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1.
Multielemental determination and the assessment of purity of cobalt metal used in the preparation of Ni-based super-alloys have been carried out by glow discharge quadrupole mass spectrometry (GD-QMS). Relative sensitivity factors (RSF) generated from certified iron matrix reference samples (NIST 663 and 664 low alloy steel pin standards) could be used for the determination of different trace element constituents of the sample. Different wet chemical procedures were also carried out for the determination of the trace constituents in the sample. The GD-QMS results are in reasonably good agreement with those obtained from wet chemical procedures, validating the use of the RSF values generated on low alloy steel standards for the computation of trace element concentrations in cobalt metal. A variety of molecular ions formed through the reaction of cobalt (matrix) with the discharge gas (argon) were also detected.  相似文献   
2.
The kinetics of polymerization of acrylonitrile initiated by KHSO5 and catalyzed by Ag(I) have been investigated in an aqueous medium over the temperature range of 35–50°C. The rates of polymerization Rp have been calculated and studied with respect to monomer and initiator. The catalytic activity of various metal ions on the initiator has been determined from a comparison of Rp values. The effects of monomer, catalyst, neutral salts, various amines, and inhibitor (hydroquinone) on the initial rate as well as maximum conversion have been studied. From the kinetics results a suitable reaction scheme has been proposed.  相似文献   
3.
Because Nitrosomonas europaea contains ammonia-oxidizing enzyme, nitrite reductase, and nitrous oxide reductase, the conversion of ammonia to dinitrogen was tried with different reaction conditions. In aerobic reaction conditions, ammonium was converted to nitrite (NO 2 ), while under oxygen-limiting or oxygen-free conditions, NO 2 -N formed from ammonia oxidation by N. europaea was reduced to N2O and dinitrogen with 22% conversion. During denitrification, optimal pH for the production of N2O and dinitrogen was found to be 7.0–8.0. Dinitrogen was not produced in acidic pH<7.0. A low partial oxygen pressure as well as oxygen-free conditions are favorable for high production of dinitrogen.  相似文献   
4.
The standard potentials of silver—silver bromide and silver—silver iodide electrodes in glycerol+water mixtures containing 5, 10, 20 and 30 wt% glycerol were determined from electromotive force measurements of the cell Ag(s), AgX(s), KX(c)//KCl(c), AgCl(s), Ag(s), where X is Br or I, at seven different temperatures in the range 5–35°C. The standard potentials in each solvent are represented as a function of temperature. The standard thermodynamic functions for the electrode reactions, the primary medium effects of various solvents upon X, and the standard thermodynamic quantities for the transfer of 1 g-ion of X from water to the respective glycerol + water media are evaluated and discussed in the light of ion—solvent interactions as well as the structural changes of the solvents. From the values of the Ag/Ag+ and Ag/AgX, X electrodes, the thermodynamic solubility product constants of silver chloride, silver bromide and silver iodide have been determined in glycerol + water solvent mixtures at different temperatures.  相似文献   
5.
Recent positron lifetime studies made on the Au/GaAs interface with an applied electric field returning a significant fraction of bulk implanted positrons to the interface have revealed the presence of microvoids( 1 nm diameter) at the interface. In this work an attempt has been made to study these microvoids by observing the Doppler broadening on the annihilation radiation coming from them. This is done both by observing theS-parameter as a function of applied bias and by applying the generalized least-squares method to the deconvolution of the annihilation radiation lineshape. The general conclusion is that the Doppler-broadened data are consistent with the majority of positrons trapping into microvoids, probably associated with grain boundaries. The data suggest that these open volume defects are more associated with the Au film rather than the Au-Ga alloyed interfacial region.Paper presented at the 132nd WE-Heraeus-Seminar on Positron Studies of Semiconductor Defects, Halle, Germany, 29 August to 2 September 1994  相似文献   
6.
The cis-decalin based gamma-amino alcohols, 1-5, were synthesized, resolved, and employed as catalysts in the addition of organozincs to benzaldehyde. Despite large facial differentiation in the RZn adducts of the ligands, the enantioselectivities were found to be moderate. Transition structure calculations were done using several quantum chemical methods to examine the underlying causes of the selectivity for three gamma-amino alcohols, 1, 2, and 3. The tricyclic mu-oxo (6/4/4), rather than the bicyclic six-membered (6/6), transition structures were found to explain the observed enantioselectivity for 2 and 3. MP2 calculations gave the best correlation to the experimental results compared to B3LYP and HF calculations. The conformational flexibility of the chiral ligands was found to be an important factor in the selectivity.  相似文献   
7.
The cyclooctatetraene-bis(phosphinimino)methanide complex [[CH(PPh2NSiMe3)2]Sm(eta8-C8H8)] has been prepared; although this compound has no alkyl or amide ligand it shows moderate activity as a catalyst for the hydroamination/cyclisation reaction.  相似文献   
8.
Diametrically strapped calix[4]pyrrole-metalloporphyrin conjugates, potential hosts for anionic guests, have been synthesized and characterized. The syntheses rely on the acid-catalyzed condensation of two dipyrromethane bearing Ni(II) porphyrins with acetone. An (1)H NMR spectroscopic titration experiment indicated that the resulting receptors selectively trapped fluoride anions in organic media but not other, larger halide anions. The experimental results from titration and Job plots indicated that the bound fluoride anion must reside inside the cavity. The current systems provide a well-defined illustration of how size-selective anion receptors may be synthesized by incorporating recognition functions, such as Lewis acidity, hydrogen bonding, and encapsulating moieties into established recognition motifs, calix[4]pyrrole in the present instance.  相似文献   
9.
[structure: see text] The synthesis and characterization of a series of low-valent organoselenium compounds derived from 1-bromo-4-tert-butyl-2,6-di(formyl)benzene (22) is described. The synthesis of diselenide 25 was achieved by the lithiation route whereas bis(4-tert-butyl-2,6-di(formyl)phenyl) diselenide (26) was synthesized by treating 22 with disodium diselenide. A series of monoselenides (27, 28, and 29) was obtained by facile nucleophilic substitution of bromine in 22, using the corresponding selenolates as nucleophiles. The halogenation reactions of bis(4-tert-butyl-2,6-di(formyl)phenyl) diselenide (26) did not afford the corresponding selenenyl halides but resulted in the isolation of an unexpected cyclic selenenate ester 34 as a product. The selenide 32 was synthesized by the treatment of dimethoxymethyl diselenide with trilithiated 2-bromo-5-tert-butyl-N,N'-di(phenyl)isophthalamide. The existence of potential Se...O intramolecular nonbonding interactions was examined by IR, (1)H, and (77)Se NMR spectroscopy, X-ray crystallography, and computational studies. The X-ray crystal structures of 26 and 27, having two ortho formyl groups, reveal the absence of any Se...O interactions. However, the Se...O interactions were observed in the selenenate ester 34 where one of the formyl groups has been utilized for the selenenate ring formation. The crystal structures of 26 and 27 exhibited intermolecular short-range C-H...Se interactions (hydrogen bonding). Although there are four heteroatoms in carbamoyl moieties ortho to selenium capable of forming a five-membered ring on intramolecular coordination, no such intramolecular Se...X (X = N, O) interaction was observed in the crystal structure of 32. The density functional theory calculations at the B3LYP/6-31G* level predicted that for all the diformyl systems (47a-c, 48a-c), the anti,anti conformer (when both formyl oxygen atoms point away from the selenium) is more stable. This preference was found to be reversed in the monoformyl-substituted systems (50a,b, 51a,b), where the syn conformer (when formyl oxygen is near the selenium) is energetically more favorable than the anti conformer.  相似文献   
10.
Vinyl polymerization of acrylonitrile initiated by the Ce(IV)/thioacetamide redox system has been investigated in aqueous sulfuric acid in the temperature range of 10–20°C. The rate of polymerization (Rp) and the rate of Ce(IV) disappearance (?RCe) were measured. The effect of certain water-soluble organic solvents, added electrolytes, and aromatic and heterocyclic organic nitrogen compounds on the rate of polymerization has been investigated. Depending on the experimental results, we have suggested a suitable reaction scheme for the system which involves the production of initiating radicals from the oxidation of thioacetamide (TAm) by ceric ion and the termination of the polymer chain by metal ions.  相似文献   
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