Insight into why the Langmuir-Hinshelwood mechanism is generally preferred

In heterogeneous catalysis, the two main reaction mechanisms which have been proposed are the Langmuir-Hinshelwood and the Eley-Rideal. For the vast majority of surface catalytic reactions, it has been accepted that the Langmuir-Hinshelwood mechanism is preferred. In this study, we investigate catalytic CO oxidation on Pt(111). It is found that reaction barriers for Langmuir-Hinshelwood mechanisms actually tend to be higher than those for Eley-Rideal ones. An explanation is presented as to why it is still more probable for the reaction to proceed via the Langmuir-Hinshelwood mechanism, despite its higher reaction barrier. (C) 2002 American Institute of Physics.

The Langmuir probe as a diagnostic of the electron component within low temperature laser ablated plasma plumes

A Langmuir probe has been used as a diagnostic of the temporally evolving electron component within a laser ablated Cu plasma expanding into vacuum, for an incident laser power density on target similar to that used for the pulsed laser deposition of thin films. Electron temperature data were obtained from the retarding region of the probe current/voltage (I/V) characteristic, which was also used to calculate an associated electron number density. Additionally, electron number density data were obtained from the saturation electron current region of the probe (I/V) characteristic. Electron number density data, extracted by the two different techniques, were observed to show the same temporal form, with measured absolute values agreeing to within a factor of 2. The Langmuir probe, in the saturation current region, has been shown for the first time to be a convenient diagnostic of the electron component within relatively low temperature laser ablated plasma plumes. (C) 1999 American Institute of Physics. [S0034-6748(99)01503-8].

Langmuir probe measurements of plasma parameters in the late stages of a laser ablated plume

A simple Langmuir probe technique has been used to measure the electron density, electron temperature, and plasma potential in the late stages (>5 mu s) of a laser ablated plasma plume. In the plasma, formed following 248 nm laser irradiation of a copper target, in vacuum at a laser fluence of 2.5 J cm(-2), electron densities of similar to 10(18) m(-3) and temperatures of similar to 0.5 eV were measured. These values are comparable with those reported previously using Faraday cup detectors and optical emission spectroscopy, respectively. (C) 1997 American Institute of Physics.

Nonlinear hydrodynamic Langmuir waves in fully degenerate relativistic plasma

The combined effect of special relativity and electron degeneracy on Langmuir waves is analyzed by utilizing a rigorous fully relativistic hydrodynamic model. Assuming a traveling wave solution form, a set of conservation laws is identified, together with a pseudo-potential function depending on the relativistic parameter p<inf>F</inf>/(m c) (where p<inf>F</inf> is the Fermi momentum, m is the mass of the charge carriers and c the speed of light), as well as on the amplitude of the electrostatic energy perturbation.

A Revised Disrupted Langmuir-Adsorption Model of Photocatalysis

The increasingly popular disrupted Langmuir–adsorption (DLA) kinetic model of photocatalysis does not contain an explicit function for the dependence of rate on the irradiance, ρ, but instead has a term αρθ, where, α is a constant of the system, and θ is also a constant equal to 1 or 0.5 at low or high ρ values, respectively. Several groups have recently replaced the latter term with an explicit function of the form χ1(−1 + (1 + χ2ρ)1/2), where χ1 and χ2, are constants that can be related to a proposed reaction scheme. Here the latter schemes are investigated, and revised to create a more credible form by assuming an additional hole trapping step. The latter may be the oxidation of water or a surface saturated with O2–. Importantly, this revision suggests that it is only applicable for low quantum yield/efficiency processes. The revised disrupted Langmuir–adsorption model is used to provide good fits to the kinetic data reported for a number of different systems including the photocatalytic oxidation of nitric oxide (NO), phenol (PhOH), and formic acid (FA).

Adsorption isotherm models for basic dye adsorption by peat in single and binary component systems

Coloured effluents from textile industries are a problem in many rivers and waterways. Prediction of adsorption capacities of dyes by adsorbents is important in design considerations. The sorption of three basic dyes, namely Basic Blue 3, Basic Yellow 21 and Basic Red 22, onto peat is reported. Equilibrium sorption isotherms have been measured for the three single component systems. Equilibrium was achieved after twenty-one days. The experimental isotherm data were analysed using Langmuir, Freundlich, Redlich-Peterson, Temkin and Toth isotherm equations. A detailed error analysis has been undertaken to investigate the effect of using different error criteria for the determination of the single component isotherm parameters and hence obtain the best isotherm and isotherm parameters which describe the adsorption process. The linear transform model provided the highest R2 regression coefficient with the Redlich-Peterson model. The Redlich-Peterson model also yielded the best fit to experimental data for all three dyes using the non-linear error functions. An extended Langmuir model has been used to predict the isotherm data for the binary systems using the single component data. The correlation between theoretical and experimental data had only limited success due to competitive and interactive effects between the dyes and the dye-surface interactions.

Relevance of heterometallic binding energy for metal underpotential deposition

We present first-principles calculations for a number of metals adsorbed on several different metallic substrates. Some of these systems are very relevant in electrochemistry, especially in the field of underpotential deposition phenomena. The present studies reveal the existence of a relationship between the excess binding energy and the surface energy difference between substrate and adsorbate. Comparisons with experimental underpotential shifts show that excess binding energies are systematically underestimated. By analyzing experimental information on different systems, we conclude that this discrepancy between our vacuum calculations and experiments carried out in an electrolytic solution is likely to be due to anion adsorption and/or solvent effects.

Monte Carlo simulation of properties of monolayers and metal islands adsorbed on metallic (111) surfaces

To obtain the surface stress changes due to the adsorption of metal monolayers onto metallic surfaces, a new model derived from thermodynamic considerations is presented. Such a model is based on continuum Monte Carlo simulations with embedded atom method potentials in the canonical ensemble, and it is extended to consider the behavior on different islands adsorbed onto (111) substrate surfaces. Homoepitaxial and heteroepitaxial systems are studied. Pseudomorphic growth is not observed for small metal islands with considerable positive misfit with the substrate. Instead, the islands become compressed upon increase of their size. A simple model is proposed to interpolate between the misfits of atoms in small islands and the pseudomorphic behavior of the monolayer.

Kinetic Monte Carlo study of electrochemical growth in a heteroepitaxial system

Structural and kinetic aspects of 2-D irreversible metal deposition under potentiostatic conditions are analyzed by means of dynamic Monte Carlo simulations employing embedded atom potentials for a model system. Three limiting models, all considering adatom diffusion, were employed to describe adatom deposition. The first model (A) considers adatom deposition on any free substrate site on the surface at the same rate. The second model (B) considers adatom deposition only on substrate sites which exhibit no neighboring sites occupied by adatoms. The third model (C) allows deposition at higher rates on sites presenting neighboring sites occupied by adatoms. Under the proper conditions, the coverage (theta) versus time (t) relationship for the three cases can be heuristically fitted to the functional form theta = 1 - exp(-betat(alpha)), where alpha and beta are parameters. We suggest that the value of the parameter alpha can be employed to distinguish experimentally between the three cases. While model A trivially delivers a = 1, models B and C are characterized by alpha 1, respectively.

Competitive adsorption of reactive dyes from solution: equilibrium isotherm studies in single and multisolute systems

Experimental data of the adsorption of reactive dyestuffs onto Filtrasorb 400 activated carbon (FS400) were determined in an equilibrium isotherm study. As most industrial wastewater contains more than one pollutant, an investigation into the effect of multisolute systems (using the unhydrolysed form of the reactive dyes) on the adsorption capacity was undertaken. Equilibrium isotherm models were employed to describe the adsorption capacities of single, binary and ternary dye solutions. The results of these analyses showed that adsorption of reactive dyes from single and multisolute systems can be successfully described by Langmuir, and Redlich–Peterson equilibrium isotherm models. Experimental data indicated that competitive adsorption for active sites on the carbon surface results in a reduction in the overall uptake capacity of the reactive dyes investigated.

Plasma dynamics in an inductively coupled magnetic neutral loop discharge

Magnetic neutral loop discharges (NLDs) can be operated at significantly lower pressures than conventional radio-frequency (rf) inductively coupled plasmas (ICPs). These low pressure conditions are favourable for technological applications, in particular anisotropic etching. An ICP–NLD has been designed providing excellent diagnostics access for detailed investigations of fundamental mechanisms. Spatially resolved Langmuir probe measurements have been performed in the plasma production region (NL region) as well as in the remote application region downstream from the NL region. Depending on the NL gradient two different operation modes have been observed exhibiting different opportunities for control of plasma uniformity. The efficient operation at comparatively low pressures results in ionization degrees exceeding 1%. In this regime neutral dynamics has to be considered and can influence neutral gas and process uniformity. Neutral gas depletion through elevated gas temperatures and high ionization rates have been quantified. At pressures above 0.1 Pa, gas heating is the dominant depletion mechanism. At lower pressures neutral gas is predominantly depleted through high ionization rates and rapid transport of ions by ambipolar diffusion along the magnetic field lines. Non-uniform profiles of the ionization rate can, therefore, result in localized neutral gas depletion and non-uniform processing. We have also investigated the electron dynamics within the radio-frequency cycle using phase resolved optical emission spectroscopy and Thomson scattering. In these measurements electron drift phenomena along the NL torus have been identified.

Spatial structures of plasma parameters in a magnetic neutral loop discharge

Spatial structures of plasma parameters in a radio-frequency inductively coupled magnetic neutral loop discharge are investigated under various parameter variations using spatially resolved Langmuir probe measurements. A strong coupling between the plasma production region, in the neutral loop (NL) plane, and the axially remote substrate region is observed. The two regions are connected through the separatrices and therefore, spatial profiles in the substrate region are strongly influenced by the plasma production region and the structure of the separatrices. The electron temperature in the plasma production region peaks in the centre of the NL while the maximum in electron density is shifted radially inwards due to diffusion. Details of the structures in both regions, the production region and the substrate region, are determined through the position of the NL and the gradient of the inhomogeneous magnetic field around the NL confinement region. Parameter combinations are found providing higher plasma densities and better uniformity than in common inductively coupled plasmas without applying an additional magnetic field. The uniformity can be further improved using temporal variations of the magnetic field structure.

Plasma boundary sheath in the afterglow of a pulsed inductively coupled RF plasma

The sheath dynamics in the afterglow of a pulsed inductively coupled plasma, operated in hydrogen, is investigated. It is found that the sheath potential does not fully collapse in the early post-discharge. Time resolved measurements of the positive ion flux in a hydrogen plasma, using a mass resolved ion energy analyser, reveal that a constant 2 eV mean ion energy persists for several hundred micro-seconds in the afterglow. The presence of a finite sheath potential is explained by super-elastic collisions between vibrationally excited hydrogen molecules and electrons in the afterglow, leading to an electron temperature of about 0.5 eV. Plasma density decay times measured using both the mass resolved energy analyser and a Langmuir probe are in good agreement. Vibrational temperatures measured using optical emission spectroscopy support the theory of electron heating through super-elastic collisions with vibrationally excited hydrogen molecules. Measurements are also supported by numerical simulations and modelling results.