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121.
Chemical kinetics of benzonitrile nitration with mixed acid is investigated in the temperature range 283–299 K. Pseudo-first-order rate constants are evaluated by means of rate experiments on homogeneous reacting mixtures having large stoichiometric excesses of nitric acid. The second-order kinetic constants for nitronium ion attack to the aromatic substrate are derived on the basis of the assessed nitration mechanism. An activation energy of 604 ± 37 kJ mol?1 is calculated for this reaction step. © 1993 John Wiley & Sons, Inc.  相似文献   
122.
123.
In situ measurements of gas-liquid surface reactions of single aerosol microdroplets are presented. By means of optical levitation in combination with elastic (Mie) and inelastic (Raman) light scattering it is possible to get information on the chemistry of e.g. acid/base reactions as well as the physical behavior of single microparticles.  相似文献   
124.
125.
Taking advantage of the long 13C T1 values generally encountered in solids, selective saturation and inversion of more than one resonance in 13C CP/MAS experiments can be achieved by sequentially applying several DANTE pulse sequences centered at different transmitter frequency offsets. A new selective saturation pulse sequence is introduced composed of a series of 90 degrees DANTE sequences separated by interrupted decoupling periods during which the selected resonance is destroyed. Applications of this method, including the simplification of the measurement of the principal values of the 13C chemical shift tensor under slow MAS conditions, are described. The determination of the aromaticity of coal using a relatively slow MAS rate is also described.  相似文献   
126.
The Liouville operator for an infinite-particle Hamiltonian dynamics corresponding to interaction potentialU is used to introduce the concept of a locally weakly invariant measure on the phase space and to show that if a Gibbs measure with potential of general form is locally weakly invariant then its Hamiltonian is asymptotically an additive integral of the motion of the particles with the interactionU.Moscow State University. Translated from Teoreticheskaya i Matematicheskaya Fizika, Vol. 90, No. 3, pp. 424–459, March, 1992.  相似文献   
127.
TheSU(2) rotation matricesD (j), specified in terms of axis and angle of rotation, are expressed as linear combination of normalized irreducible tensorial matricces (NITM) of rankl = 0 to 2j rotated to the polar angles of the axis. The rotated NITM are constructed from spherical harmonics of the same rank. Since this formulation requires no matrix products, it may be computationally more efficient than Euler angle formulas, particularly for largej. Rotated NITM and formulas for theD (j) withj = 1/2 andj = 1 are written out explicitly. A formula for the structure constants of the products of conformable NITM is also given in terms of 3-j and 6-j symbols.  相似文献   
128.
We examine the influence of relativistic and QED effects on the existence of the 1,3P o H- resonances between n = 2 and 3 hydrogen thresholds, the relativistic and QED corrections and the coupling effects between the high singlet and triplet states are considered as first-order perturbations. We firstly obtain accurate non-relativistic resonant energies and widths of fifteen 1P o resonances, and fifteen 3P o resonances. The fifteen 1P o resonances are classified to be 3 (2, 0) - n ( 4 ? n ? 12) and 3 (1, 1) + n ( 3 ? n ? 8). The fifteen 3P o resonances are classified to be 3 (2, 0) + n ( 3 ? n ? 12) and 3 (1, 1) - n ( 4 ? n ? 8). We found there exist six Feshbach resonances for 3 (2, 0) - n (1P o ) series, four Feshbach resonances for 3 (1, 1) + n (1P o ) series, seven Feshbach resonances for 3 (2, 0) + n (3P o ) series, and three Feshbach resonances for 3 (1, 1) - n (1P o ) series. Received 22 February 2002 Published online 24 September 2002  相似文献   
129.
This work is devoted to the numerical solution of the Navier–Stokes equations for compressible viscous fluids. Finite element approximations and stabilization techniques are addressed. We present methods to implement discontinuous approximations for the pressure and the density. An upwinding methodology is being investigated which combines the ideas behind the stream line Petrov–Galerkin method and the flux limiter methods aiming to introduce numerical diffusion only where it is necessary.  相似文献   
130.
The irradiation of hybrid photopolymer systems consisting of a free radically polymerizable multifunctional acrylate monomer and a cationically polymerizable epoxide or oxetane monomer was conducted under conditions where only the free radical polymerization takes place. This results in the formation of a free‐standing polyacrylate network film containing quiescent oxonium ions along with the unreacted cyclic ether monomer. The subsequent application of a point source of heat to the film ignites a cationic ring‐opening frontal polymerization that emanates from that site and propagates to all portions of the irradiated sample. This article examines the impact of various molecular structural and experimental parameters on these novel hybrid frontal polymerizations that produce interpenetrating network polymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4331–4340, 2007  相似文献   
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