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11.
A theoretical study of π-electron spin density distributions has been made for a series of fluoro-substituted hydrocarbon radical cations using unrestricted Hartree-Fock theory. Although some of the predicted proton splittings are not in very good agreement with experiment, the overall agreement with experiment can be passed as fairly satisfactory considering the approximate nature of the theory used. The experimental fluorine splittings can be well predicted by using a one-parameter relationship between the isotropic fluorine splitting (aF) and the π-electron spin density (ρCC) on the attached carbon. It has been further shown that both ρCC and the proportionality constant (Qeff) in the linear relation, are fairly insensitive to the parameter choice. 相似文献
12.
Soot deep oxidation catalyzed by molybdena and molybdates: a thermogravimetric investigation 总被引:2,自引:0,他引:2
Molybdena (MoO3) and molybdates of bismuth (Bi2Mo3O12), chromium (Cr2Mo3O12), barium (BaMoO4), manganese (MnMoO4) and copper (Cu3Mo2O9) were synthesized and characterized by X-ray powder diffractometry and infrared spectroscopy. They were then assessed as ‘loose contact' catalysts for soot deep oxidation (combustion) in air by thermogravimetry. A similar assessment was carried out on commercial chromia (Cr2O3) and tungsta (WO3). Observed high oxidation activity of MoO3, as compared to both Cr2O3 and WO3, is attributed to the higher volatility (mobility) of MoOx species. On similar grounds, observed high activity of MoO3 and Cu3Mo2O9, as compared to the other test molybdates, is explained. Relatively speaking, however, a higher activity was observed for Cu3Mo2O9 than MoO3, whereby soot ignition temperature decreased from 571°C (uncatalyzed oxidation) to 430°C, to occur within the temperature range of diesel exhaust (200–450°C). This observation is ascribed to copper-promoted redox conduct of Mo(VI) in the oxidation reaction of soot. Kinetics of the reaction was studied non-isothermally, and the kinetic parameters (A, k, ΔE and the reaction order) were calculated. 相似文献
13.
A. N. Thakur 《Journal of Radioanalytical and Nuclear Chemistry》1997,215(2):161-167
Neutron induced -ray spectra from various geological samples were analyzed to evaluate the usefulness of continuum spectra in deriving the chemical composition information. A fast Fourier transform technique has been used to estimate the signal content of selected energy bands of the continuum spectra. Monte Carlo calculations have been performed using the major -ray energy sources (due to Fe, Ca, Si and Al) to generate the corresponding detected -ray spectra. The experimental spectra are compared to the simulated spectra to check the consistency of the signal distribution between the peak and the continuum. The continuum above and below a chosen -ray line is calculated to find what fraction of the lower energy continuum is due to that line. The accuracy of the relative elemental concentrations determined by this method is confirmed through comparison with laboratory elemental analysis of the samples. It is found that using the continuum could greatly increase the sensitivity and precision of the measurement of elemental concentrations determined from -ray spectra of thick target sources, for spectra having peaks of poor statistical significance. However, for thin target sources or spectra with very good statistics in their peaks, this method may not be very advantageous. 相似文献
14.
The extraction behaviour of thorium(IV) from aqueous nitric acid employing 3-phenyl-4-benzoyl-5-isoxazolone (HPBI) in the presence of tri-n-octyl phosphine oxide (TOPO) as well as tri-n-butyl phosphate (TBP) in xylene medium was investigated. The extraction constant (log k(ex)) for the binary organic phase species Th(PBI)(4) was determined to be 8.26 which is by far the largest amongst the corresponding values known for other beta-diketones. The overall extraction constant (log K) for the ternary species Th(PBI)(4) TBP and Th(PBI)(4).2TOPO were estimated to be 14.96 and 20.96 respectively. An inverse correlation of the adduct formation constant (log K(s)) with the pK(a) of the beta-diketones, 2-thenoyltrifluoroacetone, 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone and HPBI, was observed. The steric as well as the electronic effects of adduct formation have been discussed. Analytical application of HPBI for the separation of (234)Th radiotracer from natural uranium (99.3% (238)U) has been suggested. 相似文献
15.
Das DD Mahapatra R Pradhan J Das SN Thakur RS 《Journal of colloid and interface science》2000,232(2):235-240
Removal of hexavalent chromium from aqueous medium by using activated cow dung carbon was studied. Cow dung was carbonized and activated by treating with concentrated H(2)SO(4) followed by heating for 24 h at 120 degrees C. The extent of adsorption was studied as a function of pH, contact time, amount of adsorbent, concentration of adsorbate, and temperature. At lower pH (<3.5), the prepared sorbent was capable of removing approximately 90% Cr(VI) at 5 ppm concentration from aqueous synthetic solution. The dynamics of migration of the sorbate ions from the bulk onto the sorbent surface was studied and the results obtained under various experimental conditions were found to follow standard adsorption isotherms. The reaction kinetics was found to be of first order. Copyright 2000 Academic Press. 相似文献
16.
C.S. Hoad R.W. Matthews M.M. Thakur D.G. Gillies 《Journal of organometallic chemistry》1977,124(3):c31-c36
Thallium-205, carbon-13 and proton NMR spectra have been determined for some monomethylthallium(III) derivatives CH3TlX2 (X anion) permitting comparison of NMR parameters in the series CH3TlX2, (CH3)2TlX, (CH3)3Tl. 相似文献
17.
Colorimetric method for the determination of captafol (difolatan) in commercial formulations and residues on grains and apples. 总被引:1,自引:0,他引:1
A simple and rapid colorimetric method for the microdetermination of captafol (difolatan), based on its reaction with a dithiocarbamate, has been developed. The bright yellow colour which develops instantaneously on mixing the fungicide with the reagent is stable for at least 12 h. The method has been successfully adapted to the determination of captafol in its formulated products and residues on grains and apples. 相似文献
18.
N-Methylaminothioformyl-N'-phenylhydroxylamine forms a 1:2 (metal:ligand) greenish yellow complex with cobalt(II). This complex has maximum absorption at 470 nm with a molar absorptivity of 1.65 x 10(4) 1.mole(-1).cm(-1). Beer's law is obeyed over the concentration range 6 x 10(-6)-6 x 10(-5)M. The effect of diverse ions is described. 相似文献
19.
Spectrophotometric Determination of Rhenium(IV) with Thiocyanate,TX-100 and N,N′-Diphenylbenzamidine
A spectrophotometric method to determine rhenium(IV) at trace level is based on the extraction of Re(IV)-SCN? complex in sulphuric acid media with N,N′-diphenylbenzamidine(DPBA) in presence of a non-ionic surfactant triton X-100 (TX-100) in chloroform. The complex shows maximum absorbance at 435 nm with amolar absorptivity value of 4.24 × 104 L mol?1 cm?1 at an acidity range 3.5-6.5 M H2SO4. The method followed Beer's Law for the system Re(IV)-SCN?(TX-100)-DPBA upto 4.0 μg Re(IV) mL?1. The detection limit of the method is 5 ppb. None of the tested foreign ions, except molybdenum(VI), interfere with the determination of rhenium. The interference due to molybdenum could effectively be removed by prior precipitation with oxine. The effect of various analytical parameters on the extraction of the metal are discussed. 相似文献
20.
A simple and sensitive field detection and spectrophotometric method for determination of copper described herewith is based on the formation of a red coloured species of copper(II) with 1-[pyridyl-(2)-azo]-naphthol-(2) (PAN), TX-100 and N,N'-diphenylbenzamidine (DPBA) at pH range 7.8-9.4. The red coloured Cu(II)-PAN-(TX-100)-DPBA complex in chloroform shows maximum absorbance at 520 nm with molar absorptivity value of 1.14x10(5) l mol(-1) cm(-1). The detection limit of the method is 2 ng ml(-1) organic phase. The system obeys Beer's law up to 0.6 mug Cu(II) ml(-1) in organic solution. Most of the common metal ions generally found associated with copper do not interfere. The repeatability of the method was checked by finding relative standard deviation (RSD) (n=10) value for solutions each containing 0.2 mug ml(-1) of Cu(II) and the RSD value of the method was found to be 1.5%. The validity of the method has been satisfactorily examined for the determination of copper in soil and airborne dust particulate samples. 相似文献