The solution of a convection–diffusion–reaction equation arising from cathodic reduction in a pulsating crack

This paper derives the convection–diffusion-reaction equation governing the reaction between the dissolved oxygen in sea-water and the steel walls of a pulsating crack. By the neglect of the diffusion term it is shown that an exact solution of the convection-reaction equation can be obtained. A numerical method for the solution of the complete convection–diffusion-reaction equation is derived by the use of finite differences. The numerical computation of the initial transient and the final periodic steady-state values is also discussed.     

Inner-sphere oxidation of iron(II) by tris(malonato)cobaltate(III)

The kinetics of oxidation of Fe²⁺ by [Co(C₃H₂O₄)₃]^3? in acidic solutions at 605 nm showed a simple first-order dependence in each reactant concentration. The second-order rate constant dependence on [H⁺] is in accordance with eqn (i) k₂ = k′₂ + k₃[H⁺] (i) where k′₂ and k₃ have values of 73.4 ± 14.0 M ^?1 s^?1 and 353 ± 41 M^?2 s^?1, respectively, at 1.0 M ionic strength (NaClO₄) and 25°C. At 310 nm the formation and decomposition of an intermediate, believed to be [FeC₃H₂O₄]⁺, was observed. The increase in the rate of oxidation with increasing [H⁺] was interpreted in terms of a “one-ended” dissociation mechanism which facilitates chelation of Fe₂₊ by the carbonyl oxygens of malonate in the transition state.     

Polymerization of butadiene on nanoparticles’ surfaces and formation of metal/polymer nanocomposites

In this paper, we demonstrate that laser vaporization of metals in the presence of a small concentration of butadiene vapor leads to the polymerization of butadiene and incorporation of the metal nanoparticles within the polymer matrix. The metal nanocomposites are characterized by electron microscopy, X-ray diffraction and EDX. The results from high pressure mass spectrometry indicate that multiple additions of butadiene molecules on the metal cations Fe⁺, Ni⁺ and Pt⁺, generated by laser vaporization, take place at room temperature thus providing an efficient means of initiating further polymerization reactions. The Pt⁺ reactions show extensive fragmentations and elimination steps generating hydrocarbon ions. The laser vaporization/polymerization method provides the ability to encapsulate several different metals or metal oxides which undoubtedly will play a significant role in tuning the various properties of the polymer composites.     

Absorption and emission dynamics in concentrated optical ensembles under laser excitation

A new theoretical model describing the emission and absorption dynamics in an ensemble of molecules under intense coherent pulsed pumping is developed on the basis of the concepts of cooperative light-induced luminescence (CLIL). The CLIL development is described within the framework of formalism of the system density matrix in the space of photon wave functions. It is shown that the fast growth of CLIL relates to the development of coherent states of the quantum field in the area of efficient cooperative interactions of molecules (coherence volume). A system of equations for the calculation of CLIL energy, population of excited states, and optical absorption of the system in dependence on the laser pump energy density is solved. The theoretical results obtained are in good agreement with the experimental data.     

Reaction of 2-formyl-1,3-cyclohexanediones with cyanoacetamide

Chemistry of Heterocyclic Compounds -     

Complex dynamics of a simple distributed self-oscillatory model system with delay

A simple model for a distributed self-oscillatory system with cubic nonlinearity and delay is presented. Conditions for oscillation self-excitation and stationary oscillation conditions, as well as the stability of the oscillations, are analyzed. Nonstationary self-modulation regimes (including conditions of complex dynamics and chaos) are simulated numerically over a wide range of control parameters. As the factor of nonequilibrium grows, regular and chaotic regimes alternate in a complex manner. The transitions to chaos may follow all scenarios known for finite-dimensional systems. The model suggested is somewhat akin to a number of earlier finite-dimensional models aimed at studying mode competition in resonance electron masers.     

Numerical simulation and experimental validation of heat transfer within rotating flows for three‐dimensional non‐axisymmetric,turbulent conditions

A control volume type numerical methodology for the analysis of steady three‐dimensional rotating flows with heat transfer, in both laminar and turbulent conditions, is implemented and experimentally tested. Non‐axisymmetric momentum and heat transfer phenomena are allowed for. Turbulent transport is alternatively represented through three existing versions of the k–ε model that were adjusted to take into account the turbulence anisotropy promoted by rotation, streamline curvature and thermal buoyancy. Their relative performance is evaluated by comparison of calculated local and global heat balances with those obtained through measurements in a laboratory device. A modified version of the Lam and Bremhorst, low Reynolds number model is seen to give the best results. A preliminary analysis focused on the flow structure and the transfer of heat is reported. Copyright © 2002 John Wiley & Sons, Ltd.