Electrophilic Addition of Phenylisocyanate at gamma-CH of Thio-beta-diketonates of Some Transition Metals

The quasi-aromatic property of metal chelates of thio-beta-diketones has been studied by reacting them with phenylisocyanate, where addition takes place at the gamma-CH in a stepwise manner. Mono-thiodiketonates of Ni(II), Pd(II), cu(II) and Co(III) and the dithio-acetylacetonate of Ni(II) react with phenylisocyanate to produce mono-, di- and triphenylamido [with cobalt (III) only] substituted derivatives. In the case of tris (ethylthioacetoacetato) cobalt (III), it is found that the reaction with phenylisocyanate gives two isomers, a chocolate coloured isomer in which the phenylamido carbonyl is not coordinated while the green coloured isomer has bonding through phenylemido carbonyl oxygen. The reactions of the thiodiketonates have been compared with those of beta-diketonates and beta-ketoiminates. The reaction products have been characterised by elemental analyses, magnetic moments, and electronic, IR and 1H NMR spectral studies.

A Novel Approach to the Study of Surface Oxidation States and Oxidation of Transition Metals by Auger Electron Spectroscopy

L$_{23}$ M$_{45}$ M$_{45}$/L$_{23}$ M$_{23}$ M$_{45}$, L$_{23}$ M$_{45}$ M$_{45}$/L$_{23}$ M$_{23}$ M$_{23}$ and L$_{23}$ M$_{23}$ M$_{45}$/L$_{23}$ M$_{23}$ M$_{23}$ Auger intensity ratios in transition metal oxides and sulphides are shown to be directly related to the number of valence electrons in the metal as well as to its oxidation state. The metal Auger intensity ratios provide a unique probe, independent of O (KLL) intensity, to study surface oxidation states of metals. These intensity ratios have been effectively employed to investigate surface oxidation of nickel, iron and copper. The oxidation studies have unravelled some interesting aspects of surface oxidation.

Investigation of surface activity and photoinduced diffusion of metals in solution deposited amorphous films of As2S3

Surface activity of solution deposited (SD) amorphous films of As2S3 has been investigated. Silver and copper are readily deposited on such films from appropriate aqueous ionic solutions. The metals diffuse into the films upon irradiation with energetic photons. Structure and properties of SD films have been investigated using electron microscopy, optical spectroscopy and differential scanning calorimetry. The amorphous films tend to crystallize upon metal diffusion. The stability of amorphous films, the deposition of metals on their active surfaces and the photo-induced diffusion may all be attributed to the presence or production of charged defects in amorphous chalcogenide films.

Adsorption of carbon monoxide on the surfaces of polycrystalline transition metals and alloys: electron energy loss and ultraviolet photoelectron spectral studies1

Adsorption of CO has been investigated on the surfaces of polycrystalline transition metals as well as alloys by employing electron energy loss spectroscopy (eels) and ultraviolet photoelectron spectroscopy (ups). CO adsorbs on polycrystalline transition metal surfaces with a multiplicity of sites, each being associated with a characteristic CO stretching frequency; the relative intensities vary with temperature as well as coverage. Whilst at low temperatures (80- 120 K), low coordination sites are stabilized, the higher coordination sites are stabilized at higher temperatures (270-300 K). Adsorption on surfaces of polycrystalline alloys gives characteristic stretching frequencies due to the constituent metal sites. Alloying, however, causes a shift in the stretching frequencies, indicating the effect of the band structure on the nature of adsorption. The up spectra provide confirmatory evidence for the existence of separate metal sites in the alloys as well as for the high-temperature and low-temperature phases of adsorbed CO.

Molecularly adsorbed oxygen on metals: electron spectroscopic studies

Oxygen is shown to adsorb molecularly on gold as well as on Ag and Pt. UV and X-ray photoelectron spectroscopy and Auger electron spectroscopy have been employed to investigate electron states of molecularly adsorbed oxygen.

Radical Enhanced Atomic Layer Deposition of Metals and Oxides

Atomic Layer Deposition (ALD) is a chemical, gas-phase thin film deposition method. It is known for its ability for accurate and precise thickness control, and uniform and conformal film growth. One area where ALD has not yet excelled is film deposition at low temperatures. Also deposition of metals, besides the noble metals, has proven to be quite challenging. To alleviate these limitations, more aggressive reactants are required. One such group of reactants are radicals, which may be formed by dissociating gases. Dissociation is most conveniently done with a plasma source. For example, dissociating molecular oxygen or hydrogen, oxygen or hydrogen radicals are generated. The use of radicals in ALD may surmount some of the above limitations: oxide film deposition at low temperatures may become feasible if oxygen radicals are used as they are highly reactive. Also, as hydrogen radicals are very effective reducing agents, they may be used to deposit metals. In this work, a plasma source was incorporated in an existing ALD reactor for radical generation, and the reactor was used to study five different Radical Enhanced ALD processes. The modifications to the existing reactor and the different possibilities during the modification process are discussed. The studied materials include two metals, copper and silver, and three oxides, aluminium oxide, titanium dioxide and tantalum oxide. The materials were characterized and their properties were compared to other variations of the same process, utilizing the same metal precursor, to understand what kind of effect the non-metal precursor has on the film properties and growth characteristics. Both metals were deposited successfully, and silver for the first time by ALD. The films had low resistivity and grew conformally in the ALD mode, demonstrating that the REALD of metals is true ALD. The oxide films had exceptionally high growth rates, and aluminium oxide grew at room temperature with low cycle times and resulted in good quality films. Both aluminium oxide and titanium dioxide were deposited on natural fibres without damaging the fibre. Tantalum oxide was also deposited successfully, with good electrical properties, but at slightly higher temperature than the other two oxides, due to the evaporation temperature required by the metal precursor. Overall, the ability of REALD to deposit metallic and oxide films with high quality at low temperatures was demonstrated.

Controls on trace metals in urban stream sediments : implications for pollution monitoring using sediment chemistry data

Contamination of urban streams is a rising topic worldwide, but the assessment and investigation of stormwater induced contamination is limited by the high amount of water quality data needed to obtain reliable results. In this study, stream bed sediments were studied to determine their contamination degree and their applicability in monitoring aquatic metal contamination in urban areas. The interpretation of sedimentary metal concentrations is, however, not straightforward, since the concentrations commonly show spatial and temporal variations as a response to natural processes. The variations of and controls on metal concentrations were examined at different scales to increase the understanding of the usefulness of sediment metal concentrations in detecting anthropogenic metal contamination patterns. The acid extractable concentrations of Zn, Cu, Pb and Cd were determined from the surface sediments and water of small streams in the Helsinki Metropolitan region, southern Finland. The data consists of two datasets: sediment samples from 53 sites located in the catchment of the Stream Gräsanoja and sediment and water samples from 67 independent catchments scattered around the metropolitan region. Moreover, the sediment samples were analyzed for their physical and chemical composition (e.g. total organic carbon, clay-%, Al, Li, Fe, Mn) and the speciation of metals (in the dataset of the Stream Gräsanoja). The metal concentrations revealed that the stream sediments were moderately contaminated and caused no immediate threat to the biota. However, at some sites the sediments appeared to be polluted with Cu or Zn. The metal concentrations increased with increasing intensity of urbanization, but site specific factors, such as point sources, were responsible for the occurrence of the highest metal concentrations. The sediment analyses revealed, thus a need for more detailed studies on the processes and factors that cause the hot spot metal concentrations. The sediment composition and metal speciation analyses indicated that organic matter is a very strong indirect control on metal concentrations, and it should be accounted for when studying anthropogenic metal contamination patterns. The fine-scale spatial and temporal variations of metal concentrations were low enough to allow meaningful interpretation of substantial metal concentration differences between sites. Furthermore, the metal concentrations in the stream bed sediments were correlated with the urbanization of the catchment better than the total metal concentrations in the water phase. These results suggest that stream sediments show true potential for wider use in detecting the spatial differences in metal contamination of urban streams. Consequently, using the sediment approach regional estimates of the stormwater related metal contamination could be obtained fairly cost-effectively, and the stability and reliability of results would be higher compared to analyses of single water samples. Nevertheless, water samples are essential in analysing the dissolved concentrations of metals, momentary discharges from point sources in particular.

An XPS study of the surface oxidation states of metals in some oxide catalysts

Calcined samples of chromia supported on Al2O3, ZnO, or SnO2 show both Cr(VI) and Cr(III) on the surface, Cr(VI) being preponderant in the case of Al2O3-supported catalysts. The proportion of Cr(VI) decreases with increase in Cr content of the calcined catalysts. Reduction of the supported chromia catalysts in H2 at 720 K for 1 hr gives rise to Cr(III) and Cr(V). On carrying out the dehydrogenation of cyclohexane on the chromia catalysts a higher proportion of Cr(V) is found than after treatment with hydrogen. Vanadia supported on Al2O3 or MoO3 shows significant proportion of V(IV) on carrying out the oxidation of toluene on the catalysts. Calcined MoO3 (10%)/Al2O3 shows only Mo(VI) on the surface at 300 K, but on heating to 670 K in vacuum shows the presence of a considerable proportion of Mo(V) which on cooling disproportionates to Mo(IV) and Mo(VI). Mo(V) is noticed on surfaces of this catalyst on reduction with hydrogen as also on carrying out dehydrogenation of cyclohexane. While Bi2MoO6 shows only Mo(VI) on the surface at 300 K, heating it to 670 K in vacuum changes it entirely to Mo(V) which then gives rise to Mo(IV) and Mo(VI) on cooling.

Preparation and thermal stability of trioxalatocobaltates of bivalent metals KM2+ [Co(C2O4)3]·xH2O

Trioxalatocobaltates of bivalent metals KM2+[Co(C2O4)3]·x H2O, with M2+ = Ba, Sr, Ca and Pb, have been prepared, characterized and their thermal behaviour studied. The compounds decompose to yield potassium carbonate, bivalent metal carbonate or oxide and cobalt oxide as final products. The formation of the final products of decomposition is influenced by the surrounding atmosphere. Bivalent metal cobaltites of the types KM2+CoO3 and M2+CoO3—x are not identified among the final products of decomposition. The study brings out the importance of the decomposition mode of the precursor in producing the desired end products.

Reaction of sulphuryl chlorofluoride with a few metals and metal oxides

Sulphuryl chlorofluoride has no observable reaction with metals and metal oxides at room temperature. Metals like copper, silver, iron, and zinc react with the chlorofluoride in the temperature range 200–400°C. Metal chlorides, metal fluorides and sulphur dioxide are the main products of these reactions. With the corresponding metal oxides, on the other hand, the respective metal sulphates are formed in addition to the metal chlorides and fluorides. In the case of lead and lead oxide, lead chlorofluoride is formed instead of lead chloride and lead fluoride. Sulphuryl fluoride is formed in small quantities in all these reactions by the decomposition of the chlorofluoride. Glass is not attacked by sulphuryl chlorofluoride below 500°C.

Concentration levels of heavy metals and polycyclic aromatic hydrocarbons in car parks at Queensland University of Technology

This study investigates the level of pollutants (polycyclic aromatic hydrocarbons (PAHs) and heavy metals) in three car parks at QUT, one at Kelvin Grove campus and two at the Gardens Point campus. In addition, comparisons between site designs were assessed to identify the possible sources of heavy metals and PAHs. The main contributing source for heavy metals was identified to be from vehicle debris and emissions, while the source of PAHs was identified to be from petrol and diesel engine vehicle emissions. The highest concentration of pollutants was typically found for the 63 micro meter dust samples, proposed to be due to increased surface areas and thus available adsorption sites.

Structure and Bonding in N-Methylacetamide Complexes of Alkali and Alkaline Earth Metals

A detailed crystallographic investigation of N-methylacetamide complexes of Li, Na, K, Mg and Ca has been made in view of its importance in the coordination chemistry and biochemistry of alkali and alkaline earth metals. The metal ions bind to the amide oxygen causing an increase in the carbonyl distance and a proportionate decrease in the central C-N bond distance. The decrease in the central C-N distance is accompanied by an increase in the distance of the adjacent C-C bond and a decrease in the adjacent C-N bond distance. The metal ion generally deviates from the direction of the lone pair of the carbonyl oxygen and also from the plane of the peptide, the out-of-plane deviation varying with the ionic potential of the cation. The metal-oxygen distance in alkali and alkaline earth metal complexes of a given coordination number also varies with the ionic potential of the cation, as does the strength of binding of the cations to the amide. The amide molecules are essentially planar in these complexes, as expected from the increased bond order of the central C-N bond. The NH bonds of the amide are generally hydrogen bonded to anions. The structures of the amide complexes are compared with those of other oxygen donor complexes of alkali and alkaline earth metals. The structural study described here also provides a basis for the interpretation of results from spectroscopic and theoretical investigations of the interaction of alkali and alkaline earth metal cations with amides.

Low-field hopping conductivity in granular metals

The hopping conductivity of granular metals is known to be of the form sigma varies as exp (-(T0/T)12/) in the temperature range 20K

Build-up of toxic metals on the impervious surfaces of a commercial seaport

In the context of increasing threats to the sensitive marine ecosystem by toxic metals, this study investigated the metal build-up on impervious surfaces specific to commercial seaports. The knowledge generated in this study will contribute to managing toxic metal pollution of the marine ecosystem. The study found that inter-modal operations and main access roadway had the highest loads followed by container storage and vehicle marshalling sites, while the quay line and short term storage areas had the lowest. Additionally, it was found that Cr, Al, Pb, Cu and Zn were predominantly attached to solids, while significant amount of Cu, Pb and Zn were found as nutrient complexes. As such, treatment options based on solids retention can be effective for some metal species, while ineffective for other species. Furthermore, Cu and Zn are more likely to become bioavailable in seawater due to their strong association with nutrients. Mathematical models to replicate the metal build-up process were also developed using experimental design approach and partial least square regression. The models for Cr and Pb were found to be reliable, while those for Al, Zn and Cu were relatively less reliable, but could be employed for preliminary investigations.