Investigation of coal fired combined-cycle cogeneration plants for power, heat, syngas, and hydrogen

The methodology for determination of technical and economic efficiency of coal fired combined-cycle cogeneration plant (CCCP) with low-pressure steam-gas generator and continuous flow gasifier at combined production of power, heat, syngas, and hydrogen is considered. The results of investigation are presented. Such CCCP have higher technical and economic efficiency than the pulverized coal cogeneration plant modified by gas-turbine.     

Raman and photoluminescence spectroscopy of zinc tungstate powders

ZnWO₄ powders, synthesized using co-precipitation technique and annealed in air at different temperatures in the range of 80-, were studied by Raman and photoluminescence spectroscopy. ZnWO₄ single crystal was used for comparison. The interpretation of the observed variations of the Raman spectra and intrinsic photoluminescence band upon annealing is suggested.     

On the relationship between the luminescence of heterometallic terbium-copper-podand complexes and the ligand structure

The formation conditions and luminescence of heterometallic Tb-Cu complexes with structurally similar podands containing different numbers of oxymethylene fragments were studied (n = 2?7). The component ratio in mono- and different-metal complexes were 1: 1 and 1: 1: 1, respectively. The possibility of complex formation for the carbonyl and enol forms was estimated by molecular mechanics. The results were in good agreement with experimental data. The most pronounced enhancement of luminescence intensity of Tb(III) ions in heterometallic Tb-Cu complexes was observed for podands containing two and three oxymethylene fragments (L1 and L2, respectively) and the probability of complex formation with these podands is higher than with the podands containing four to seven oxymethylene fragments (L3–L5).     

Computational study of singlet and triplet sulfonylnitrenes insertion into 1,3‐butadienes: 1,2‐ or 1,4‐cycloaddition?

The formation of N‐trifluoromethylsulfonyl‐2‐vinylaziridine and N‐trifluoromethylsulfonyl‐3‐pyrroline by the reaction of the singlet and triplet trifluoromethanesulfonylnitrenes with s‐cis‐ and s‐trans‐1,3‐butadienes was studied theoretically at the B3LYP/6‐311++G(d,p) and M06‐2X/6‐311++G(d,p) levels of theory. The singlet trifluoromethanesulfonylnitrene adds to s‐cis‐ and s‐trans‐1,3‐butadiene exothermally in one step to give the product of 1,2‐cycloaddition, N‐trifluoromethylsulfonyl‐2‐vinylaziridine, the energy decreasing by 88.5 and 86.2 kcal/mol at the B3LYP level and by 105.2 and 103.0 kcal/mol at the M06‐2X level, respectively. The formed 2‐vinylaziridine can undergo rotation about the C(2)–C_sp2 bond with the barrier not exceeding 3.5 kcal/mol and to rearrange into N‐trifluoromethylsulfonyl‐3‐pyrroline. The triplet trifluoromethanesulfonylnitrene reacts with s‐cis‐ and s‐trans‐1,3‐butadiene in two steps. The first exothermic step is the formation of the triplet diradical adducts. The second step is the spin inversion with the energy raising by 5.8 and 17.8 kcal/mol at the B3LYP level and by 11.0 and 20.8 kcal/mol at the M06‐2X level for the adducts to s‐cis‐ and s‐trans‐1,3‐butadiene, respectively. Recombination of the radical centers occurs selectively to give N‐trifluoromethylsulfonyl‐2‐vinylaziridine that is exothermally rearranged into N‐trifluoromethylsulfonyl‐3‐pyrroline with the energy barrier of 40 kcal/mol at the B3LYP level and of 50 kcal/mol at the M06‐2X level. Copyright © 2014 John Wiley & Sons, Ltd.     

Remarks on the “Non-canonicity Puzzle”: Lagrangian Symmetries of the Einstein-Hilbert Action

Given the non-canonical relationship between variables used in the Hamiltonian formulations of the Einstein-Hilbert action (due to Pirani, Schild, Skinner (PSS) and Dirac) and the Arnowitt-Deser-Misner (ADM) action, and the consequent difference in the gauge transformations generated by the first-class constraints of these two formulations, the assumption that the Lagrangians from which they were derived are equivalent leads to an apparent contradiction that has been called “the non-canonicity puzzle”. In this work we shall investigate the group properties of two symmetries derived for the Einstein-Hilbert action: diffeomorphism, which follows from the PSS and Dirac formulations, and the one that arises from the ADM formulation. We demonstrate that unlike the diffeomorphism transformations, the ADM transformations (as well as others, which can be constructed for the Einstein-Hilbert Lagrangian using Noether’s identities) do not form a group. This makes diffeomorphism transformations unique (the term “canonical” symmetry might be suggested). If the two Lagrangians are to be called equivalent, canonical symmetry must be preserved. The interplay between general covariance and the canonicity of the variables used is discussed.     

Influence of interparticle interactions on the kinetics of self-assembly and mechanical strength of nanoparticulate aggregates

Computer simulations based on Discrete Element Method have been performed in order to investigate the influence of interparticle interactions on the kinetics of self-assembly and the mechanical strength of nanoparticle aggregates.Three different systems have been considered.In the first system the interaction between particles has been simulated using the JKR (Johnson,Kendall and Roberts) contact theory,while in the second and third systems the interaction between particles has been simulated using van der Waals and electrostatic forces respectively.In order to compare the mechanical behaviour of the three systems,the magnitude of the maximum attractive force between particles has been kept the same in all cases.However,the relationship between force and separation distance differs from case to case and thus,the range of the interparticle force.The results clearly indicate that as the range of the interparticle force increases,the self-assembly process is faster and the work required to produce the mechanical failure of the assemblies increases by more than one order of magnitude.     

Fundamentals and properties of zinc oxide nanostructures: Optical and sensing applications

In this paper we will give an overview of the status of catalytic growth and of low-temperature chemical growth of ZnO nanostructures performed in our laboratory. Particularly results employing different substrates will be discussed. The second part deals with structural and optical properties of ZnO nanorods. The results from high resolution transmission electron microscope (HRTEM), scanning electron microscope (SEM), photoluminescence (PL), Cathodoluminescence (CL), and Electroluminescence (EL), on single nanowires will be shown. Our results on surface morphology, bulk and the position of the catalyst as well as the optical properties including UV emission, lasing and white emission will all be presented and discussed. In the third part experimental results from electroluminescence of ZnO nanorods on different substrates in the UV in addition to excellent white light emission obtained from samples grown at low temperature are to be given and discussed. Finally the sensing of molecules in water by ZnO nanorods will be discussed from a theoretical point of view. Also fundamental properties of polaritons and excitons in ZnO nanostructures are to be highlighted.     

A parameter-free smoothness indicator for high-resolution finite element schemes

This paper presents a postprocessing technique for estimating the local regularity of numerical solutions in high-resolution finite element schemes. A derivative of degree p ≥ 0 is considered to be smooth if a discontinuous linear reconstruction does not create new maxima or minima. The intended use of this criterion is the identification of smooth cells in the context of p-adaptation or selective flux limiting. As a model problem, we consider a 2D convection equation discretized with bilinear finite elements. The discrete maximum principle is enforced using a linearized flux-corrected transport algorithm. The deactivation of the flux limiter in regions of high regularity makes it possible to avoid the peak clipping effect at smooth extrema without generating spurious undershoots or overshoots elsewhere.     

DNA Effect on Cis–Trans Equilibrium and Fluorescent Properties of 3,3′-Diethyl-9-thiomethylthiacarbocyanine Iodide in Aqueous Solution

The influence of DNA on the cis–trans equilibrium and fluorescent properties of 3,3-diethyl-9-thiomethylthiacarbocyanine iodide (DTTC) in a phosphate buffer (pH 7) was studied by various photochemical techniques. The interaction of dye molecules with DNA leads to the formation of stable noncovalently bonded complexes. Data obtained from DTTC absorption and fluorescence spectra suggest that complexation proceeds primarily through the cis-form of the dye. Complexation with DNA leads to a substantial increase in the quantum yield of the triplet state of DTTC molecules. The rate constant for quenching the dye triplet state by oxygen turned out to be significantly lower than the diffusion-controlled value.     

Analysis of molecular chirality using the lattice model of spatial structure

A lattice model of the spatial structure of a molecule is suggested. A broken line is constructed to characterize atoms and molecular fragments. The line is a spiral (left or right) embracing the whole lattice containing the molecule. The mutual arrangement of molecular fragments along the broken line is described by a molecular code. The code contains all the necessary information about molecular conformation and configuration in compressed form. Comparing the codes makes it possible to evaluate the structural similarity and dissimilarity of molecules. For example, one can easily estimate the chirality level for enantiomers. Using this approach is demonstrated on various model structures. A. V. Bogatskii Physicochemical Institute, Ukrainian Academy of Sciences. Odessa State University. Translated fromZhurnal Strukturnoi Khimii, Vol. 39, No. 3, pp. 541–546, May–June, 1998. This work was supported by INTAS grant INTAS-UA 95-0060.