An Auger spectroscopic study of the kinetic behavior of adsorbed oxygen on palladium

The adsorption of oxygen on polycrystalline palladium, the kinetics of the reaction of adsorbed oxygen with carbon monoxide and the amount of adsorbed oxygen present during the catalyzed reaction, $\text{CO +}\text{1}\text{2}\text{O}{}_2\text{→ CO}{}_2$, were studied by Auger electron spectroscopy. At temperatures below 783 K, the initial sticking probability is high (~0.8). Adsorbed oxygen and CO react with high probability and low activation energy to form carbon dioxide. The reaction is first order with respect to carbon monoxide pressure and zero order in oxygen coverage. Oxygen coverages measured during the CO-oxidation reaction decrease sharply around P_CO ? P_O2 and are very small when P_CO >P_O2. The reaction kinetics are discussed using a modified Eley-Rideal mechanism involving strongly adsorbed oxygen atoms and surface carbon monoxide in a short-lived state. The oxygen adsorption phenomena are correlated with the reaction kinetics.     

Oscillatory oxidation of Co over a Pt catalyst

We report measurements of the temporal oscillatory oxidation rates of CO over a polycrystalline Pt wire. The experiments were conducted near atmospheric pressure in a clean flow reactor system. Reproducible oscillations in both the temperature of the Pt wire and in the rate of CO₂ production were found over a wide range of gas compositions, $\text{0.001 <}\text{P}{}_{\mathrm{CO}}\text{P}{}_{\mathrm{O}}{}_2\text{< 0.045,}$ and temperatures, 150°C < T_g < 350°C, where PCO and po₂ are the respective partial pressures of carbon monoxide and oxygen in the gas stream, and T_g is the temperature of the gas. The oscillations are believed to occur between two branches of a Langmuir-Hinshelwood reaction mechanism. It is suggested that the slow formation and removal of subsurface oxygen drives the reaction between the two branches. A simple kinetic model based on this hypothesis gives excellent qualitative agreement with the observed oscillations.     

Hydrogenation kinetics of carbonaceous layers on polycrystalline iron

Carbonaceous layers were formed on iron by the $\text{CO}\text{H}{}_2$ reaction at 560 K and 1 bar total pressure. These layers were characterized by the C 1 s electron binding energy and peak area. Subsequently they were hydrogenated in 1 bar H₂ at 560 K to predominantly methane. There are two distinct stages of carbon hydrogenation: a fast initial stage where the rate depends sensitively on the total amount of deposited carbon, and a very slow second stage. The first stage corresponds to the removal of CH_x and carbidic carbon phases whereas the presence of graphitic carbon is indicated during the second stage. The initial rate of carbon hydrogenation is directly proportional to the rate of methane production from $\text{CO}\text{H}{}_2$ (at constant carbon coverage). From this behavior it was concluded that methane is formed by a direct hydrogenation of atomically adsorbed carbon.     

Oscillatory oxidation of co over Pd and Ir catalysts

Oscillations in the rate of CO₂ production have been observed for the first time over Pd and Ir catalysts. The experiments were conducted near atmospheric pressure in a clean flow reactor system using polycrystalline Pd or Ir wire. For Pd, sustained oscillations were found over a wide range of gas compositions and temperatures (230 < T_g < 350°C), where P_CO and P_O2 are the respective partial pressures of carbon monoxide and oxygen in the gas stream, and Tg is the temperature of the gas. For Ir, oscillations were found for and 180 < T_g < 250°C. As proposed for CO oxidation over a Pt catalyst, it is believed that the oscillations occur between two branches of a Langmuir-Hinshelwood reaction mechanism, and that the slow formation and removal of subsurface oxygen drives the reaction between these two branches. These experiments suggest that oscillations in surface reactions are more general than previously suspected.     

The application of XPS to the determination of the kinetics of the co oxidation reaction over the Ir(111) surface

The coverages of adsorbed oxygen and CO on an Ir(111) surface have been determined using X-ray photoelectron spectroscopy (XPS) during the steady-state catalytic production of CO₂. Correlating the coverages of the reacting adsorbates with the rate of CO₂ production allows the kinetics of the CO oxidation reaction to be determined. The reaction is found to obey a Langmuir-Hinshelwood rate expression of the form , where R_CO2 is the rate of CO₂ production, k⁰ is the pre-exponential factor of the reaction rate coefficient, [CO] and [O] are the surface coverages of CO and oxygen, respectively, and E_a is the activation energy for the oxidation reaction. The activation energy for this catalytic oxidation reaction is found to be approximately 9 $\text{kcal}\text{mole}$.     

Anomalous two-electron auger resonance in thorium near the 5d(O5) photothreshold

The photoexcited $\text{O}{}_5\text{P}{}_3\text{V (5d}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{6p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{valence}\text{)}$ Auger emission line for thorium metal shows an anomalous increase in kinetic energy of ～ 1 eV as the photon energy hv is increased through the atomic-like 5d → 5f resonant excitation at hv_r = 89 eV. Possible mechanisms for this anomalous behavior are discussed, and it is suggested that it can be interpreted as a two-electron resonance involving the O₅P₃V Auger excitation and a shake-up satellite of the $\text{6p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ core level excitation.     

Deposition of nickel from Ni(CO)4 on palladium and iron surfaces studied by X-ray photoelectron spectroscopy

The interaction of nickel carbonyl, Ni(CO)₄, with evaporated palladium and iron surfaces has been studied at 90 and 290 K by X-ray photoelectron spectroscopy. The carbonyl is weakly adsorbed in molecular form at 90 K on the metals giving a $\text{Ni 2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ peak at 854.6 eV, a C 1s at 287.2 eV and an O 1s at 533.8 eV. Some fraction of the carbonyl decomposes even at 90 K on iron to give deposited nickel atoms. In the interaction with palladium at 290 K, deposited nickel atoms $\text{(Ni 2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{= 852.9 eV)}$ and chemisorbed CO are observed. A satellite feature of the $\text{Ni 2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ peak varies depending on the quantity of the deposited nickel atoms; the main peak-satellite separation increases with increase in the quantity. The same variation is observed for evaporated nickel-palladium alloys. This can be ascribed to the difference in the electronic states of the nickel atoms. The difference is reflected in the reactivity of the atoms with O₂. With iron the deposited nickel atoms show an increase in binding energy of 0.4 eV in the $\text{Ni 2p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ Peak and no satellite when the number of nickel atoms is small. The oxidation of the surface is also studied.     

CO2 dissociation on rhodium: Measurement of the specific rates on Rh(111)

The measured rates for CO₂ dissociation on Rh(111) are reported for a $\text{H}{}_2\text{CO}{}_2$ reaction mixture at a total pressure of 100 Torr and a CO₂ partial pressure of 1 Torr. The activation energy associated with the conversion of CO₂ to CO is $\text{17}\text{kcal}\text{mol}$. The reaction probabilities for CO₂ dissociation range from 10^?5 at 750 K to 10^?8 at 444 K. The probability of CO₂ dissociation on Rh(111) is shown to be on the order of 10^?11 at 300 K rather than the previously reported value near 10^?1.     

The co-adsorption of copper and oxygen on a tungsten {100} surface

The co-adsorption of Cu on O₂ and a W{100}surface is studied by Auger electron spectroscopy (AES), thermal desorption (TD), low energy electron diffraction (LEED) and by work function change (δø) measurements. It is shown that the presence of Cu on the surface initially decreases s_O, the sticking coefficient of O₂. For longer oxygen exposures and for higher adsorption temperatures, θ_O reaches values larger than those on the clean surface for the same O₂ exposure. Except at the highest θ_O values and temperatures, the sticcking coefficient for copper, s_Cu, is unity and is independent of the oxygen coverage θ_O in the range studied (0 ? θ_O ? 2). Co-adsorption at room temperatures does not produce any long range order while co-adsorption at elevated temperature leads to the ordered structures (1 × 1), p(2 × 1), p(2 × 2) and c(2 × 2). The saturation coverage of the two dimensional co-adsorbate at 800 K is given by the relation $\text{θ}{}_{\mathrm{Cu}}\text{+}\text{8}\text{5}\text{θ}{}_{\mathrm{O}}\text{= 2}$. The work function is a complicated function of θ_O and θ_Cu and is determined predominantly by the temperature at which oxygen is adsorbed. At high temperatures the sequence of adsorption has no influence, in contrast to the room temperature behavior.     

Conductivite electrique totale du protoxyde de cuivre en fonction de sa composition definie par des electrodes d'alliage or-cuivre

The total electrical conductivity of cuprous oxide has been measured from 800 to 1100°K as a function of its composition, especially in the range of very low oxygen pressures up to the limit of equilibrium with copper. These measurements have been carried out by means of a new method using copper-gold alloy electrodes in order to have given activities of components.The results indicate for cuprous oxide a p semi-conduction throughout its stability range.The conductivity σ (ohm^?1. cm^?1) is given as a function of the temperature T (K) and the partial pressure P_o2 (torr) of oxygen in equilibrium with the oxide by the following equation:

     

Oxygen and carbon monoxide isotope exchange reactions on rhenium

The catalytic efficiency, E, of rhenium at high temperatures for the equilibration of a mixture of carbon monoxide isotopes (¹²C¹⁸O + ¹³C¹⁶O) is reduced by pre-adsorbed oxygen; E at 1300 K declines linearly to zero at an oxygen uptake of about 5 × 10¹⁴ atoms cm^?2. The replacement of one pre-adsorbed carbon monoxide isotope by another can be correlated with the characteristic desorption temperatures of the two main states (α and β) of CO on Re. The observation that a considerable fraction of CO is non-replaceable at filament temperatures below 700 K suggests a high activation energy for migration of some adsorbed CO. The probability of exchange of ¹⁶O between an oxygenated rhenium filament and gaseous ¹²C¹⁸O for oxygen coverages ?4 × 10¹⁴ O atoms cm^?2 is 0.012 per 10¹⁴ O atoms cm^?2 per collision with the filament at 900 K. The surface reaction $\text{Re-}{}^{16}\text{O +}{}^{12}\text{C}{}^{18}\text{O}{}_{\mathrm{(g)}}\text{= Re-}{}^{18}\text{O +}{}^{12}\text{C}{}^{16}\text{O}{}_{\mathrm{(g)}}$ is completely reversible. However, in the presence of nitrous oxide no reaction is observed until the filament temperature exceeds 1600 K, when continuous decomposition of N₂O is appreciable. Possible transition states for isotope exchange are discussed.     

The influence of potassium and the role of coadsorbed oxygen on the chemisorptive properties of Pt(100)

The adsorption of K on Pt(100) has been followed by thermal desorption spectroscopy (TDS) and Auger electron spectroscopy (AES); carbon monoxide was used as a probe for the modification of the chemical properties of K promoted surfaces. The role of subsequent adsorption of oxygen on the K modified surfaces has also been measured. For low potassium coverage (θ_K = 0 to 0.35), the mass-28 TDS peak temperature of adsorbed CO increases continuously with the K coverage, indicating an increase of the adsorption energy of CO which has been explained by a substantial charge donation from K into the $\text{2π}{}^1$ orbitals of CO via long range interactions through the platinum substrate. No oxygen uptake was detected after oxygen exposure at room temperature. For high potassium content (θ_K = 0.45 to 1), the mass-28 TDS peak temperature of coadsorbed CO is very narrow and remains constant at 680 K. We propose the formation of a COKPt surface complex which decomposes at 680 K, since K desorption is detected concomitantly to CO. On such K covered surfaces, the oxygen uptake is promoted, and it cancels the modifications of the surface properties induced by potassium.     

Infrared spectrum of acetonitrile: Analysis of Coriolis resonance

The Coriolis resonance between ν₄ and ν₇ in CH₃CN and between ν₁ and ν₅, ν₃ and ν₆, and ν₄ and ν₇ in CD₃CN has been analyzed, applying the technique developed by DiLauro and Mills, to obtain the signs of [$\text{ζ}{}_{\mathrm{r,sa}}{}^{\mathrm{y}}\text{(}\text{?p}\text{?Q}{}_{\mathrm{r}}\text{)(}\text{?p}\text{?Q}{}_{\mathrm{sa}}\text{)}$] and the ratio of $\text{?μ}\text{?Q}{}_{\mathrm{r}}$ to $\text{?μ}\text{?Q}{}_{\mathrm{s}}$ for the interacting pairs in CD₃CN. For (ν₄, ν₇) in both CH₃CN and CD₃CN, the sign of [$\text{ζ}{}_{\mathrm{r,sa}}{}^{\mathrm{y}}\text{(}\text{?p}\text{?Q}{}_{\mathrm{r}}\text{)(}\text{?p}\text{?Q}{}_{\mathrm{sa}}\text{)}$] is found to be negative as it is also for (ν₁, ν₅) in CD₃CN. For (ν₃, ν₆) the sign of this interaction term is found to be positive. For a given definition of normal coordinates the signs of these interaction terms give the relative signs of $\text{?p}\text{?Q}{}_{\mathrm{r}}$ and $\text{?p}\text{?Q}{}_{\mathrm{sa}}$; our study also gives approximate values for the corresponding ratio [$\text{(}\text{?p}\text{?Q}{}_{\mathrm{r}}\text{)}\text{(}\text{?p}\text{?Q}{}_{\mathrm{sa}}\text{)}$]     

A thermo-chemical study of the defect structure of barium oxide

A study of BaO has been made by use of thermogravimetric analysis, oxygen concentration analysis, and X-ray lattice parameter measurements in the temperature range 850°C ? T ? 1420°C and oxygen pressure range 7 × 10^-6 atm ? p_O2 ? 0·820 atm. Both the weight gain by the BaO samples and subsequently determined excess oxygen concentration were found to be directly proportional to . The enthalpy of incorporation oxygen in the lattice

$\text{1}\text{2}\text{O}{}_2\text{(g)=O(excess)}$

was determined to be ?0·395 ± 0·034 eV. Creation of vacancies on cation sites or of oxygen interstitials are consistent with the experimental results. As an alternative, the formation of O₂^2? ions, (as in BaO₂) as a result of incorporation of excess oxygen in the lattice, has been suggested.     

The reaction 55Mn(d, t)54Mn

Neutron pick-up cross sections and vector analyzing powers have been measured for the reaction ⁵⁵Mn($\text{d}$, t)⁵⁴Mn at 17 MeV. The mixture of $\text{p}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ to $\text{p}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ transfer to the low-lying l_n = 1 states has been found. Evidence of the $\text{f}{}_{\mathrm{<mtext>7</mtext><mtext>2</mtext>}}$ hole nature of several strong l_n = 3 states above 1 MeV has been obtained.     

Phenomenological predictions of the SO(10) supersymmetric grand unified model

The phenomenological predictions of the SO(10) supersymmetric grand unified model (SO(10) SGUM) for the mass scales M₁, M₂, weak angle ifsin²θ_w, quark-leptons mass ratios $\text{m}{}_{\mathrm{<mtext>b</mtext>}}\text{m}{}_{\mathrm{\tau }}$, $\text{m}{}_{\mathrm{t}}\text{m}{}_{\mathrm{<mtext>b</mtext>}}$, $\text{m}{}_{\mathrm{\tau }}\text{m}{}_{\mathrm{\nu }}{}_{\mathrm{\tau }}$ and proton lifetime τ_p are estimated by using renormalization group analysis at one-loop level. In contrast with SU(5) SGUM, we find that the SO(10) SGUM still has problems with τ_p but not with sin²θ_w and $\text{m}{}_{\mathrm{<mtext>b</mtext>}}\text{m}{}_{\mathrm{\tau }}$, which may suggest that supersymmetry would be bro at a mass scale $\text{?10}{}^7\text{GeV}$.     

Interaction of NO and O2 with Pd(111) surfaces. II

At least three different types of oxygen atoms may be present in the surface region of Pd(111) which may be distinguished by their thermal, chemical, structural and electronic properties. Exposure to O₂ at low temperatures causes the formation of 2 × 2 and $\text{3}\text{×}\text{3}\text{R30°}$ structures from chemisorbed oxygen, the latter being probably stabilized by small amounts of H_ab or CO_ab on the surface. The initial sticking coefficient was estimated to be about s₀ ≈ 0.3, the adsorption energy ~55 kcal/mole. The photoelectron spectrum exhibits an additional maximum at 5 eV below E_F. During thermal desorption dissolution of oxygen in the bulk strongly competes; on the other hand absorbed oxygen may diffuse to the surface giving rise to high temperature peaks in the flash desorption spectra. High temperature (~1000 K) treatment of the sample with O₂ causes the formation of a more tightly bound surface species also characterized by a 2 × 2 LEED pattern which is chemically rather stable and which is considered to be a transition state to PdO. The latter compound is only formed by interaction with NO at about 1000 K via the reaction $\text{Pd}\text{+}\text{NO}\text{→}\text{PdO}\text{+}\text{1}\text{2N}{}_2$ which offers a rather high “virtual” oxygen pressure. This reaction leads to drastic changes of the photoelectron spectrum and is also identified within the LEED pattern.     

The law of corresponding states for metals

Using the similarity of the effective potentials seen by ions in metals a reduced phonon equation of state is derived. It is shown that the melting point T_m(0) and the atomic volume Ω₀ at T = 0 K and at p = 0 are suitable macroscopic parameters for scaling ? and σ characterizing the interatomic potentials of metals having similar structures. The temperature and pressure dependence of thermodynamical quantities reduced with the above parameters are discussed and the results are compared with the experiment. It is shown that the pressure dependence of the reduced thermodynamic quantities can be described by the pressure dependence of the scaling parameters T_m(p) and Ω₀(p).The general form of the reduced equation of state (containing the electronic contributions as well) obtained gives that the reduced pressure is a universal function of the following reduced variables: the volume, temperature, de Broglie wavelength, Gibbs free energy of electrons $\text{3}\text{5}\text{zE}{}_{\mathrm{fo}}\text{?}$ (E_fo is the Fermi energy at T = 0 K) and depe of the valence z as well. It is shown that $\text{E}{}_{\mathrm{fo}}\text{?}$ is a function of $\text{Ω}{}_{\mathrm{o}}{}^{\mathrm{<mtext>?1</mtext><mtext>2</mtext>}}$ and $\text{(}\text{E}{}_{\mathrm{fo}}\text{/?}\text{)Ω}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ is approximately constant within the same sub-group of the periodic table.