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61.
Selective laser-induced phototautomerism of free-base porphin in different n-alkanes (n-hexane, n-heptane, n-octane, nnonane, n-decane, n-undecane and n-dodecane) has been used to identify tautomer splittings in a number of sites in polycrystalline samples at 2 K. Pairs or lines arising from the two molecular orientations in each site can be reversibly transformed into each other. In the odd n-alkanes the occupation of different sites was not dependent on the rate at which the samples were frozen, but in the even n-alkanes metastable sites were only occupied following rapid quenching. 相似文献
62.
Fu-Sheng S 《Talanta》1983,30(6):446-448
The conditions for the reaction between phenylarsenazo (PAA) (2-[(2-arsonophenyl)azoj-7-(phenylazo)-1, 8-dihydroxynaphthalene-3,6-disulphonic acid) and chromium(III) have been studied. A blue 1:1 complex is formed at pH 2.2 on heating the reactants at 100 degrees for 15 min. It has maximum absorption at 635 nm and is stable for at least 24 hr. The molar absorptivity is 3.3 x 10(4) 1.mole(-1).cm(-1). Beer's law is obeyed in the chromium concentration range 0-1.4 mug ml . The reaction has been successfully applied to determination of chromium in alloy steel. 相似文献
63.
Let (F,G) be a pair of matrices defined over an arbitrary field, Fn × n, Gn × m. Consider the natural action of GLn x GLm on this pair given by (F,G) ? (gFg-1,gGh-1), where (g,h) ∈ GLn × GLm. This action is of interest in system theory as well as the representation theory of quivers. In this paper we study the stabilizer subgroup of this action stab(F,G), i.e. . 相似文献
64.
Spectrophotometric determination of the formation constants of iron(III)-8-hydroxyquinoline complexes in 0.1 M sodium perchlorate solution at 25° gave the values K1=[FeOx2+]/([Fe3+][Ox-])=4.9·1013, K2=[FeOx2+]/([FeOx2+][Ox-])=4.2·1012 and K3=[FeOx3]/([FeOx2+][Ox-])=3.9·1010. FeOx2OH and FeOx(OH)2 are obtainable as solid phases. FeOx3 (Ksp=3·10-44, intrinsic solubility 1.6·10-7 M) dissolves in basic solutions to form FeOx2(OH)2 -In a solution saturated with FeOx3, ([FeOx2(OH)2-][Ox-])/[OH-]2=7.7·10-5. 相似文献
65.
It is shown by proton NMR and quantum chemical PCILO calculations that monothio-β-ketones in solution exist as different isomers depending on substituents, solvent and temperature. In solvents with low dielectric constants the hydrogen-bridged cis enol form predominates, and is in fast equilibrium (in the NMR scale) with nonchelated trans enol forms down to ?100°C at least. Transition enthalpies are of the order of 7–15 kJ mol?1. In compounds with R2 = Me the rotation of the Me -CS group around the neighbouring C-C- bond can be detected and the thermodynamic and kinetic parameters estimated. The reason for the slowing down of this rotation, inferred from the line broadening in NMR, is probably the stabilization of a trans isomer by interaction between the protons of the methyl group and the lone pairs of the oxygen atom. There are no indications for the presence of chelated and non-chelated enethiol isomers from the PMR studies and quantum chemical calculations performed. 相似文献
66.
R. Lefbvre 《Chemical physics letters》1980,70(3):430-433
The complex rotation method is applied to the determination of widths and shifts of an harmonic oscillator predissociated by a linear potential, for when exact analytical formulas are available in the limit of small interchannel coupling. Excellent agreement is obtained. 相似文献
67.
Equilibria and kinetics for the extraction of nickel(II) and copper(II) by 2-hydroxy-5-nonylbenzophenone oxime (LIX 65N) in seven organic solvent systems were studied in order to test the validity of several hypotheses related to the role of the solvent in equilibrium and kinetic aspects of metal chelate extraction. For the nickel—LIX 65N system, the extraction constant is essentially independent of the solvent system, whereas for the copper—LIX 65N system, the extraction constant is not independent of solvent; this indicates that while the stoichiometry of the nickel chelate remains the same in all solvents, that of copper does not. The observed rate constant for the nickel—LIX 65N extraction was found to vary inversely with the LIX 65N distribution constant as predicted from a mechanism involving slow formation of the 1:1 complex. The observed reaction rate constant for the copper—LIX 65N varied inversely with the square of the distribution constant, also in accordance with the previously postulated mechanism of the slow formation of the 2:1 copper complex. This study, therefore, unequivocally eliminates the interfacial mechanism in favor of the homogeneous chemical reaction mechanism for the extraction of metal ions by LIX 65N, as well as by other similar high-molecular-weight extractants. 相似文献
68.
The monomeric ν(N—H) vibrations of various trisubstituted ureas of the R2UPh type and -thioureas of the R2TUPh type have been studied. The trans—out isomerism in the former and the trans—out—cis isomerism in the latter are discussed from the point of view of steric effect. The monomeric ν(N—H) vibrations of RPhUPh and RPhTUPh are also examined. The single band appearing in the spectrum of both ureas is characteristic of the cis form; this suggests the existence of phenyl—phenyl interaction (the stacking interaction proposed by Galabov et al. [10]). Behavior of ν(N—H) vibrations at several concentrations is shown to be clearly different in the three forms (trans, out and cis). The presence of the cis form is confirmed by solvent effect experiments. 相似文献
69.
Ab initio calculations are presented for H2 and D2 relative Raman intensities originating from common rotational levels for both vibrational-rotational and pure rotational transitions. Factors f(J) required to correct measured intensities for molecular non-rigidity (e.g. in temperature measurements) are tabulated. The calculations are compared with literature perturbation-theory equations (significant differences at large J in vibration-rotation) and with experiment. 相似文献
70.
The fluorescence decay of the tertiary aliphatic animes trimethylamine (TMA), triethylamine (TEA) and tri-n-propylamine (TPA) in the vapour phase excited between 260 and 215 nm has been shown to consist of a single, wavelength-dependent, component when the first excited state is uniquely excited, but two components when the first and second excited states are simultaneously excited. This dual exponentiality persists at pressures as low as 10 mTorr, and it is argued that the two-component decay does not arise from collisional vibrational relaxation. 相似文献