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981.
P E S?rensen R A McClelland R D Gandour 《Acta chemica Scandinavica (Copenhagen, Denmark : 1989)》1991,45(6):558-566
The ring-chain tautomerism in aqueous solution of some aryl-substituted morpholinium salts (bromides), has been studied and equilibrium constants are reported. In the crystals the substrates exist entirely in their cyclic forms as hemiacetals, but in aqueous solution NMR measurements reveal that an equilibrium is established between the cyclic (hemiacetal) and the noncyclic (ketone) form, the degree of ring-opening being more pronounced with electron-donating aryl substituents at the carbonyl carbon. The kinetics of the ring-chain interconversion in water has been investigated spectrophotometrically by a 'pH jump' stopped-flow technique. General base catalysis is observed with a Br?nsted beta value apparently independent of substituent and equal to 0.60. The Hammett rho values for various base catalysts are close to those for very similar intermolecular reactions involving hemiacetal breakdown, leading to the suggestion of a 'normal' class n mechanism for base catalysis. For acid catalysis, however, a quite different situation is encountered, since no general acid but only (weak) catalysis by the hydronium ion can be detected. We believe this deviation from 'normal' general acid catalysis is caused by an electrostatic interaction, and we suggest that it might result from a change in the usual class e mechanism for general acid catalysis by a situation in which rate-limiting concerted proton transfer is replaced by rate-limiting preprotonation. This is supported by the observed drastic change in Hammett rho value for catalysis by the hydronium ion, compared with the 'normal' case. An interesting case is encountered for the 4-aminophenyl-substituted substrate, in which the amino group becomes protonated in acid solution, thus representing a new substituent. Despite this complication, the various equilibrium and rate constants may also be evaluated experimentally for this substrate. 相似文献
982.
983.
G. O. Balabanyan 《Theoretical and Mathematical Physics》1991,89(1):1106-1119
Moscow Institute of Electronic Engineering. Translated from Teoreticheskaya i Matematicheskaya Fizika, Vol. 89, No. 1, pp. 132–150, October, 1991. 相似文献
984.
A. L. Itkin E. G. Kolesnichenko 《Journal of Applied Mechanics and Technical Physics》1991,32(4):580-581
Translated from Zhurnal Prikladnoi Mekhaniki i Tekhnicheskoi Fiziki, No. 4, pp. 122–123, July–August, 1991. 相似文献
985.
986.
Summary Global average temperatures from 1860 to 1989 were analysed with a simple fitting procedure. The temperature records can be
fitted with a rising exponential up to 1946 and with the same exponential minus an increasing cooling action from 1946 to
1989. It is shown that the results are compatible with the hypothesis of an albedo increase caused by SO2 emissions. This hypothesis gives satisfactory explanations of the temperature drop in the years 1940–1970, of the different
warming of the northern and southern hemispheres and of the slower warming observed over North America. The results give an
indication that the greenhouse warming in the next years could be faster than predicted until now.
Due to the relevance of its scientific content, this paper has been given priority by the Journal Direction. 相似文献
987.
A new microscopic model of anomalous muonium for the elemental semiconductors is proposed. The relevant configuration consisting
of both a diamagrentic molecule Si−Mu and an unpaired orbital e− is contained into a semivacancy of the real lattice. By using the unrestricted Hartree-Fock computational method the principal
properties of the system are established. A dynamical version of the model together with a question on the formation of such
system are discussed. 相似文献
988.
An explicit expression is obtained for the Green's functions of a massive scalar field for nonnull temperatures and density in the form of a series in powers of m/T. The equivalence of the spectral-geometric approach and the temperature technique of Matsubara and Bernard is demonstrated. Corrections to the Stefan-Boltzmann law are obtained on the basis of the calculated Green's functions. The energy density is calculated in regions of high and low temperatures. The formulas obtained can prove to be useful in the discussion of the phase transition hadrons-quark-gluon plasma.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 7, pp. 32–40, July, 1991. 相似文献
989.
A random-medium model which is a correlated distribution of points (particles) randomly positioned in the 3-dimensional space
is considered. The construction of the medium starts from a noncorrelated (Poisson) distribution of parent particles, each
of them initiates a finite Markov chain of its descendants. The complete collection of correlation functions of all orders
within the scope of the model have been obtained. The use of the 3-dimensional stable law (Lévy law) as a transition probability
allows us to present the correlation function in an explicit form.
Proceedings of the XVII Seminar on Stability Problems for Stochastic Models, Kazan, Russian, 1995, Part II. 相似文献
990.