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961.
Chromatographic retention data and thermodynamic properties of six pine terpenes (α-pinene, β-pinene, camphene, limonene, α-phellandrene and p-cymene) on six different liquid phases, with a wide range of polarity, are reported at temperatures from 80 to 120 °C. The retention behaviour and selectivity of liquid phases for the separation of binary solute systems are discussed in terms of activity coefficients and specific interactions. Solubility parameters for the liquid phases are reported using the regular solution theory and the Takamiya equation and a good correlation between polarity and solubility parameters is observed. 相似文献
962.
Villar-Rodil S. Paredes J. I. Martínez-Alonso A. Tascón J.M.D. 《Journal of Thermal Analysis and Calorimetry》2002,70(1):37-43
The pyrolysis behaviour of Nomex, poly(m-phenylene isophthalamide) fibres under argon has been investigated up to a temperature of 1173 K with different methods to
get direct information on the progressive changes taking place in the solid material and its carbon fibre residues. The main
stages of the pyrolytic degradation of the fibres were determined by thermal analysis (TG and DTA) and their chemical and
morphological evolution through the different steps was subsequently followed by Fourier transform infrared spectroscopy (FTIR)
and atomic force microscopy (AFM) measurements, respectively, on samples treated to various temperatures.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
963.
Summary A comparison of three binary mobile phases in LC separation of C60 and C70 fullerences on chemically bonded 2,4-dinitroanilinopropyl (DNAP) stationary phase was carried out, n-Hexane-benzene has been found to be the best mobile phase for efficient separation of the all-carbon molecules permitting high loads in preparative LC. 相似文献
964.
M. N. Moreno-Carretero J. M. Salas-Peregrín 《Journal of Thermal Analysis and Calorimetry》1984,29(5):1053-1059
The following cadmium(II) complexes of deprotonated 6-amino-5-nitroso-uracil (AH), deprotonated 6-amino-3-methyl-5-nitroso-uracil (BH) and neutral 6-amino-1-methyl-5--nitroso-uracil (CH) have been prepared and their thermal behaviour studied by TG and DSC techniques: CdA2 · 3 H2O, CdB2 · 2 H2O, CdB2 and CdCl2(CH)2 · 2 H2O.Dehydration processes of these complexes take place in only one step and the enthalpy values associated with them are comprised in the 42.7–80.5 kJ · mole–1 H2O range. The pyrolytic reactions finish in the 630–900 C temperature range, remaining as final residue in the case of CdA2 · 3 H2O, CdB2 · 2 H2O and CdB2 complexes, cadmium oxide. The pyrolytic decomposition of CdCl2(CH)2 · 2 H2O complex does not yield any residue, due to the elimination of cadmium chloride.
Zusammenfassung Folgende Cadmium(II)-Komplexe von deprotoniertem 6-Amino-5-nitrosouracil (AH), deprotoniertem 6-Amino-3-methyl-5-nitroso-uracil (BH) und neutralem 6-Amino-1-methyl-5-nitroso-uracil (CH) wurden hergestellt: CdA2 · 3 H2O, CdB2· 2 H2O, CdB2 und CdCl2(CH)2 · 2 H2O. Das thermische Verhalten dieser Komplexe wurde mittels TG und DSC untersucht. Die Dehydratisierung der Komplexe verlÄuft in nur einem Schritt. Die Enthalpiewerte für diese Prozesse liegen im Bereich von 42.7–80.5 kJ · mol–1 H2O. Die pyrolytischen Reaktionen verlaufen im Temperaturbereich von 630–900C zu Ende, wobei im Falle der Komplexe CdA2 · 3 H2O, CdB2 · 2 H2O und CdB2 Cadmiumoxid als Rückstand zurückbleibt. Die pyroytische Zersetzung von CdCl2(CH)2 · 2 H2O verlÄuft wegen der Flüchtigkeit von CdCl2 rückstandslos.
CdA2 · 3 H2O, CdB2 · 2 H2O, CdB2 CdCl2(CH)2 · 2 H2O, A — 6--5-, B — 6--3--5- CH — 6--1--5- . . 42.7–80.5 · –1. 630–900, . CdCl2(CH)2 · 2 H2O - , .相似文献
965.
Liquid—liquid extraction of divalent palladium by solutions of the hexachloroderivate of cobalt dicarbolide (HBCl6) in the mixture of solvents (30 v/v % nitrobenzene+20 v/v % n-dodecane +50 v/v/ % toluene) from nitric acid medium has been studied. Besides HBCl6 the organic phase contained also 2,2′-dipyridyl (dipy). The yield of palladium extraction from 0.5M HNO3 is greater than 99.0%. The species extracted into the organic phase corresponds to the formula [Pd(dipy)2] (BCl6)2. 相似文献
966.
An analytical potential energy surface (PES) representation of the O(+)((4)S)+H(2)(X (1)Sigma(g) (+)) system was developed by fitting around 600 CCSD(T)/cc-pVQZ ab initio points. Rate constant calculations for this reaction and its isotopic variants (D(2) and HD) were performed using the quasiclassical trajectory (QCT) method, obtaining a good agreement with experimental data. Calculations conducted to determine the cross section of the title reaction, considering collision energies (E(T)) below 0.3 eV, also led to good accord with experiments. This PES appears to be suitable for kinetics and dynamics studies. Moreover, the QCT results show that, although the hypotheses of a widely used capture model are not satisfied, the resulting expression for the cross section can be applied within a suitable E(T) interval, due to errors cancellation. This could be a general situation regarding the application of this simple model to ion-molecule processes. 相似文献
967.
A new type of carbon paste electrode modified with clay mineral and covered with a mercury film is presented in this work.
Electrodeposition of the mercury film was performed on the carbon paste electrode modified with montmorillonite. The mercury
film was deposited by both electrodeposition in situ and a preliminary electrodeposition. The pre-deposited film of mercury showed to be suitable for anodic stripping voltammetry.
An open-circuit sorption of Cd, Pb, and Cu with subsequent anodic stripping voltammetry exhibited higher current responses
of metals. Besides the enhanced sensitivity superior separation of the current responses during a simultaneous stripping of
metals is expected to be achieved by means of the newly prepared electrode.
Presented at the 57th Congress of Chemical Societies, Tatranské Matliare, 4–8 September 2005. 相似文献
968.
García-Río L Leis JR Moreira JA Araujo E Norberto F Ribeiro L 《The Journal of organic chemistry》2003,68(11):4330-4337
A kinetic study was carried out on the hydrolysis of two N-nitrosoguanidines, 1-nitroso-1-methyl-3-tolylsulfonylguanidine (TSGNO) and 1-nitroso-1-methyl-3-benzoylguanidine (BCGNO). We observed an absence of buffer catalysis using H(2)PO(4)(-)/HPO(4)(2)(-), H(3)BO(3)/H(2)BO(3)(-), and HCO(3)(-)/CO(3)(2)(-) regulators and a complex dependency of the rate constant on the pH. We discovered the existence of three simultaneous reaction paths: spontaneous decomposition of the neutral form of the N-nitrosoguanidine, decomposition of the monoanion, and decomposition through the form of the dianion. The analysis of the kinetic data has allowed us to obtain the acidity constant for the formation of the monoanion of the N-nitrosoguanidine, with values of p = 11.5. The reaction rate for the process through the monoanion, k(2), decreases as the acidity increases. The application of the principle of nonperfect synchronization shows that the basicity and reactivity do not correlate when there exists a possibility of stabilization of the negative charge by resonance. This behavior is consistent with the mechanism E1cB whereby the stabler the negative charge, the slower the elimination reaction. When dealing with the case of the elimination through the neutral form we observe that the reaction rate increases together with the capacity of stabilization of the positive charge on the nitrogen atom adjacent to the imino group. For the reaction through the dianion we used a maximum value of k(3) = 10(10) s(-)(1) to estimate the value of p for the formation of the dianion of the N-nitrosoguanidine, obtaining values of p < 24. 相似文献
969.
The reaction of 1,3-dicloro-2-butene (1; 5:1 Z:E-mixture) with lithium powder and a catalytic amount of 4,4′-di-tert-butylbiphenyl (DTBB, 1% molar) in the presence of different electrophiles [EtCHO, PriCHO, ButCHO, c-C6H11CHO, Me2CO, Et2CO, (CH2)4CO, (CH2)5CO, (c-C3H5)2CO, Me3SiCl] in THF at temperatures ranging between −78 and −50°C gives, after hydrolysis with water, the corresponding products 2 in different Z:E-ratios depending on the electrophile used. Treatment of some diols 2 with hydrochloric acid gives dienic alcohols 3 or substituted dihydropyrans 4, depending on the structure of the starting diol. Finally, the same dichlorinated starting material is transformed into the corresponding allylic amines derived from morpholine and benzyl methyl amine and submitted to the same DTBB-catalysed lithiation as above, so after reaction with different electrophiles [ButCHO, c-C6H11CHO, Me2CO, Et2CO, (CH2)4CO, (CH2)5CO, Me3SiCl] and final hydrolysis with water, compounds 7 are isolated having a Z-configuration. A mechanistic explanation for this behaviour is given. 相似文献
970.
Fernández EJ Laguna A López-De-Luzuriaga JM Mendizabal F Monge M Olmos ME Pérez J 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(2):456-465
The reactions of solutions of TlPF(6) and OPPh(3) in tetrahydrofuran or acetone with NBu(4)[AuR(2)] (R=C(6)Cl(5), C(6)F(5)) gave the new complexes [Au(C(6)Cl(5))(2)](2)[Tl(OPPh(3))][Tl(OPPh(3))(L)] (L=THF (1), acetone (2)) and the previously reported [Tl(OPPh(3))(2)][Au(C(6)F(5))(2)] (3). The crystal structures of complexes 1 and 2 display extended unsupported chains with short intermolecular interactions between alternating gold(I) and thallium(I) centres. Moreover, the Tl(I) centres show two different types of geometrical environments, such as pseudotetrahedral and distorted trigonal-bipyramidal, due to the presence of solvent molecules that act as ligands in the solid-state structure. Quasirelativistic and nonrelativistic ab initio calculations were performed to study the nature of the intermetallic Au(I)-Tl(I) interactions and are consistent with the presence of a high ionic contribution (80 %) and dispersion-type (van der Waals) interaction with a charge-transfer contribution (20 %) when relativistic effects are taken into account. All complexes are luminescent in the solid state at room temperature and at 77 K. Complexes 1 and 2 show site-selective excitation, probably due to the different environments around the Tl(I) centres. The DFT and time-dependent (TD)-DFT calculations are in agreement with the experimental excitation spectra for all complexes and confirm the site-selective excitation behaviour as a function of the Tl(I) geometrical environment. 相似文献