigerator which employs oxygen to provide cooling at 60 to 100 K. The invention includes dual vessels containing an oxygen absorbent material, alternately heated and cooled to provide a continuous flow of high pressure oxygen, multiple heat exchangers for precooling the oxygen, a Joule-Thomson expansion valve system for expanding the oxygen to partially liquefy it and a liquid oxygen pressure vessel. The primary novelty is that, while it was believed that once oxygen combined with an element or compound the reaction could not reverse to release gaseous oxygen, in this case oxygen will indeed react in a reversible fashion with certain materials and will do so at temperatures and pressures which make it practical for incorporation into a cryogenic refrigeration system.
For chemisorption and oxidation on Pt/HOPG (highly-orientated pyrolytic) graphite, reflectance Fourier Transform Infrared (FTIR)-microspectrometry reveals a variable state and reactivity for CO. Even for model surface science systems, where surface heterogeneity is minimal, surface diffusion may be too slow relative to the reaction rate to avoid segregation of reactants into surface islands under steady-state conditions. Thus in CO oxidation on Pt (where the relevant surface diffusion coefficients are such that D sub O less than D sub CO) then reactant CO islands exists at the perimeters of which the surface reaction is thought to occur. Furthermore CO can chemisorb on metals in linear and bridge forms to extents which vary with precise faces predominantly exposed coverage, etc. Infrared has long been used to probe the nature of adsorbed CO on model film and heterogeneous surfaces, but it may now be that FTIR-microspectrometry will allow the state of this adsorbate and reactant to be investigated with a spatial resolution of 4.4 microns on model (and real) catalytic surfaces.
The value of in situ analysis on CO chemisorption, titration and oxidation over supported Pt catalysts using calorimetry, catalytic and micro-FTIR methods is illustrated using silica- and titania-supported samples. Isothermal CO-O and O2-CO titrations have not been widely used on metal surfaces and may be complicated if some oxide supports are reduced by CO titrant. However, they can illuminate the kinetics of CO oxidation on metal/oxide catalysts since during such titrations all O and CO coverages are scanned as a function of time. There are clear advantages in following the rates of the catalyzed CO oxidation via calorimetry and gc-ms simultaneously. At lower temperatures the evidence they provide is complementary. CO oxidation and its catalysis of CO oxidation have been extensively studied with hysteresis and oscillations apparent, and the present results suggest the benefits of a combined approach. Silica support porosity may be important in defining activity-temperature hysteresis. FTIR microspectroscopy reveals the chemical heterogeneity of the catalytic surfaces used; it is interesting that the evidence with regard to the dominant CO surface species and their reactivities with regard to surface oxygen for present oxide-supported Pt are different from those seen on graphite-supported Pt.