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981.
Relative protonation energies in the primary, secondary and tertiary aliphatic series of amines are calculated by a semiempirical
method employing the virtual charge model. The method accounts quite well for the observed differences between the gas-phase
protonation affinities and the protonation enthalpies in solution, but when allowance is made for steric shielding from the
bulk solvent for “non-edge” atoms, some anomalies in the uncorrected model are removed. The calculated solute-solvent interactions
are related to experimental enthalpies of solution and to trends expected from the Born model. 相似文献
982.
C. Auguet J. L. Seguin F. Martorell F. Moll V. Torra J. Lerchner 《Journal of Thermal Analysis and Calorimetry》2006,86(2):521-529
Micro-calorimetric
devices using Si-based sensors are very useful for the study of gas–solid
reactions, in which very low mass of reactants are necessary. But in fact
the consequence of using flat detectors is an increase of the uncertainty
in the measured energy. In this work a calorimetric gas sensor based on Xensor
chip is analysed studying the local x–y
contributions of dissipation to the sensitivity related to the value in the
centre. We study also the effects of the gas-flow on the sensitivity, comparing
the results obtained with two Xensor type chips. Finally we carry out a deeper
analysis of the x–y effects on the
calorimetric detector for dissipations in the reactant shell extremely close
to the detector surface to visualize the link between the power density distribution
and the output signal. 相似文献
983.
J. Sivaguru Hideaki Saito Thomas Poon Waldemar Adam Yoshihisa Inoue Nicholas J. Turro 《Tetrahedron》2006,62(28):6707-6717
On photooxygenation (methylene blue as sensitizer) of E/Z enecarbamates, equipped with the oxazolidinone chiral auxiliary, the oxidative cleavage of the alkenyl functionality releases the enantiomerically enriched methyldesoxybenzoin (MDB) product. The extent (% ee) as well as the sense (R vs S) of the stereoselectivity in the MDB formation depends on the choice of the alkene configuration; the efficacy of stereocontrol may be tuned by appropriate solvent and temperature conditions. Highlighted is the finding that the formation of the preferred MDB enantiomer (R or S) depends for the E isomer on the chosen solvent and temperature, but not for the corresponding Z isomer. The activation parameters for the various solvents disclose that differential entropy effects (ΔΔS‡) dominate the conformationally more flexible E diastereomers. As mechanistic rationale for this unprecedented conformationally imposed stereochemical behavior, we propose the competitive action of stereoselective vibrational quenching of the attacking singlet oxygen by the enecarbamate versus sterically controlled stereoselective oxidative cleavage of its double bond. 相似文献
984.
Two kinds of ab initio calculations (B3LYP and HF) using the GIAO approach have been carried out for fifteen H, three Li, three B, eleven C, seven N, nine O, four F, three Si, four P, six S and five Cl containing derivatives. The calculated absolute nuclear shieldings have been compared with experimental absolute values (either measured or estimated from relative chemical shifts) when available or with relative chemical shifts (11B, 35Cl). The correlations range from good to excellent and only three compounds (PN, P2H2, SO2) deviate significantly. 相似文献
985.
V. L. Shirokii V. A. Knizhnikov T. P. Konovalov Z. P. Zubreichuk A. A. Erdman S. E. Nefedov I. L. Eremenko A. I. Yanovskii Yu. T. Struchkov N. A. Mayer 《Russian Chemical Bulletin》1993,42(4):732-733
Co-electrolysis of potassium 1,2-dicarbadodecahydroundecaborate and indene in 0.1N sodium bromide solution in dimethylsulfoxide using iron electrodes afforded -indenyl--(3)-1,2-dicarbollyliron(III).Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 764–765, April, 1993. 相似文献
986.
Electromotive force measurements were carried out on the system KCl–KNO3–H2O at constant total ionic strengths of 0.5, 1.0, 2.0 and 3.0 mol-kg–1 and at 25, 35 and 45°C using a cell consisting of a potassium ionselective electrode and a Ag/AgCl electrode. The Harned coefficients and the Pitzer binary and ternary interaction parameters for the system have been evaluated at each temperature. The osmotic coefficients, excess free energies of mixing and heats of mixing of the system have been predicted at each of the experimental temperatures and ionic strengths. The solubility data at 25°C are also interpreted. 相似文献
987.
Javad Mostaghimi Pierre Proulx Maher I. Boulos 《Plasma Chemistry and Plasma Processing》1984,4(3):199-217
A theoretical investigation of the effect of different parameters on the flow and the temperature fields in a radiofrequency
inductively coupled plasma is carried out. The parameters studied are: central injection gas flow rate, total gas flow rate,
input power, and the type of plasma gas. The results obtained for argon and nitrogen plasmas at atmospheric pressure indicate
that the flow and the temperature fields in the coil region, as well as the heat flux to the wall of the plasma confinement
tube, are considerably altered by the changes in the torch operating conditions. 相似文献
988.
A novel instrumental technique for the direct, fast, accurate, and precise determination of uranium in concentrates and other U-rich materials (as well as to mineralized rocks) is presented. The proposed technique is an absolute methodology, based on the comparison of the fluorescence of the accurately known standard with a sample of similar but unknown concentration in the low operational range of the instrument (on same sample-dilution basis), by the use of H3PO4-NH4H2PO4 as a fluorescence-enhancing reagent. The relative standard deviation of the proposed technique was 0.5-0.9% (n=9) at 18.1, 36.2, 61.2, and 99.6% U3O8. The proposed technique is suitable for the determination of uranium in samples arising from exploration projects, ores from mining operations, mill process samples, uranium ore concentrates leading to fuel fabrication as well as samples from environmental monitoring containing up to 100% uranium. The results are in good agreement with those obtained by titrimetric, gravimetric, and TBP extraction-H2O2 spectrophotometric methods. The precision of the technique is within the acceptable ‘pure geochemistry’ type of analysis (R.S.D. ∼ 1.0%) and is comparable even those obtained with titrimetric and gravimetric assay. The proposed differential technique coupled with flow injection may open up new advancement in instrumentation leading to design and development of microchemielectronic devices for direct on-line determination, more compatible with the tools of computer age as also to help in handling of radioactive solutions in chemical laboratories in uranium processing industries. 相似文献
989.
Samaresh Jana 《Tetrahedron letters》2005,46(7):1155-1157
A novel and efficient methodology has been developed for the construction of synthetically important tri-substituted tetrahydrofuran derivatives from bromo-alkenes and bromo-alkynes by radical cyclization reactions using the radical initiator Cp2TiCl, generated in situ from commercially available titanocene dichloride and Zn dust in tetrahydrofuran under argon. 相似文献
990.
Anna M. Maj Albert Demonceau Alfred F. Noels 《Journal of organometallic chemistry》2007,692(14):3048-3056
A range of new imidazolium and imidazolinium chlorides bearing biphenyl units on their nitrogen atoms was synthesized. They differed by the electron-withdrawing or -donating nature and the steric bulk of the substituents on their aromatic rings. These various N-heterocyclic carbene (NHC) precursors were combined with the [RuCl2(p-cymene)]2 dimer and potassium tert-butoxide to generate the corresponding ruthenium-arene complexes [RuCl2(p-cymene)(NHC)] in situ. The catalytic activity of these species was investigated in the photoinduced ring-opening metathesis polymerization (ROMP) of cyclooctene. The results obtained confirmed the necessity of blocking the ortho-positions of the phenyl rings in the vicinity of the metal center in order to attain high catalytic efficiencies. They also showed that changing the steric and electronic properties of the substituents on the remote phenyl rings of the biphenyl units had no significant influence on the outcome of the polymerization. 相似文献