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.     

Average polarization of 12B in 12C(μ, ν)12B(g.s.) reaction: Helicity of the π-decay muon and nature of the weak coupling

The helicity, h^?, of μ^? in π-decay has been determined as positive (h^??+0.90) from the average polarization, P_av≡〈J_B·s_μ〉, of ¹²B produced in the $\text{μ}{}^{\mathrm{?}}\text{+}{}^{12}\text{C}\text{→ν}{}_{\mathrm{\mu }}\text{+}{}^{12}\text{B}$ reaction. We obtain also dynamical information on μ-capture: (i) the weak magnetism form factor, μ=4.5±1.1, and (ii) the sum of the induced pseudoscalar (g_p) and the 2nd class induced tensor (g_T) couplings versus g_A, ($\text{g}{}_{\mathrm{<mtext>P</mtext>}}\text{+g}{}_{\mathrm{<mtext>T</mtext>}}\text{)}\text{g}{}_{\mathrm{<mtext>A</mtext>}}\text{=7.1±2.7}$. The latter result, adopting the “canonical” value of $\text{g}{}_{\mathrm{<mtext>P</mtext>}}\text{g}{}_{\mathrm{<mtext>A</mtext>}}$, leads to $\text{g}{}_{\mathrm{<mtext>T</mtext>}}\text{g}{}_{\mathrm{<mtext>A</mtext>}}\text{=+1±2.7}$ which is compatible with zero and in strong contradiction with the value ?—6 recently advocated by Kubodera, Delorme and Rho.     

Magnetic circular dichroism of transition metal ions in solids—II K2NaGaF6: Cr3+

The absorption and MCD spectra of the ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{2g}}$, ${}^4\text{A}{}_{\mathrm{2g}}$, ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{1g}}{}^{\mathrm{a}}$ and ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{1g}}{}^{\mathrm{b}}$ spin-allowed transitions of Cr³⁺ in K₂NaGaF₆ are reported. It is shown that transitions to the ${}^4\text{T}{}_{\mathrm{1g}}$. states are induced by T_1u vibratio the other spin-allowed transition, ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^4\text{T}{}_{\mathrm{2g}}$, there are three competing intensity mechanisms: electric dipole induced by T_1u vibrations, electric dipole induced by T_2u vibrations and magnetic dipole, and an estimate is made of the relative importance of these. The magnetic dipole ${}^4\text{A}{}_{\mathrm{2g}}\text{→}{}^2\text{E}{}_{\mathrm{g}}$ zero-phonon line is observed to be accompanied by a vibrational sideband for which the coupling is predominantly with T_2u vibrations. Other weak transitions are observed in MCD spectra and their origin briefly discussed.     

Specific heat and resistivity of GdSb and HoSb above the néel temperature

The specific heat C_P is found to vary as $\text{dR}\text{dT}$ in the critical region above T_N for the antiferromagnets GdSb and HoSb. This correspondence holds despite a dramatic difference between the two systems in the strength of the divergence C_P = A?^?α, $\text{? =}\text{(T ? T}{}_{\mathrm{N}}\text{)}\text{T}{}_{\mathrm{N}}$, where for HoSb we find α = 0.83 ± 0.10 while for GdSb α = 0.20 ± 0.10.     

Study by brillouin scattering of the C33 constant of thiourea submitted to an electric field

The C₃₃ constant is discontinuous for the lock-in transition at T₁ = 169 K. The variation ΔT₁ of the temperature of transition is a linear function of the applied electric field E and we find $\text{d}\text{T}{}_1\text{d}\text{E}\text{=0.82 deg.cm kV}{}^{\mathrm{?1}}$.Above a mean field E = 10 kV cm^?1 the transition observed for a first heating spreads on several degrees because damages appear in the incommensurate phase and the electric field becomes inhomogeneous.The results obtained at low fields are in very good accordance with the value of $\text{d}\text{T}{}_1\text{d}\text{E}$ calculated from the Clapeyron formula.Taking into account of the incommensurability of the phase above T₁, it can be shown that

$\text{dT}{}_1\text{dE}\text{=}\text{C}\text{2πP}{}_{\mathrm{o}}\text{3}\text{3}\text{?}\text{2}$

The knowledge of the spontaneous polarisation P₀ gives for the Curie constant C = 2.1 × 10³ K in qualitative agreement with the value deduced from measurements of the dielectric constant in the ferroelectric direction.     

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.     

Temperature derivatives at constant volume of the elastic constants of the alkali halides

Values of dC/dT)_V have been computed from experimental dC/dT)_P and dC/dP)_T for the three elastic constants (expressed as $\text{B}{}_{\mathrm{T}}\text{, C}{}_{44}\text{and}\text{(C}{}_{11}\text{?C}{}_{12}\text{)}\text{2)}$ of each of the 16 Li, Na, K, and Rb halides. The dC/dT)_V measure the explicit dependence of C on T, the effect of thermal expansion having been removed. The dC/dT)_V are all small (compared with dC/dT)_P), are all negative, and vary quite systematically and smoothly with anion, with cation and with the three elastic constants. Negative dB_T/dT)_V is accounted for both thermodynamically and by available lattice dynamical calculations. dC/dT)_V for shear constant is expressed in terms of two vibrational mode parameters, whose values can then be estimated from the observed value, and the trend of dC/dT)_V with Debye temperature.     

Electron-vibration splitting of the vibronic levels of the 1T2g state of MgO:Ni2+

Magnetic circular dichroism (MCD) and magnetic linear dichroism (MLD) measurements of the ${}^3\text{A}{}_{\mathrm{2g}}\text{→}{}^1\text{T}{}_{\mathrm{2g}}$ absorption band in MgO:Ni²⁺ are reported. It is shown that for the lowest energy vibrational peak there is considerable evidence of splitting of the T_2g × T_1u vibronic levels by the electron-vibration interaction.     

A thermodynamic study of nonstoichiometric cerium dioxide

Thermogravimetric measurements were performed on nonstoichiometric CeO_2?x in the temperature range 750–1500°C and from oxygen pressures of 10^?2 to 10^?26 atm. From this data the deviation from stoichiometry x = x(T, P_o2) was determined. The thermodynamic quantities Δ$\text{H}$_o2 and Δ$\text{S}$_o2 were calculated in the region 0.001? x ? 0.3 and found to be independent of temperature.In the composition region 0.001< x < 0.006, the variation of Δ$\text{S}$_o2 with x is consistent with a defect model involving randomly distributed doubly ionized oxygen vacancies. The experimental dependence of x and σ (electrical conductivity) is shown to be consistent with this model as Δ$\text{H}$_o2 (≈ -10 eV) exhibits a slight dependence on x. It is postulated that the variation in Δ$\text{H}$_o2 may result from lattice parameter increases with x, while the defects remain essentially randomly distributed.In the composition region 0.006 < x < 0.1, x ∝ with 1 < n < 5, and in the region 0.1 < x < 0.3, x ∝ with n increasing rapidly with x to n? 30. This behavior is believed to result from increasing defect interaction with increasing departures from stoichiometry. It is interesting to note that the ordered phase observed by Bevan and Kordis between CeO_1·72 and CeO_1·70 was not observed in this study at temperatures between 1300° and 1500°C.     

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 $\text{kcal}\text{mole}$.     

A model for phase transitions in Tetrathiafulvalene-Tetracyanoquinodimethane (TTF-TCNQ)

The observed phase transitions in Tetrathiafulvalene-Tetracyanoquinodimethane (TTF-TCNQ) are discussed using a simple model for the interchain coupling of charge density waves. Estimates based on Coulomb energies show that for 38 K < T < 49 K the components $\text{q}{}_{\mathrm{x}}\text{=}\text{π}\text{a}\text{+ q′}{}_{\mathrm{x}}$ and q_z of the wave vector associated with the charge density wave satisfy $\text{q}{}_{\mathrm{z}}\text{c}\text{q′}{}_{\mathrm{x}}\text{a?0.1}$, with $\text{q′}{}_{\mathrm{x}}\text{a～(T}{}_2\text{? T)}{}^{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$ and T₂ = 49 K. A possible mechanism for the first order transition at 38 K is proposed. The results are compared with neutron and X-ray scattering and with isotope shifts of the transition temperatures.     

Observation of high transverse momentum electrons at the CERN ISR

A search for high transverse momentum electrons directly produced in proton-proton collisions has been performed at the CERN ISR. The apparatus included a magnetic spectrometer with wire spark chambers, a lead-glass counter array, and a threshold gas ?erenkov counter. At a centre-of-mass energy √s = 52.7 GeV, a signal has been observed in the range $\text{1.6<p}{}_{\mathrm{T}}{}^1\text{<4.7}\text{GeV}\text{/c}$. The signal occurs at a level of approximately 10^?4 of the inclusive pion cross-section.     

Intensities and pressure-broadened widths of CO2 R-branch lines at 15 μm from tunable laser measurements

Intensities and half-widths of individual lines, over the temperature range 200–325°K in the 15 μm bands of ¹²C¹⁶O₂, have been determined with a tunable diode laser spectrometer. Measurements were made on pure CO₂ and on dilute CO₂-in-N₂ mixtures on the R-branches of the 01¹0-00⁰0 and 02²0-01¹0 transitions. Intensities are approximately equal to those listed in the AFGL compilation. The pressure-broadened half-widths follow the general relationship $\text{b}{}_{\mathrm{L}}{}^0\text{(T) = b}{}_{\mathrm{L}}{}^0\text{(T}{}_0\text{) [}\text{T}{}_0\text{T}\text{]}{}^{\mathrm{n}}$ where n varies considerably from line to line but is always greater than $\text{1}\text{2}$.     

Light scattering study of dispersion and attenuation of hypersound in adamantane

The Brillouin scattering techniques have been used to measure the velocity dispersion of hypersonic acoustic waves in the “high temperature” disordered cubic phase of adamantane. Shear waves, characteristic of the C₄₄ elastic constant, show no significant dispersion. Longitudinal waves propagating in the (001) plane show strong velocity dispersion. The measures have been performed at the same temperature T = 295.7 K. Using a classical single relaxation time model for the dispersion as a function of frequency at temperature T, the L-mode data have been correctly fitted.The importance of the dispersion $\text{(C}{}_{\mathrm{\infty }}\text{? C}{}_{\mathrm{o}}\text{)}\text{C}{}_0$ for the elastic constants is 20% for C₁₁, 51% for C₁₂ #1% for C₄₄ and ?2.8% for $\text{(C}{}_{11}\text{? C}{}_{12}\text{)}\text{2}$. The fitted relaxation time is τ ? 9 × 10^?11 sec.     

A Mössbauer study of amorphous Fe40Ni40B20

Amorphous Fe₄₀Ni₄₀B₂₀ (VITROVAC 0040) alloy has been investigated using ⁵⁷Fe Mössbauer Spectroscopy. The Curie temperature T_c is found to be well defined and is 695 ± 1 K. The quadrupole splitting just above T_c is 0.64 mm sec^?1. The crystallization temperature is 698 ± 2 K, close to but definitely above T_c. The average hyperfine field H_eff(T) of the glassy state shows a temperature dependence of $\text{H}{}_{\mathrm{<mtext>eff</mtext>}}\text{(0)[1 ? B}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{(T/T}{}_{\mathrm{c}}\text{)}{}^{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}\text{? C}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{(T/T}{}_{\mathrm{c}}\text{)}{}^{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{? …]}$ indicative of the existence of spin wave excitations. The values of $\text{B}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ and $\text{C}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}$ are found to be 0.40 and 0.06, respectively, for T/T_c ? 0.72. At temperatures close to T_c, H_eff(T) varies as (1 ? T/T_c)^β where β is one of the critical exponents and its value is found to be 0.29 ± 0.02.     

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.     

Temperature shift of the CdxHg1−xTe energy gap

The temperature coefficient of the Cd_xHg_1?xTe energy gap dE_g/dT as a sum of lattice dilatation and the phonon-electron interaction terms has been calculated as the function of molar composition x, for 0?x?0.3, in the temperature range 4.2–300 K. A non-linear dependence of $\text{d}\text{E}{}_{\mathrm{g}}\text{d}\text{T}$ vs x and a strong effect of temperature on $\text{d}\text{E}{}_{\mathrm{g}}\text{d}\text{T}$ values have been obtained and a comparison with experimental data is discussed.     

Measurement of the parameter η&#x0304; in the radiative decay of the muon as a test of the v-a structure of the weak interaction

The parameter η&#x0304; of muon decay has been measured in the radiative decay $\text{μ}{}^{\mathrm{+}}\text{→}\text{e}{}^{\mathrm{+}}\text{ν}{}_{\mathrm{<mtext>e</mtext>}}\text{ν}\text{?}{}_{\mathrm{\mu }}\text{γ}$ of unpolarized positive muons. The result $\text{η}\text{?}\text{?0.083}$ (68% confidence) or $\text{η}\text{?}\text{= ?0.03±0.10}$ with ρ fixed at $\text{3}\text{4}$ yields an improvement of the previous value by more than a factor of two. An analysis of all data on muon decay that are presently available slightly improves the constraints on the weak coupling constants to: g_s?0.29g_v, g_p?0.27g_v, g_T?0.23g_v and 0.92g_v?g_A?1.2g_v     

The Grüneisen parameter γ of KBr,RbCl and Bi through high pressure phase transitions

High pressure values for the adiabatic pressure derivative of temperature $\text{(}\text{?T}\text{?P}\text{)}{}_{\mathrm{s}}$ have been obtained by measuring the temperature change caused by a small rapid increase in pressure. Values for KBr and RbCl in phases B1 and B2 and for Bi in phases I, II and III are given for T = 295 K. The Grüneisen parameter γ is given by $\text{γ =}\text{B}{}_{\mathrm{s}}\text{(}\text{?T}\text{?P}\text{)}{}_{\mathrm{s}}\text{T}$ where B_s is the adiabatic bulk modulus. Ultrasonic and statk compressibility data are used to estimate the pressure and phase dependence of B_s. Dramatic increases in both γ and (?T/?P)_s are observed as the pressure increases through a phase transition. Values for the logarithmic derivate $\text{q ≡ (? ln}\text{γ}\text{?}\text{ln V}{}_{\mathrm{T}}$ are given.