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131.
Ribeiro da Silva MA Gomes JR Ferreira AI 《The journal of physical chemistry. B》2005,109(27):13356-13362
The standard (p degrees = 0.1 MPa) molar enthalpies of formation of 2-, 3-, and 4-chloroaniline were derived from the standard molar energies of combustion, in oxygen, at T = 298.15 K, measured by rotating bomb combustion calorimetry. The Calvet high-temperature vacuum sublimation technique was used to measure the enthalpies of vaporization or sublimation of the three isomers. These two thermodynamic parameters yielded the standard molar enthalpies of formation of the three isomers of chloroaniline, in the gaseous phase, at T = 298.15 K, as 53.4 +/- 3.1 kJ.mol(-1) for 2-chloroaniline, 53.0 +/- 2.8 kJ.mol(-1) for 3-chloroaniline, and 59.7 +/- 2.3 kJ.mol(-1) for 4-chloroaniline. These values, which correct previously published data, were used to test the computational methodologies used. Therewith, gas-phase acidities, proton affinities, electron donor capacities, and N-H bond dissociation enthalpies were calculated and found to compare well with available experimental data for these parameters. 相似文献
132.
Chaudhuri RK Freed KF Hose G Piecuch P Kowalski K Włoch M Chattopadhyay S Mukherjee D Rolik Z Szabados A Tóth G Surján PR 《The Journal of chemical physics》2005,122(13):134105
Tests have been made to benchmark and assess the relative accuracies of low-order multireference perturbation theories as compared to coupled cluster (CC) and full configuration interaction (FCI) methods. Test calculations include the ground and some excited states of the Be, H(2), BeH(2), CH(2), and SiH(2) systems. Comparisons with FCI and CC calculations show that in most cases the effective valence shell Hamiltonian (H(v)) method is more accurate than other low-order multireference perturbation theories, although none of the perturbative methods is as accurate as the CC approximations. We also briefly discuss some of the basic differences among the multireference perturbation theories considered in this work. 相似文献
133.
134.
Sérgio L. C. Ferreira Marcus L. S. F. Bandeira Valfredo A. Lemos Hilda C. dos Santos A. C. Spinola Costa Djane S. de Jesus 《Analytical and bioanalytical chemistry》1997,357(8):1174-1178
A simple and very sensitive method has been developed for the determination of ascorbic acid based on the oxidation of ascorbic
acid to dehydroascorbic acid by iron(III), followed by a complexation of iron(II) with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol(Br-PADAP).
The iron(II) complex is formed immediately, with absorption maxima at 560 and 748 nm and a molar absorptivity of 1.31 × 105 l mole–1cm–1 and 5.69 × 104 l mole–1cm–1, respectively. The ascorbic acid determination is possible with a linear range up to 2.4 μg ml–1, a calibration sensitivity of 0.744 ml μg–1 at 560 nm and 0.323 ml μg–1 at 748 nm, and a detection limit of 15 ng ml–1 and 44 ng ml–1, respectively. The procedure was used for the ascorbic acid determination in several fruit juices and pharmaceutical formulations.
The results demonstrated a good precision (R.S.D. < 1%) and are in agreement with those obtained with others methods. The
Br-PADAP method proposed is six times more sensitive than the method using the iron(II)-1,10-phenanthroline system.
Received: 7 May 1996 / Revised: 1 July 1996 / Accepted: 8 August 1996 相似文献
135.
Denilson S.S. dos Santos Alete P. Teixeira José T.P. Barbosa Sérgio L.C. Ferreira Maria das Graças A. Korn Leonardo S.G. Teixeira 《Spectrochimica Acta Part B: Atomic Spectroscopy》2007
In this work, the use of cetyltrimethylammonium bromide as surfactant for the preparation of oil-in-water emulsions for the determination of Cu and Cr in gasoline by electrothermal atomic absorption spectrometry (ET AAS) was evaluated. The surfactant amount was tested in the range of 25 to 300 mg, added to 2 ml of gasoline, and completed to 10 mL with 0.1% (v/v) nitric acid solution. 150 mg of surfactant was found optimum, and a sonication time of 10 min sufficient to form an oil-in-water emulsion that was stable for several hours. The ET AAS temperature program was established based on pyrolysis and atomization curves. The pyrolysis temperatures were set at 700 and 1300 °C for Cu and Cr, respectively and the selected atomization temperatures were 2400 and 2500 °C. The time and temperature of the drying stage and the atomization time were experimentally tested to provide optimum conditions. The limits of detection were found to be 5 μg L− 1 and 1.5 μg L− 1 for Cu and Cr, respectively in the original gasoline samples. The relative standard deviation (RSD) ranged from 4 to 9% in oil-in-water emulsions spiked with 5 μg L− 1 and 15 μg L− 1 of each metal, respectively. Recoveries varied from 90 to 98%. The accuracy of the proposed method was tested by an alternate procedure using complete evaporation of the gasoline sample. The method was adequate for the determination of Cu and Cr in gasoline samples collected from different gas stations in Salvador, BA, Brazil. 相似文献
136.
Basallote MG Estevan F Feliz M Jesús Fernández-Trujillo M Hoyos DA Llusar R Uriel S Vicent C 《Dalton transactions (Cambridge, England : 2003)》2004,(4):530-536
The novel incomplete cuboidal cluster [W3Se4H3(dmpe)3](PF6), [1](PF6), has been prepared by reduction of [W3Se4Br3(dmpe)3](PF6) with LiBH4 in THF solution. The trihydroxo complex [W3Se4(OH)3(dmpe)3](PF6), [2](PF6), was obtained by reacting [W3Se4Br3(dmpe)3](PF6) with NaOH in MeCN-H2O solution. The complexes [1](PF6) and [2](PF6) were converted to their BPh4- salts by treatment with NaBPh4. Recrystallisation of [1](BPh4) in the presence of traces of water affords the mixed dihydride hydroxo complex [W3Se4H2(OH)(dmpe)3](BPh4). The crystal structures of [1](BPh4), [2](BPh4) and [W3Se4H2(OH)(dmpe)3](BPh4) have been resolved. Although the [1]+ trihydride does not react with an excess of halide salts, reaction with HX leads to [W3Se4X3(dmpe)3]+ (X = Cl, Br). The kinetics of this reaction has been studied at 25 degrees C in MeCN-H2O solution (1:1, v/v) and found to occur with two consecutive kinetic steps. The first step is independent of the nature and concentration of the X(-) anion but shows a first order dependence on the concentration of acid (k1 = 12.0 mol(-1) dm(3) s(-1)), whereas the second one is independent of the nature and concentration of both the acid and added salts (k2 = 0.024 s(-1)). In contrast, the reaction of [2]+ with acids occurs in a single step with kobs = 0.63 s(-1)(HCl) and 0.17 s(-1)(HBr). These kinetic results are discussed on the basis of the mechanism previously proposed for the reactions of the analogous [W3S4H3(dmpe)3]+ cluster, with special emphasis on the effects caused by the change of S by Se on the rate constants for the different processes involved. 相似文献
137.
L. F. Brum Malta Marta Eloisa Medeiros 《Journal of Thermal Analysis and Calorimetry》2005,81(1):149-152
Summary This work reports the room-temperature stabilization of the Bi4V2-xFexIIO11-1.5x γ ‘ phase, a promising ionic conductive material that finds application in solid oxide fuel cell and oxygen sensor devices. The Fe(II) cation proved to be a better stabilizer than Fe(III), which was previously used, since a lower substitution degree of V5+ is needed for the former. Powder X-ray diffraction, Fourier-transform infrared spectroscopy and differential scanning calorimetry were used in these experiments. 相似文献
138.
Factorial design in the optimization of preconcentration procedure for lead determination by FAAS 总被引:1,自引:0,他引:1
The present paper proposes a preconcentration procedure for lead determination using flame atomic absorption spectrometry (FAAS). It is based on lead(II) ions extraction as brilliant cresyl blue (BCB) complex and its sorption onto Diaion HP-2MG, a methacrylic ester copolymer. The optimization step was carried out using factorial design and the variables studied were pH, shaking time and reagent concentration. In the established experimental conditions, lead can be determinate with a limit of detection of 3.7 μg L−1 lead (N = 20) and a relative standard deviation of 7% for a lead concentration of 100 μg L−1. The accuracy was confirmed by analysis of a certified reference material, the stream sediment furnished by National Research Centre for Certified Reference Materials (NRCCRM), China (GBW 07310). Effect of other ions in the procedure proposed was also studied. The method was applied for lead determination in real samples of water, tea, soil and dust. Tests of addition/recovery in the experiments for lead determination in water samples revealed that the proposed procedure could be applied satisfactorily for analysis of these samples. 相似文献
139.
Adriana C. Ferreira 《Microchemical Journal》2004,78(1):77-83
A method for preconcentration and determination of trace amounts of cadmium in high saline samples is described. It is based on the adsorption of the metal in the activated carbon as complex cadmium(II)-4-(2-pyridylazo-resorcinol) (PAR). The final determination was carried by flame atomic absorption spectrometry (FAAS). The optimization of extraction parameters such as the pH effect, PAR mass, activated carbon mass and shaking time was carried out using a two-level full factorial design (24) and two Doehlert matrix designs. The results of the factorial design, considering the analysis of variance (ANOVA), demonstrate that all these factors are statistically significant, as well as the interactions (pH×PAR mass), (pH×activated carbon mass) and (activated carbon mass×shaking time). The final optimization was carried out using Doehlert matrix designs considering the results of the factorial design. The recoveries were quantitative (96.0-106.7%) for seawater samples spiked with Cd at concentrations of 0.125 and 0.625 μg l−1. A preconcentration factor of 149 was obtained. The effect of diverse metallic ions on the proposed procedure was investigated too. The procedure was used for cadmium determination in surface seawater samples collected in Salvador City, Brazil. The cadmium content in the analysed samples varies from 0.035 to 0.17 μg l−1. These results are agreement with other data reported in the literature. 相似文献
140.
A reliable solid-phase extraction (SPE) method for the simultaneous determination of 2,4,6-trichloroanisole (TCA) and 2,4,6-tribromoanisole (TBA) in wines has been developed. In the proposed procedure 50 mL of wine are extracted in a 1 mL cartridge filled with 50 mg of LiChrolut EN resins. Most wine volatiles are washed up with 12.5 mL of a water:methanol solution (70%, v/v) containing 1% of NaHCO3. Analytes are further eluted with 0.6 mL of dichloromethane. A 40 microL aliquot of this extract is directly injected into a PTV injector operated in the solvent split mode, and analysed by gas chromatography (GC)-ion trap mass spectrometry using the selected ion storage mode. The solid-phase extraction, including sample volume and rinsing and elution solvents, and the large volume GC injection have been carefully evaluated and optimized. The resulting method is precise (RSD (%) < 6% at 100 ng L(-1)), sensitive (LOD were 0.2 and 0.4 ng/L for TCA and TBA, respectively), robust (the absolute recoveries of both analytes are higher than 80% and consistent wine to wine) and friendly to the GC-MS system (the extract is clean, simple and free from non-volatiles). 相似文献