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981.
The 2,2'-azobis(isobutyronitrile)(AIBN)-induced autoxidation of gamma-terpinene (TH) at 50 degrees C produces p-cymene and hydrogen peroxide in a radical-chain reaction having HOO* as one of the chain-carrying radicals. The kinetics of this reaction in cyclohexane and tert-butyl alcohol show that chain termination involves the formal HOO. + HOO. self-reaction over a wide range of gamma-terpinene, AIBN, and O2 concentrations. However, in acetonitrile this termination process is accompanied by termination via the cross-reaction of the terpinenyl radical, T., with the HOO. radical under conditions of relatively high [TH] (140-1000 mM) and low [O2] (2.0-5.5 mM). This is because the formal HOO. + HOO. reaction is comparatively slow in acetonitrile (2k approximately 8 x 10(7) M(-1) s(-1)), whereas, this reaction is almost diffusion-controlled in tert-butyl alcohol and cyclohexane, 2k approximately 6.5 x 10(8) and 1.3 x 10(9) M(-1) s(-1), respectively. Three mechanisms for the bimolecular self-reaction of HOO. radicals are considered: 1) a head-to-tail hydrogen-atom transfer from one radical to the other, 2) a head-to-head reaction to form an intermediate tetroxide, and 3) an electron-transfer between HOO. and its conjugate base, the superoxide radical anion, O2-.. The rate constant for reaction by mechanism (1) is shown to be dependent on the hydrogen bond (HB) accepting ability of the solvent; that by mechanism (2) is shown to be too slow for this process to be of any importance; and that by mechanism (3) is dependent on the pH of the solvent and its ability to support ionization. Mechanism (3) was found to be the main termination process in tert-butyl alcohol and acetonitrile. In the gas phase, the rate constant for the HOO. + HOO. reaction (mechanism (1)) is about 1.8 x 10(9) M(-1) s(-1) but in water at pH< or =2 where the ionization of HOO. is completely suppressed, this rate constant is only 8.6 x 10(5) M(-1) s(-1). The very large retarding effect of water on this reaction has not previously been explained. We find that it can be quantitatively accounted for by using Abraham's HB acceptor parameter, beta(2)(H), for water of 0.38 and an estimated HB donor parameter, alpha(2)(H), for HOO. of about 0.87. These Abraham parameters allow us to predict a rate constant for the HOO. + HOO. reaction in water at 25 degrees C of 1.2 x 10(6) M(-1) s(-1) in excellent agreement with experiment. 相似文献
982.
The distribution of hydrodesulfurization (HDS) products of thiophene was compared on 9 different catalysts at different degrees
of sulfidation and at aging in H2/thiophene mixtures. The main products of HDS were C4 and Cl-C3 hydrocarbons. The effect of sulfur uptake on the productsmin distribution was similar for Co and Ni promoted, and reverse
to that on Pd and Pt promoted samples. The effect of aging was similar for all samples.
This revised version was published online in August 2006 with corrections to the Cover Date. 相似文献
983.
Modeling and simulation of free radical polymerization of styrene under semibatch reactor conditions
The first part of this approach is concerned with the elaboration of a radical polymerization model of styrenne, based on
a kinetic diagram that includes chemical and thermal initiation, propagation, termination by recombination and chain transfer
to the monomer. Furthermore, volume contraction during polymerization is considered, as well as the gel and glass effects.
The mathematical formalism that describes the model in terms of moments is explored in detail. The model was then used to
predict the changes in monomer conversion and molecular weight after intermediate addition of initiator and monomer. The results
of this operation are dependent on the conditions of the reaction mass, quantity, and moment of substance addition. Therefore,
the simulations were performed at different times with respect to the gel effect; before, during and after this phenomenon,
and also with respect to different temperatures and initiators. Increasing the initiator concentration before the gel effect
leads to an earlier appearance of the phenomenon and to a decrease in molecular weight. The ratio
reveals a polydispersity index smaller for the intermediate addition of initiator. No significant changes take place during
or after the gel effect. If along with the initiator, unreacted monomver (used to dissolve the initiator) enters the reactor,
a small dip in conversion is observed. The general conclusion of this paper reveals the intermediate addition of initiator
as a method to control polymer properties and to prevent the “dead-end” polymerization of styrene. 相似文献
984.
研究了低于300 ℃时两种氧化铈对稀燃阶段NOx存储性能的影响,催化剂由2%(w)Pt/Al2O3(PA)与CeO2-X(X=S,I)机械混合制备. X射线衍射(XRD),BET表面积和扫描电子显微镜(SEM)用于表征材料的物理结构. X射线光电子能谱(XPS)和H2程序升温还原(H2-TPR)用于表面Ce3+和活性氧定量. 原位漫反射傅里叶变换红外光谱(in-situ DRIFTS)用于分析表面NOx吸附物种. 相比于CeO2-I,CeO2-S 具有优良的物理化学性能,包括高比表面积、丰富的空隙结构、较高的抗老化能力及表面Ce3+浓度. 因而,Pt/Al2O3+CeO2-S 表现出优异的NOx存储能力. 此外,PA+CeO2-X(X=S,I)上存在Pt 与CeO2之间的相互作用,可提高表面氧物种的活性进而促进NO氧化及NOx存储. PA+CeO2-S上的这种相互作用要强于PA+CeO2-I. 研究表明,表面Ce3+浓度和活性氧含量对NOx存储起到重要作用. 然而经过水热处理后,Pt 与老化的氧化铈(ACS,ACI)之间的相互作用降低,并且两种氧化铈NOx存储性能显著下降. 另外,与PA+ACS(ACI)相比,PA+PACS(PACI)样品NOx存储能力得到改善,这归因于表面氧物种活性增加能促进硝酸盐的形成. 相似文献
985.
Olle Nilsson 《Journal of separation science》1982,5(1):38-44
The total length-based second moment contribution from longitudinal sample diffusion in both phases on a column, σD , is derived by adding individual partial differential contributions to a partial differential equation accounting for the longitudinal diffusion processes only. Although each diffusion-dispersed sample part is equilibrated between two phases, the resulting σ,D (= 2D mt m + 2D st s) can be interpreted as the sum of two independent contributions in accordance with the variance addition rule. (D m and D s are the mean diffusion coefficients and t mand t s the mean residence times of the sample in the mobile and stationary phases, respectively.) The same σD expression is derived from the random walk model of Giddings by treating the diffusional process in each phase as statistically independent of the other processes. Under these conditions the broadening contribution from longitudinal diffusion in the mobile phase is shown to be independent of the velocity profile. 相似文献
986.
Angelika Baranowska Magdalena Siedlecka Andrzej J. Sadlej 《Theoretical chemistry accounts》2007,118(5-6):959-972
Recent studies of the perturbation-dependent basis sets have indicated the possibility of a significant reduction of the size
of the usual CGTO sets without considerable loss of accuracy in calculations of molecular electric properties. The resulting
(ZPolX) basis sets have been developed for several atoms of the first and second row of the Periodic Table. The same method
of the ZPolX basis set generation is extended for the first-row transition metals and the corresponding contracted ZPolX basis
sets of the size [6s5p3d1f] are determined for both nonrelativistic and scalar relativistic calculations. The performance
of the ZPolX basis sets is verified in calculations on the first-row transition metal oxides at the level of the ROHF, ROHF/CASPT2,
and ROHF/CCSD(T) approximations. Also the study of the dipole polarizability of TiCl4 confirms the excellent features of these very compact basis sets. The ZPolX basis sets for nonrelativistic and relativistic
calculations of molecular electric properties are available on the web page http://www.chem.uni.torun.pl/zchk/basis-sets.html. 相似文献
987.
N. C. van de Merbel M. Stenberg R. Öste G. Marko-Varga L. Gorton H. Lingeman U. A. Th. Brinkman 《Chromatographia》1995,41(1-2):6-14
Summary A two-dimensional, column liquid chromatographic system is used for the determination of the D- and L-enantiomers of amino acids in biological samples. Separation of the amino acids is first on ion-exchange column by gradient elution with a sodium citratesodium chloride buffer. Enantioseparation is by subsequent injection of 3 l heart-cuts of the individual amino acids onto a second column with a chiral crown ether stationary phase. Finally, fluorescence detection is after post-column labelling of the amino acids using ano-phthalaldehyde-2-mercaptoethanol reagent solution. The high separation power and selectivity of the system allow processing of complex samples with hardly any additional treatment and the determination of small quantities of D-amino acids in the presence of excess L-form. Applicability of the system is illustrated by the determination of D- and L-aspartate, serine, glutamate and alanine in various complex biological samples, such as protein hydrolysates, urine and biotechnological and food samples. Data are given on detectability, repeatability and linearity. 相似文献
988.
A. A. Ishchenko 《Russian Chemical Bulletin》1994,43(7):1161-1174
The general characteristics that relate the length of the polymethine chain of symmetrical cyanine dyes to their spectral-luminescent properties depending on the electron-donor character of the heterocycles and the nature of the solvent are formulated. For various types of symmetrical cyanines, the Stokes shifts decrease with the elongation of the polymethine chain due to weakening of the vibronic interactions. The vinylene shifts of the band maxima are essentially constant and fall within the range 100 to 130 nm depending on the nature of the heterocycles and the solvent. When the polymethine chain elongates the fluorescence quantum yields first increase and then decrease. The greater the effective length of the heterocycle the stronger the decrease. The fluorescence decay occurring when the polymethine chain gets longer is associated with intensification of the internal conversion. For symmetrical cyanines, the changes in the shapes of the electronic bands (their width, asymmetry, excess, and fine structure) as the chain elongates are governed by the competing effects of the vibronic and intermolecular interactions. The former decrease as the chain lengthens, causing the narrowing of the absorption bands for the lower vinylogs. On the other hand, the latter increase as chain lengthens, which leads to broadening of the bands for the higher vinylogs. The higher the solvent nucleophilicity and the greater the deviation of the electron-donor ability of the heterocycle from the average value the greater the broadening. Any elongation of the polymethine chain of symmetrical cyanines causes only narrowing of the bands and an increase in the asymmetry, excess, and structuring in the fluorescence spectra, which, unlike the absorption spectra, is independent of the electron-donor character of the heterocycles and the nature of the solvent. These effects are caused by the fact that, in contrast to absorption, changes in the shape of emission bands with increasing chain length are governed predominantly by vibronic rather than by intermolecular interactions.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1227–1239, July, 1994. 相似文献
989.
Based on the MNDO calculations of the electronic structure of the molecules of acrolein, glyoxal, and butadiene, possible mechanisms of the conjugation in systems containing conjugated C=C and C=O bonds have been analyzed. In the electronic ground state ofs-trans-acrolein, the , -conjugation is very small, whereas in the first excited electronic state, the conjugation is substantial, In the ground state ofs-trans-glyoxal, the ,-conjugation should manifest itself clearly but should be weaker than in butadiene, whereas in the first excited electronic state, this conjugation should be more pronounced, Alternation of double and single bonds in the classic structural formula of a molecule does not ensure that this molecule exhibits the properties of a -conjugated system even in planar conformations.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1648–1652, July, 1996. 相似文献
990.
CrIII Phthalocyaninates: Synthesis, Properties, and Crystal Structure of l-Bis(triphenylphosphine)iminium trans-Di(nitrito(O))phthalocyaninato(2–)chromate(III) [Cr(H2O)2Pc2?]Ix reacts with excess (PNP)NO2 in dimethylformamide to yield less soluble greenblack l-bis(triphenylphosphine)iminium trans-di(nitrito(O))phthalocyaninato(2–)chromate(III), l(PNP)trans[Cr(ONO)2Pc2?], which crystallizes in the triclinic space group P1 (No. 2) with Z = 2. The Cr atom is in the center of the Pc2? ligand and the two nitrite ions are monodentate O-coordinated in a mutually trans arrangement to the Cr atom. The Cr? O and Cr? Niso bond distances are 1.9898(14) und 1.981(2) Å, respectively. The geometric data of the coordinated nitrite ion are: d(N? O) = 1.307(2) Å; d(N? O) = 1.205(2) Å; ?(O? N? O) = 113.7(2)°; ?(Cr? O? N) = 116.85(12)°. The non-bonding O atoms are trans to the Cr atom. The Pc2? ligand is slightly saddled. Three weak spin-allowed trip-quartet(TQ) transitions (in 103 cm?1): TQ1 (8.20) < TQ2 (11.3) < TQ3 (20.33) and the characteristic π-π* transitions of the Pc2? ligand: B (14.68) < Q1 (27.1) < Q2 (29.0) < N (35.4) are observed in the UV-VIS-NIR spectrum. Prominent luminescence spectra are obtained by excitation within the TQ1 region, in which the spin-forbidden trip-sextet transition at 7376 cm?1 dominates at low temperatures (T < 50 K). The vibrational spectra are discussed. In coincidence of the excitation lines with TQ3, vs(Cr? O) at 378 cm?1 is selectively resonance Raman (RR) enhanced. vas(Cr? O) is observed in the FIR spectrum at 391 cm?1. The following internal vibrations (in cm?1) of the nitrito ligand are in the MIR spectrum: vas(N? O)/1447 > vas(N? O)/1018/1029 > δ(O? N? O)/828 and in the RR-spectrum: vs(N? O)/1410 > vs(N? O)/952, the last followed by three overtones. 相似文献