The oxidation of carbon monoxide on polycrystalline rhodium under knudsen conditions: I. Reaction with oxygen

The reaction between oxygen and carbon monoxide on a polycrystalline rhodium ribbon under stationary conditions is followed by mass spectrometry. At temperatures from 300–1100 K the ratio of the partial pressures of reactants varies between 0.1 < p_O2/p_CO < 100. The value of the total pressure in the reactor varies between 10^?5 and 10^?4 Torr. The reaction on rhodium shows similar features as in the case of platinum. The results are consistent with a simple elementary reaction sequence but quantitative agreement by model calculations was not obtained.     

Bistability of the reaction rate in the oxidation of carbon monoxide by nitrogen monoxide on polycrystalline platinum

Multiplicity of the stationary reaction rate of CO oxidation by NO is observed under reducing conditions at pressures below 4×10^?4 mbar in the temperature range 500<T<525 K. The two branches of the reaction rate coalesce at a point where sustained oscillations are observed.     

Correlation and isotope effects for cation diffusion in magnetite

The simultaneous diffusion of ⁵²Fe and ⁵⁹Fe has been measured in Fe₃O₄ as a function of equilibrium oxygen partial pressure (10^?9 <p_o2 < 10^?4 atm) at 1200°C. The p_o2 dependence of D goes through a minimum near 10^?6 atm in agreement with earlier data of Dieckmann and Schmalzried. Comparison of the isotope effect results with correlation-factor calculations suggests that at p_o2 γ 10^?6, diffusion occurs predominantly by vacancy jumps between the normally occupied octahedral sites on the spinel lattice; jumps between tetrahedral sites probably play a lesser role. At p_o2< 10^?6 atm, diffusion occurs by an interstitialtype mechanism involving the simultaneous migration of two atoms. Five of the seven interstitialcy jumps considered in our correlation-factor calculations are consistent with the experimental results.     

Die kinetik der reaktion zwischen no und co an polykristallinem platin bei niedrigen drucken: I. Messmethode und experimenteller Befund

The reaction between NO and CO on a polycrystalline platinum ribbon under stationary conditions is followed by mass-spectrometry using isotopically labelled ¹³CO. At temperatures from 300 to 1100 K the ratio of the partial pressure of reactants varies between 0.1 < $\text{P}{}_{\mathrm{<mtext>NO</mtext>}}\text{P}{}_{\mathrm{<mtext>CO</mtext>}}$ < 10, the value of total pressure in the reactor being 1.75 × 10^?4 or 4.2 × 10^?3 Torr. The main reaction to N₂ and CO₂ is accompanied by the parallel reaction to N₂O and CO₂ which attains under certain conditions up to 50% of the total reaction. The pronounced temperature dependence of the reaction rate leads to maximum values between 500 and 650 K, the corresponding values of the reaction probabilities are as high as 0.3.     

Bonding and composition diagrams for sputtered a-Si : H

The combined influence of H partial pressure (p_H) and deposition rate (R_D) on Si-H bonding and total H content in diode-sputtered a-Si : H is presented in two simple graphs for the case of substrate temperature (T_s) equal to 225°C. Similar to a phase diagram, the graphs predict the H content and Si-H bonding that will result if a deposition is carried out with any prescribed pair of values (p_H, R_D), where 0.04 < p_H < 10 Paand 0.01 < R_D < 1 nm/sec. Well defined regions of Si-H bonding represented by dominant infrared stretching absorptions at 2000, 2090 and 2150 cm^?1 are obvious in the bonding diagram. The absorption at 2090 cm^?1 is the most commonly observed and is obtainable over a wide range of intermediate values of p_H and R_D. The absorption at 2000 cm^?1 is dominant only for the lowest p_H and the highest R_D. The absorption at 2150 cm^?1 is dominant in films deposited at high p_H and low R_D. The composition diagram shows that highest total H content is obtained for low R_D and high p_H, and lowest total H content results for high R_D and low p_H     

Measurement of the single-spin asymmetry in the reaction π − d ↑ → π 0 X in the beam-fragmentation region at 40 GeV and p T of up to 2 GeV/c

The single-spin asymmetry A _N in the reaction π ^? + d _↑ → π ⁰ + X in the beam-fragmentation region at the energy of 40 GeV was investigated by using the PROZA setup installed at the U-70 accelerator of the Institute for High Energy Physics (IHEP, Protvino). It was measured to be A _N = (13.6 ± 2.6(stat.) ± 2.0(syst.))% in the intervals 0.7 < x _F < 1.0 and 1.0 < p _T < 1.8 GeV/c. The results agree with the asymmetry of π ⁰ mesons in the charge-exchange reaction π ^? + p _↑ → π ⁰ + n at the same values of the transverse momentum and beam energy. The asymmetry in the reaction K ^? + d _↑ → π ⁰ + X was simultaneously measured and found to be A _N = (11 ± 14)% for p _T > 1.2 GeV/c.     

Absolute coverage and isostemc heat of adsorption of deuterium on Pt(111) studied by nuclear microanalysis

The absolute coverage (θ) of deuterium adsorbed on Pt(111) in the ranges 180< T<440 K and 5 × 10^?6 < P < 5 × 10^?2 Pa D₂ has been determined by nuclear microanalysis using the D(³He, p)⁴He reaction. From these data, the isosteric heat of adsorption (E_a) has been determined to be 67 ± 7 kJ mol^?1 at θ ? 0.3. This heat of adsorption yields values of the pre-exponential for desorption (10^?5 to 10^?2 cm² atom^?1 s^?1) that lie much closer to the normal range for a second order process than those determined from previous isosteric heat measurements. The E_a versus θ relationship indicates that the adsorbed D atoms are mobile and that there is a repulsive interaction of 6–8 kJ mol^?1 at nearest neighbour distances. At 300 K the coverage decreases to ? 0.05 monolayer (? 8 × 10¹³ D atoms cm^?2) as P→ 0, apparently invalidating a recent model of site exchange in the adsorbed layer.     

Criteria determination to choose piezoelectric materials for BAW resonator applications via colored picosecond acoustics

A great number of piezoelectric materials which could be used in the fabrication of BAW resonators were investigated via colored picosecond acoustics technique in order to study the required parameters for designing and fabricating improved devices. These parameters concerns acoustic longitudinal velocity, v_L, elastic stiffness constant, C^D₃₃, intrinsic mechanical loss, tanδ, and electromechanical coupling coefficient, k²_t. We first quantify the effect of the ratio between the wavelength pulse of a femtosecond laser and the period of Brillouin oscillations, λ_p/T. It is found that C^D₃₃ depends linearly on λ_p/T. Then, we deduced novel relations for stiffness constant and mechanical coupling coefficient. Moreover, the determination of different parameters (density, refractive index and v_L) of piezoelectric film is achieved, with good agreement with literature. The optimized conditions for the parameter choice of BAW resonators are found to be: 300?GPa?<?C^D₃₃?<?500?GPa and 1.7?GPa?<?e²₃₃/ε^s₃₃?<?28.5?GPa with λ_p/T?>?37 10³?m/s where e₃₃ and ε^s₃₃ are the piezoelectric constant and the materials permittivity in the direction 3, respectively.     

Carbon monoxide and carbon dioxide interaction with tantalum

The adsorption of carbon monoxide and carbon dioxide on tantalum and the dissolution of these gases in the adsorbent at T ? 300 K have been studied. The flash-filament method (FFM) in a monopole mass-spectrometer and a field emission microscopy was used in the same apparatus. Carbon monoxide and carbon dioxide dissociate on the tantalum surface, carbon monoxide being desorbed in both cases during the flash. The desorption curves of CO reveal three different binding states: two of them (α and $\text{}\text{?}$gb₁) for the adsorbed particles whereas the high temperature desorption state relates to the adsorbate dissolved in the metal, For the $\text{}\text{?}$gb₁ state of CO the activation energy, the pre-exponential factor and the kinetic order in the kinetic equation of desorption have been estimated. They turned out to be E = 110 kcal/mol, C = 3 × 10¹²sec^?1, and ν = 1. The activation energy of diffusion for CO in tantalum and the energy of outgassing for the metal were found to be 9.4 and 49 kcal/mole, respectively.     

Deuterium–tritium catalytic reaction in fast ignition: Optimum parameters approach

One of the main concerns about the current working on nuclear power reactors is the potential hazard of their radioactive waste. There is hope that this issue will be reduced in next generation nuclear fusion power reactors. Reactors will release nuclear energy through microexplosions that occur in a mixture of hydrogen isotopes of deuterium and tritium. However, there exist radiological hazards due to the accumulation of tritium in the blanket layer. A catalytic fusion reaction of DT _x mixture may stand between DD and an equimolar DT approach in which the fusion process continues with a small amount of tritium seed. In this paper, we investigate the possibility of DT_x reaction in the fast ignition (FI) scheme. The kinematic study of the main mechanism of the energy gain–loss term, which may disturb the ignition and burn process, was performed in FI and the optimum values of precompressed fuel and proton beam driver were derived. The recommended values of fuel parameters are: areal density ρ R ≥ 5g · cm^?2 and initial tritium fraction x ≤ 0.025. For the proton beam, the corresponding optimum interval values are proton average energy 3 ≤ E _p ≤ 10 MeV, pulse duration 5 ≤ t _p ≤ 15 ps and power 5 ≤ W _p ≤ 12 × 10²² (keV·cm³ · ps^?1). It was proved that under the above conditions, a fast ignition DT _x reaction stays in the catalytic regime.     

Search for macroscopic CP violating forces using a neutron EDM spectrometer

The search for CP violating forces between nucleons in the so-called axion window of force ranges λ between 2 × 10^?5 m and 0.02 m is interesting because only little experimental information is available there. Axionlike particles would induce a pseudo-magnetic field for neutrons close to bulk matter. A laboratory search investigates neutron spin precession close to a heavy mirror using ultracold neutrons in a magnetic resonance spectrometer. From the absence of a shift of the magnetic resonance we established new constraints on the coupling strength of axion-like particles in terms of the product g _s g _p of scalar and pseudo-scalar dimensionless constants, as a function of the force range λ, g _s g _p λ² ≤ 2 × 10^?21 [cm²] (C.L.95%) for 10^?4 cm < λ < 1 cm. For 0.1 cm < λ < 1 cm previous limits are improved by 4 to 5 orders of magnitude.     

Chemical reactivity of solid [PtnC60] towards carbon monoxide

Evidence of chemical reactivity of solid platinum-fullerene [Pt_nC₆₀] compounds towards carbon monoxide is presented. The interaction was systematically studied by means of infrared spectroscopy, X-ray powder diffraction and thermogravimetric analysis. The interaction of carbon monoxide, even under low pressure, is confirmed by the appearance of infrared absorption bands in the CO stretching region at 2064, 2014 and 1991 cm⁻¹ for the carbonylation products. The exceptions were those products with low Pt:C₆₀ ratios, which also displayed bands at 1870 and 1830 cm⁻¹. The data suggest that the CO coordination depends on the specific morphology of the solids, the original Pt:C₆₀ ratio, and the carbon monoxide nominal pressure. Therefore, these results indicate the formation of [(CO)_xPt]_m species supported in a fullerene matrix mixed with [Pt_n−mC₆₀] compounds. As there is a competition between carbon monoxide and fullerene molecules for the electronic density at the platinum centers, the nature of the CO interaction with [Pt_nC₆₀] was found to be destructive, leading to the displacement of the latter. Nevertheless, the platinum-carbonyl species formed presents relatively high stability, as shown by desorption tests.     

The adsorption of carbon monoxide,ammonia, and wet air on gold

The work functions of gold films which were deposited on glass substrates in UHV were 0.5–0.9 eV higher than the work function of a well-baked gold sheet. The contact potential difference between a film and the sheet was reduced by wet air admitted to both surfaces at room temperature. Carbon monoxide admitted to both surfaces reduced the contact potential difference reversibly at pressures from 1 × 10^? to 2 × 10^?2 torr, and the evidence suggested that most of the change was owing to a reduction in the work function of the gold film. This reduction varied linearly with the gas pressure; it also depended on the temperature; decreasing from 2.8 eV torr^? at 17°C to < 0.25 eV torr^? at 72°C. The results for CO fitted a simple classical model, from which the mean adsorption energy for CO/Au was estimated as 11.3 ± 0.3 kcal mole^?. Ammonia at 17°C caused a similar reduction of work function at much lower pressures, ～ 10^?4 torr, and its adsorption energy was estimated as 13.6 kcal mole^?1. The films and the sheet gold were polycrystalline with their crystal orientations random in two directions, but their {100} planes were preferentially parallel to the exposed surface. The films were rougher than the sheet. The positive surface potentials for CO/Au and NH₃/Au seem to be due either to weakly bound electropositive states, or to their molecules penetrating into the sub-surface region of the film.     

Spectroscopic Studies on the Thermodynamics of L-Cysteine Capped CdSe/CdS Quantum Dots��BSA Interactions

CdSe/CdS quantum dots (QDs) capped with L-cysteine can provide an effective platform for the interactions with bovine serum albumin (BSA). In this study, absorption and fluorescence (FL) spectroscopy were used to study the binding reactions of QDs with BSA, respectively. The binding constant (??10⁴ M^-1) from FL quenching method matches well with that determined from the absorption spectral changes. The modified Stern-Volmer quenching constant (5.23?×?10⁴, 5.22?×?10⁴, and 4.90?×?10⁴ M^-1) and the binding sites (??1) at different temperatures (304 K, 309 K, and 314 K) and corresponding thermodynamic parameters were calculated (?G?<?0, ?H?<?0, and ?S?<?0). The results show the quenching constant is inversely correlated with temperature. It indicates the quenching mechanism is the static quenching in nature rather than dynamic quenching. The negative values of free energy (?G?<?0) suggest that the binding process is spontaneous, ?H?<?0 and ?S?<?0 suggest that the binding of QDs to BSA is enthalpy-driven. The enthalpy and entropy changes for the formation of ground state complex depend on the capping agent of QDs and the protein types. Furthermore, the reaction forces were discussed between QDs and BSA, and the results show hydrogen bonds and van der Waals interactions play a major role in the binding reaction.     

The reaction of carbon monoxide with palladium supported on cerium oxide thin films

In this study we probe the reaction of carbon monoxide with Pd nanoparticles supported on cerium oxide thin films. With the use of soft X-ray photoelectron spectroscopy (sXPS), and temperature programmed desorption (TPD) the surface intermediates and pathways leading to reaction products of CO on Pd supported on ceria were investigated. When Pd is supported on the stoichiometric CeO₂ surface (Ce⁺⁴) only the molecular adsorption of CO on Pd is visible (286.4 eV). All of the CO desorbs below 520 K, however a small amount of O exchange between the CO and the ceria was indicated through the acquisition of labeled ¹⁸O from the substrate in the desorbed CO. The Pd nanoparticles are activated on partially reduced CeO_x to promote the dissociation of <10% of the CO as indicated by a C-Pd species (284.4 eV) in sXPS. The C recombines with O from the ceria and desorbs between 600 and 700 K. The majority of the CO does not dissociate, however, and the degree of dissociation does not increase with the degree of ceria reduction. This result is in contrast with Rh nanoparticles supported on ceria where the degree of dissociation increased with the degree of ceria reduction and nearly total dissociation was obtained when the ceria was highly reduced.     

Monte Carlo simulation of carbon monoxide,carbon dioxide and methane adsorption on activated carbon

In this study, the adsorption capacity of pure and activated carbon with regard to carbon monoxide (CO), carbon dioxide (CO₂) and methane (CH₄) gases at 298?K and pressure from 0.01 up to 2.0?MPa has been investigated computationally. Computational work refers to Monte Carlo (MC) simulation of each adsorbed gas on a graphite model with varying density of activation sites. The Grand Canonical Monte Carlo (GCMC) simulation technique was employed to obtain the uptake of each adsorbed gas by considering a graphite model of parallel sheets activated by carboxyl and hydroxyl groups, as observed experimentally. The simulation adsorption data for these gases within the examined carbon pore material are presented and discussed in terms of the adsorbate fluid molecular characteristics and corresponding interactions between adsorbate species and adsorbent material. We found that the simulated adsorption uptake of the examined graphite model under these conditions with regard to the aforementioned fluids increases in the order CO?<?CH₄?<?CO₂.     

Coherent excitation of the soft polariton mode in BaTiO3

Coherent excitation of the soft polariton mode in BaTiO₃ is obtained by a two-beam method. The relative power variation on one beam is measured as a function of the polariton frequency (0 < ω_p < 30 cm^?1) for a scattering angle of 0.14° (|k_p| ? 4500 cm^?1) and shows a maximum at ω_p ? 13 cm^?1. By fitting experimental results to the theoretical power variations, the atomic displacive coefficient is determined.     

Conductivity enhancement in fluorite-structured Ba1−xLaxF2+x solid solutions

The ionic conductivity of single crystals of the fluorite-structured solid solutions Ba_1?xLa_xF_2+x(10^?3 <×<0.45) has been studied as a function of temperature and composition in the range 300–900 K. Three regions can be discerned in the concentration dependence of the ionic conductivity: a dilute concentration region (x<10^?3), where classic relations between solute content and ionic conductivity hold; an intermediate concentration region (10^?3<x?5×10^?2), where large changes occur in the conductivity activation enthalpy and the magnitude of the conductivity; and a concentrated solid solution region (x?5×10^?2) characterized by enhanced ionic motion. In the dilute region the migration enthalpy for interstitial fluoride ions is determined to be 0.714 eV, while a value of 0.39 eV is found for the (La_BaF_i)^X association enthalpy. The defect chemistry in the intermediate concentration region is shown to be controlled by a superlinear increase of the concentration of mobile defects, while in the concentrated solid solution region a composition-independent amount of ≈1 mole% of interstitial fluoride ions with enhanced mobility, carry the current.