Low-frequency electrochemical impedance of benzene oxidation on anode of boron-doped diamond

Kinetics of low-frequency adsorption of benzene oxidation products are studied in 0.5 M K₂SO₄ on an anode of boron-doped diamond. A combination of current polarograms and impedance with analysis of the impedance spectroscopy in the frequency range of 0.05–10 Hz allowed studying in detail the mechanism of adsorption oxidation of benzene under the conditions of competition between this process and the more anodic process of oxygen evolution that is also based on adsorption. A frequency-polarization diagram of dependences of characteristic frequencies (CFs) of adsorption and desorption stages on potential was obtained for the product of benzene oxidation and oxygen-containing intermediate of the oxygen evolution reaction. Controlled stages of coupled processes, potentials, and characteristic frequencies of the points of changes in the reaction mechanism are determined: 0.22 Hz at 2.0 V for benzene oxidation; 0.63 Hz at 2.22 V for oxygen evolution. The potential of maximum adsorption of the organic substance is 2.15 V. The obtained results can be useful in the studies of the mechanism of coupled reactions including organic and inorganic intermediate adsorbates.     

Bounds on the performance of back-to-front airplane boarding policies

We provide bounds on the performance of back-to-front airplane boarding policies. In particular, we show that no back-to-front policy can be more than 20% better than the policy which boards passengers randomly.     

Reduction of underdetermined systems of ordinary differential equations: III

We consider the problem on the restriction of underdetermined systems of ordinary differential equations linear in the derivatives to a manifold.     

On categories and foundations of the theory of nonlinear control dynamical systems: VII

In the present paper, we show how the solution of an important problem of control theory (invariance under perturbations) can be obtained with the use of the categorical notion of a quotient system.     

Formation of 2D spherulites in Langmuir films of amphiphilic T-shaped liquid crystals

Langmuir films of facial T-shaped amphiphilic liquid crystals were studied at the air-water interface. The liquid crystals were composed of three incompatible segments: a central rigid rodlike p-terphenyl (TP) group, two flexible hydrophobic n-alkyl terminal chains of identical length linked through ether bonds, and one hydrophilic lateral chain of three ethylene oxide units with a carboxyl end group. In order to determine the influence of the alkyl chain length on the characteristics of condensed films three TPs having n-alkyl chains with eight (TP8/3), ten (TP10/3) or 16 (TP16/3) carbon atoms were investigated. Surface pressure - mean molecular area isotherms revealed clear differences. TP8/3 and TP10/3 exhibit an extended plateau region where a phase transition from monolayer to multilayer takes place. On the other hand, the TP16/3 isotherm showed a distinct maximum ('spike') corresponding to a surprising surface crystallization process which is reported for the first time for a Langmuir film of a liquid crystal. Brewster angle microscopy clearly confirmed these differences: TP8/3 and TP10/3 formed circular domains with liquid crystalline order, while TP16/3 formed well-defined two-dimensional polycrystalline spherulites which are fractured after further compression. The film thickness determined by X-ray reflectivity measurements correlated with a multilayer formation for TP10/3. The morphology of Langmuir-Blodgett (LB) films transferred onto silicon wafers and studied by atomic force microscopy also confirmed the striking different behavior (multilayer formation vs. 2D crystallization) of the TPs under investigation.     

Electrochemical behavior of tungsten-containing nanocomposite with siloxane matrix

Electrochemical properties of a thin-film nanocomposite “silicon-carbon matrix-tungsten carbide” deposited onto pyroceramics (“sitall”) substrate are studied by potentiodynamic curves and electrochemical impedance spectroscopy. Transfer coefficients in model redox system [Fe(CN)₆]^3?/4? are measured. With the decreasing of the films’ electrical resistance, their experiment behavior gradually changed from that of “poor conductor” till nearly metal-like one. In particular, the electrode differential capacitance increases, which is explained by the increase in the number of conducting metal-containing clusters in the film bulk and at the film/electrolyte solution interface. Some specific features of the complex-plane plots of impedance spectra are tentatively explained by the adsorption at the nanocomposite surface elements.     

Low-Light Trees, and Tight Lower Bounds for Euclidean Spanners

We show that for every n-point metric space M and positive integer k, there exists a spanning tree T with unweighted diameter O(k) and weight w(T)=O(k⋅n ^1/k )⋅w(MST(M)), and a spanning tree T′ with weight w(T′)=O(k)⋅w(MST(M)) and unweighted diameter O(k⋅n ^1/k ). These trees also achieve an optimal maximum degree. Furthermore, we demonstrate that these trees can be constructed efficiently.