Intramolecular hemiacetals. The acid-base-catalyzed ring-chain interconversion of 2-substituted 2-hydroxy-4,4-dimethylmorpholinium cations in aqueous solution.

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.     

Simulating the Kinematic Dynamo Forced by Heteroclinic Convective Velocity Fields

We report on the integration of the kinematic dynamo problem in a spherical domain forced by velocity fields that are convective fluid flows resulting from a bifurcation analysis of the spherical Bénard problem. We derive a code based on generalized spherical harmonics that ensures a divergence-free magnetic field. We determine the growth or decay of a magnetic field in the kinematic dynamo equation for various physically relevant velocity fields which are stationary as well as time-periodic and chaotic. Velocity signals that are produced by heteroclinic cycles are used as an input to an energy-saturated kinematic dynamo equation that limits the growth of the linearly unstable modes. Preliminary calculations indicate the possibility of reversals of the magnetic field for this case of forcing. Received 8 October 1996 and accepted 28 April 1997     

Finite temperature QCD coupling constant —imaginary versus real time framework

The correspondence between the imaginary time and real time thermal running coupling constant is discussed. The temperature dependence is derived in pure QCD at one-loop order in a generalized momentum subtraction (MOM) renormalization scheme.     

q\bar q pair creation in a flux tube with confinement

We calculate the effect of radial confinement on the Schwinger pair production rate by solving the Dirac equation in a flux-tube cylinder containing a constant chromoelectric field in the longitudinal direction. We show how the Dirac equation separates into radial and longitudinal equations for a mass term which has an arbitrary radial dependence and introduce radial confinement by having a finite mass inside the cylinder and an infinitely large mass outside. The resulting boundary conditions are equivalent to the MIT boundary condition. The equations are solved analytically for a constant quark mass inside the flux-tube, which acts like a waveguide. The discretization of the transverse wave vector which has a continuous spectrum in the non-confined case leads to a large suppression of the Schwinger pair-production rate for small radii. The minimal radius where pairs are created decreases with increasing field strength. The suppression turns out to be larger for heavier quarks than for light quarks.     

Mössbauer study of spin-glass Fe x Zn1−x F2 system

⁵⁷Fe Mössbauer effect measurements in the diluted Ising antiferromagnet Fe _x Zn_1?x F₂ withx=0.25 andx=0.57 at temperatures between 4.2 and 55 K, are reported. DC suceptibility measurements show a spin-glass (SG) phase at low temperatures forx≤0.31. Our Mössbauer spectra show a phase transition to a SG state with antiferromagnetic order (AFSG) forx=0.25 and only antiferromagnetic order forx=0.57.     

Book Reviews

Unsigned book reviews are by the Book Review Editor.     

Resistance of composite flywheel rim to radial tensile stresses from centrifugal forces based on results of pure bending of a rim segment

A method is proposed for evaluating the resistance of a flywheel rim to radial stresses in free rotation. The method is based on loading a rim segment in pure bending and calculating the limiting moment and the corresponding limiting angular velocity. Applicability of the method is substantiated theoretically by investigating the similarity of the radial stress diagrams in rotation and pure bending. The method is verified experimentally for the strained state of a rim segment in pure bending.Translated from Mekhanika Kompozitnykh Materialov, Vol. 29, No. 4, pp. 521–526, July–August, 1993.     

Crystal and molecular structure of bis(2-isotropyliminomethinylphenyl) telluride

Scientific-Research Institute of Physical and Organic Chemistry, Rostov State University. A. N. Nesmeyanov Institute of Heteroorganic Compounds, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 32, No. 3, pp. 104–106, May–June, 1991.