Polymerization of 1,3‐Butadiene Initiated by Neodymium Versatate/Triisobutylaluminum/Ethylaluminum Sesquichloride: Impact of the Alkylaluminum Cocatalyst Component

Abstract

The polymerization of 1,3‐butadiene (BD) by the ternary Ziegler/Natta (Z/N) catalyst system neodymium versatate (NdV)/ethylaluminum sesquichloride (EASC)/aluminum alkyl is investigated. Special attention is paid to the impact of the aluminum alkyl on the polymerization kinetics and on the control of molar masses. In this respect diisobutyl aluminumhydride (DIBAH) and triisobutylaluminum (TIBA) are compared. Within a broad range of n _Al‐Alkyl/n _NdV‐ratios for both aluminum compounds the features of a living polymerization with a reversible exchange of the living polybutadienyl chains between neodymium (Nd) and aluminum are observed. The equilibrium position of this reaction is different for TIBA and DIBAH. At the same molar loadings DIBAH results in polybutadienes with molar masses which are 1/8 of those obtained in the presence of the cocatalyst TIBA. This difference is explained by a significantly more facile substitution of a hydride moiety from DIBAH than an isobutyl group from either DIBAH or TIBA by a living polybutadienyl chain.     

Complexation with Diol Host Compounds. Part 35: Inclusion Compounds of 1,1,6,6-Tetraphenylhexa-2,4-diyne-1,6-diol with CCl4, CHCl3, CH2Cl2 and CH3CN

Inclusion compounds were formed with 1,1,6,6-tetraphenylhexa-2,4-diyne-1,6-diol (H) and carbon tetrachloride, chloroform, dichloromethane and acetonitrile. 1 (H·1/2CCl⁴), 2 (H·1/2CHCl³) and 3 (H·1/2CH²Cl²) are true clathrates with the guest molecules situated in cages created by the host. 4 (H·2CH³CN) exhibits a different packing arrangement with the guest molecules located in channels. The crystal structures and stability of these inclusion compounds were investigated.     

THE ADSORPTION OF AN ANIONIC SURFACTANT AT THE OIL WATER INTERFACE DURING EMULSION HOMOGENIZATION

Adsorption of sodium dodecylbenzene sulfonate (NaDBS) on the surfaces of dispersed oil globules during homogenization of paraffin oil in water emulsions has been studied. NaDBS concentration was changed over a wide interval comprising critical micelle concentration. For the emulsions homogenized for different time intervals the total quantity and the percentage of NaDBS adsorbed, the amount and number of NaDBS molecules adsorbed per unit inter-facial area, as well as the specific surface area of dispersed phase and the area per emulsifier molecule have been determined.

The amount adsorbed and density of the emulsifier layer, I.e., the area per NaDBS molecule adsorbed on the oil globule surfaces, depend not only on Initial NaDBS concentration but also, on the homogenization time and the homogenization action. This makes a difference between the adsorption behaviour under the conditions of emulsion formation and its subsequent homogenization, and the adsorption behaviour of the emulsifier at a plane quiescent Interface.     

Studies on the Phenol Oxidation with H2O2 Catalyzed by Metallomicelle Made from Crowned Schiff Base Mn(III) Complexes

Metallomicelles made from two Schiff base manganese(III) complexes (MnL¹ and MnL²) and surfactants (CTAB and Brij35) were used as mimetic peroxidase in the catalytic oxidation of phenol by H₂O₂. The catalytic activity of the complexes (MnL¹ and MnL²) were investigated. The mechanism and a kinetic mathematic model of the phenol catalytic oxidation were also studied. The results show the optimum acidity of the enzyme-like system in the paper is ca. pH 7.0, the optimum temperature which is ca. 35°C and the optimum molar ratio of H₂O₂ to the complex is ca. 30 in the complexes-H₂O₂-buffered solution; the Schiff base manganese(III) complexes and their metallomicelles as peroxidase mimics exhibit good catalytic activity and similar catalytic character to natural enzyme.     

Analytical and kinetic study of the aqueous hydrolysis of four organophosphorus and two carbamate pesticides

The hydrolysis of six selected pesticides has been studied in aqueous solution. Four organophosphorus pesticides (disulfoton, isofenfos, isazofos and profenfos) and two N-methylcarbamate derivatives (oxamyl and ethiofencarb) were selected. Hydrolysis was performed in purified buffered water at different pH in the range 7.0–10.0 (ionic strength?=?2.5?mM, T?=?25°C). At pH?=?8.0, isofenfos and disulfoton (t _1/2?≈?4 years, t _1/2?≈?1 year, resp.) were found to be far more stable than isazofos (t _1/2?≈?5 months), ethiofencarb and profenofos (t _1/2<1 month), themselves more stable than oxamyl (t _1/2?≈?1 day). As expected, a strong dependence on pH was observed for all pesticides: the rate of degradation increased when the pH increased. Degradation products were identified by GC–MS and/or LC–MS. Possible structures are presented in the article.     

Micellar Effects on the Oxidation of d‐Glucose by Chromic Acid in Perchloric Acidic Medium

Kinetics of the reaction between d‐glucose and Cr(VI) in the absence and presence of surfactant micelles have been studied by a spectrophotometric method in aqueous‐acidic solutions of perchloric acid. It was observed that the reaction has a nonautocatalytic followed by an autocatalytic pathway. The rate of the initial stage increases with increase in [glucose], [HClO₄] and temperature. Due to precipitation, the effect of cationic micelles of cetyltrimethylammonium bromide (CTAB) could not be studied whereas the oxidation is catalyzed by anionic micelles of sodium dodecyl sulfate (SDS) and nonionic micelles of Triton X‐100 (TX‐100). The results are discussed in terms of the pseudo‐phase kinetic model. Activation parameters are evaluated and a mechanism consistent with the results is proposed. A rate law for the reaction has also been derived. The redox reaction occurs through a Cr(VI)→Cr(IV) path.     

Evaluation of Acacia nilotica as a non conventional low cost biosorbent for the elimination of Pb(II) and Cd(II) ions from aqueous solutions

In the present study a biomass derived from the leaves of Acacia nilotica was used as an adsorbent material for the removal of cadmium and lead from aqueous solution. The effect of various operating variables, viz., adsorbent dosage, contact time, pH and temperature on the removal of cadmium and lead has been studied. Maximum adsorption of cadmium and lead arises at a concentration of 2 g/50 ml and 3 g/50 ml and at a pH value of 5 and 4, respectively. The sorption data favored the pseudo-second-order kinetic model. Langmuir, Freundlich and Dubinin–Radushkevich (D–R) models were applied to describe the biosorption isotherm of the metal ions by A. nilotica biomass. Based on regression coefficient, the equilibrium data found were fitted well to the Langmuir equilibrium model than other models. Thermodynamic parameters such as free energy change (ΔG°), enthalpy change (ΔH°) and entropy change (ΔS°) have been calculated, respectively revealed the spontaneous, endothermic and feasible nature of adsorption process. The activation energy of the biosorption (Ea) was estimated as 9.34 kJ mol⁻¹ for Pb and 3.47 kJ mol⁻¹ for Cd from Arrhenius plot at different temperatures.     

Anaerobic biological treatment of dye bearing water in anaerobic sequencing batch reactor: Performance and kinetics studies

Textile and dye industries are main sources of dye bearing effluent. In present studies the anaerobic biological degradation of Acid Red 3BN dye water (AR3BNDW) and mixed dye water (MDW) for reduction of color and COD were studied in sequential batch reactor (SBR). The sludge as sources of microorganism was arranged from maize processing bio methanation wastewater treatment plant, which was acclimatized for treatment of AR3BNDW and MDW. After the acclimatization, dyes degradation were studied in SBR At optimum operation condition of hydraulics retention time (HRT) = 2.5 d, and treatment time (t_R) = 16 h, AR3BNDW have gone maximum 87% color reduction of 500 mg/L dye, and 82.8% COD reduction of 380 mg/L COD. At same operating condition, 84.5% color reduction of 500 mg/L dye, and 79.42% COD reduction of 413 mg/L COD achieved for MDW. The second order Grau model was fitted well for COD and dye reductions. The kinetics parameter were evaluated for both the dye water.     

A simple method for removal of toxic dyes such as Brilliant Green and Acid Red from the aquatic environment using Halloysite nanoclay

This project explains an easy, simple and eco-friendly method to remove some toxic dyes like Brilliant Green and Acid Red from aquatic solution by technique of solid-phase extraction that uses Halloysite nanoclay eco-friendly solid phase as absorbent surface for adsorption of dye. The physical properties of the HNC such as scanning electron microscopy, transmission electron microscope, X-ray diffraction, Fourier transform infrared spectroscopy, and surface area analysis were studied. The best conditions like pH of the solution, HNC weight, contact shaking time, the temperature of the solution, and ionic strength were investigated for removal effectiveness. The experimental data of the adsorption process showed that HNC can remove most of the dyes within 30 min, with an adsorption capacity of 12.5 mg/g for A.R dye and 13.9 mg/g for B.G dye on HNC solid phase at optimum conditions. The removal process of dyes on HNC was studied kinetically and thermodynamically, and the data confirms that the pseudo-second-order kinetic model was able to describe the adsorption process. Thermodynamic data confirms the process was spontaneous andexothermic in nature for A.R dye, while was spontaneous and endothermic in nature for B.G dye. Finally, the effectiveness of HNC was inspected by removing dyes from three various real samples, and the results showed high performance in removing dyes on HNC for four consecutive cycles.