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1.
Unsteady motion in single-line flow-injection systems consisting of n tubular elements with valve or hydrodynamic injection is studied theoretically. A formula for the duration of the initial period of unsteady flow is derived. This initial period is much shorter than the mean residence time of the analyte in practical systems. It can therefore be neglected in mathematical modelling of such systems. Experimental data obtained with single-line systems with valve and hydrodynamic injection confirmed the validity of the theoretical equations. 相似文献
2.
Upper rim substituted tetraiodo calix[4]arenes are coupled to a variety of acrylamides using the palladium catalysed Heck reaction. Tetra-acrylamido upper rim substituted calix[4]arenes are obtained in good yields with exceptionally high stereoselectivity, to produce the all-trans isomers. Tetra-acrylamido calix[4]arenes derived from secondary acrylamides are shown to dimerise via eight hydrogen bonds to form dimeric capsules, which are able to include small organic molecules. 相似文献
3.
Kolev TM Yancheva DY Stamboliyska BA 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2003,59(8):1805-1813
The FTIR spectra of pyridinium-betaine of squaric acid in 4000-100 cm(-1) frequency region in solid state were measured. In addition, the structure and harmonic vibrational frequencies of this molecule were theoretically evaluated using restricted Hartree-Fock and B3LYP density functional methods. The computed vibrational frequencies are used to determine the types of molecular motions associated with each of the experimental bands observed. Comparison with the experimental spectra provides important information about the ability of these computational methods to describe the vibrational modes in these highly polar strained ring compounds. 相似文献
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Determination of rate constants and reaction orders with an open-closed flow-injection configuration
A new, very useful application of open-closed configurations to kinetic studies is reported. The multipeak recordings provided by the manifold used, which features a single conventional photometric detector, were used to calculate the rate constants and reaction orders of a chemical system, namely the ligand displacement reaction between the cobalt(II)-EGTA complex and PAR. 相似文献
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Yuriy G. Denisenko Victor V. Atuchin Maxim S. Molokeev Alexander E. Sedykh Nikolay A. Khritokhin Aleksandr S. Aleksandrovsky Aleksandr S. Oreshonkov Nikolai P. Shestakov Sergey V. Adichtchev Alexey M. Pugachev Elena I. Salnikova Oleg V. Andreev Illaria A. Razumkova Klaus Müller-Buschbaum 《Molecules (Basel, Switzerland)》2022,27(13)
Praseodymium sulfate was obtained by the precipitation method and the crystal structure was determined by Rietveld analysis. Pr2(SO4)3 is crystallized in the monoclinic structure, space group C2/c, with cell parameters a = 21.6052 (4), b = 6.7237 (1) and c = 6.9777 (1) Å, β = 107.9148 (7)°, Z = 4, V = 964.48 (3) Å3 (T = 150 °C). The thermal expansion of Pr2(SO4)3 is strongly anisotropic. As was obtained by XRD measurements, all cell parameters are increased on heating. However, due to a strong increase of the monoclinic angle β, there is a direction of negative thermal expansion. In the argon atmosphere, Pr2(SO4)3 is stable in the temperature range of T = 30–870 °C. The kinetics of the thermal decomposition process of praseodymium sulfate octahydrate Pr2(SO4)3·8H2O was studied as well. The vibrational properties of Pr2(SO4)3 were examined by Raman and Fourier-transform infrared absorption spectroscopy methods. The band gap structure of Pr2(SO4)3 was evaluated by ab initio calculations, and it was found that the valence band top is dominated by the p electrons of oxygen ions, while the conduction band bottom is formed by the d electrons of Pr3+ ions. The exact position of ZPL is determined via PL and PLE spectra at 77 K to be at 481 nm, and that enabled a correct assignment of luminescent bands. The maximum luminescent band in Pr2(SO4)3 belongs to the 3P0 → 3F2 transition at 640 nm. 相似文献
9.
Jordanka Petrova Nikolai G. Vassilev Marko Kirilov 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3-4):457-463
Abstract The reaction of the lithium derivative of diethyl ester of phenylmethanephosphonic acid (1-Li) with alkanones, cycloalkanones, alkylaryl and diarylketones 2s-b is studied at -70°C in THF. The corresponding adducts-diethyl esters of l-phenyl-2,2-dialkyl(phenyl)-2-hydroxyethanephosphonic acids 3s-h are isolated, their yields being usually higher at short reaction time. The olefination of 3-Li as well as of 3 (both by thermolysis or in acidic media) proceeds in low degree, while in the case of 3-Na the yields of alkenes 4 are good. The relative configurations of 3b. 31 and 3g are determined by IR and NMR-spectra, as well as by their stereospecific olefination. “Threo”-stereoselectivity of the addition stage of the reaction of 1-Li with 2b, 21 and 2g is observed, the “threo”/“erythro” ratio remaining independent on the reaction time. 相似文献
10.
Attila G. Császár Tamás Szidarovszky Nikolai F. Zobov Oleg L. Polyansky Jonathan Tennyson 《Journal of Quantitative Spectroscopy & Radiative Transfer》2010,111(9):1043-1106
A new, accurate, global, mass-independent, first-principles potential energy surface (PES) is presented for the ground electronic state of the water molecule. The PES is based on 2200 energy points computed at the all-electron aug-cc-pCV6Z IC-MRCI(8,2) level of electronic structure theory and includes the relativistic one-electron mass-velocity and Darwin corrections. For H216O, the PES has a dissociation energy of D0 = 41 109 cm−1 and supports 1150 vibrational energy levels up to 41 083 cm−1. The deviation between the computed and the experimentally measured energy levels is below 15 cm−1 for all the states with energies less than 39 000 cm−1. Characterization of approximate vibrational quantum numbers is performed using several techniques: energy decomposition, wave function plots, normal mode distribution, expectation values of the squares of internal coordinates, and perturbing the bending part of the PES. Vibrational normal mode labels, though often not physically meaningful, have been assigned to all the states below 26 500 cm−1 and to many more above it, including some highly excited stretching states all the way to dissociation. Issues to do with calculating vibrational band intensities for the higher-lying states are discussed. 相似文献