Separation of weak and strong acids by electro-electrodialysis—Experiment and theory

The experimental results of the separation of acetic acid (HA) from the sulfuric acid by the electro-electrodialysis (EED) method and the modeling of process have been presented. The Neosepta membranes CMX and ACM have been used. It has been found that the efficiency of retention of HA is high (>0.9) when the process is conducted below the limiting current density with respect to HSO₄⁻ or SO₄²⁻ anions. The observed current efficiency of the H₂SO₄ removal was rather low (CE_S = ca. 0.7, when the initial concentration of H₂SO₄ in the mixture was 1 or 2 M) which was caused by the nonideal selectivity of the anion-exchange membrane. The experimental results have been described by the model based on the extended Nernst-Planck equation and the Donnan equilibrium. Since the efficiency of the process depended mainly on the selectivity of anion-exchange membrane (ACM), the concentration of fixed charges of that membrane, , and the ratio of volume fraction of pores to their squared tortuosity, V_p/θ², have been chosen as the main fitting parameters. It has been found that the fitting of the EED data depends mainly on , whereas in the modeling of diffusion experiment (or an EED experiment conducted at low current density) both parameters are important. The best fit has been obtained for , i.e. ca. one order smaller than that determined experimentally. The obtained optimal value of V_p/θ², equal to 0.013, is consistent with those previously obtained for other Neosepta anion-exchange membrane.     

Methacrylic acid–acrylamide-g-poly(ethyleneterephthalate) fibres for urea hydrolysis

This paper presents the results of urease immobilization onto methacrylic acid–acrylamide grafted poly(ethyleneterephthalate) fibres. The graft yield strongly affected the maximum activity of the immobilized enzyme up to a value of 70·2%. Higher grafting caused a decline in urease activity and led to the degradation of the fibres. The minor changes observed in K_m and V_max demonstrated that the conformational changes existed during immobilization were not extensive. However, 70·2% methacrylic acid–acrylamide-g-fibres containing urease were more stable towards acidic and alkaline pH, high temperature and storage conditions compared with free enzyme. Apart from the increase in stability to heat inactivation, the initial enzymatic activity of the urease–fibre system remained almost unchanged even after 40 repeated assays corresponding to 10 h of operation in 4 months, indicating the excellent durability of the system.     

In situ13C NMR study of tert-butanol interaction with moderately concentrated sulfuric acid

An in situ NMR study of tert-butanol dehydration in 95 and 85% sulfuric acid did not indicate the formation of tert-butyl cations as active reaction intermediates. Instead, only NMR lines from oxonium ions under the condition of fast exchange with water and the acid were observed. It is most likely that, in the concentrated acid, the active intermediates of this reaction are represented by tert-butyl sulfuric ester which probably is a precursor of invisible tert-butyl carbenium ions representing short-lived excited or transition states.     

Environmentally friendly, heterogeneous acid and base catalysis for the methylation of catechol: Chances for the control of chemo-selectivity

The properties of catalysts with (i) Brønsted-type acidity (H-mordenite and Al/P mixed oxide), (ii) Lewis-type acidity (Al trifluoride) or (iii) basic characteristics (Mg/Fe mixed oxide) were investigated in the gas-phase methylation of catechol. When methanol was used as the methylating agent, H-mordenite and AlF₃ gave high selectivities to guaiacol (the product of O-methylation) under mild reaction conditions, that is at very low catechol conversions. An increase in temperature led to the transformation of guaiacol to phenol and cresols, and to considerable catalyst deactivation. The basic catalyst Mg/Fe/O also favored an extensive degradation of guaiacol to phenol. On the mildly acidic catalyst Al/P mixed oxide a stable catalytic performance and a high selectivity to guaiacol at 40% catechol conversion were obtained. When methylformate, a more reactive methylating agent, was used with AlF₃ and Mg/Fe mixed oxide as catalysts, higher catechol conversions and slower deactivation rates could be achieved under mild reaction conditions, with a low extent of guaiacol degradation. However, methylformate rapidly decomposed when temperatures above 350 °C were used. Finally, tests were made by reacting catechol and diethoxymethane with acid catalysts, with the aim of synthesizing methylenedioxybenzene. The latter product was obtained with high selectivity, but with very low yield, due to both catalyst deactivation and decomposition of diethoxymethane.     

Trifluoromethanesulphonic acid catalysed transalkylation between tetrabromobisphenol-a and toluene for the production of 2,6-dibromophenol

The preparation of 2,6-dibromophenol is described. This compound, useful as raw material for brominated poly(phenyleneoxide) and pyrogallol or derived pharmaceuticals/pesticides, was prepared in 80% (isolated) yield by a transalkylation reaction between tetrabromobisphenol-A and toluene. The catalyst, trifluoromethanesulphonic acid, can be simply recovered and recycled. Perfluorinated resin sulphonic acid (NAFION-H®, DuPont) did not effectively catalyse this transalkylation.     

The microbiology of mixed salad containing raw and cooked ingredients without dressing

Growth of aerobic mesophilic bacteria in mixed salad without dressing, containing cooked sweet corn and raw endive, was similar to that of raw endive alone. At 9°C, sweet corn permitted the growth of the lactic acid bacterium Leuconostoc mesenteroides , whenever the bacterium was present on raw endive, whereas no growth of lactic acid bacteria was recorded on raw endive alone. Listeria monocytogenes , artificially inoculated in the samples, grew more in the mixed salad than in the raw endive alone, for products stored at 6°C and 9°C. Acidification of sweet corn to pH 5.0 was proposed to reduce the development of L. monocytogenes in the mixed salad to a level similar to that recorded in the raw endive alone. Acidification with citric acid reduced spoilage of sweet corn, whereas acetic acid caused necrosis on the leaves of raw endive.     

Component fatty acids of Cladosporium herbarum fat

Cladosporium herbarum grown as a surface culture in a chemically defined medium of sucrose and inorganic salts gave a high yield of fat (29.2%). The component acids of this fat have been found to be palmitic (34.2%); oleic (15.9%); linoleic (34.2%) and linolenic (15.7%). The combined proportion of linoleic and linolenic acids being about 50 per cent, the fat will be of great value for the manufacture of oil-modified resins as the films produced by such resins do not become yellow with age.     

磷酸异戊酯萃取U,Np,Pu性能的研究

测定磷酸异戊酯（ＴｉＡＰ）对Ｕ（Ⅵ）、Ｎｐ（Ⅳ）、Ｎｐ（Ⅴ）、Ｎｐ（Ⅵ）、Ｐｕ（Ⅳ）和Ｐｕ（Ⅲ）的萃取性能及对Ｔｈ（代替Ｐｕ）的萃取容量。研究了二乙三胺五乙酸（ＤＴＰＡ）络合剂对上述核素形成配合物的条件。结果表明，在用ＴＢＰ和ＴｉＡＰ作萃取剂时，可用ＤＴＰＡ络合Ｎｐ（Ⅵ）、Ｐｕ（Ⅲ）．从而改善乏燃料后处理中Ｕ产品对Ｎｐ、Ｐｕ和Ｐｕ产品对Ｎｐ的去污。     

The Synthesis of Covalent Triazine-Based Frameworks via Friedel–Crafts Reactions of Cyanuric Chloride with Thienyl and Carbazolyl Derivatives for Fluorescence Sensing to Picric Acid,Iodine and Capturing Iodine

A multifunctional thiophene-based covalent triazine framework (TTPATTh) with triphenylamine as core is synthesized by Friedel–Crafts reaction of cyanuric chloride with thienyl derivative for the first time. The yield of TTPATTh (99.59%) is far higher than that of the carbazole-based CTF (TTPATCz, 47.03%). TTPATTh and TTPATCz possess high BET surface areas with 1235 and 2501 m² g^–1 as well as high pore volumes with 1.60 and 2.23 cm³ g^–1, respectively. TTPATTh and TTPATCz have high thermal stability with high thermal decomposition temperatures of 514 and 598 °C in nitrogen atmosphere. With the introduction of triazine rings, the fluorescence sensing sensitivities of TTPATTh and TTPATCz to picric acid and iodine are improved significantly. Especially for TTPATTh, the K_sv values reach 5.95 × 10⁵ and 1.61 × 10⁴ L mol^–1, and LODs reach 1.02 × 10^–12 and 1.86 × 10^–12 mol L^–1. To the best of the knowledge, this is the most sensitive value among thiophene-based porous organic polymers to PA and I₂. Furthermore, TTPATTh and TTPATCz can also adsorb iodine in vapor phase, cyclohexane solution and aqueous solution, and release iodine by heating or in ethanol solution. The efficiency of controlling the release of iodine is higher than that in ethanol.