Physico-chemical aspects of polyethylene processing in an open mixer. Part 26: Formal kinetics of aldehyde and carboxylic acid formation at a constant rate

Formation of carboxylic acids at a constant rate can be easily explained. It seems to result from the formation and decomposition of α,γ-keto-hydroperoxides. Formal kinetics based on formation and decomposition of these structural units is in agreement with the experimental findings. The activation energy deduced from the calculations is negligible, in agreement with the experimental data showing the constant rate to be practically temperature independent. Comparison of the acids with the hydroperoxides and ketones formed initially shows that the rate of oxygen addition to alkyl radicals is significantly smaller than in low molecular mass liquids. The same conclusion is reached on comparing directly the acids formed on decomposition of α,γ-keto-hydroperoxides in polyethylene melt and in hexadecane. The rate of oxygen addition in polyethylene melt is closer to 2 × 10⁵ than to 6 × 10⁵ (s⁻¹) that is valid in hexadecane.It is possible to attribute the relatively small amount of aldehydes that might be formed at a constant rate to different reactions of alkoxy radicals that are not in a cage with other radicals. These alkoxy radicals result from the addition of peroxy radicals to unsaturated bonds. This addition is followed mainly by epoxide formation and simultaneous release of an alkoxy radical.     

Negative molecular ions of azafullerenes and their hydrogenated derivatives

The formation and decay of negative molecular ions of azafullerenes and their hydrogenated derivatives are investigated by mass spectrometry. The mechanisms of resonant electron capture and the lifetimes of negative molecular ions with respect to the electron autodetachment in azafullerene molecules are discussed. A comparative analysis of the data obtained for azafullerenes and hydrogenated fullerene derivatives is carried out.     

Studies aimed at the synthesis of morphine V an economic approach to (±)-reticuline from 3,4-dihydropapaverine

Regioselective demethylation of 3,4-dihydropapaveraldine ($\text{2}$a) at 7 and 3' positions affords a properly substituted diphenolic key intermidiate ($\text{2}$d) for the synthesis of reticuline and N-norreticuline.     

A simplified method of computing the process of opening of a parachute

We propose a simplified method of determining the integral characteristics of the opening of a parachute which makes it possible to compute the maximal stress on a parachute and the trajectory parameters of the motion of the load in the region of the opening of the parachute, and to determine the size of the portion of the canopy at the time of maximal stress.Translated fromDinamicheskie Sistemy, No. 6, 1987, pp. 38–41.     

An expedient route to diaza-spirocycles utilizing a sequential multicomponent α-aminoallylation/ring-closing metathesis strategy

A general method for the preparation of diaza-spirocycles is reported. This method used an olefin metathesis in order to construct the desired spirocyclic framework. Beginning with commercially available protected amino ketones, this strategy ultimately produced pharmacologically relevant diaza-scaffolds in an efficient and high-yielding process.     

A Class of C ·0-Contractions: Hyperinvariant Subspaces and Intertwining Operators

We consider a class of C_·0-contractions that is a generalization of the class of C_·0-contractions with finite defect indices. Some results of Uchigama and Wu for C_·0-contractions with finite defect indices are generalized: the lattices of hyperinvariant subspaces of such a contraction T is isomorphic to that of its Jordan model and is generated by subspaces of the form Ker ϕ(T) and Ran ϕ(T), where ϕ ∈ H^∞. The form of the inverse to an isomorphism of the invariant subspace lattices given by an intertwining quasiaffinity is also studied. Next, for C_·0-contractions in question, the characteristic disc related to the lattice of invariant subspaces is computed. Bibliography: 13 titles. __________ Translated from Zapiski Nauchnykh Seminarov POMI, Vol. 315, 2004, pp. 48–62.     

Effect of Alkali Metal Cation on Copolymerization of Acrylamide with Salts of 2-Acrylamido-2-methylpropanesulfonic Acid in Aqueous Solutions

The kinetics of radical copolymerization of acrylamide with lithium, sodium, and potassium 2-acrylamido-2-methylpropanesulfonates in concentrated aqueous solutions in the presence of potassium persulfate as initiating agent at pH 9 and 50°C was studied by dilatometry.     

Contact Interaction of Two Elastic Wedges

We consider the problem of contact of two elastic wedges and assume that only the vertices of the wedges touch before loading. After loading, the edges of both wedges come in contact near their common vertex. We reduce the constructed system of dual integral equations to a Fredholm integral equation of the second kind with difference kernel given on the semiaxis. We analytically solve the Fredholm equation by reducing it to the boundary-value Riemann problem for analytic functions. We obtain an analytic expression for contact stresses.     

A NOTE ON FINITE DIFFERENCE ESTIMATION OF ACOUSTIC PARTICLE VELOCITY

The influence of instrumentation amplitude and phase mismatch on finite difference measurement of mean square particle velocity is examined. It is shown theoretically and demonstrated experimentally that the resulting error depends on two properties of the sound field, the ratio of the active intensity to the mean square particle velocity and the ratio of the reactive intensity to the mean square particle velocity. Very large errors can occur near particle velocity nodes in interference fields even with well-matched state-of-the-art sound intensity measurement systems. However, outside of such regions, moderate phase mismatch has very little influence on the performance of the measurement system. Amplitude mismatch is somewhat more problematic.