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31.
A method has been developed for the speciation of trace dissolved Fe(II) and Fe(III) in water by coupling gallic acid (GA) modified nanometer-sized alumina micro-column separation with inductively coupled plasma mass spectrometry (ICP-MS). The separation of Fe(II) and Fe(III) was achieved based on the obvious difference in reaction kinetics between Fe(II) and Fe(III) with GA. Fe(III) was selectively retained on the micro-column at pH 5.5-6.5, while Fe(II) could not be retained by the micro-column at the whole tested pH range of 1.0-6.5, and passed through the micro-column. The Fe(II) can be determined by ICP-MS directly without preconcentration/separation procedure, while Fe(III) retained on the micro-column was then eluted with 1.0 mL of 1 mol L(-1) HCl and determined by ICP-MS. The parameters affecting the separation of Fe(II) and Fe(III) were investigated systematically and the optimum separation conditions were established. Under the optimized conditions, the detection limits of 0.48 microg L(-1) and 0.24 microg L(-1) with relative standard deviation of 5.6% and 4.3%(C= 5 microg L(-1), n= 7) for Fe(II) and Fe(III) were found, respectively. No obvious effect on the speciation of Fe(II) and Fe(III) was found with the change of the ratio of Fe(II) and Fe(III) from 0 ratio 10 to 10 ratio 0. The proposed method was applied for the determination of trace Fe(II) and Fe(III) in environmental water and the recoveries for spiked samples were found to be in the range of 97-105%. 相似文献
32.
The electrophoretic mobilities of chloro-, bromo- and iodo-complexes of Hg, Bi, Cd, Pb, and Cu, obtained by heavy current electrophoresis on filter paper, are presented in diagrams as a function of the logarithm of the concentrations of the halogen ions KC1, HCl, KUr, HBr and KJ, mainly in concentrations between 0.1N and 4N, were selected as complexing agents Straight lines were obtuned with characteristic slopes, breaks and parallelisms. Furthermore it can be seen from the diagiarns, that the tendency to form complexes increases on the one hand in the sequence chloro - bromo -iodo, and on the other for the chloro- and bromo-complexes in the sequence Cu - Pb - Cd - Bi -Hg In the case of the lodo-complexes the sequence is (Pb + Cd) - Hg - Cu.Figures that show the electrophoretie scpartion of a mixture of Hg - Bi - Cd - Pb - Cu in Voirious concentrations of KC1, KBr and HBr, are given. The separation of these metals in the form of halogeno-complexes can be most satisfactorily accomplished in 0.5N KBr or 0.5NHBr. 相似文献
33.
34.
35.
The double bond migration of butene catalyzed by 1-ethyl-3-methyl-imidazolium fluoride (EmimF) has been studied using quantum chemical method. The geometries of reactant, transition state and product for the isomerization have been optimized by density functional theory (DFT) at the B3PW91/6-31G(d,p), 6-311++G(d,p) and aug-cc-PVDZ levels. The computed results show that the 4-H atom on imidazole ring of EmimF has a good catalytic activity to the double bond migration of butene and the catalytic reaction of 1-butene to 2-butene is a synergetic and elementary process. The apparent activation energy of isomerization is about 197 kJ/mol. 相似文献
36.
Jinzhang Gao Yongjun Liu Wu Yang Lumei Pu Jie Yu Quanfang Lu 《Central European Journal of Chemistry》2005,3(3):377-386
A plasma induced degradation process has been studied to treat 4-nitrotoluene (4-NT) present as an aqueous pollutant. The
plasma was locally generated from a glow discharge around a tip of a platinum anode in an electrolytic solution. The influence
of initial pH and Fe2+ on the degradation was examined. Major intermediates resulting from the degradation process were identified. Amongst the
aromatic intermediates, p-hydroxybenzoic acid was the predominant degradation product. The formation of oxalic acid, malic
acid was also observed. The final products of degradation were NH
4
+
, NO
3
−
and CO2. Based on the analysis of intermediates and the kinetic considerations, the degradation was shown to follow a pseudo-first
order reaction hence, a possible reaction pathway was proposed. 相似文献
37.
trans-RhCl(CO)(TPPTS)2 (TPPTS=tris(m-sulfonatophenyl)phosphine) has been intercalated into Zn-Al layered double hydroxides (LDHs) by the method of ion exchange. The structure, composition and thermal stability of the composite material have been characterized by powder X-ray diffraction, Fourier transform infrared and 31P solid-state magic-angle spinning nuclear magnetic resonance spectroscopy, elemental analysis, thermogravimetry, and differential thermal analysis. The geometry of trans-RhCl(CO)(TPPTS)2 was fully optimized using the PM3 semiempirical molecular orbital method, and a schematic model for the intercalated species has been proposed. The thermal stability of trans-RhCl(CO)(TPPTS)2 is significantly enhanced by intercalation, which suggests that such materials may have prospective application as the basis of a supported catalyst system for the hydroformylation of higher olefins. 相似文献
38.
Novel chiral bisbinaphthyl compounds have been synthesized for the enantioselective fluorescent recognition of mandelic acid. By introducing dendritic branches to the chiral receptor unit, the fluorescence signals of the receptors are significantly amplified because of the light-harvesting effect of the dendritic structure. This has greatly increased the sensitivity of the sensors in the fluorescent recognition. Study of the three generation sensors demonstrates that the generation zero sensor is the best choice for the recognition of mandelic acid because of its greatly increased fluorescence signal over the core and its high enantioselectivity. This sensor is potentially useful for the high throughput screening of chiral catalysts for the asymmetric synthesis of alpha-hydroxycarboxylic acids. 相似文献
39.
Cheng YM Pu SC Yu YC Chou PT Huang CH Chen CT Li TH Hu WP 《The journal of physical chemistry. A》2005,109(51):11696-11706
Comprehensive excitation behaviors of 7-N,N-diethylamino-3-hydroxyflavone (I) have been investigated via steady state, temperature-dependent emission, and fluorescence upconversion to probe the excited-state intramolecular proton transfer (PT) reaction. Upon excitation, I undergoes ultrafast (<120 fs), adiabatic type of charge transfer (CT), so that the dipolar vector in the Franck-Condon excited state is much different from that in the ground state. In polar solvents such as CH2Cl2 and CH3CN, early relaxation dynamics clearly reveals the competitive rates between solvent relaxation and PT dynamics. After reaching thermal equilibrium, a relatively slow, solvent-polarity-dependent rate (a few tens of picoseconds(-1)) of PT takes places. Firm support of the early relaxation dynamics is rendered by the spectral temporal evolution, which resolves two distinct bands ascribed to CT and PT emission. The results, in combination with ab initio calculations on the dipolar vectors for various corresponding states, led us to conclude that excited-state normal (N*) and excited proton-transfer tautomer (T*) possesses very different dipole orientation, whereas the dipole orientation of the normal ground state (N) is between that of N* and T*. PT is thus energetically favorable at the Franck-Condon excited N*, and its rate is competitive with respect to the solvent relaxation dynamics induced by CT. Unlike the well-known PT system, 4'-N,N-diethylamino-3-hydroxyflavone, in which equilibrium exists between solvent-equilibrated N(eq)* and T(eq)*, N(eq)* --> T(eq)* PT for I is a highly exergonic, irreversible process in all solvents studied. Further temperature-dependent studies deduce a solvent-polarity-perturbed energy barrier of 3.6 kcal/mol for the N(eq)* --> T(eq)* PT in CH3CN. The proposed dipole-moment-tuning PT mechanism with the associated relaxation dynamics is believed to apply to many PT molecules in polar, aprotic solvents. 相似文献
40.