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51.
Density of supercritical CO_2-tetrahydrofuran binary mixture and the partial molar volume of the cosolvent 总被引:1,自引:0,他引:1
The densities of supercritical CO2-tetrahydrofuran (cosolvent) binary mixture weremeasured at temperatures in range of 308.15 to 323.15 K and at pressure up to 16.5 MPa.The concentrations of tetrahydrofuran were from 0 to 0.57 mol/L.The partial molar volume of tetrahydrofuran was calculated based on the relationship between the density of the mixture and the concentration of the cosolvent.It is observed that the partial molar volume of the cosolvent is negative and the absolute value decreases with increasing pressure and the concentration of the cosolvent. 相似文献
52.
Changeable size moving window partial least squares (CSMWPLS) and searching combination moving window partial least squares (SCMWPLS) are proposed to search for an optimized spectral interval and an optimized combination of spectral regions from informative regions obtained by a previously proposed spectral interval selection method, moving window partial least squares (MWPLSR) [Anal. Chem. 74 (2002) 3555]. The utilization of informative regions aims to construct better PLS models than those based on the whole spectral points. The purpose of CSMWPLS and SCMWPLS is to optimize the informative regions and their combination to further improve the prediction ability of the PLS models. The results of their application to an open-path (OP)/FT-IR spectra data set show that the proposed methods, especially SCMWPLS can find out an optimized combination, with which one can improve, often significantly, the performance of the corresponding PLS model, in terms of low prediction error, root mean square error of prediction (RMSEP) with the reasonable latent variable (LVs) number, comparing with the results obtained using whole spectra or direct combination of informative regions for a compound. Regions consisting of the combinations obtained can easily be explained by the existence of IR absorption bands in those spectral regions. 相似文献
53.
在低钯含量活性非均布Pd/Al2O3催化剂上,实现了富氧条件下,氢部分选择性催化还原NO过程,低温、富氧条件下NO的转化率高达80%-100%。NO直接分解实验表明,600℃,NO分解转化率在无氧时为17.3%,有0.5%氧存在时接近于0。氢非选择性还原NO条件下,100℃以下,NO转化率为100%。根据实验结果及文献,推测了氢部分选择性还原NO过程中可能存在的反应,不同的反应温度下,NO脱除反应有所不同。在115℃以下,NO还原产物为NH3;115℃-155℃,NO还原产物为NH3、N2O和N2;155℃以上,NO还原产物中无NH3存在。NO还原反应与氢氧反应是平行的竞争反应。 相似文献
54.
The chromatographic separation properties of long, thin adsorption tubes enable substance-specific quantitative enrichment and reduction to be achieved when sampling and thermal desorption are carried out in the same flow direction. The specific retention volumes, and also the breakthrough and peak end volumes, of 69 compounds in the boiling range between-164 and 126°C and of a relative molecular mass between 16 and 119 were determined at temperatures between 30 and 130°C: normal alkanes, isoalkanes, cycloalkanes, alkenes, polyenes, alkynes, aromatics, ethers, alcohols, aldehydes, ketones, carboxylic acids and their esters, nitroalkanes, O-heterocycles, S-heterocycles, chloroalkanes, water, nitrogen monoxide, nitrogen dioxide, carbon dioxide, and sulfur dioxide. The correlation between adsorbent temperature and specific retention volume of these components, presented in the form of diagrams, permits the required quantity of adsorbent to be determined for a given sample volume. Contrary to literature sources, even extremely volatile compounds such as propane, propene, methanol, formaldehyde, formic acid, and chloromethane can be quantitatively retained on Tenax provided the operating conditions are appropriately selected. 相似文献
55.
The concentration dependence of the apparent molar volumes of lithium halides (and electrolytes in general) in alcohols (and
solvents permitting association in general) is, in the first instance, due to changes in the degree of association and to
the inherent difference between the apparent molar volumes of the ions and of the ion pairs. Previous publications on the
molar volumes of electrolytes in organic solvents, disregarding altogether ion pairing, appear to be incorrect. Data from
the literature for lithium chloride and lithium bromide in normal primary alcohols and several branched alcohols from C1 to C8 and data from our laboratory for lithium halides in 1-hexanol and 2-ethyl-1-hexanol served for the determination of φ
V
and φ
E
. Electrical and structural contributions to the values of these functions for the ions and for the ion pairs are discussed. 相似文献
56.
The densities of H2O, D2O, and MeOH solutions in acetonitrile with the solute concentrations up to 0.07 molar fractions at 278.15, 288.15, 298.15, 308.15, and 318.15 K were measured using vibrating-tube densimetry with an error 8·10–6 g cm–3. The limiting partial molar volumes for the H/D isotopomers of water and IaII in acetonitrile (V–
2
) and the isotope effects in V–
2
and in excess molar volumes of acetonitrile—water mixtures were calculated. Molecules of H2O, D2O, and IaII form associates with acetonitrile molecules via hydrogen bonds. The associates have the packing volumes close to those in the individual solute. The water and methanol molecules were assumed to be incorporated into the acetonitrile structure without substantial changes in the latter. However, this process results in some compression of the system with a simultaneous increase in its expansibility. 相似文献
57.
The apparent molal volumes and compressibilities of NaCl, KCl, and CsCl in mixtures of 18-Crown-6 and water have been calculated from density and speed-of-sound measurements at 25°C. The partial molal volumes and compressibilities of the salts when all cations have formed complexes with 18-Crown-6 molecules have been evaluated. The sign and magnitude of the volume and compressibility changes of complex formation strongly suggest that the charge of the cation becomes very effectively screened by the crown ether. 相似文献
58.
The key factors influencing the Diels—Alder reaction rate at ambient and elevated pressures were elucidated using data on the reactivity of various diene—dienophile systems in usual and Lewis acid-catalyzed Diels—Alder reactions, the reaction enthalpy, complex formation, dissolution, and solvation, and the donor-acceptor properties of the reactants. It was found that taking account of both the orbital interaction energy and the balance of bond rupture and formation energies allows correct prediction of the reaction rate in the absence or in the presence of Lewis acids. 相似文献
59.
Starting from the natural neo-clerodane diterpenoid teubotrin (1) several neo-clerodane derivatives (3-7,9-11) have been obtained. The naturally occurring diterpenoid teuscordinon (12) has also been synthesized from teubotrin (1), showing thereby how some of these transformations can be useful for the synthesis of other natural neo-clerodane diterpenes. The latter are of interest due to their activity as insect antifeedants and other important biological properties. 相似文献
60.
Excess Molar Volume and Viscosity of Isobutyric Acid + Water Binary Mixtures Near and Far Away from the Critical Temperature 总被引:1,自引:0,他引:1
The excess molar volume VE, shear viscosity deviation Δη and excess Gibbs energy of activation ΔG∗E of viscous flow have been investigated by using density (ρ) and shear viscosity (η) measurements for isobutyric acid + water (IBA+W) mixtures over the entire range of mole fractions at five different temperatures,
both near and close to the critical temperature (2.055K ≤ (T−Tc)≤ 13.055K). The results were also fitted with the Redlich–Kister equation. This system exhibited very large negative values
of VE and very large positive values of Δη due to increased hydrogen bonding interactions and correlation length between unlike molecules in the critical region and
to very large differences between the molar volumes of the pure components at low temperatures. The activation parameters
ΔH∗ and ΔS∗ have been also calculated and show that the critical region has an important effect on the volumetric properties. 相似文献