Combined chemical and phase equilibrium for the hydration of ethylene to ethanol calculated by means of the Peng-Robinson-Stryjek-Vera equation of state and the Wong-Sandler mixing rules

Due to the economics of the ethylene market and the subsidized production of fermentation-based ethanol in some countries, use of the ethylene hydration process to make ethanol has been steadily declining. The economics of this process might improve by combining the reaction and separation in a reactive distillation column, whose conceptual design requires a study of the combined chemical and phase equilibrium (CPE) of the reacting system. In this work, the Peng-Robinson-Stryjek-Vera equation of state was combined with the UNIQUAC activity coefficient model through the Wong-Sandler (WS) mixing rules in order to correlate the available experimental data for the vapor-liquid equilibria (VLE) of the ethylene-water, ethylene-ethanol, and ethanol-water binary systems at 200 °C. The interaction energies of the UNIQUAC model and the binary interaction coefficient of the WS mixing rules were used as the fitting parameters. From the optimum values of these parameters, both the VLE and the combined CPE of the ethylene-water-ethanol ternary system were predicted at 200 °C and various pressures. At this temperature, the catalytic activity of a H-pentasil zeolite has already been reported to exhibit a maximum for ethylene hydration, and also the experimentally measured two-phase region of the ternary system is sufficiently wide. By means of the reactive flash method, the chemical equilibrium compositions of the liquid and vapor phases were determined for several pressures, and the equilibrium conversion and the vapor fraction were calculated as functions of the ethylene to water feed mole ratio. It turns out that the vapor-liquid mixed-phase hydration of ethylene achieves equilibrium conversions much higher than those computed for a vapor-phase reaction that would hypothetically occur at the same conditions of pressure and feed mole ratio. It was found that the reactive phase diagram of the ternary system exhibits a critical point at 200 °C and 155 atm.     

Binuclear zinc(II) complexes with the anti-inflammatory compounds salicylaldehyde semicarbazone and salicylaldehyde-4-chlorobenzoyl hydrazone (H2LASSBio-1064)

Complexes [Zn₂(HL¹)₂(CH₃COO)₂] (1) and [Zn₂(L²)₂] (2) were synthesized with salicylaldehyde semicarbazone (H₂L¹) and salicylaldehyde-4-chlorobenzoyl hydrazone (H₂LASSBio-1064, H₂L²), respectively. The crystal structure of (1) was determined. Upon recrystallization of previously prepared [Zn₂(HL²)₂(Cl)₂] (3) in 1:9 DMSO:acetone crystals of [Zn₂(L²)₂(H₂O)₂]·[Zn₂(L²)₂(DMSO)₄] (3a) were obtained. The crystal structure of 3a was also determined. All crystal structures revealed the presence of phenoxo-bridged binuclear zinc(II) complexes.     

Dansyl-anthracene dyads for ratiometric fluorescence recognition of Cu2+

Dansyl-anthracene dyads 1 and 2 in CH(3)CN-H(2)O (7:3) selectively recognize Cu(2+) ions amongst alkali, alkaline earth and other heavy metal ions using both absorbance and fluorescence spectroscopy. In absorbance, the addition of Cu(2+) to the solution of dyads 1 or 2 results in appearance of broad absorption band from 200 nm to 725 nm for dyad 1 and from 200 nm to 520 nm for dyad 2. This is associated with color change from colorless to blue (for 1) and fluorescent green (for 2). This bathochromic shift of the spectrum could be assigned to internal charge transfer from sulfonamide nitrogen to anthracene moiety. In fluorescence, under similar conditions dyads 1 and 2 on addition of Cu(2+) selectively quench fluorescence due to dansyl moiety between 520-570 nm (for 1)/555-650 nm (for 2) with simultaneous fluorescence enhancement at 470 nm and 505 nm for dyads 1 and 2, respectively. Hence these dyads provide opportunity for ratiometric analysis of 1-50 μM Cu(2+). The other metal ions viz. Fe(3+), Co(2+), Ni(2+), Cd(2+), Zn(2+), Hg(2+), Ag(+), Pb(2+), Li(+), Na(+), K(+), Mg(2+), Ca(2+), Ba(2+) do not interfere in the estimation of Cu(2+) except Cr(3+) in case of dyad 1. The coordination of dimethylamino group of dansyl unit with Cu(2+) causes quenching of fluorescence due to dansyl moiety between 520-600 nm and also restricts the photoinduced electron transfer from dimethylamino to anthracene moiety to release fluorescence between 450-510 nm. This simultaneous quenching and release of fluorescence respectively due to dansyl and anthracene moieties emulates into Cu(2+) induced ratiometric change.     

Noisy colored point set matching

We propose a process for determining approximated matches, in terms of the bottleneck distance, under color preserving rigid motions, between two colored point sets A,B∈R², |A|≤|B|. We solve the matching problem by generating all representative motions that bring A close to a subset B^′ of set B and then using a graph matching algorithm. We also present an approximate matching algorithm with improved computational time. In order to get better running times for both algorithms we present a lossless filtering preprocessing step. By using it, we determine some candidate zones which are regions that contain a subset S of B such that A may match one or more subsets B^′ of S. Then, we solve the matching problem between A and every candidate zone. Experimental results using both synthetic and real data are reported to prove the effectiveness of the proposed approach.