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51.
The kinetics and the equilibrium constant of the chlorine transfer reaction between monochloramine NH2Cl and the amines: C2H5NH2, (CH3)2CHNH2, (CH3)2NH, and (C2H5)2NH are investigated by spectrophotometry in aqueous medium at 25°C, in the pH range from 8 to 13 and for an ionic strength equal to 1.03 ± 0.05M. For a concentration of total ammonia equal to 1M, the observed rate constant is pH independent below 8 and above 12.8 and reaches a maximum located between the pKas of NH4+ and RR'NH2+. From these results and those obtained earlier for NH2Cl and CH3NH2, the reaction is shown to involve an interaction between neutral molecules NH2Cl and RR'NH, subject to general acid catalysis. The ability of an interaction corresponding to a specific catalysis and involving NH3Cl+ and RR'NH rather than NH2Cl and RR'NH2+ is also discussed. The activation parameters are given for each reaction. 相似文献
52.
The first object of this paper is to introduce a new evolution equation for the characteristic function of the boundary Γ
of a Lipschitzian domain Ω in the N-dimensional Euclidean space under the influence of a smooth time-dependent velocity field. The originality of this equation is that the evolution takes place in an Lp-space with respect to the (N − 1)-Hausdorff measure. A second more speculative objective is to discuss how that equation can be relaxed to rougher velocity
fields via some weak formulation. A candidate is presented and some of the technical difficulties and open issues are discussed.
Continuity results in several metric topologies are also presented. The paper also specializes the results on the evolution
of the oriented distance function to initial sets with zero N-dimensional Lebesgue measure. 相似文献
53.
54.
Philippe Boyer Gilles Renversez Evgeny Popov Michel Nevière 《Optical and Quantum Electronics》2006,38(1-3):217-230
The present work adapts a recent grating theory called “Fast Fourier factorization” to cylindrical coordinates in order to study microstructured optical fibers (MOFs). Compared with the classical differential method, this new differential method takes into account the truncation of Fourier series and the discontinuities of the fields across the diffracting surface with the help of new factorization rules. The main advantage of this method is that the directrix of the diffracting cylindrical surface is arbitrary and permits anisotropic and inhomogeneous media although its numerical application needs longer computation time, compared with other well-known numerical methods. The S-propagation algorithm is used to avoid numerical contaminations. The numerical results are validated and compared with the well-established Multipole method in the case of a MOF with six circular cylinders. Further, a new cross-sectional profile (with sectorial inclusions) that the Multipole method cannot consider is studied. 相似文献
55.
Michel Talagrand 《Probability Theory and Related Fields》2006,134(3):339-382
We compute at any temperature the free energy of the multi p-spin spherical model when only terms for p even are considered.
Work partially supported by an NSF grant 相似文献
56.
We consider the inverse problem of identifying locations and certain properties of the shapes of small elastic inclusions
in a homogeneous background medium from dynamic boundary measurements for a finite interval in time. Using particular background
solutions as weights, we present an asymptotic method based on appropriate averaging of the dynamic boundary measurements
and propose non-iterative algorithms for solving our inverse problem. 相似文献
57.
58.
D. Bisello G. Busetto A. Castro M. Nigro M. Penzo L. Pescara M. Posocco P. Sartori L. Stanco Z. Ajaltouni A. Falvard J. Jousset B. Michel J. C. Montret A. Antonelli R. Baldini A. Calcaterra G. Capon M. Schioppa J. -E. Augustin G. Cosme F. Couchot B. Dudelzak F. Fulda G. Grosdidier B. Jean-Marie S. Jullian D. Lalanne V. Lepeltier F. Manè C. Paulot R. Riskalla Ph. Roy G. Szklarz DM Collaboration 《Zeitschrift fur Physik C Particles and Fields》1988,39(1):13-19
Thee + e ?→K + K ? cross section has been measured from about 750 events in the energy interval \(1350 \leqq \sqrt s \leqq 2400 MeV\) with the DM2 detector at DCI. TheK ± form factor |F F ±| cannot be explained by the ρ, ω, ? and ρ′(1600). An additional resonant amplitude at 1650 MeV has to be added as suggested by a previous experiment. 相似文献
59.
Sabbe MK Saeys M Reyniers MF Marin GB Van Speybroeck V Waroquier M 《The journal of physical chemistry. A》2005,109(33):7466-7480
A complete and consistent set of 95 Benson group additive values (GAV) for the standard enthalpy of formation of hydrocarbons and hydrocarbon radicals at 298 K and 1 bar is derived from an extensive and accurate database of 233 ab initio standard enthalpies of formation, calculated at the CBS-QB3 level of theory. The accuracy of the database was further improved by adding newly determined bond additive corrections (BAC) to the CBS-QB3 enthalpies. The mean absolute deviation (MAD) for a training set of 51 hydrocarbons is better than 2 kJ mol(-1). GAVs for 16 hydrocarbon groups, i.e., C(C(d))(3)(C), C-(C(d))(4), C-(C(t))(C(d))(C)(2), C-(C(t))(C(d))(2)(C), C-(C(t))(C(d))(3), C-(C(t))(2)(C)(2), C-(C(t))(2)(C(d))(C), C-(C(t))(2)(C(d))(2), C-(C(t))(3)(C), C-(C(t))(3)(C(d)), C-(C(t))(4), C-(C(b))(C(d))(C)(H), C-(C(b))(C(t))(H)(2), C-(C(b))(C(t))(C)(H), C-(C(b))(C(t))(C)(2), C(d)-(C(b))(C(t)), for 25 hydrocarbon radical groups, and several ring strain corrections (RSC) are determined for the first time. The new parameters significantly extend the applicability of Benson's group additivity method. The extensive database allowed an evaluation of previously proposed methods to account for non-next-nearest neighbor interactions (NNI). Here, a novel consistent scheme is proposed to account for NNIs in radicals. In addition, hydrogen bond increments (HBI) are determined for the calculation of radical standard enthalpies of formation. In particular for resonance stabilized radicals, the HBI method provides an improvement over Benson's group additivity method. 相似文献
60.
Denise Baudry Michel Ephritikhine Hugh Felkin Yves Dromzee Yves Jeannin 《Journal of organometallic chemistry》1984,272(3):403-409
Bis(triphenylphosphine)(η-cyclohexa-1,3-diene)rhenium trihydride, (Ph3P)2(η-C6H8)ReH3 (I) crystallises in the space group C2/c with cell dimensions a 22.76(2), b 10.14(1) c 29.813(6) Å, β 97.69(8)°. The final refinement of 126 variables using 1580 non-zero reflections resulted in a final R value of 0.064. In spite of uncertainties in some of the atomic positions, the structure of I is compatible with a trihydrido diene compound with a distorted pentagonal bipyramidal configuration, rather than with a dihydrido cyclohexenyl compound having an “agostic” CH ? Re interaction. The factors which govern the structure of the complexes (Ph3P)2(η-1,3-diene)ReH3 are discussed. 相似文献