The kinetics of D2 desorption from Ni(110) (2 × 1)C in the presence of reactive intermediates

A kinetic study of D₂ formation from HCOOD decomposition on Ni(110) (2 × 1)C was performed using the flash desorption technique. The surface structure and surface composition were monitored by low energy electron diffraction (LEED) and Auger electron spectroscopy (AES). Flash curves were obtained using initial coverage and heating rate variations. D₂ formation exhibited a single second-order rate-determining step. Three different techniques were employed in obtaining the activation energy, two of which did not require the assumption of reaction order. Using an average value of 12.6 kcal/mole for the activation energy the pre-exponential factor was calculated to be 2.7 × 10^?4 cm² molecules^?1 sec^?1. Good agreement was achieved with the theoretically generated second-order flash curves only up to the peak temperature. The discrepancy on the high temperature side was explained using the model proposed by Clavenna and Schmidt utilizing a coverage dependent pre-exponential factor.     

Thermal desorption and surface lifetimes of bromine and iodine adsorbed on an ionizer of LaB6

Thermal desorption of bromine and iodine from an ionizer surface made of cold pressed and sintered LaB₆ powder has been studien in the temperature interval 800–1300°C. A new technique, where the extraction field is accelerating only during short intervals, has been developed to monitor separately the neutral desorption of readily ionized elements. The technique has been combined with the modulated beam and the modulated voltage methods for measurements of residence times and ionization efficiencies. It has also been combined with the temperature programmed desorption method used for determination of the Arrhenius parameters of desorption. The following values were obtained for l_? and l₀, the activation energies of ionic and neutral desorption, and for the corresponding pre-exponential factors C and D (D = 4C) for halogens): Bromine: l_? = 3.8 eV, l₀ = 4.3 eV, C = 2.0 × 10¹³ s^?1; Iodine: l_? = 3.4 eV, l₀ = 3.7 eV, C = 1.1 × 10¹³ s^?1. The ionization efficiencies measured at 1100°C, 0.95 for bromine and 0.7 for iodine, correspond well to what is given by the Saha-Langmuie equation using a work function of 2.7 eV. All measurements were performed with the number of adsorbed particles well below 10¹⁷ atoms/m². For higher coverages l_? was found to increase linearly by about 0.15 eV for an adsorption of 10¹⁸ atoms/m².     

Experimental verification of a zero order desorption model: D2 on Ni(110)

The rate of desorption of deuterium from the low temperature (α) state on Ni(110) follows nearly zero order kinetics. Simultaneous measurements of intensities and profiles of half-order diffraction beams and changes in work function during isothermal desorptionof D₂, have shown that the zero order region is associated with the presence of islands of the (1 × 2) phase which act as reservoirs of deuterium. These results are discussed in terms of a recent model for zero order desorption which requires the presence of 3 deuterium surface phases in equilibrium. The activation energy for desorption of the α-state is 67 ± 6 kJ mol⁻¹.     

Fractional-order desorption of D2 from a Pd(110) surface

The desorption of deuterium from the low temperature (α₂) state on a Pd(110) surface was studied by TDS, LEED and Δφ. Simultaneous measurements of the isothermal desorption of the α₂ state, intensity of a half-order beam of the (1 × 2) phase and work function change show clearly that the desorption of this low temperature state is associated with the phase transition (1 × 2) to (2 × 1). This transition correlation with a work function change of ∼ 70 mV. The desorption follows nearly zero-order kinetics with an activation energy of ∼ 71 kJ mol⁻¹. The desorption kinetics are thus closely analogous to those on Ni(110).     

Interaction of aluminum with iridium surface: Adsorption, desorption, dissolution, and formation of surface compounds

The interaction of aluminum with an iridium (111) surface was studied in ultrahigh vacuum by Auger electron spectroscopy over the broad temperature range 300–2000 K. At room temperature, layer-by-layer growth of an aluminum film was observed, with a monolayer forming in coherent relation to the substrate. Deposition at 1100–1300 K gives rise to the formation of surface aluminide Ir₄Al with an adatom concentration N _Al = (4.20 ± 0.15) × 10¹⁴ cm^?2. It was shown that aluminum escapes out of the surface aluminide by thermal desorption in the 1300–1700-K temperature interval, with the desorption activation energy changing from ～4.5 to ～5.7 eV as the coverage decreases from the value corresponding to the surface aluminide (taken for unity) down to zero.     

The adsorption and desorption of oxygen on the Pt(110) surface; A thermal desorption and LEED/AES study

The interaction of oxygen with a Pt(110) crystal surface has been investigated by thermal desorption mass spectroscopy, LEED and AES. Adsorption at room temperature produces a β-state which desorbs at ~800 K. Complete isotopic mixing occurs in desorption from this state and it populates with a sticking probability which varies as (1 ? θ)², both observations consistent with dissociative adsorption. The desorption is second order at low coverage but becomes first order at high coverage. The saturationcoverage is 3.5 × 10¹⁴ mol cm^?2. The spectra have been computer analysed to determine the fraction desorbing by first (β₁) and second (β₂) order kinetics as a function of total fractional coverage θ using this fraction as the only adjustable parameter. The β₁ desorption commences at θ ～ 0.25 and β₁ and β₂ contribute equally to the desorption at saturation. The kinetic parameters for β₁ desorption were calculated from the variation of peak temperature with heating rate as ν₁ = 1.7 × 10⁹ s^?1 and E^≠₁ = 32 kcal mole^?1 whereas two different methods of analysis gave consistent parameters ν₂ = 6.5 × 10^?7 cm² mol^?1 s^?1 and E^≠₂ = 29 and 30 kcal mole^?1 for β₂ desorption. The kinetics of desorptior are discussed in terms of the statistics for occupation of near neighbour sites. While many fea tures of the results are consistent with this picture, it is concluded that simple models considering either completely mobile or immobile adlayers with either strong or zero adatom repulsion are not completely satisfactory. The thermal desorption surface coverage has been correlated with the AES measurements and it has been possible to use the AES data for PtO as an internal standard for calibration of the AES oxygen coverage determination. At low temperature (170 K) oxygen populates an additional molecular α-state. Adsorption into the α- and β-states is competitive for the same sites and pre-saturation of the β-state at 300 K excludes the α-state. This, together with the AES observation that the adsorption is enhanced and faster at 450 than 325 K suggests a low activation energy for adsorption into the β-state.     

A molecular beam study of the adsorption and desorption of oxygen from a Pt(111) surface

The adsorption and desorption of O₂ on a Pt(111) surface have been studied using molecular beam/surface scattering techniques, in combination with AES and LEED for surface characterization. Dissociative adsorption occurs with an initial sticking probability which decreases from 0.06 at 300 K to 0.025 at 600 K. These results indicate that adsorption occurs through a weakly-held state, which is also supported by a diffuse fraction seen in the angular distribution of scattered O₂ flux. Predominately specular scattering, however, indicates that failure to stick is largely related to failure to accommodate in the molecular adsorption state. Thermal desorption results can be fit by a desorption rate constant with pre-exponential ν_d = 2.4 × 10^?2 cm² s^?1 and activation energy E_D which decreases from 51 to 42 kcal/mole^?1 with increasing coverage. A forward peaking of the angular distribution of desorbing O₂ flux suggests that part of the adsorbed oxygen atoms combine and are ejected from the surface without fully accomodating in the molecular adsorption state. A slight dependance of the dissociative sticking probability upon the angle of beam incidence further supports this contention.     

Small Molecule Sorption and Desorption in and Out of Iota‐Carrageenan Gels

Small molecule sorption and desorption in and out of Iota‐Carrageenan was studied by using steady‐state fluorescence (SSF) technique. Pyranine dissolved in water used as fluorescence probe. Fluorescence emission intensity, I _p from pyranine was monitored for studying sorption and desorption processes at various temperatures. The Fickian model was applied to produce sorption, D_s, early desorption, D_ed, and desorption, D_d, coefficients. Corresponding activation energies were obtained and found to be 20.5 kJ mol^?1, 7.0 kJ mol^?1 and 34.9 kJ mol^?1, respectively. The observed D_ed value is an order of magnitude smaller than the D_s and D_d coefficients. On the other hand, sorption processes were shown to be twice as fast as desorption processes.     

Chemisorption of H2 on W(100): Absolute sticking probability,coverage, and electron stimulated desorption

Measurements of both the absolute sticking probability near normal incidence and the coverage of H₂ adsorbed on W(100) at ~ 300K have been made using a precision gas dosing system; a known fraction of the molecules entering the vacuum chamber struck the sample crystal before reaching a mass spectrometer detector. The initial sticking probability S₀ for H₂/W(100) is 0.51 ± 0.03; the hydrogen coverage extrapolated to S = 0 is 2.0 × 10¹⁵ atoms cm^?2. The initial sticking probability S₀ for D₂/W(100) is 0.57 ± 0.03; the isotope effect for sticking probability is smaller than previously reported. Electron stimulated desorption (ESD) studies reveal that the low coverage β₂ hydrogen state on W(100) yields H⁺ ions upon bombardment by 100 eV electrons; the ion desorption cross section is ~ 1.8 × 10^?23 cm². The H⁺ ion cross section at saturation hydrogen coverage when the β₁ state is fully populated is ? 10^?25 cm². An isotope effect in electron stimulated desorption of H⁺ and D⁺ has been found. The H⁺ ion yield is ? 100 × greater than the D⁺ ion yield, in agreement with theory.     

Time resolved measurements of methanol decomposition on Ni(100) utilizing laser induced desorption

A new method utilizing laser induced desorption (LID) is used to study the decomposition of methanol on Ni(100) in real time. The dependence of the rate of decompositition on surface coverage and on surface temperature is measured. The decomposition rate decreases during reaction in a manner characteristic of a self-poisoned reaction. The rate data are fit to a model in which the energy barrier to reaction increases in proportion to the coverage of the CH₃O product. The energy barrier obtained is 9 kcal mol^?1 plus 4 kcal mol^?1 monolayer^?1 of CH₃O. The frequency factor of 2 × 10⁹ s^?1 suggests there is significant entropy barrier to decomposition. Substitution of deuterium for the alcoholic hydrogen alters de decomposition rate appreciably and identifies the breaking of the OH bond as the rate determining step.     

Cesium ion desorption from graphite surfaces: Kinetics and dynamics of diffusion and desorption steps

The field reversal method was used to study the kinetics of Cs and Cs⁺ desorption from a pyrolytic graphite basal surface. Double-exponential decay was observed especially at high temperatures. Desorption of ions using an external flux from a Cs beam gave the primary rate parameters 2.60 eV and 5.3 × 10¹⁴ s⁻¹, at T = 1100–1600 K. The secondary rate parameters were 0.28 eV and 2.2 × 10⁵ s⁻¹, observed at T = 1250–1600 K. Due to the high sensitivity of the method, the kinetics of desorption of the previously absorbed Cs, diffusing out from the bulk crystal, could also be studied. These processes were more complex, giving the primary rate parameters 1.87 eV and 1.1 × 10¹⁴ s⁻¹, and the secondary rate parameters 2.07 eV and 1.97 × 10¹¹ s⁻¹ for T = 1400–1600 K. The variation of the primary and secondary rates and the field reversal peak heights as functions of retarding field time were also studied, as well as the field reversal peak variation with temperature. These results, as well as the ones found in previous studies of this system, indicate the existence of three adsorbed states on the more or less polycrystalline graphite surface. One apparently ionic state correlates with the diffusing state in the crystallites and with ionic states outside the surface. Conversion processes to and from this state, induced by the external field, were also observed.     

Surface segregation of InGaAs films by the evolution of reflection high-energy electron diffraction patterns

Surface segregation is studied via the evolution of reflection high-energy electron diffraction (RHEED) patterns under different values of As 4 BEP for InGaAs films. When the As 4 BEP is set to be zero, the RHEED pattern keeps a 4×3/(n×3) structure with increasing temperature, and surface segregation takes place until 470 C. The RHEED pattern develops into a metal-rich (4×2) structure as temperature increases to 495 C. The reason for this is that surface segregation makes the In inside the InGaAs film climb to its surface. With the temperature increasing up to 515 C, the RHEED pattern turns into a GaAs(2×4) structure due to In desorption. While the As 4 BEP comes up to a specific value (1.33×10 4 Pa–1.33×10 3 Pa), the surface temperature can delay the segregation and desorption. We find that As 4 BEP has a big influence on surface desorption, while surface segregation is more strongly dependent on temperature than surface desorption.     

Evidence for electron emission stimulated desorption from negative electron affinity GaAs surfaces

While desorption from surfaces caused by impinging electrons (electron stimulated desorption) is a well-established effect, electrons to be emitted also may give rise to desorption from an emitting surface (electron-emission stimulated desorption). Evidence for this effect is derived from data on the degradation of electron emission from negative electron affinity GaAs surfaces. The time dependence of the degradation is calculated, and agreement with the observed linear time dependence is found. Using the experimental degradation ata, the desorption cross section for the electron-emission stimulated desorption is obtained as 2 × 10^?25 cm².     

Isotope effects in the kinetics of simultaneous H and D thermal desorption from Pd

The kinetics of simultaneous hydrogen and deuterium thermal desorption from PdH_xD_y has been investigated. A novel experimental approach for the study of the transition state (TS) characteristics of the surface recombination reaction is proposed based on the analysis of the H and D partitioning into H₂, HD and D₂ molecules. It has been found that the hydrogen molecular isotopes distribution is determined by the energy differences of the corresponding TS of the atom-atom recombination reactions. On the other hand, the mechanisms and activation energies of the desorption process have been obtained. At 420 K, the desorption reaction changes from a surface recombination limiting mechanism during desorption from β-PdH_xD_y to a reaction limited by the rate of β to α phase transformation during the two phase coexistence. Surface recombination reaction becomes again rate limiting above 480 K, due to a change in the catalytic properties of the Pd surface. TS energies obtained from the kinetic analysis of the thermal desorption spectra are in good accordance with those obtained from the analysis of the H₂, HD and D₂ distributions. Anomalous TS energies have been observed for the H-D recombination reaction, which may be related to the heteronuclear character of this molecule.     

Laser-induced desorption of polyatomic molecules with a CO2 laser

Laser-induced thermal desorption (LITD) has been increasingly employed as a tool for investigating surface processes. In LITD, a pulsed laser beam that is focused onto a surface induces a rapid temperature rise that causes desorption. In spite of the success enjoyed by the CO₂ laser in studies of diatomic molecules, its use with polyatomic molecules is shown to be severely limited by laser-induced dissociation. In desorption experiments with CH₃OH, HCOOH, CH₃NH₂ and NH₃ dissociation occurs only when the laser frequency coincides with an infrared absorption band of the molecule. Fragmentation may take place either on the surface or in the dense gas phase present above the surface during the laser pulse.     

On the adsorption and desorption of H2 at metal surfaces

Recent technological developments have made possible measurements of the distribution of internal levels of molecules desorbing from a hot surface. Such measurements provide new information concerning the desorption process and the potential energy surface (PES) that governs it. Associative, or re-combinative desorption is of particular interest because the distributions of internal levels reflect the manner in which the molecular bond is formed as the desorbing species leaves the surface. As the simplest associative desorption systems, H₂ and D₂ adsorbing on and desorbing from metal surfaces deserve special attention and serve as prototypes for systems with a more complex chemistry. In this note I review briefly from the theoretical point of view some features of the interaction of H₂ with metals and their relevance to associative adsorption and dissociative sticking.     

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.     

Thermal desorption of cyanogen from Pt(100)

Thermal desorption of cyanogen adsorbed on Pt(100) was studied by flash desorption mass spectrometry. By investigating the parent ion and all possible fragmentation products in the mass spectrometer during desorption it was concluded, that desorption takes place exclusively as molecular C₂N₂. Three desorption peaks were observed at 140, 410 and 480°C denoted as α, β₁ and β₂. The respective surface coverages at saturation were determined by quantitative evaluation of the flash desorption curves to be 2.0 ± 0.2 × 10¹⁴ and 5.5 ± 1.0 × 10¹⁴$\text{molecules}\text{cm}{}^2$ for the α and the β states, respectively. First order desorption kinetics was suggested by the coverage dependencé of the desorption spectra for both α and β states with desorption energies of 12 and 38–42 $\text{kcal}\text{mole}$, respectively. A large difference in the sticking probabilities of α and β states was observed with initial values of 0.06 (α) and 0.9 (β). Adsorption experiments at elevated temperatures led to the assumption, that α and β states coexist on the surface with no or very little interactions between them. The results are discussed in terms of different models for the adsorption states.     

Interaction of aluminum with the rhenium surface: Adsorption, desorption, and growth of surface compounds

The interaction of aluminum with the ( $10\bar 10$ ) rhenium surface was studied experimentally within a broad temperature range, 300–2000 K. Surface aluminide (SA) ReAl with a concentration of adsorbed Al atoms N _Al=1.6×10¹⁵ cm^?2 was found to form. It was shown that aluminum escapes from the surface by thermal desorption at temperatures from 1300 to 1600 K, with the desorption activation energy changing abruptly from ～3.6 to ～4.2 eV when passing through the concentration corresponding to the SA.     

Chemisorption of CO on tungsten (100): Combined flash desorption and electron stimulated desorption study. II

The chemisorption of CO on W(100) at ~ 100K has been studied using a combination of flash desorption and electron stimulated desorption (ESD) techniques. This is an extension of a similar study made for CO adsorption on W(100) at temperatures in the range 200–300K. As in the 200–300 K CO layer, both α₁-CO and α₂-CO are formed in addition to more strongly bound CO species upon adsorption at ~ 100K; the α-CO states yield CO⁺ and O⁺ respectively upon ESD. At low CO coverages, the α₁ and α₂-CO states are postulated to convert to β-CO or other strongly bound CO species upon heating. At higher CO coverages, α₁-CO converts to α₂-CO upon thermal desorption or electron stimulated desorption. There is evidence for the presence of other weakly-bound states in the low temperature CO layer having low surface concentration at saturation. The ESD behavior of the CO layer coadsorbed with hydrogen on W(100) is reported, and it is found that H(ads) suppresses either the concentration or the ionic cross section for α₁ and α₂-CO states.