The importance of hydrogen's potential-energy surface and the strength of the forming R-H bond in surface hydrogenation reactions

An understanding of surface hydrogenation reactivity is a prevailing issue in chemistry and vital to the rational design of future catalysts. In this density-functional theory study, we address hydrogenation reactivity by examining the reaction pathways for N+H -> NH and NH+H -> NH2 over the close-packed surfaces of the 4d transition metals from Zr-Pd. It is found that the minimum-energy reaction pathway is dictated by the ease with which H can relocate between hollow-site and top-site adsorption geometries. A transition state where H is close to a top site reduces the instability associated with bond sharing of metal atoms by H and N (NH) (bonding competition). However, if the energy difference between hollow-site and top-site adsorption energies (Delta E-H) is large this type of transition state is unfavorable. Thus we have determined that hydrogenation reactivity is primarily controlled by the potential-energy surface of H on the metal, which is approximated by Delta E-H, and that the strength of N (NH) chemisorption energy is of less importance. Delta E-H has also enabled us to make predictions regarding the structure sensitivity of these reactions. Furthermore, we have found that the degree of bonding competition at the transition state is responsible for the trend in reaction barriers (E-a) across the transition series. When this effect is quantified a very good linear correlation is found with E-a. In addition, we find that when considering a particular type of reaction pathway, a good linear correlation is found between the destabilizing effects of bonding competition at the transition state and the strength of the forming N-H (HN-H) bond. (c) 2006 American Institute of Physics.

Correction of dielectric losses in practical leaky-wave antenna designs

In this paper, the leaky-mode theory is applied to take into account for the dielectric losses in millimetre waveband inhomogeneous leaky-wave antennas. A practical dielectric-filled cosine-tapered periodic leaky-wave antenna working in the 45GHz band is studied, showing how the desired sidelobes level and directivity are spoilt due to the effect of the losses. An iterative procedure is used to correct the negative effects of the losses in the radiation patterns of the leaky-wave structure. It is also shown the practical limits of the proposed correction approach. The leaky-mode theory is applied for the first time to compensate the losses in a practical leaky-wave antenna in hybrid waveguide printed circuit technology. This leaky-mode theory is validated with full-wave three-dimensional finite element method simulations of the designed antenna.

Control of leaky-mode propagation and radiation properties in hybrid dielectric-waveguide printed-circuit technology: Experimental results

Experimental results are presented to show how a planar circuit, printed on a laterally shielded dielectric waveguide, can induce and control the radiation from a leaky-mode. By studying the leaky-mode complex propagation constant, a desired radiation pattern can be synthesized, controlling the main radiation characteristics (pointing direction, beamwidth, sidelobes level) for a given frequency, This technique leads to very flexible and original leaky-wave antenna designs. The experiments show to be in very good agreement with the leaky-mode theory.

Tailoring the AMC and EBG characteristics of periodic metallic arrays printed on grounded dielectric substrate

The artificial magnetic conductor (AMC) and electromagnetic band gap (EBG) characteristics of planar periodic metallic arrays printed on grounded dielectric substrate are investigated. The currents induced on the arrays are presented for the first time and their study reveals two distinct resonance phenomena associated with these surfaces. A new technique is presented to tailor the spectral position of the AMC operation and the EBG. Square patch arrays with fixed element size and variable periodicities are employed as working examples to demonstrate the dependence of the spectral AMC and EBG characteristics on array parameters. It is revealed that as the array periodicity is increased, the AMC frequency is increased, while the EBG frequency is reduced. This is shown to occur due to the different nature of the resonance phenomena and the associated underlying physical mechanisms that produce the two effects. The effect of substrate thickness is also investigated. Full wave method of moments (MoM) has been employed for the derivation of the reflection characteristics, the currents and the dispersion relations. A uniplanar array with simultaneous AMC and EBG operation is demonstrated theoretically and experimentally.

Effect of solution pH, ionic strength, and temperature on adsorption behavior of reactive dyes on activated carbon

The adsorption behavior of C.I. Reactive Blue 2, C.I. Reactive Red 4, and C.I. Reactive Yellow 2 from aqueous solution onto activated carbon was investigated under various experimental conditions. The adsorption capacity of activated carbon for reactive dyes was found to be relatively high. At pH 7.0 and 298 K, the maximum adsorption capacity for C.I. Reactive Blue 2, C.I. Reactive Yellow 2 and C.I. Reactive Red 4 dyes was found to be 0.27, 0.24, and 0.11 mmol/g, respectively. The shape of the adsorption isotherms indicated an L2-type isotherm according to the Giles and Smith classification. The experimental adsorption data showed good correlation with the Langmuir and Ferundlich isotherm models. Further analysis indicated that the formation of a complete monolayer was not achieved, with the fraction of surface coverage found to be 0.45, 0.42, and 0.22 for C.I. Reactive Blue 2, C.I. Reactive Yellow 2 and C.I. Reactive Red 4 dyes, respectively. Experimental data indicated that the adsorption capacity of activated carbon for the dyes was higher in acidic rather than in basic solutions, and further indicated that the removal of dye increased with increase in the ionic strength of solution, this was attributed to aggregation of reactive dyes in solution. Thermodynamic studies indicated that the adsorption of reactive dyes onto activated carbon was an endothermic process. The adsorption enthalpy (?H) for C.I. Reactive Blue 2 and C.I. Reactive Yellow 2 dyes were calculated at 42.2 and 36.2 kJ/mol, respectively. The negative values of free energy (?G) determined for these systems indicated that adsorption of reactive dyes was spontaneous at the temperatures under investigation (298-328 K). © 2007 Elsevier Ltd. All rights reserved.

Solvent strength of ionic liquid/CO2 mixtures

Previously we have shown that organic solutes can be extracted from ionic liquids (ILs) with supercritical CO2 and that ILs can be induced to separate from organic and aqueous mixtures by applying gaseous CO2 pressure. Thus, we are interested in the solvent strength of IL/CO2 mixtures. Here we use 4-nitroaniline, N,N-diethyl-4-nitroaniline and Reichardt's dye 33 to determine the Kamlet-Taft parameters for four different imidazolium based ILs and their mixtures with CO2 at 25 and 40degreesC. The effect of temperature and carbon dioxide concentration on these parameters was determined. The polarizability parameter depends weakly on the CO2 concentration. However, the hydrogen bond donating ability and the hydrogen bond accepting ability are virtually independent Of CO2 pressure. The results indicate that the strong interactions between ILs and probe molecules are not influenced by CO2.

Effect of Mixture Composition on Relative Strength of Highly Flowable Underwater Concrete

Concrete used for underwater repair is often proportioned to spread readily into place and self-consolidate, and to develop high resistance to segregation and water dilution. An investigation was carried out to determine the effect of the dosage of antiwashout admixture, water-cementitious materials ratio (w/cm), and binder composition on the relative residual strength of highly flowable underwater concrete. Two types of antiwashout admixtures were used: a powdered welan gum at 0.07 and 0.15% by mass of binder, and a liquid-based cellulosic admixture employed at a high dosage of 1 to 1.65 L/100 kg of cementitious materials. The w/cms were set at 0.41 and 0.47 to secure adequate performance of underwater concrete for construction and repair. Four binder compositions were used: a Canadian Type 10 cement; a cement with 10% silica fume replacement; a cement with 50% replacement of granulated blast-furnace slag; and a ternary binder containing 6% silica fume and 20% Class F fly ash. Test results indicate that for a given washout mass loss and slump flow consistency, greater relative residual strength can be secured when the dosage of antiwashout admixture is increased, the w/cm is reduced, and a binary binder with 10% silica fume substitution or the ternary binder are employed. Such mixtures can develop relative residual compressive strengths of 85 and 80%, compared to mixtures cast in air, when the value of washout loss is limited to 4 and 6% for mixtures with slump flow values of 450 and 550 mm, respectively.