Photochemische Primärprozesse von Xanthenfarbstoffen. III. Blitzlichtspektroskopische Untersuchungen zum Einfluß von kationischen Mizellen auf die Photoredoxprozesse von Selenopyronin

Photochemical Primary Processes of Xanthene Dyes. III. Investigations of the Influence of Cationic Micelles on the Photoredox Processes of Selenopyronine by Flash Excitation Cationic micelles have no influence on the decay of the triplet state of selenopyronine (³F⁺). The products of photoredox reactions ³F⁺ + ³F⁺ (F⁺) → F^· + F and ³F⁺ + DABCO → F^· + DABCO live longer in the presence of the cationic micelles. The reason for the change of the lifetime is a separation of the photoredox products by micelles. F^. is stored in the interior of the micelles. The positively charged F and DABCO are repelled from the micelles and the electron back transfer is hindered.     

Mass transport process for the adsorption of Cr(VI) onto water‐insoluble cationic starch synthetic polymers in aqueous systems

Dynamic adsorption behaviors between Cr(VI) ion and water‐insoluble amphoteric starches was investigated. It was found that the HCrO ion predominates over the initial pH ∼ 2–4, the CrO ion predominates over the initial pH ∼ 10–12, and both ions coexist over the initial pH ∼ 6–8. The sorption process occurs in two stages: the external mass transport process occurs in the early stage and the intraparticle diffusion process occurs in the long‐term stage. The diffusion coefficient of the early stage (D₁) is larger than that of the long‐term stage (D₂) for the initial pH 4 and pH 10. The diffusion rate of HCrO ion is faster than that of CrO ion for both processes. The D₁ and D₂ values are ∼ 1.38 × 10⁻⁷–10.1 × 10⁻⁷ and ∼ 0.41 × 10⁻⁷–1.60 × 10⁻⁷ cm² s⁻¹, respectively. The ion diffusion rate in both processes is concentration dependent and decreases with increasing initial concentration. The diffusion rate of HCrO ion is more concentration dependent than that of CrO ion for the external mass transport process. In the intraparticle diffusion process, the concentration dependence of the diffusion rate of HCrO and CrO ions is about the same. The external mass transport and intraparticle diffusion processes are endothermic and exothermic, respectively, for the initial pH 4 and pH 10. The k_d values of the external mass transport and intraparticle diffusion processes are ∼ 15.20–30.45 and ∼ −3.53 to −12.67 kJ mol⁻¹, respectively. The diffusion rate of HCrO ion is more temperature dependent than that of CrO ion for both processes. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 2409–2418, 1999     

Über den Kationenaustausch bei anionischen Polyurethan-Dispersionen mit Natriumsulfonat-gruppen

In aqueous dispersions of anionic polyurethanes with SO groups and Na⁺ as counter-ion, Na⁺ was ion exchanged for other cations (H⁺, Ag⁺, Ca⁺⁺, Ba⁺⁺, Ni⁺⁺, Cu⁺⁺, Zn⁺⁺, Pb⁺⁺ and AI⁺⁺⁺). With the exception of AI⁺⁺⁺ the ion exchange took place nearly quantitatively, indicating that site binding of counter-ions did not occur at the particle surface. In addition, the influence of the counter-ion was studied with respect to stability of the dispersion and the mechanical properties of the films.     

Cationic grafting from carbon black. III. Grafting of polyesters from carbon black by ring-opening polymerization of lactones initiated by CO+ClO groups on carbon black

It was found that the cationic ring-opening polymerization of δ-valerolactone (VL), ε-caprolactone (CL), and β-propiolactone (PL) was initiated by carbon black containing CO⁺ClO groups, which were introduced by the reaction of COCl groups with AgClO₄. The polyester was propagated from CO⁺ClO groups and effectively grafted onto carbon black surface. The polymerizability of these lactones by CO⁺ClO groups decreased in the following order: VL > CL > PL. The increasing temperature of the polymerization caused an increase in the rate of the chain transfer reaction of the growing chains and brought about the decrease of grafting ratio of polyester onto carbon black.     

Zur Polarographie von Peroxiden im Null-Volt-Bereich II: Oszillopolarogramme von Hydroperoxiden,Quecksilbersalzen und Hg-Ionen in Gegenwart von Diacylperoxiden

Polarography of Peroxides in Zero-Volt Range II: Oscillo-Polarogramms of Hydroperoxides, Mercury Salts and Hg-Ions in the Presence of Diacyl Peroxides Further experiments carried out in order to explain the occurrence of each of the two polarographic peak currents and current step-ups, A₁ and A₂ respectively, of peroxides in zero-volt range are reported. Occurrence of both the peak currents is probably due to the reduction of monovalent mercury ions. A part of the Hgions which were formed by the oxidation of the Hg-electrode due to the peroxides, is reduced at A₁, and the other part is chemically oxidized by the peroxides further to Hg²⁺ions. The latter can, in a similar fashion, give rise to Hgions by reaction with the Hg electrode. The Hgions are probably reduced at A₂, the reduction being influenced by the nature of binding of the Hg-ions and the catalytic action of chlorides.     

Synthesis,characterization, and metal‐ion uptake studies of chelating resins derived from formaldehyde‐condensed azodyes of aniline and 4,4′‐diaminodiphenylmethane coupled with phenol/resorcinol

The diazonium salts of aniline and 4,4′‐diaminodiphenylmethane coupled with phenol and resorcinol were condensed with formaldehyde in alkaline media to yield polymeric resins. These polymers were found to readily react with metal ions like Cu²⁺ and UO, forming polychelates. The azodyes, resins, and polychelates were characterized by several instrumental techniques such as elemental analysis, FTIR, ¹H‐NMR, GPC, XRD, TG–DTG, and DSC studies. The chelating capacity of the resins toward Cu²⁺ and UO ions was studied by spectrophotometry. The extent of metal loading of the resins was studied by varying the time of contact, metal‐ion concentration, and pH of the reaction medium. The alkali and alkaline earth metal ions had little effect on the metal‐ion uptake behavior of the resins. The resin derived from the azodye of 4,4′‐diaminodiphenylmethane was found to be more efficient in removing the metal ions from solution than were the resins from aniline. The optimum conditions for effective separation of Cu²⁺ from UO were determined. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 77: 3128–3141, 2000     

Influence of anionic form on thermal degradation of TMAHP–cellulose

Trimethylammoniumhydroxypropyl (TMAHP)–cellulose in 10 anionic forms (F^?, Cl^?, Br^?, I^?, HSO, NO, OH^?, HCO, H₂PO, CH₃COO^?) was prepared, and the influence of each anion on thermal degradation in inert atmosphere was studied. With the help of dynamic and isothermal thermogravimetry (TG) it was found that H₂PO ions had the greatest retarding effect on TMAHP–cellulose degradation. From the values of rate constants it can be seen that all ionic forms of TMAHP–cellulose have the starting rate of thermal degradation greater than unmodified cellulose. The calculated values of activation energy of thermal degradation for different ionic forms are decreasing in following sequence: H₂PO > F^? > NO > I^? > Br^? > HCO > Cl^? > HSO > OH^? > unmodified cellulose > CH₃COO^?. From the results of pyrolyse measurements in combination with gas chromatography and mass spectrometry (Py–GC–MS) it follows that the products of the elimination of quarternary ammonium salts are trimethylamine, 3-hydroxy-2-propanone, and, in the case of OH^? form, water. In all other ionic forms the third product is the corresponding acid.     

Adsorption of casein onto alkali treated bentonite

The adsorption measurements of casein onto alkali treated bentonite were performed at room temperature and fixed pH (11.8) with an object to study the mode of casein adsorption at the alkali treated bentonite surfaces. The adsorption isotherm was found to have a Langmuir nature. The adsorption was pH dependent and increased with a decrease in temperature. The adsorption was quite sensitive to the presence of Cl⁻, SO, and PO ions and showed many interesting variations with increasing concentrations of the added anions. Various kinetic and adsorption parameters such as the adsorption coefficient, rate constants for adsorption and desorption, diffusion constant, and penetration rate constant were calculated. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 1656–1663, 2000     

Some observations in the aqueous and emulsion polymerizations of common vinyl monomers initiated by sodium metabisulfite (Na2S2O5) at 50°C

Analytical grade sodium metabisulfite (Na₂S₂O₅) has been found to initiate the polymerizations of methyl methacrylate (MMA) and ethyl methacrylate (EMA) in the aqueous media in the presence and absence of detergents, and of styrene in the presence of detergents only, but it fails to initiate the polymerization of methylacrylate (MA) at low concentrations of the initiator and of acrylonitrile (AN) in the absence of cationic detergent micelles. If a mixture of AN (2.0%, v/v) and metabisulfite (1.60%, w/v) is kept for 16 h at 50°C in the presence of nitrogen, no polymerization occurs, but if a little ferric chloride (0.001%, w/v) is added to this mixture in nitrogen atmosphere, the initiation of AN polymerization is found to occur. MA can be polymerized partly by adding metabisulfite to an aqueous solution of MA and a cationic detergent (above CMC) in the presence and absence of air. Very little polymer is found under similar conditions with AN. No polymerizations were found to occur with any of the above-mentioned monomers if hydroquinone was present in the system. In the Na₂S₂O₅—MMA and Na₂S₂O₅—EMA systems, the average rates of the aqueous polymerizations were found to decrease with the increase of the initiator concentrations (from 1.316 × 10^?3 to 2.63 × 10^?1 m/L) at 50°C in the presence of nitrogen, and to be approximately inversely proportional to the sqare root of the initiator concentrations. It is suggested that the bisulfite (produced by the reaction of S₂O^2?₅ ions with water) adds to vinyl monomers as well as initiaing polymerization reactions by the reduction activation of the monomers in the presence of nitrogen. The presence of bulky groups such as methyl, phenyl, etc., at the β-position of the ethylenic double bond of the monomer, probably prevents or slows down the bisulfite addition reactions due to the steric hindrance, and so the polymerization reactions will predominate in the system of MMA, EMA, and styrene-like monomers. The complex species formed due to the interactions of the cetyltrimethyl ammonium bromide (CTAB) micelles and free CTAB cations with HSO and S₂O ions initiate the polymerizations of MA and of AN in the presence of nitrogen or air. Cationic detergent micelles protect the monomers from the direct attack of the HSO/S₂O ions.     

Fotosensibilisierte Ausbleichung von Azomethinfarbstoffen

Fotosensitized Fading of Azomethine Dyes The quantum yields of photofading of the azomethine dyes 1a—h were determined in the presence of the sensitizers benzophenone (B), michler's ketone (MK) and anthracen (A), in isopropanol and benzene. In isopropanol, excluding oxygen, the leuco dyes 5 are formed by benzophenone in high quantum yield (Φ = 0.4). Photofading also takes place using Michler's ketone (Φ ≅ 3 · 10⁻³) and anthracene (Φ ≅ 1 · 10⁻⁴), but 5 was not found. With benzophenone (Φ ≅ 7 · 10⁻³), Micher's ketone (Φ ≅ 1 · 10⁻³) and anthracene (Φ ≅ 1 · 10⁻⁴) as sensitizers the chromophore of 1a—h were destroyed, when oxygen was present. The photofading with benzophenone and Michler's ketone is a result of radicalic processes. Radical scavangers 8 and 9 , therefore, give a strong decrease of the quantum yield of photofading. The photofading in benzene corresponds to the results in isopropanol considering the lower potential of this solvent for photoreduction processes.     

Forced oscillations in continuous flow stirred tank reactors with nonlinear step growth polymerization

The self-step growth polymerization of RA_f monomers in homogeneous, continuous flow stirred tank reactors (HCSTRs) is simulated under conditions of periodic feed concentration (with frequency ω and amplitude α). By having periodic operation, the polydispersity index of the polymer is found to increase by about 35% over the values at steady state. Periodic operation of HCSTRs is found to lead to gelation only for certain values of the frequency and the dimensionless residence time τ^*. Gelling envelopes have been obtained to give conditions under which HCSTRs should be operated. These envelopes can be described in terms of two critical dimensionless residence times, τ and τ such that nongelling operation is always ensured when τ^* < τ. For τ^* > τ, periodic operation always leads to gelation, and HCSTRs cannot be used. For τ < τ^* < τ, the gelling behavior is found to depend on the functionality f, amplitude α, and the dimensionless residence time τ^*.     

Influence of anionic form on thermooxidation of TMAHP–cellulose

With the help of DTA, DTG elementary analysis of carbonized residues and ESR spectroscopy the influence of anionic form on thermooxidation of trimethylammoniumhydroxyprophyl (TMAHP)–cellulose was studied. At 300°C the percentage of carbon in carbonized residue thermolyzed in oxidative atmosphere is higher than for the sample degraded in inert atmosphere. The percentage of hydrogen decreases simultaneously. The concentration of free radicals in thermolyzed residue also increases due to the presence of oxygen. We propose that oxygen is abstracting the hydrogen atoms from polysaccharide and unpaired electrons on carbon atoms are produced. At 400°C the percentage of carbon in residues prepared at inert atmosphere is higher than for residue formed at oxidative atmosphere. Also the concentration of free radicals in thermolyzed residues obtained in inert atmosphere is greater than for those from oxidative ones. That is why suppose that at this temperature oxygen is bonded to polysaccharide residue and free radicals are terminated. From the semiquantitative DTA we can make the following sequence of samples according to their increasing thermooxidative effect: unmodified cellulose < A–HSO < A–Br^? < A–I^? < A–NO < A–H₂PO < A–CH₃COO^? < A–HCO < A–F^? < A–Cl^?1 < A–OH^p?.     

Removal of ammonium cations from aqueous solution using arene‐sulphonic acid functionalised SBA‐15 as adsorbent

Removal of ammonium cations from aqueous solution was investigated using an arene‐sulphonic acid functionalised mesostructured SBA‐15 material as adsorbent. Arene‐sulphonic acid‐SBA‐15 (AS‐SBA‐15) was prepared via a co‐condensation strategy using tetraethylorthosilicate (TEOS) and 2‐(4‐chlorosulphonylphenyl)ethyltrimethoxysilane (CSPTMS) as framework precursors under acidic conditions. The material exhibited high surface area (680 m²/g) and total pore volume (0.84 mL/g). The effects of adsorbent loading, initial ammonium concentration, temperature, pH and the presence of competitive ions on the adsorption performances were investigated. The ammonium removal increased with the increase of the adsorbent loading and the decrease of the initial concentration. The adsorption capacity decreased with increasing the temperature. Maximum adsorption capacity obtained at 5°C was ca. 19 mg NH/g adsorbent. The isotherms data were studied using different adsorption models and thermodynamic parameters were calculated. Competitive ions such K⁺ and Na⁺ slightly affected the ammonium adsorption. After six adsorption–desorption cycles, the adsorbent retained its adsorption capacity.     

Synthesis and electrochemistry of grafted copolymers of cellulose with 4-vinylpyridine, 1-vinylimidazole, 1-vinyl-2-pyrrolidinone,and 9-vinylcarbazole

Some new cellulosic materials, suitable for the adsorption of noble metal ions, were syn-thesized by chemical and electrochemical modification of cellulose. The polymerizable groups were introduced in cellulose with ∼ 80% yield of substitution by esterification with acryloyl chloride. The vinyl monomers (4-vinylpyridine, 1-vinylimidazole, 1-vinyl-2-pyrrolidinone, and 9-vinylcarbazole) were readily grafted into cellulose acrylate via radical polymerization in acetonitrile. The grafted copolymers of cellulose with 4-vinylpyridine and 4-vinylimidazole were reacted with methyl iodide and the corresponding 1-methylpyridinium iodide ( 6 ) and 3-methylimidazolium iodide ( 7 ) copolymers of cellulose were obtained. Copolymers 6 and 7 were transformed into new polymeric regents, differing in anions (ClO, CF₃COO⁻, NO, p-TsO⁻, BF, PF) by using a supporting electrolyte carrying the desired anions through the ion-exchange-electrochemical oxidation of the released iodide at a controlled anodic potential. © 1996 John Wiley & Sons, Inc.     

Cation selective tubular carrier-PVC-membranes containing polymeric plasticizer with low tendency of migration for Solid State Contact Electrodes

The lifetime of cation selective carrier-PVC-membranes partially depends on the components' remaining in the membrane. An exchange of monomeric by polymeric plasticizers with low tendency to migrate lengthens the function time drastically. Other than for Na⁺ - and NH-selective membranes, it is essential for K⁺ - and Ca²⁺-selective membranes and optional for H⁺-selective membranes to incorporate lipophilic anions in order to make the phase transfer catalysis more efficient. The resistence to saponification of phthalic acid polyester gives H⁺-selective membranes a high stability of measured values even in the alkaline range. For anion selective PVC-membranes, instead of cation selective plasticizers the plasticizing qualities of a liquid charged ligand should be used. The tubular carrier-PVC-membranes of our ion selective flow through measuring systems are diffusion welded to the ends of two PVC-tubes [1] so that they are absolutely tight with no risk of potential leakage. Migration of the membrane components plasticizer and ionophore across this border as well as their extraction [2, 3] into the measuring solution [4] will naturally reduce the membrane's functionning time [5].     

Comment

Electrolytic manganese dioxide is dissolved in the mixed non-aqueous solvent dimethyl sulfoxide–sulfur dioxide (DMSO–SO₂) to form manganese disulfate as a final product. Sulfur dioxide does not change the oxidation state of the metal cations in DMSO–SO₂ solvent. However, oxidation of sulfur(IV) to sulfur(VI) is possible. The complete MnO₂ dissolution occurs in 50 min at a stirring speed of 650 rpm, pH 1, 0.2% solids concentration, 35 × 44 mesh particle size, and 36°C. IR and FTIR evidence has been presented in favor of the formation of SO, S₂O, (CH₃)₂S⁺ as intermediate species for the proposed mechanism. In the mixed non-aqueous solvent system the kinetics of leaching is controlled by a mass transport process. The equation 1–?α–(1–α)^2/3 = kt fits the experimental data very well. This is further supported by scanning electron micrographs, which show a product layer formation on the surface of the MnO₂ particle, and by the dependence of k on 1/r.     

Intrinsic birefringence of nylon 6

Different values are reported in the literature for the intrinsic birefringence of the crystalline (Δn) and the amorphous (Δn) phases in nylon 6. Mostly, these values have either been determined by extrapolation (and then it is assumed that Δn = Δn) or calculated theoretically. In this study, intrinsic birefringence values Δn and Δn for nylon 6 were determined using the Samuels two-phase model which correlates sonic modulus with structural parameters. Three series of fiber samples were used: (1) isotropic samples of different degrees of crystallinity for estimation of E and E moduli at two temperatures. The following modulus values were obtained: 1.62 × 10⁹ and 6.66 × 10⁹ N/m² for 28.5°C, and 1.81 × 10⁹ and 6.71 × 10⁹ N/m² for ?20°C; (2) anisotropic, amorphous fiber samples for estimation of Δn = 0.076 and E = 1.63 × 10⁹ N/m² at 28.5°C; (3) semicrystalline samples of various draw ratios for estimations of Δn = 0.089 and Δn = 0.078. All measurements were carried out with carefully dried samples to avoid erroneous results caused by moisture.     

The transformation: Brushite → calcium monofluorophosphate under aqueous conditions

The reaction between CaHPO₄. 2H₂O and 10^?1 M solution of Na₂PO₃F have been studied in the pH range 7 to 5 at 25 °C. The formation of CaPO₃F · 2H₂O, rather than CaF₂ or Ca₅F (PO₄)₃ by initial hydrolysis and subsequent reaction with the F^? formed, appeared to occur. The value of ΔG for CaPO₃F · 2H₂O has been calculated as – 530.9 kcal mol^?1. A comparison is drawn to the exchange reactions reported here, and to the similar reactions reported to occur in calcium deficient apatite.     

Elastic characteristics of branched-network polymers

The computed dependencies of elastic characteristics of branched-network polymers were obtained on the basis of the Takayanagi series model. The moduli ratio (λ) for branched-network and branched polymers increases as a result of an increase of the moduli ratio of network and branched phases (E/E) and the network phase fraction (V_net). The λ-increase as a function of V_net is larger than in the case of the E/E dependence. On the basis of computed dependencies, the experimental results for the radiation crosslinked SBS block copolymer were considered. The experimental results agree with the computed de-pendencies for the hetergeneous branched-network polymers with E/E ≈︁ 20. The influence of entanglements on the elastic characteristics of branched-network polymers is discussed. © 1996 John Wiley & Sons, Inc.     

Large-scale anaerobic/aerobic treatment of complex industrial wastewater using immobilized biomass in fluidized bed and air-lift suspension reactors

Warm concentrated industrial wastewaters are preferably treated in an anaerobic reactor for reasons of energy generation and low surplus sludge production. Problems to be solved in the practical application concern a low growth rate of the micro-organisms, their low settling rate, process instability and the need for after treatment of the noxious anaerobic effluent which often contains NH and HS^?. The use of biomass immobilized on small suspended carriers (< 0.5 mm) has proven to be a suitable means to overcome most of these problems. Results are presented on pilot and full-scale pretreatment of industrial wastewater in an anaerobic 2-state fluidized bed reactor for CH₄-production and laboratory and pilot scale post-treatment of the anaerobic effluent, which contains NH and HS^? in an aerobic air-lift suspension reactor for the production of NO and SO.