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 reduction of NO with D2 over the (110) surface of iridium

The heterogeneously catalyzed reaction between NO and D₂ to produce N₂, ND₃ and D₂O over Ir(110) was investigated under ultra-high vacuum conditions for partial pressures of the reactants between 5 × 10^?8 and 1 × 10^?6Torr, total pressures between 10^?7 and 10^?6 Torr, and surface temperatures between 300 and 1000 K. Mass spectrometry, LEED, UPS, XPS and AES measurements were used to study this reacting system. In addition, the competitive coadsorption of NO and deuterium was investigated via thermal desorption mass spectrometry and contact potential difference measurements to gain further insight into the observed steady state rates of reaction. Depending on the ratio of partial pressures ($\text{R }\text{P}{}_{\mathrm{<mtext>D</mtext>}}{}_2\text{P}{}_{\mathrm{<mtext>NO</mtext>}}$), the rate of reduction of NO to N₂ shows a pronounced enhancement when the surface is heated above a critical temperature. As the surface is cooled, the rate maintains a high value independent of temperature until a lower critical temperature is reached, where the rate drops precipitously. This hysteresis is due to a change in the structure and composition of the surface. For sufficiently large values of R and for an “activated” surface, N₂ and ND₃ are produced competitively between 470 and 630 K. Empirical models of the different regimes of the steady state reaction are presented with interpretations of these models.     

42P fine-structure mixing in potassium by collisions with N2, H2, CO,and CH4

Cross sections for $\text{4}{}^2\text{P}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{?4}{}^2\text{P}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ fine-structure mixing in potassium, induced in collisions with N₂, H₂, CO, and CH₄, were determined by methods of atomic fluorescence spectroscopy. The experiments were carried out at a temperature of 342 K, a K density of 6 × 10⁹ cm^?3 and mtorr buffer gas pressures, and yielded the following cross sections $\text{Q}{}_1\text{(4}{}^2\text{P}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{→4}{}^2\text{P}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$) and $\text{Q}{}_2\text{(4}{}^2\text{P}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{→4}{}^2\text{P}{}_{\mathrm{<mtext>3</mtext><mtext>2</mtext>}}$ (in units of 10^?6 cm²): for N₂, 79 and 54; for H₂, 57 and 39; for CO, 98 and 64; for CH₄, 86 and 58. The values for N₂ and H₂ supersede those reported previously by McGillis and Krause (1968).     

Cross sections for the quenching of the excited strontium state (51P1) measured in CO/N2O flames

The quantum efficiency of fluorescence, Y, of the 4607.33 Å Sr line $\text{(}{}^1\text{P}{}_1\text{?}{}^1\text{S}{}_0\text{transition}\text{)}$ was measured in four pre-mixed, laminar, shielded CO/N₂O flames of about 2700 K, with different quantitative compositions at 1 atm. From these data, the specific quenching cross sections for O₂, CO₂, CO and N₂ were found to be (152±20 Ų), (30±5 Ų), (49±8 Ų) and (16±3 Ų), respectively.     

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.     

Effect of surface states on the amphoteric behavior of Sn in vapor epitaxial GaAs

The amphoteric behavior of Sn, a commonly-used dopant in AsCl₃GaH₂ vapor epitaxy, is examined for Sn concentration from 5 × 10¹⁴ to 5 × 10¹⁷cm^?3. The compensation ratio $\text{(}\text{N}{}_{\mathrm{A}}\text{N}{}_{\mathrm{D}}\text{)}$ remains constant at 0.23 for low concentrations and begins to increase in the 10¹⁶cm^?3 range. This behavior can be explained quantitatively with non-equilibrium impurity incorporation model which takes into account 3 × 10¹¹ cm^?2 surface states.     

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.     

Temperature and pressure dependence of the elastic property of GeS2 glass

The sound velocities in GeS₂ glass have been measured by means of ultrasonic interferometry as a function of temperature or pressure up to 1.8 kbar. The bulk modulus K_s = 117.6 kbar and shear modulus G = 60.60 kbar were obtained for GeS₂ glass at 15°C and 1 atm. The temperature derivatives of both sound velocities and elastic moduli are negative :

$\text{(}\text{?ν}{}_1\text{?T}\text{)}$

_p =

$\text{?1.54 × 10}{}^{\mathrm{?4}}\text{km}\text{sec}$

°C,

$\text{(}\text{?ν}{}_1\text{?T}\text{)}$

_p =

$\text{?1.27× 10}{}^{\mathrm{?4}}\text{km}\text{sec}$

°C and

$\text{(}\text{?K}{}_{\mathrm{s}}\text{?T}\text{)}$

_p =

$\text{?1.27 × 10}{}^{\mathrm{?2}}\text{kbar}\text{°C}$

,

$\text{(}\text{?G}\text{?T}\text{)}$

_p = ?1.23 × 10^?2 kbar/°C,

$\text{(}\text{?Y}\text{?T}\text{)}$

_p = ?2.93 × 10^?2 their pressure derivatives are positive:

$\text{(}\text{?ν}{}_1\text{?P}\text{)}$

_T = 4.43× 10^?2km/kbar,

$\text{(}\text{?ν}{}_1\text{?P}\text{)}$

_T =

$\text{0.633 × 10}{}^{\mathrm{?2}}\text{km}\text{kbar}$

and (?K_s?P0)_T=6.81,

$\text{(}\text{?G}\text{?P)}{}_{\mathrm{T}}$

= 1.03, (?Y?T_T= 3.57. The Grüneisen parameter, γ_th= 0.298, and the second Grüneisen parameter, δ_s = 3.27, have also been calculated from these data. The elastic behavior of GeS₂ glass has proved to be normal despite the structural similarity among the tetrahedrally coordinated SiO₂, GeO₂ and GeS₂ glasses.     

Chemical diffusion in nonstoichiometric chromium sulfide,Cr2+yS3

Using the re-equilibration kinetic method the chemical diffusion coefficient in nonstoichiometric chromium sesquisulfide, Cr_2+yS₃, has been determined as a function of temperature (1073–1373 K) and sulphur vapour pressure (10?10⁴ Pa). It has been found that this coefficient is independent of sulphur pressure and can be described by the following empirical equation: $\text{D}\text{?}\text{Cr}{}_{\mathrm{2+y}}\text{S}{}_3\text{=50.86}\text{exp(-39070 cal/mole/}\text{RT)}\text{(cm}{}^2\text{s}{}^{\mathrm{?1)}}$. It has been shown that the mobility of the point defects inCr_2+yS₃ is independent of their concentration and that the self-diffusion coefficient of chromium in this sulfide has the following function of temperature and sulphur pressure: . (cm²s^?1).     

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 $\text{kcal}\text{mole}$.     

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.     

Opto-galvanic spectroscopy of broadening and shift of two-photon thallium transitions by N2 and He

This paper reports the first measurements of pressure broadening and shift of thallium 6 ${}^2\text{P}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}\text{?8}{}^2\text{P}{}_{\mathrm{<mtext>1</mtext><mtext>2</mtext>}}$$\text{3}\text{2}$ transitions by N₂ and He perturbers. Ion-detection with box-car integration was used for data collection. The number of the perturbating gases ranged from $\text{(1.1?4.7)×10}{}^{19}\text{cm}{}^3$. The red shift to N₂ and the shift due to He are found to vary linearly with pressure. The value of the effective cross section for the impact broadening was determined and van der Waals constants obtained.     

Oscillator strengths in the Cameron system of carbon monoxide

Relative oscillator strengths in the Cameron system of CO(a³Π ← X¹Σ) have been observed in absorption for six bands (υ′ = 0–5, υ″ = 0) with the result, normalized to the absolute (0, 0) band measurement of Hasson and Nicholls, $\text{?}{}_{00}\text{= (1.62±0.07) × 10}{}^{\mathrm{?7}}$, $\text{?}{}_{10}\text{= (1.96±0.09) × 10}{}^{\mathrm{?7}}$, $\text{?}{}_{20}\text{= (1.41±0.04) × 10}{}^{\mathrm{?7}}$, $\text{?}{}_{\mathrm{3\; 0}}\text{= (0.72±0.03) × 10}{}^{\mathrm{?7}}$, $\text{?}{}_{40}\text{= (0.31±0.02) × 10}{}^{\mathrm{?7}}$, $\text{?}{}_{50}\text{= (0.14±0.01) × 10}{}^{\mathrm{?7}}$. The density of CO was modulated with a motor-driven vacuum valve and synchronous fluctuations (?1 per cent) in the transmitted intensity detected with a lock-in amplifier. Peak pressure in the 21 cm absorption cell was approximately 10 torr. A curve of growth analysis was used to correct saturation effects by less than 3 per cent.     

The reactivity and auger chemical shift of oxygen adsorbed on platinum

The reaction of carbon monoxide with oxygen chemisorbcd on polycrystalline platinum has been studied using Auger spectroscopy. Two types of chemisorbed oxygen are distinguished on the basis of Auger electron chemical shifts and reactivity towards carbon monoxide. When the substrate is below 800 K, a single very reactive type of chemisorbed oxygen is formed. Above 800 K a new species begins to form which is characterized by an Auger chemical shift of about 6 eV and by low reactivity. The decay of the oxygen Auger signal using several fixed pressures of carbon monoxide was measured. The reaction is first order in carbon monoxide pressure but no clear decision can be made about the order with respect to oxygen coverage. With the reaction $\text{CO +}\text{1}\text{20}{}_2\text{→ CO}{}_2$ operating at steady-state, the oxygen coverage was measured as a function of CO pressure. In the region 363–600 K, the steady state oxygen coverage began to decline measurably when reached 0.1. When p_CO>p_O2the oxygen coverage became immeasurably small. A simple model is used to relate these phenomena to observed carbon dioxide production rates.     

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.     

Critical behaviour of a uniaxial ferromagnet,ErCl3·6H2O with predominant dipolar interactions

The parallel magnetic susceptibility χ of a uniaxial ferromagnet ErCl₃·6H₂O has been measured between 0.3 and 4.2K and specially near T_c = 0.353 K. The predominant contribution to the Curie-Weiss temperature is due to the dipolar interactions. χ is proportional to ?^?γ with $\text{? =}\text{T}\text{T}{}_{\mathrm{c}}\text{?1}$ in the range 10^?3 < ? < 5 × 10^?2. The γ value, γ = 1.01 ±0.03 is consistent with the theoretical prediction for a uniaxial dipolar ferromagnet.     

Pressure dependence of superconductivity in the pseudo-one-dimensional compound Tl2Mo6Se6

Measurements of the temperature and pressure dependences of the resistivity of the pseudo-one-dimensional ternary compound Tl₂Mo₆Se₆ are presented. We find that the conductivity parallel to the highly conducting c-axis is enhanced by pressure and the superconducting transition temperature T_c is suppressed by pressure at a rate $\text{?T}{}_{\mathrm{c}}\text{?P}\text{=?7.6×10}{}^{\mathrm{?5}}$ kbar^?1. These results are discussed in relation to the current models of transport in one-dimensional conductors.     

Defect dominated conductivity in Zn3P2

The electrical resistivity and Hall coefficient of Zn₃P₂ have been measured for single crystal and thin polycrystalline film samples which were annealed over a range of equilibrium vapor compositions and temperatures. The room temperature electrical resistivity of single crystal samples annealed at 573 K varied from approximately 10⁵Ω-cm for single crystals heated in equilibrium with zinc to 10 Ω-cm for those annealed in a phosphorus rich ambient. Hall measurements indicate that a variation in carrier concentration is responsible for these changes. The experimentally observed dependence of carrier concentration [h° ], (cm^?3) on phosphorus pressure is given by [h°] = 1.32 · 10¹⁶ [p(P₄)]^0.13 for samples annealed at 573 K. The experimentally determined pressure dependence is in good agreement with a model based on phosphorus interstitials acting as acceptors. The pressure and temperature dependence of the carrier concentration yield the equilibrium constant K_I for the formation of interstitial phosphorus defects according to the reaction

$\text{1}\text{4}\text{P}{}_4\text{→ P′}{}_{\mathrm{i}}\text{+ h°}$

where

$\text{K}{}_{\mathrm{I}}\text{= 10}{}^{\mathrm{42.4\; \pm \; 2}}\text{cm}{}^{\mathrm{?6}}\text{torr}{}^{0.25}\text{[p(P}{}_4\text{)]}{}^{\mathrm{?0.25}}\text{exp(?1.18}\text{ev}\text{kT}\text{)}$

. The accommodation of phosphorus interstitials is discussed in light of the crystal structure of Zn₃P₂.     

Stark mixing spectroscopy in cesium

We present a new technique for selectively populating excited states which are inaccessible by dipole excitation from the ground state. The method uses a static electric field to introduce a component of a dipole-allowed state into the state of interest. We have applied the method to cesium to measure lifetimes and a Stark mixing coefficient. The results are $\text{τ(6}{}^2\text{D}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)=64(2) ns}$, $\text{τ(7}{}^2\text{D}{}_{\mathrm{<mtext>5</mtext><mtext>2</mtext>}}\text{)=92.5(15) ns}$, and <6²D_{$\text{5}\text{2}$}|;ez |7²P_{$\text{3}\text{2}$}>/(E_7P?E_6D)=0.7(3)×10^?3 where is in kV/cm. 141     

SIMS,AES, work function and flash desorption measurements of the CO adsorption on NiCu alloy surfaces

The chemisorption of CO on Cu, Ni and CuNi alloy surfaces was examined by SIMS, work function measurements and desorption spectroscopy. Using a dynamic SIMS technique the M⁺, M⁺₂, MCO⁺ and M₂CO⁺ emission at different temperatures (100–400 K) was measured as a function of CO exposure. In agreement with the work function and desorption experiments an increase of M⁺ and MCO⁺ emission due to the CO adsorption on Cu was found only at low temperatures (100–190 K). On the Ni surface an increase of Ni⁺, NiCO⁺ and Ni₂CO⁺ was measured up to 400 K. The adsorption of CO on CuNi alloy surfaces — as derived from the work function measurements — can be described by the assumption of two different states of adsorbed carbon monoxide. They can be characterized by different binding energies and from sign and magnitude different work function changes. These states were interpreted as adsorption at Ni or Cu sites of the alloy surfaces, respectively. To a certain extent the SIMS results from the alloy surfaces are incompatible with the work function measurements and desorption spectroscopy and the SIMS studies on the pure metals. A Cu⁺ emission with comparable intensity to the Ni⁺ emission was found for alloys with bulk concentrations of 60 and 40 at% Cu at 300 K. The ratio $\text{Ni}{}^{\mathrm{+}}\text{Cu}{}^{\mathrm{+}}$ was nearly independent of CO pressure and temperature. The measured ratios of $\text{Cu}{}^{\mathrm{+}}{}_2\text{(}\text{Cu}{}^{\mathrm{+}}\text{+}\text{Ni}{}^{\mathrm{+}}\text{)}$, $\text{Ni}{}^{\mathrm{+}}{}_2\text{(}\text{Cu}{}^{\mathrm{+}}\text{+}\text{Ni}{}^{\mathrm{+}}\text{)}$ and $\text{CuNi}{}^{\mathrm{+}}\text{(}\text{Cu}{}^{\mathrm{+}}\text{+}\text{Ni}{}^{\mathrm{+}}\text{)}$ with values about 10^?2 can be explained the basis of a statistical arrangement of Cu and Ni atoms in the alloy surface. The intensities of the MCO⁺ emissions are 10² times smaller than the corresponding values of the pure metals. No emission of M₂CO⁺ was found on CuNi during CO adsorption.