Kinetic investigations of heterogeneously catalyzed reactions on the Ru(001) and Pt(110)-(1x2) surfaces

The initial probabilities of activated, dissociative chemisorption of methane and ethane on Pt(110)-(1 x 2) have been measured. The surface temperature was varied from 450 to 900 K with the reactant gas temperature constant at 300 K. Under these conditions, we probe the kinetics of dissociation via trapping-mediated (as opposed to 'direct') mechanism. It was found that the probabilities of dissociation of both methane and ethane were strong functions of the surface temperature with an apparent activation energies of 14.4 kcal/mol for methane and 2.8 kcal/mol for ethane, which implys that the methane and ethane molecules have fully accommodated to the surface temperature. Kinetic isotope effects were observed for both reactions, indicating that the C-H bond cleavage was involved in the rate-limiting step. A mechanistic model based on the trapping-mediated mechanism is used to explain the observed kinetic behavior. The activation energies for C-H bond dissociation of the thermally accommodated methane and ethane on the surface extracted from the model are 18.4 and 10.3 kcal/mol, respectively.

The studies of the catalytic decomposition of formic acid on the Ru(001) surface with thermal desorption mass spectrometry following the adsorption of DCOOH and HCOOH on the surface at 130 and 310 K are described. Formic acid (DCOOH) chemisorbs dissociatively on the surface via both the cleavage of its O-H bond to form a formate and a hydrogen adatom, and the cleavage of its C-O bond to form a carbon monoxide, a deuterium adatom and an hydroxyl (OH). The former is the predominant reaction. The rate of desorption of carbon dioxide is a direct measure of the kinetics of decomposition of the surface formate. It is characterized by a kinetic isotope effect, an increasingly narrow FWHM, and an upward shift in peak temperature with Ɵ_T, the coverage of the dissociatively adsorbed formic acid. The FWHM and the peak temperature change from 18 K and 326 K at Ɵ_T = 0.04 to 8 K and 395 K at Ɵ_T = 0.89. The increase in the apparent activation energy of the C-D bond cleavage is largely a result of self-poisoning by the formate, the presence of which on the surface alters the electronic properties of the surface such that the activation energy of the decomposition of formate is increased. The variation of the activation energy for carbon dioxide formation with Ɵ_T accounts for the observed sharp carbon dioxide peak. The coverage of surface formate can be adjusted over a relatively wide range so that the activation energy for C-D bond cleavage in the case of DCOOH can be adjusted to be below, approximately equal to, or well above the activation energy for the recombinative desorption of the deuterium adatoms. Accordingly, the desorption of deuterium was observed to be governed completely by the desorption kinetics of the deuterium adatoms at low Ɵ_T, jointly by the kinetics of deuterium desorption and C-D bond cleavage at intermediate Ɵ_T, and solely by the kinetics of C-D bond cleavage at high Ɵ_T. The overall branching ratio of the formate to carbon dioxide and carbon monoxide is approximately unity, regardless the initial coverage Ɵ_T, even though the activation energy for the production of carbon dioxide varies with Ɵ_T. The desorption of water, which implies C-O bond cleavage of the formate, appears at approximately the same temperature as that of carbon dioxide. These observations suggest that the cleavage of the C-D bond and that of the C-O bond of two surface formates are coupled, possibly via the formation of a short-lived surface complex that is the precursor to to the decomposition.

The measurement of steady-state rate is demonstrated here to be valuable in determining kinetics associated with short-lived, molecularly adsorbed precursor to further reactions on the surface, by determining the kinetic parameters of the molecular precursor of formaldehyde to its dissociation on the Pt(110)-(1 x 2) surface.

Overlayers of nitrogen adatoms on Ru(001) have been characterized both by thermal desorption mass spectrometry and low-energy electron diffraction, as well as chemically via the postadsorption and desorption of ammonia and carbon monoxide.

The nitrogen-adatom overlayer was prepared by decomposing ammonia thermally on the surface at a pressure of 2.8 x 10^(-6) Torr and a temperature of 480 K. The saturated overlayer prepared under these conditions has associated with it a (√247/10 x √247/10)R22.7° LEED pattern, has two peaks in its thermal desorption spectrum, and has a fractional surface coverage of 0.40. Annealing the overlayer to approximately 535 K results in a rather sharp (√3 x √3)R30° LEED pattern with an associated fractional surface coverage of one-third. Annealing the overlayer further to 620 K results in the disappearance of the low-temperature thermal desorption peak and the appearance of a rather fuzzy p(2x2) LEED pattern with an associated fractional surface coverage of approximately one-fourth. In the low coverage limit, the presence of the (√3 x √3)R30° N overlayer alters the surface in such a way that the binding energy of ammonia is increased by 20% relative to the clean surface, whereas that of carbon monoxide is reduced by 15%.

A general methodology for the indirect relative determination of the absolute fractional surface coverages has been developed and was utilized to determine the saturation fractional coverage of hydrogen on Ru(001). Formaldehyde was employed as a bridge to lead us from the known reference point of the saturation fractional coverage of carbon monoxide to unknown reference point of the fractional coverage of hydrogen on Ru(001), which is then used to determine accurately the saturation fractional coverage of hydrogen. We find that ƟSAT/H = 1.02 (±0.05), i.e., the surface stoichiometry is Ru : H = 1 : 1. The relative nature of the method, which cancels systematic errors, together with the utilization of a glass envelope around the mass spectrometer, which reduces spurious contributions in the thermal desorption spectra, results in high accuracy in the determination of absolute fractional coverages.

Simulations of phytoplankton dynamics in El Gergal Reservoir, Southern Spain (PROTECH)

The Mediterranean region is characterised by a variable climate with most of the rain falling during the winter and frequent summer droughts. Such warm, dry periods are ideal for the growth of large algal blooms that often consist of potentially toxic Cyanobacteria. This makes the management of water for human use particularly challenging in such a climate and it is important to understand how such blooms can be avoided or at least be reduced in size. PROTECH (Phytoplankton RespOnses To Environmental CHange) is a model that simulates the dynamics of different species of phytoplankton populations in lakes and reservoirs. Its distinct advantage over similar models is its ability to simulate the relative composition of the algal flora, allowing both quantitative and qualitative conclusions to be drawn e.g. whether Cyanobacteria could be a potential problem. PROTECH has been applied primarily to lakes and reservoirs in northern Europe. Recently, however, the model has been applied to water bodies in lower latitudes, including Australia to a water supply reservoir in the south of Spain, El Gergal. El Gergal is the last in a chain of reservoirs that supply water to the city of Seville. It was brought into service in April 1979 and has a maximum storage volume of 35 000 000 m3. This article summarises the application of PROTECH in order to simulate the following problems: • the effect of a large influx of Ceratium biomass into El Gergal from another reservoir • the effect of using alternative water sources instead of the Guadalquivir River (used occasionally to raise water levels in El Gergal) • the effect of installing tertiary sewage treatment on the Cala River • the effect of simulated drought conditions on phytoplankton in the reservoir.

I. Electronic states of heavily-doped molecular crystals--naphthalene. I. Theoretical. II. Experimental. II. Lowest singlet and triplet excited states of pyrazine

PART I

The energy spectrum of heavily-doped molecular crystals was treated in the Green’s function formulation. The mixed crystal Green’s function was obtained by averaging over all possible impurity distributions. The resulting Green’s function, which takes the form of an infinite perturbation expansion, was further approximated by a closed form suitable for numerical calculations. The density-of-states functions and optical spectra for binary mixtures of normal naphthalene and deuterated naphthalene were calculated using the pure crystal density-of-state functions. The results showed that when the trap depth is large, two separate energy bands persist, but when the trap depth is small only a single band exists. Furthermore, in the former case it was found that the intensities of the outer Davydov bands are enhanced whereas the inner bands are weakened. Comparisons with previous theoretical calculations and experimental results are also made.

PART II

The energy states and optical spectra of heavily-doped mixed crystals are investigated. Studies are made for the following binary systems: (1) naphthalene-h₈ and d</u>₈, (2) naphthalene--h₈ and αd</u>₄, and (3) naphthalene--h₈ and βd</u>₁, corresponding to strong, medium and weak perturbations. In addition to ordinary absorption spectra at 4˚K, band-to-band transitions at both 4˚K and 77˚K are also analyzed with emphasis on their relations to cooperative excitation and overall density-of-states functions for mixed crystals. It is found that the theoretical calculations presented in a previous paper agree generally with experiments except for cluster states observed in system (1) at lower guest concentrations. These features are discussed semi-quantitatively. As to the intermolecular interaction parameters, it is found that experimental results compare favorably with calculations based on experimental density-of-states functions but not with those based on octopole interactions or charge-transfer interactions. Previous experimental results of Sheka and the theoretical model of Broude and Rashba are also compared with present investigations.

Analysis of soils and sediments for organic pollutants

20 samples of soil or sediment (7 of which were predominantly sand) from various locations were received for analysis of their content of organic pollutants. These analyses were performed using a capillary column gas chromatograph equipped with an electron impact (E.I.) mass spectrometer as detector and using computerised data storage. In addition to the target compounds, the full scan data were examined to determine the composition of natural organic products and a series of diagnostic fragment ions was used to search for additional anthropogenic products. Organic-rich environmental samples are notoriously difficult to analyse for pollutant organics owing to the presence of high concentrations of many natural organic compounds. A single procedure for extraction and clean-up was adopted. It was designed for chlorinated aliphatic and aromatic hydrocarbons and other pesticides containing acidic functional groups and was based on published methods for the determination of organic pollutants in soils and sediments. 4 soils and 2 sands showed levels of one or two groups of PCBs slightly in excess of the detection limit, one sample showed a similar level of 2,4-D and 3 samples contained dieldrin at or just above the detection limit.

Characteristics of 980/1550 nm WDM coupler based on planar curved waveguides

A wavelength division multiplexer (WDM) for 980/1550 nm based on planar curved waveguide coupler (CWC) is proposed. Compared with conventional parallel straight waveguide coupler (SWC), this structure has more flexibility with two variable parameters of bending radius R and minimum edge-to-edge spacing do, which are the two main parameters for the splitting ratio of coupler and decrease the complexity of device design and fabrication. Based on coupled mode theory (CMT) and waveguide theory, R and do of the WDM CWC are designed to be R = 13.28 m and d(0) = 4.39 mu m. The contrast ratio (CR) and insertion loss (IL) for 980 and 1550 nm are CR1 = 24.62 dB, CR2 = 24.56 dB and IL1 = 0.014 dB, IL2 = 0.015 dB, respectively. The 3D beam propagation method (BPM) is used to verify the validity of the design result. The influence of R and d(0) variations on the device performance is analyzed. For CR > 20 dB, the variation ranges of R and d(0) should be within -0.10 to +0.44 m and -0.05 to + 0.02 mu m, respectively. (c) 2006 Elsevier GmbH. All rights reserved.

Luminescence studies of Ce : YAG using vacuum ultraviolet synchrotron radiation

Photoluminescence spectrum of Ce:YAG single crystal was studied employing vacuum ultraviolet (VUV) synchrotron radiation. Intrinsic absorption edge at about 52,000 cm(-1) was observed in the absorption spectrum. From the VUV excitation spectrum, the energy of the highest d-component of 53,191 cm(-1) (188 nm) for the Ce3+ ions in YAG was obtained at 300 K. The disappearance of the third 5d level at 37,735 cm(-1) (265 nm) in absorption and excitation spectra in our samples may be due to the impurity Fe3+ ions absorption. (C) 2006 Elsevier Ltd. All rights reserved.

Écologie de bassins de lagunage pour le traitement d'effluents domestiques en milieu tropical humide (Côte d'Ivoire)

The waste water treatment of Dabou (Côte d'Ivoire), made of three oxydation ponds (B1, B2 and B3), is designed to ensure a biological treatment of domestic sewage and a valorization of the final effluent in aquaculture. In order to understand the ecological mechanisms and the performance of this system, a pluridisciplinary program was achieved in February 1989.

L'oxygene au large de Grand Bassam (Cote d'Ivoire)

The present paper deals with the variations of the dissolved oxygen content off Grand Bassam (11 miles east of Abidjan, Côte d'Ivoire), during nearly five years (March 1966 to September 1970). Although we find in general the low oxygen values near the bottom, the dissolved oxygen content is at its absolute minimum during the upwelling. There is a good correlation between the Secchi depth and the depth of the well ventilated layer. About 10% of surface irradiance is found at the layer where the dissolved oxygen content equals 80% of the oxygen content found at surface.

Quelques observations sur la présence des Cumacés dans le zooplancton des eaux néritiques de Côte d'Ivoire

Cumacea were only observed in night plankton of the Côte d'Ivoire continental shelf. However they are not always observed and their occurrence seems to depend on the marine seasons. In September, December and April, the catches were very poor indeed, whereas May and June showed interesting results. Most of the species are rarely seen in the upper layer. Several activity rhythms could be shown for the most common species present in the hauls.

Croissance et d��termination de l'âge par lecture d'écailles d'un poisson plat de Côte d'Ivoire, Cynoglossus canariensis (Steind. 1882)

Cynoglossus canariensis has a very rapid growth. The rate of the males is 0,36 and the female one is 0,32. The asymptotic size is 55,0cm for the females and 50,5cm for the males. Females and males younger than three years (40cm), which represent 90 per cent of the Côte d'Ivoire stock have a similar growth, so the average equation: Lt=53,5 (1-e -0,34(t+1)) will be used.

État des stocks pélagiques côtiers en Côte d'Ivoire

Evolution of catch and catch by unit effort of the sardine fishing boats (purse seiners) has been examined from 1966 to 1975. The effort data has been calculated with a new computer programme: Crosardi (Soisson et Barbe, 1974). The analysis has been done on the whole stock and in more detail on the east and west stocks of Côte d'Ivoire. The Sardinella eba stock has been analysed separately. Those analyses were done using the general production model (Prodfit; Fox, 1974). The stock of the eastern area of the Côte d'Ivoire seems to be exploited at its maximum level. Nevertheless, the western area stock could be able to support a progressive increase of fishing effort.

Mathematical models for the prediction of temperature distributions resulting from the discharge of heated water into large bodies of water

Mathematical models for heated water outfalls were developed for three flow regions. Near the source, the subsurface discharge into a stratified ambient water issuing from a row of buoyant jets was solved with the jet interference included in the analysis. The analysis of the flow zone close to and at intermediate distances from a surface buoyant jet was developed for the two-dimensional and axisymmetric cases. Far away from the source, a passive dispersion model was solved for a two dimensional situation taking into consideration the effects of shear current and vertical changes in diffusivity. A significant result from the surface buoyant jet analysis is the ability to predict the onset and location of an internal hydraulic jump. Prediction can be made simply from the knowledge of the source Froude number and a dimensionless surface exchange coefficient. Parametric computer programs of the above models are also developed as a part of this study. This report was submitted in fulfillment of Contract No. 14-12-570 under the sponsorship of the Federal Water Quality Administration.

John Nathan Cobb (1868–1930): Founding Director of the College of Fisheries, University of Washington, Seattle

John Nathan Cobb (1868–1930) became the founding Director of the College of Fisheries, University of Washington, Seattle, in 1919 without the benefit of a college education. An inquisitive and ambitious man, he began his career in the newspaper business and was introduced to commercial fisheries when he joined the U.S. Fish Commission (USFC) in 1895 as a clerk, and he was soon promoted to a “Field Agent” in the Division of Statistics, Washington, D.C. During the next 17 years, Cobb surveyed commercial fisheries from Maine to Florida, Hawaii, the Pacific Northwest, and Alaska for the USFC and its successor, the U.S. Bureau of Fisheries. In 1913, he became editor of the prominent west coast trade magazine, Pacific Fisherman, of Seattle, Wash., where he became known as a leading expert on the fisheries of the Pacific Northwest. He soon joined the campaign, led by his employer, to establish the nation’s first fisheries school at the University of Washington. After a brief interlude (1917–1918) with the Alaska Packers Association in San Francisco, Calif., he was chosen as the School’s founding director in 1919. Reflecting his experience and mindset, as well as the University’s apparent initial desire, Cobb established the College of Fisheries primarily as a training ground for those interested in applied aspects of the commercial fishing industry. Cobb attracted sufficient students, was a vigorous spokesman for the College, and had ambitions plans for expansion of the school’s faculty and facilities. He became aware that the College was not held in high esteem by his faculty colleagues or by the University administration because of the school’s failure to emphasize scholastic achievement, and he attempted to correct this deficiency. Cobb became ill with heart problems in 1929 and died on 13 January 1930. The University soon thereafter dissolved the College and dismissed all but one of its faculty. A Department of Fisheries, in the College of Science, was then established in 1930 and was led by William Francis Thompson (1888–1965), who emphasized basic science and fishery biology. The latter format continues to the present in the Department’s successor, The School of Aquatic Fisheries and Science.