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931.
Sorption of n-hexane on monodimensional pure silica SSZ-35, CIT-5, ZSM-12, and ZSM-22 zeolites with different pore dimension and on recently synthesized ITQ-29 was studied by IR spectroscopic and computational chemistry methods. Heats of sorption of n-hexane on these zeolites was determined experimentally from the temperature dependence of the intensity of IR bands of sorbed hexane as well as from theoretical calculations. Calculations have shown the different orientations of sorbed hexane molecules inside zeolite channels, which depend on the type of zeolite and loading. At high loadings, ordering of hexane inside the channels is observed due to optimization of sorbate-sorbate and sorbate-zeolite interaction energies. Such ordering is responsible for the increase of the sorption energy. A decrease of the sorption energy upon increasing the pore dimension of zeolite was observed, in agreement with results previously published in the literature. Effects of pore diameter of zeolites and ordering of molecules inside zeolite channels on the sorption energy of hexane are discussed. 相似文献
932.
The molar single ion activity coefficients associated with hydrogen, copper(II), cadmium(II) and lead(II) ions were determined at 25 degrees C and ionic strengths between 0.100 and 3.00 M (NaClO4), whereas for acetate the ionic strengths were fixed between 0.300 and 2.00 M, held with the same inert electrolyte. The investigation was carried out potentiometrically by using proton-sensitive glass, copper, cadmium and lead ion-selective electrodes and a second-class Hg|Hg2(CH3COO)2 electrode. It was found that the activity coefficients of these ions (y(i)) can be assessed through the following empirical equations: log y(H) = -0.542I(0.5) + 0.451I; log y(Cu) = -1.249I(0.5) + 0.912I; log y(Cd) = -0.829I(0.5) + 0.448I(1.5); log y(Pb) = -0.404I(0.5) + 0.117I(2); and log y(Ac) = 0.0370I 相似文献
933.
A method for the determination of salicylamide at concentrations between 25 and 350 ng ml(-1) by use of matrix isopotential synchronous fluorescence spectrometry (MISF) in combination with derivative techniques is proposed. The method allows the determination of compounds in samples with unknown background fluorescence without the need for tedious pre-separation. Synchronous scans are performed along a trajectory that connects points of identical intensity in a three-dimensional fluorescence spectrum. The unknown analytical signal of the serum is suppressed from the MISF spectrum, by calculating its first derivative at lambda(exc)=324 nm and lambda(em)=392 nm. In order to ensure maximum sensitivity and adequate selectivity, the experimental variables affecting the fluorescence intensity of the salicylamide band at lambda(exc)=328 nm and lambda(em)=418 nm were studied. Based on the results, the determination was performed in an aqueous medium at pH 12 that was adjusted with a sodium phosphate/hydrogen phosphate buffer. Calibration graphs were subjected to a comprehensive statistical analysis. The error propagation has been considered in order to calculate the detection limit by the criterium of Clayton. 相似文献
934.
M. A. Ilatovskaya Z. Rummel' Yu. V. Isaev S. M. Yunusov N. D. Lenenko M. German M. Varen Yu. N. Novikov V. B. Shur 《Russian Chemical Bulletin》1991,40(8):1722-1722
Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 8, pp. 1935–1936, August, 1991. March 13, 1991. 相似文献
935.
Inoue K Kawaguchi M Okada F Yoshimura Y Nakazawa H 《Analytical and bioanalytical chemistry》2003,375(4):527-533
A novel method based on column-switching high-performance liquid chromatography-electrospray mass spectrometry (LC-MS) coupled with an on-line extraction column containing conjugated avidin has been developed for direct injection analysis of di(2-ethylhexyl) phthalate (DEHP) and its metabolite, mono(2-ethylhexyl) phthalate (MEHP), in blood samples. The sample preparation for on-line extraction involved the mixing of blood samples with internal standards, DEHP-d(4) and MEHP-d(4), in LC glass vials. A linear response was found for column-switching LC-MS when tests were conducted within the validated range of 25 to 1000 ng mL(-1) for DEHP and 5 to 1000 ng mL(-1) for MEHP, with correlation coefficients (r) greater than 0.999. In addition, the recoveries of DEHP and MEHP from human plasma were calculated by using this method with on-line extraction, yielding recoveries of up to 91.2% (RSD<5%). We measured the background levels of DEHP and MEHP in six human plasma samples from healthy volunteers and three fetal bovine serum samples for cell-line culture. DEHP and MEHP were not detected in all human plasma samples (N.D. is <25 ng mL(-1) for DEHP, and N.D. is <5.0 ng mL(-1) for MEHP). In contrast, high DEHP contamination of commercially available fetal bovine serum samples was found by this method. 相似文献
936.
Arturo Ponce Francisco M. Morales Sergio I. Molina Lucía Barbadillo Manuel Cervera Marí J. Hernández Pedro Rodríguez Juan Piqueras 《Mikrochimica acta》2004,145(1-4):165-169
In the present work, high-doses (1017–1018cm–2) of carbon, nitrogen, and boron (BF2+) ions were coimplanted on silicon (111) substrates at 21, 25 and 77keV, respectively. Two series of samples have been implanted (series A and B) and subsequently annealed. Series A samples have been implanted at room temperature and treated one minute by rapid thermal annealing (RTA) and 3 hours at 1200°C. Series B samples have been implanted at 600°C and subsequently annealed at 1200°C during 3 hours. The annealing in both series has been carried out in N2 at atmospheric pressures.The structure of the buried layers has been determined by conventional and high resolution transmission electron microscopy (CTEM and HRTEM). Polycrystalline silicon and new crystalline phases are observed by electron diffraction patterns. The polycrystalline silicon inclusions have been confirmed from analysis of HRTEM images. 相似文献
937.
Tárraga A Molina P López JL Velasco MD 《Dalton transactions (Cambridge, England : 2003)》2004,(8):1159-1165
The structure-redox chemistry relationship of a new type of azaferrocenophane-based chemosensors, 3 and 4, in the presence of protons and several kinds of metal ions, has been studied. Electrochemical studies, carried out in CH2Cl2, in the presence of increasing amounts of Mg2+, Ca2+, Zn2+ and Ni2+ showed that the wave corresponding to the Fc/Fc+ couple of the uncomplexed ligands is gradually replaced by a new reversible wave at more positive potentials corresponding to the Fc/Fc+ couple of the complexed ligands. The maximum shift of the ferrocene oxidation wave was found for 4b in the presence of Mg2+, whereas for 3f a selective sensing response for Mg2+ in the presence of hydrated Ca2+ cations was observed, with a concomitant highly visual output response consisting of a deep purple colour. 相似文献
938.
N. D. Kagramanov A. A. Kutin N. V. Peschanskii A. Ya. Zapevalov L. S. German 《Russian Chemical Bulletin》1991,40(7):1321-1325
The pyrolysis of perfluoroolefin oxides has been studied by gas chromatography/mass spectrometry at 400–700°C, in a current of He (110 dilution, contact time 1 sec). For oxides containing a terminal CF2 group, the sole degradation route is through the elimination of difluorocarbene. Pyrolysis of symmetrical disubstituted oxides results in the elimination of a perfluoroalkylfluorocarbene, which subsequently isomerizes to the corresponding perfluoroolefin. In the pyrolysis of unsymmetric disubstituted oxides the elimination of perfluoroalkylfluorocarbenes occurs by both of the possible routes. Trisubstituted oxides eliminate bis-perfluoroalkylcarbenes. The decomposition of tetrasubstituted oxides proceeds along several directions concurrently.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1497–1502, July, 1991. 相似文献
939.
(19)F NMR chemical shifts are calculated in order to study the F(-) environment in double four ring (D4R) containing Si/Ge-zeolites. The calculations with the DFT/CSGT/B3PW91 methodology yielded an agreement within 2 ppm with respect to the experimental peaks corresponding to the D4R units containing 8Si0Ge, 7Si1Ge and 0Si8Ge of the octadecasil zeolite. The optimisation of the 7Si1Ge-, 6Si2Ge-, 5Si3Ge- and 4Si4Ge-D4R units with DFT/B3LYP methodology shows that a covalent Ge-F bond is formed and therefore a Ge atom in the D4R is pentacoordinated. The displacement of the fluoride ion towards a Ge atom in the Ge-containing D4R units locates four Si/Ge atoms in the close vicinity of the F(-) and this makes possible a rationalization of the (19)F NMR signals in groups according to the number of Si (n) and Ge (m) atoms in the nearest F(-) environment, F-Si(n)Ge(m) (where n+m=4). Thus, the calculated chemical shifts show that higher values are observed when the number of Ge atoms in the nearest F(-) environment increases. 相似文献
940.
de Benzo Zully A. Castro German Carrión Nereida Flores Johnny 《Mikrochimica acta》1986,88(5-6):311-324
Preliminary investigations concerning the surface and lifetime of rejuvenated graphite tubes were carried out in order to recuperate exhausted graphite tubes considered unusable for flameless atomic absorption spectroscopy. The effect of a tungsten carbide surface on the sensitivity and precision of Cu and Cr and the lifetime of the new surface in oxidant media are reported. 相似文献