The reactivity of 3-methyl- and 5-methyl-1-vinylpyrazoles in free-radical polymerization

3-Methyl-l-vinylpyrazole (M3VP) and 5-methyl-1-vinylpyrazole (M5VP) were isolated as individual substances by vacuum rectification of their mixture (M3VP: M5VP 60 40). For each of them the kinetics of free-radical polymerization in MeOH were measured at low conversions. In both cases the rate of polymerization is proportional to 0.5 order with respect to the initiator (AIBN) concentration. On the other hand, a first order of reaction with respect to monomer concentration is observed only when the latter is relatively low (3M). At higher initial concentrations of monomers the order of reaction becomes less than unity. The overall rate of polymerization for M5VP was higher than for M3VP, whereas the initiation rate remained constant in the whole range of monomer concentrations and did not depend on the exact structure of the monomer. The difference in the rates of polymerization observed for M3VP and M5VP is probably connected with the difference in the key parameterk _p/k _t ^1/2 for each of the two isomers. It is concluded that the correct kinetic information about homo- and co-polymerization of M3VP and M5VP cannot be obtained without their adequate separation.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 413–415, February, 1993.     

The Properties of Functions and Approximation by Summation Rational Operators on the Real Axis

In the space $C(\mathbb{R})$ , we construct special summation operators of Jackson type with rational kernels and under a suitable choice of poles we obtain order estimates for deviations of these operators from functions belonging to certain classes.     

Numerical-Asymptotic Expansion Matching for Computing a Viscous Flow Around a Sharp Expansion Corner

A computational technique which is based on a numerical-asymptotic expansion matching for computing the local singular behavior of a viscous flow around a sharp right-angle expansion corner is presented. Moffatt's (1964) asymptotic solution is extended and a matching with a time-marching finite-difference scheme of the Navier--Stokes equations is formulated. Local mesh refinement around the corner is required to meet the validity of the asymptotic solution. Flows in an expanding channel with expansion ratio D/d=3 at various Reynolds numbers 1≤Re≤700 are simulated. The results are compared with those from a standard finite-difference scheme that uses second-order forward/backward differences near the corner. It is found that the results of the standard scheme converge toward those of the present technique as the level of local refinement near the corner is increased. The time-dependent parameters of the first two terms of the asymptotic solution at the steady-state solution are also described for various cases of Re and D/d. It is demonstrated that the present method enhances the accuracy of the simulations and requires less refinements near the corners to achieve converged numerical results. Received 14 August 2000 and accepted 25 October 2001     

Estimates of the derivative of a rational function

We investigate some regular rational functions on the real axis, with fixed poles, conjugate in pairs, of half-integer order. An extremal equality is obtained, which generalizes one of L. V. Taikov's results for trigonometric polynomials.Translated from Matematicheskie Zametki, Vol. 13, No. 4, pp. 493–498, April, 1973.     

Photoelectric properties of In/p-(Cu, Ag)Ga(Se, Te)2 surface-barrier structures

Based on single crystals of AgGaSe₂, AgGaTe₂, CuGaTe₂ of the p-type, surface-barrier structures were manufactured by vacuum thermal deposition on illumination of which the photovoltaic effect was observed. It is established that the longwave edge of the photosensitivity of such structures possesses several inflections attributable to photoactive absorption involving paracipation of levels of lattice defects. It is shown that In/p-(Cu, Ag)Ga(Se, Te)₂ surface-barrier structures can be used as wide-band transducers and photoanalyzers of linearily polarized radiation. Translated from Zhurrnal Prikladnoi Spektroskopii, Vol. 66, No. 1, pp. 141–144, January–February, 1999.     

Synthesis of Cyclohexylideneacetonitrile on Zeolites

Condensation of cyclohexanone with acetonitrile on zeolites with different carcass structures was studied. The highest yield of cyclohexylideneacetonitrile (80 wt %) at a 98% selectivity of the process was attained with NaX zeolite containing 0.5 wt % KOH. Factors responsible for different catalytic activities and selectivities of zeolites are discussed.