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Alkaline Medium (alkaline + medium)
Selected AbstractsThe Nanocrystalline Nickel with Catalytic Properties on Methanol Oxidation in Alkaline MediumFUEL CELLS, Issue 5 2009R. M. A. Tehrani Abstract The hexagonal closed packed (hcp) nanocrystalline nickel (Ni), with an average diameter of 9.7,±,2.27,nm was deposited uniformly on composite graphite (CG) by the rapid scanning (6,500,mVs,1) voltammetry technique. The hcp-nano Ni-modified CG electrode was investigated for the catalytic oxidation of methanol in alkaline medium through the formation of NiOOH. A high anodic current was obtained at peak potential of +570,mV vs Ag/AgCl. Both the scan rate and the methanol concentration affected the oxidation of methanol. The results showed that catalytic activity had increased with decrease in Ni particle diameter. It was also shown that the hcp-nano Ni/CG modified electrode was the most efficient catalyst in the oxidation of methanol. [source] ChemInform Abstract: Cyclization of 3-Alkylamino-4-hydroxybutanamides in Alkaline Medium.CHEMINFORM, Issue 41 2001Z. I. Tyukhteneva Abstract ChemInform is a weekly Abstracting Service, delivering concise information at a glance that was extracted from about 100 leading journals. To access a ChemInform Abstract of an article which was published elsewhere, please select a "Full Text" option. The original article is trackable via the "References" option. [source] A Novel Synthesis of 2-Amino-2-deoxy- D -gluconic Acid and Its Complexation with Cu(II) in Alkaline MediumCHINESE JOURNAL OF CHEMISTRY, Issue 10 2006Wen-Xiu Gu Abstract A novel synthesis of the functional carbohydrate 2-amino-2-deoxy- D -gluconic acid was introduced and its complex formation with Cu(II) was investigated to obtain the stability constant for its further applications to the food and pharmaceutical industries. The equilibrium was investigated by spectrophotometric measurements and processed by dual-series linear regression method. Results:the yield of 2-amino-2-deoxy- D -gluconic acid is 70%. The complexation molar ratio is 1:2, the molar apsorptivity of the complex is 39.906 L·mol,1·cm,1 at 630 nm, and the stability constant ,nis 6.24×105. [source] Kinetics and Mechanism of Oxidation of Ethylene Glycol Monoethylether by Diperiodatonickelate(IV) in Alkaline MediumCHINESE JOURNAL OF CHEMISTRY, Issue 11 2003Jin-Huan Shan Abstract The kinetics of oxidation of ethylene glycol monoethylether (EGE) by diperiodatonickelate(IV) ion (DPN) was studied by spectrophotometry in alkaline medium. The reaction rate showed first order dependence on Ni(IV) and positive fractional order with respect to EGE. The pseudo-first order rate constants, kobs increased with the increase of [OH,] and decreased with the increase of [IO4,]. Added salts had little effect on the rate and no free radical was detected. Based on these, the mechanism including the equilibrium between DPN and EGE was proposed. Furthermore, the activation parameters of the reaction were calculated. [source] Selective determination of famotidine in human plasma by high performance liquid chromatography in alkaline media with solid phase extractionJOURNAL OF SEPARATION SCIENCE, JSS, Issue 8 2003Eva Anzenbacherová Abstract A new method is described for the determination of famotidine by solid phase extraction from alkalinized human plasma followed by reversed phase (RP) HPLC in acetonitrile/alkaline buffer with molsidomine as an internal standard. Different acetonitrile/aqueous buffer mobile phases as well as various RP columns were used. Alkaline medium allowed the limit of quantitation to be lowered to 5 ng/mL of plasma as the famotidine gives more intense absorption at about 286 nm (at pH values higher than 7). Moreover, work in alkaline media and at this wavelength is highly selective as peaks corresponding to impurities present in most samples are well separated. A method using a mildly alkaline mobile phase (acetonitrile/10 mM phosphate with 10 mM 1-heptanesulphonic acid, pH 7.5) was successfully used for determination of famotidine in human plasma in a pharmacokinetic study. [source] Voltammetric Determination of Free and Total Sulfur Dioxide in BeerELECTROANALYSIS, Issue 5-6 2003J. Almeida Abstract A voltammetric method for the determination of free and total sulfur dioxide in beer is described. First, volatile aldehydes (mainly acetaldehyde) are purged with nitrogen from a beer sample diluted in alkaline medium, collected in an appropriate electrolyte trapping solution and determined, after derivatization with hydrazine, by voltammetry using a hanging mercury drop electrode. Then, the remaining beer solution is strongly acidified and (total) sulfur dioxide is purged with nitrogen, collected in an appropriate electrolyte trapping solution and determined by voltammetry. The free sulfur dioxide concentration is calculated by difference between (total) sulfur dioxide and acetaldehyde concentrations. The proposed method has a relative standard deviation of about 2.1% and 4.4%, respectively for (total) sulfur dioxide and free sulfur dioxide concentrations normally found in beer, and results are in good agreement with those obtained by the p -rosaniline reference method. [source] Indirect laser-induced fluorescence detection for capillary electrophoresis using a frequency-doubled diode laserELECTROPHORESIS, Issue 3 2003Natalia Ragozina Abstract A blue (452 nm) frequency-doubled diode laser with a quasi-cw optical output power of 10 ,W is used for indirect laser-induced fluorescence detection in combination with the capillary electrophoretic separation of inorganic anions. As fluorescing probe ion the anion of 8-hydroxypyrene-1,3,6-trisulfonic acid (HPTS) was selected having an absorption maximum of 454 nm in alkaline medium. Employing a capillary coated with linear acrylamide, baseline separation of eight inorganic anions was possible within 5 min. With a separation buffer containing 50 ,mol·L -1 HPTS and 10 mmol·L -1 lysine the limits of detection for sulfate, nitrite, nitrate, azide, thiocyanate, and chlorate were between 0.9 and 4.7 ,mol·L -1. Separation of chloride and sulfate was achieved by adding 0.25 mmol·L -1 calcium hydroxide to the separation buffer. Inorganic anions in several mineral and tap water samples have been determined with the technique developed and results are compared to data obtained by ion chromatography in combination with conductivity detection after conductivity suppression. [source] Mössbauer Investigation of Peroxo Species in the Iron(III),EDTA,H2O2 SystemEUROPEAN JOURNAL OF INORGANIC CHEMISTRY, Issue 21 2005Virender K. Sharma Abstract The reaction of a diiron(III),EDTA complex with H2O2 in alkaline medium is studied by Mössbauer spectroscopy in conjunction with the rapid-freeze/quench technique in order to identify possible intermediate species during the formation and decomposition of the purple (EDTA)FeIII(,2 -O2)3, complex ion. Starting from the six-coordinate [FeIIIEDTA], species at acidic pH, it is demonstrated that mononuclear complexes formed at a pH of about 1 are convert into the diiron(III),EDTA complex [(EDTA)FeIII -O-FeIII(EDTA)]4, upon raising the pH to around 10.4. H2O2 reacts with the diiron(III) complex to give peroxide/hydroperoxide related adducts. Initially, the reaction tears apart the dimers to form a peroxo adduct, namely the seven-coordinate mononuclear [(EDTA)FeIII(,2 -O2)]3,, which is stable only at very high pH. The decomposition of this peroxo adduct gives two new species, which are reported for the first time. The Mössbauer parameters of these species suggest a six-coordinate ,-peroxodiiron(III) complex [(EDTA)FeIII -(OO)-FeIII(EDTA)]4, and a seven-coordinate ,-hydroxo-,-peroxodiiron(III) complex [(EDTA)FeIII -(OO)(OH)-FeIII(EDTA)]5,. A badly resolved, extremely broad component is observed in the Mössbauer spectra during the conversion of the monomer to dimeric peroxo species, which may be attributed to the short-lived [(EDTA)FeIII -OO]3, or [(EDTA)FeIII -OOH]2, intermediate species. (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2005) [source] Interplay of Properties and Functions upon Introduction of Mesoporosity in ITQ-4 ZeoliteADVANCED FUNCTIONAL MATERIALS, Issue 9 2010Danny Verboekend Abstract The introduction of mesoporosity in zeolites is often directly coupled to changes in their overall catalytic performance without the detailed assessment of other key functions required for the rational design of the catalytic process such as accessibility, adsorption, and transport. This study presents an integrated approach to study property,function relationships in hierarchical zeolites. Accordingly, desilication of the 1D ITQ-4 zeolite in alkaline medium is applied to develop different degrees of mesoporosity. Along with porosity modification, significant changes in composition, structure, and acidity occur. Relationships are established between the physicochemical properties of the zeolites and their characteristics in the adsorption and elution of light hydrocarbons (C2 to C5, alkanes and alkenes) as well as in the catalytic activity in low-density polyethylene (LDPE) pyrolysis. The recently introduced hierarchy factor can appropriately relate porosity changes to catalytic performance. [source] The Nanocrystalline Nickel with Catalytic Properties on Methanol Oxidation in Alkaline MediumFUEL CELLS, Issue 5 2009R. M. A. Tehrani Abstract The hexagonal closed packed (hcp) nanocrystalline nickel (Ni), with an average diameter of 9.7,±,2.27,nm was deposited uniformly on composite graphite (CG) by the rapid scanning (6,500,mVs,1) voltammetry technique. The hcp-nano Ni-modified CG electrode was investigated for the catalytic oxidation of methanol in alkaline medium through the formation of NiOOH. A high anodic current was obtained at peak potential of +570,mV vs Ag/AgCl. Both the scan rate and the methanol concentration affected the oxidation of methanol. The results showed that catalytic activity had increased with decrease in Ni particle diameter. It was also shown that the hcp-nano Ni/CG modified electrode was the most efficient catalyst in the oxidation of methanol. [source] Tailored Mesoporosity Development in Zeolite Crystals by Partial Detemplation and DesilicationADVANCED FUNCTIONAL MATERIALS, Issue 1 2009Javier Pérez-Ramírez Abstract Partial detemplation of zeolites followed by desilication in alkaline medium is demonstrated as a powerful and elegant approach to design hierarchical zeolites with tailored degree of mesoporosity. This achievement, illustrated for large beta crystals, is based on the fact that the template-containing zeolite is virtually inert to Si leaching upon treatment in aqueous NaOH solutions. Partial removal of the structure-directing agent creates regions in the crystal susceptible to mesopore formation by subsequent desilication, while template-containing regions are protected from silicon extraction. Variation of the calcination temperature in the range 230,550,°C determines the amount of template removed and enables control of the extent of mesopore formation in the zeolite (20,230,m2,g,1) upon alkaline treatment. The functionality of the introduced mesoporosity in the hierarchical beta crystals is demonstrated by the improved performance in the catalytic pyrolysis of low-density polyethylene. The partial detemplation,desilication treatment enhances the tuning options of this demetallation method. [source] Synthesis of New Resorcinarenes Under Alkaline ConditionsHELVETICA CHIMICA ACTA, Issue 10 2005Jean-Marc Bourgeois The preparation of functionalized resorcinarenes is described. Thus, 2-nitroresorcinol (=,2-nitrobenzene-1,2-diol), 2-acetylresorcinol (=,1-(2,6-dihydroxyphenyl)ethanone), and 2,6-dihydroxybenzoic acid were treated with formaldehyde in alkaline medium to give the corresponding resorcinarenes 1,3 (Scheme,1). This method is also applicable for resorcinol (=,benzene-1,3-diol) itself, but the yields are poorer. In this case, the molecule formed is the simplest resorcinarene 4 on which a number of substituents can be inserted between the two OH groups. Thus, bromation of 4 yields 5 (Scheme,2). Some properties and conformations of these new products are discussed, and the X-ray crystal structures of the nitro and bromo compounds 1 and 5, respectively, are presented. [source] Kinetics of the simultaneous oxidation of nickel(II) and sulfur(IV) by oxygen in alkaline medium in Ni(II),sulfur(IV),O2 systemINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 8 2010Anil Kumar Sharma In the Ni(II),S(IV),O2 system in the region of pH > 8.4, both Ni(II) and S(IV) are simultaneously autoxidized, and when sulfur is consumed fully NiOOH precipitates. At pH > 8.4, ethanol has no effect on the rate, whereas ammonia strongly inhibits the reaction when pH > 7.0. The kinetics of the reaction, in both the presence and the absence of ethanol, is defined by the rate law where k is the rate constant, KO is the equilibrium constant for the adsorption of O2 on Ni(OH)2 particle surface. In ammonia buffer, the factor F is defined by where K, KOH, K1, K2, K3, and K4 are the stability constants of NiSO3, NiOH+, Ni(NH3)2+, Ni(NH3), Ni(NH3), and Ni(NH3), respectively. In unbuffered medium, the factor F reduces to The values of k and Ksp were found to be (1.3 ± 0.08) × 10,1 s,1 and (4.2 ± 3.5) × 10,16, respectively, at 30°C. A nonradical mechanism that assumes the adsorption of both SO32, and O2 on the Ni(OH)2 particle surface has been proposed. At pH , 8.2, Ni(II) displays no catalytic activity for sulfur(IV)-autoxidation and it is also not oxidized to NiOOH. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 464,478, 2010 [source] Oxidation of diclofenac sodium by diperiodatoargantate(III) in aqueous alkaline medium and its determination in urine and blood by kinetic methodsINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 6 2010P. N. Naik The kinetics and oxidation of diclofenac sodium (DFS) by diperiodatoargentate(III) (DPA) in alkaline medium at 298 K and at a constant ionic strength of 0.60 mol dm,3 were studied spectrophotometrically. The oxidation products were [2-(2,6-dicloro-phynylamino)-phenyl]-methenol and Ag(I), identified by LC-ESI-MS and IR spectral studies. The reaction between DFS and DPA in alkaline medium exhibits 1:1 stoichiometry. The reaction is first order in [DPA] and has a less than unit order dependence each in [DFS] and [alkali]. Increasing concentrations of IO,4 retard the reaction. The active species of DPA proposed to be monoperiodatoargentate(III), and a mechanism is suggested. The rate constants involved in the different steps of the mechanism were determined and are discussed. The activation parameters with respect to a rate-limiting step of the mechanism were determined. The thermodynamic quantities were also determined. Using the oxidation of DFS by DPA, DFS was analyzed by kinetic methods in urine and blood sample. The proposed method enables DFS analysis in the range from 5.0 × 10,5 to 5.0 × 10,3 mol dm,3. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 336,346, 2010 [source] Kinetics and mechanism of oxidation of the drug mephenesin by bis(hydrogenperiodato)argentate(III) complex anionINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 8 2007Shigang Shen Mephenesin is being used as a central-acting skeletal muscle relaxant. Oxidation of mephenesin by bis(hydrogenperiodato)argentate(III) complex anion, [Ag(HIO6)2]5,, has been studied in aqueous alkaline medium. The major oxidation product of mephenesin has been identified as 3-(2-methylphenoxy)-2-ketone-1-propanol by mass spectrometry. An overall second-order kinetics has been observed with first order in [Ag(III)] and [mephenesin]. The effects of [OH,] and periodate concentration on the observed second-order rate constants k, have been analyzed, and accordingly an empirical expression has been deduced: k, = (ka + kb[OH,])K1/{f([OH,])[IO,4]tot + K1}, where [IO,4]tot denotes the total concentration of periodate, ka = (1.35 ± 0.14) × 10,2M,1s,1 and kb = 1.06 ± 0.01 M,2s,1 at 25.0°C, and ionic strength 0.30 M. Activation parameters associated with ka and kb have been calculated. A mechanism has been proposed to involve two pre-equilibria, leading to formation of a periodato-Ag(III)-mephenesin complex. In the subsequent rate-determining steps, this complex undergoes inner-sphere electron transfer from the coordinated drug to the metal center by two paths: one path is independent of OH, whereas the other is facilitated by a hydroxide ion. In the appendix, detailed discussion on the structure of the Ag(III) complex, reactive species, as well as pre-equilibrium regarding the oxidant is provided. © 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39: 440,446, 2007 [source] Kinetic evidence for the copper peroxide intermediate with two copper ions in proximityINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 7 2006S. Selvarani The decomposition of caroate (peroxomonosulfate, PMS) is catalyzed by Cu(II) ions even at 5 × 10,5 M in aqueous alkaline solution. The rate is second order in copper(II) ions concentrations and first order in [PMS]. The rate constant values are found to decrease with increase in hydroxide ion concentrations. The turnover number for the reaction is estimated as >1000. The experimental results suggest that the formation of peroxide type intermediate with two copper(II) ions is the rate-determining step. This peroxide intermediate reacts with another molecule of PMS to give the products oxygen, SO and copper ions. The overall entropy of activation is positive with a value of ,20 cals/mol/K. The very high turnover number suggests that Cu(II) ion is one of the best catalysts for the decomposition of caroate ions in alkaline medium. The reaction also represents a system in which metal ion catalyzed decomposition of caroate does not involve radical intermediates. © 2006 Wiley Periodicals, Inc. Int J Chem Kinet 38: 439,443, 2006 [source] Kinetics of oxidation of reducing sugars by catalytic amount of osmium(VIII) in presence of periodateINTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 8 2004Rashmi Tripathi The kinetics of oxidation of some reducing sugars viz. glucose, galactose, fructose, maltose, and lactose by osmium(VIII) in presence of sodium metaperiodate in alkaline medium have been investigated. The reactions are zero order in periodate. The order of reaction in substrate and OH, decreases from unity to zero at higher [substrate] or [OH,], respectively. Rate of oxidation is proportional to [Osmium(VIII)]. Osmium(VIII) serves as an effective oxidant which oxidizes reducing sugars and itself reduces to osmium(VI). Role of IO4, is to regenerate osmium(VIII) from osmium(VI). An evidence for the complex formation between osmium(VIII) and reducing sugar has also been obtained. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36:441,448, 2004. [source] Kinetic study of the ruthenium(VI)-catalyzed oxidation of benzyl alcohol by alkaline hexacyanoferrate(III)INTERNATIONAL JOURNAL OF CHEMICAL KINETICS, Issue 7 2002A. E. Mucientes The kinetics of the Ru(VI)-catalyzed oxidation of benzyl alcohol by hexacyanoferrate(III), in an alkaline medium, has been studied using a spectrophotometric technique. The initial rates method was used for the kinetic analysis. The reaction is first order in [Ru(VI)], while the order changes from one to zero for both hexacyanoferrate(III) and benzyl alcohol upon increasing their concentrations. The rate data suggest a reaction mechanism based on a catalytic cycle in which ruthenate oxidizes the substrate through formation of an intermediate complex. This complex decomposes in a reversible step to produce ruthenium(IV), which is reoxidized by hexacyanoferrate(III) in a slow step. The theoretical rate law obtained is in complete agreement with all the experimental observations. © 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 421,429, 2002 [source] Arbutin determination in medicinal plants and creamsINTERNATIONAL JOURNAL OF COSMETIC SCIENCE, Issue 2 2009W. Thongchai Synopsis A simple flow injection (FI) manifold with spectrophotometric detection was fabricated and tested for arbutin determination. It is based on the measurement of a red-coloured product at 514 nm formed by the complexation reaction between arbutin and 4-aminoantipyrine (4-AP) in the presence of hexacyanoferrate (III) in an alkaline medium. On injecting 300 ,L standard solutions at various concentrations of arbutin into the FI system under optimum conditions, a linear calibration graph over the range of 1.0,30.0 ,g mL,1 arbutin was established. It is expressed by the regression equation y = 0.2188 ± 0.0036x + 0.1019 ± 0.0366 (r2 = 0.9990, n = 5). The detection limit (3,) and the limit of quantitation (10,) were 0.04 ,g mL,1 and 0.13 ,g mL,1, respectively. The RSD of intraday and interday precisions were found to be 1.2,1.4% and 1.7,2.7%, respectively. The method was successfully applied in the determination of arbutin in four selected fruits and three commercial whitening cream extracts with the mean recoveries of the added arbutin over the range of 96.2,99.0%. No interference effects from some common excipients used in commercial whitening creams were observed. The method is simple, rapid, selective, accurate, reproducible and relatively inexpensive. Résumé Un collecteur simple pour injection en flux (FI) avec détection spectrométrique a été fabriqué et testé pour le dosage de l'arbutine. Son principe repose sur la mesure à 514 nm du produit rouge formé par la réaction de complexation entre l'arbutine et le 4-aminoantipyrine (4-AP) en présence d'hexacyanoferrate (III) en milieu alcalin. On procède à une injection de 300 ,L des solutions standards à diverses concentrations d'arbutine dans le système FI aux conditions optimales, puis on réalise un graphe de calibration linéaire dans l'intervalle de 1,0 à 30,0 ,g mL,1 d'arbutine. Le graphe correspond à l'équation de régression y = 0.2188 ± 0.0036x + 0.1019 ± 0.0366 (r2 = 0.9990, n = 5). La limite de détection (3,) et la limite de quantification (10,) sont respectivement de 0.04 ,g mL,1 et 0.13 ,g mL,1. La RSD des précisions intra et inter jours sont respectivement de 1.2,1.4% et 1.7,2.7%. La méthode a été appliquée avec succès à la mesure de l'arbutine dans 4 fruits sélectionnés et 3 extraits de crèmes de blanchiment commercialisées avec une recouvrance moyenne de l'arbutine ajoutée de 96.2 à 99%. Aucune interférence avec les excipients communément utilisés dans les crèmes de blanchiment commerciales n'a été observée. La méthode est simple, rapide, sélective, précise, reproductible et relativement bon marché. [source] Synergistic effect of halide ions and polyethylene glycol on the corrosion inhibition of aluminium in alkaline mediumJOURNAL OF APPLIED POLYMER SCIENCE, Issue 6 2009S.A. Umoren Abstract The corrosion inhibition of aluminium in alkaline medium was studied at 30 and 40°C in the presence of polyethylene glycol (PEG) using gravimetric (weight loss) and thermometric techniques. The effect of halides (KCl, KBr, and KI) on the inhibitory action of PEG was also studied. It was found that PEG acted as inhibitor for aluminium corrosion in the alkaline medium. Inhibition efficiency increased with increasing inhibitor concentration. An increase in temperature led to increase in both the corrosion rate and inhibition efficiency in the absence and presence of inhibitor and halides. Phenomenon of chemical adsorption mechanism is proposed from the values of Ea, Qads, and ,G obtained. The adsorption of PEG on the surface of aluminium was found to obey Flory,Huggins and Temkin adsorption isotherms. The synergism parameter, S1 evaluated was found to be greater than unity indicating that the enhanced inhibition efficiency caused by the addition of halides is synergistic in nature. The inhibition efficiency, surface coverage and synergism parameter increased in the order; I,> Br,> Cl, showing that a joint adsorption of PEG and halide ions on aluminium plays a significant role in the adsorption process. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Synthesis and characterization of imine-coupled polyphenols containing carbazole unitsJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2009smet Kaya Abstract Imine coupled phenolic monomers containing carbazole unit were synthesized in four steps. The monomers were polymerized via oxidative polycondensation by air as oxidant in an aqueous alkaline medium at 50°C. The structures of compounds were confirmed by ultraviolet,visible (UV,vis), Fourier transform infrared, and 1H- and 13C-NMR techniques. The conductivity measurements of these polymers were made by the four-point probe technique and iodine was used as doping agent. The highest occupied molecular orbital, the lowest unoccupied molecular orbital, and electrochemical and optical band gap values were calculated by the results of the UV,vis and the cyclic voltammetry measurement, respectively. The number-average molecular weight, weight-average molecular weight, and polydispersity index values were determined by the size exclusion chromatography technique. Also, thermal behavior of these polymers was determined by thermogravimetric/differential thermal analysis measurements in a N2 atmosphere between 20 and 1000°C. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Synthesis, characterization, and kinetic of thermal degradation of oligo-2-[(4-bromophenylimino)methyl]phenol and oligomer-metal complexesJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2009smet Kaya Abstract Oligo-2-[(4-bromophenylimino)methyl]phenol (OBPIMP) was synthesized from the oxidative polycondensation reaction of 2-[(4-bromophenylimino)methyl]phenol (BPIMP) with air and NaOCl oxidants in an aqueous alkaline medium between 50 and 90°C. The yield of OBPIMP was found to be 67 and 88% for air and NaOCl oxidants, respectively. Their structures were confirmed by elemental and spectral such as IR, ultraviolet,visible spectrophotometer (UV,vis), 1H-NMR, and 13C-NMR analyses. The characterization was made by TG-DTA, size exclusion chromatography, and solubility tests. The resulting complexes were characterized by electronic and IR spectral measurements, elemental analysis, AAS, and thermal studies. According to TG analyses, the weight losses of OBPIMP, and oligomer-metal complexes with Co+2, Ni+2, and Cu+2 ions were found to be 93.04%, 59.80%, 74.23%, and 59.30%, respectively, at 1000°C. Kinetic and thermodynamic parameters of these compounds investigated by Coats-Redfern, MacCallum-Tanner, and van Krevelen methods. The values of the apparent activation energies of thermal decomposition (Ea), the reaction order (n), preexponential factor (A), the entropy change (,S*), enthalpy change (,H*), and free energy change (,G*) obtained by earlier-mentioned methods were all good in agreement with each other. It was found that the thermal stabilities of the complexes follow the order Cu(II) > Co(II) > Ni(II). © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009 [source] Microporous activated carbon spheres prepared from resole-type crosslinked phenolic beads by physical activationJOURNAL OF APPLIED POLYMER SCIENCE, Issue 5 2008Arjun Singh Abstract Microporous activated carbon spheres (ACSs) with a high specific Brunauer,Emmet,Teller (BET) surface area were prepared from resole-type spherical crosslinked phenolic beads (PBs) by physical activation. The PBs used as precursors were synthesized in our laboratory through the mixing of phenol and formaldehyde in the presence of an alkaline medium by suspension polymerization. The effects of the gasification time, temperature, and flow rate of the gasifying agent on the surface properties of ACSs were investigated. ACSs with a controllable pore structure derived from carbonized PBs were prepared by CO2 gasification. Surface properties of ACSs, such as the BET surface area, pore volume, pore size distribution, and pore diameters, were characterized with BET and Dubinin,Reduchkevich equations based on N2 adsorption isotherms at 77 K. The results showed that ACSs with a 32,88% extent of burn-off with CO2 gasification exhibited a BET surface area ranging from 574 to 3101 m2/g, with the pore volume significantly increased from 0.29 to 2.08 cm3/g. The pore size and its distribution could be tailored by the selection of suitable conditions, including the gasification time, temperature, and flow rate of the gasifying agents. The experimental results of this analysis revealed that ACSs obtained under different conditions were mainly microporous. The development of the surface morphology of ACSs was also studied with scanning electron microscopy. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008 [source] Characterization and solution properties of a partially hydrolyzed graft copolymer of polyacrylamide and dextranJOURNAL OF APPLIED POLYMER SCIENCE, Issue 3 2008S. Krishnamoorthi Abstract Graft copolymers of dextran (Dx) and polyacrylamide (PAM) were synthesized through the grafting of PAM chains onto a Dx backbone with a ceric-ion-induced solution polymerization technique. By the variation of the amount of the initiator (ceric ammonium nitrate), four different grades of graft copolymers were synthesized. The partial alkaline hydrolysis of Dx- g -PAM was carried out in an alkaline medium. Three grades of partially hydrolyzed products were synthesized through the variation of the amount of alkali. These hydrolyzed graft copolymers were characterized with elemental analysis, infrared spectroscopy, neutralization equivalent measurements, a rheological technique, scanning electron microscopy, thermal analysis, viscometry, and X-ray diffraction. The flocculation efficiency and viscosifying characteristics of the graft copolymers were enhanced upon their alkaline hydrolysis. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008. [source] Kinetics of graft copolymerization of poly(hexanedioic acid ethylene glycol) and methyl acrylate initiated by potassium diperiodatocuprate(III)JOURNAL OF APPLIED POLYMER SCIENCE, Issue 4 2007Libin Bai Abstract A redox system, potassium diperiodatocuprate(III) [DPC]/poly(hexanedioic acid ethylene glycol) (PEA) system, was employed to initiate graft copolymers of methyl acrylate (MA) and PEA in alkaline medium. The results indicate that the equation of the polymerization rate (Rp) is as follows: Rp = k [MA]1.62[Cu(III)]0.69, and that the overall activation energy of graft polymerization is 42.5 kJ/mol. The total conversion at different conditions (concentration of reactants, temperature, concentration of the DPC, and reaction time) was also investigated. The infrared spectra proved that the graft copolymers were synthesized successfully. Some basic properties of the graft copolymer were studied by instrumental analyses, including thermogravimetry and scanning electron microscope. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2376,2381, 2007 [source] Evaluation of N -hydroxymethylphthalimide in alkaline medium: Novel entry to the tricyclic [1,3]oxazepine core via an intramolecular , and O -cationic cyclizationJOURNAL OF HETEROCYCLIC CHEMISTRY, Issue 3 2003Armelle Cul Fused isoindolo[1,3]benzo(or thieno)oxazepines 8a,b and one of their positional isomers aromatic tricyclic N,O -acetals 13b are reported to occur efficiently in a three-step sequence from N -hydroxy-methylphthalimide (6). The key step of this methodology is the intramolecular arylation of an endocyclic and/or exocyclic N -acyliminium cation. The mechanism leading to these species, in particular to a tricyclic lactam 13b, is discussed. [source] Kinetics and mechanism of sodium N -halo- p -toluenesulfonamides oxidation of diclofenac in alkaline mediumAICHE JOURNAL, Issue 12 2009Puttaswamy Abstract Diclofenac belongs to a class of drugs called nonsteroidal antiinflammatory drugs. The kinetics and mechanism of oxidation of diclofenac by sodium N -halo- p -toluenesulfonamides viz., chloramine-T and bromamine-T in NaOH medium have been studied at 293 K. Under comparable experimental conditions, reactions with both the oxidants follow identical kinetics with a first-order dependence on each [oxidant]o and a fractional-order dependence on each [diclofenac]o and [NaOH]. Activation parameters have been computed. N -hydroxyldiclofenac is identified as the oxidation product of diclofenac. Michaelis-Menten type of mechanism has been suggested. The rate of oxidation of diclofenac is about four-fold faster with bromamine-T when compared with chloramine-T. This may be attributed to the difference in electrophilicities of Cl+ and Br+ ions and also the van der Waal's radii of chlorine and bromine. Plausible mechanism and related rate law have been designed for the observed kinetics. © 2009 American Institute of Chemical Engineers AIChE J, 2009 [source] Oxidation of 2,3-butanediol by alkaline hexacyanoferrate(III) using Ru(III) or Ru(VI) as catalyst,JOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 8-9 2006F. J. Poblete Abstract The reactions of 2,3-butanediol by hexacyanoferrate(III) in alkaline medium using ruthenium compounds as catalysts have been studied spectrophotometrically. The effect on the reaction rate of concentration of substrate, oxidant, catalyst and basicity of the medium leads to similar experimental rate equations for both catalysts, Ru(III) and Ru(VI). The reaction mechanism involves the formation of a catalyst,substrate complex that yields a carbocation for Ru(VI) or a radical for Ru(III) oxidation. Hexacyanoferrate(III)'s role is the catalyst regeneration. The rate constants of complex decomposition and catalyst regeneration have been determined. Copyright © 2006 John Wiley & Sons, Ltd. [source] Effects of non-ionic and mixed non-ionic,cationic micelles on the rate of aqueous cleavages of phenyl benzoate and phenyl salicylate in alkaline mediumJOURNAL OF PHYSICAL ORGANIC CHEMISTRY, Issue 5 2004M. Niyaz Khan Abstract Pseudo-first-order rate constants (kobs) for the hydrolysis of phenyl salicylate (PSH) and phenyl benzoate (PB) in the alkaline medium show a monotonic decrease with the increase in [C16E20]T (total concentration of Brij 58) at constant [CH3CN] and [NaOH]. This micellar effect is explained in terms of the pseudophase model of micelles. These results show a characteristic difference between the effects of [C16E20]T and previously published effects of [C12E23]T (total concentration of Brij 35) on the rates of aqueous cleavage of PSH and PB at [CnEm]T/[NaOH],,3. The values of kobs, obtained at different [C16E20]T in the presence of a constant amount of CTABr, follow the empirical relationship kobs=(k0+,K[C16E20]T)/(1+K[C16E20]T), where , and K are empirical parameters. The values of , are not affected whereas the values of K decrease with increase in [CTABr]T in a mixed C16E20,CTABr micellar system. The values of , at different [CTABr]T show that ,>k0 for hydrolysis of PSH and , Raman and pulse radiolysis studies of the antioxidant properties of quercetin: Cu(II) chelation and oxidizing radical scavengingJOURNAL OF RAMAN SPECTROSCOPY, Issue 5 2005Armida Torreggiani Abstract Quercetin (Querc), a pentahydroxyflavonol, is suggested to give protection to living organisms by both direct scavenging of free radicals and metal chelation. The scavenging ability of Querc towards oxidizing radicals, such as ,OH, N3, and NO2,, was evaluated by pulse radiolysis studies in aqueous solutions at different pH. Phenoxyl radicals are the final transient products and are formed either by water elimination from ,OH-adducts or by one-electron transfer from the deprotonated OH groups. Their formation rate is strongly affected by pH and reaches the maximum values in alkaline medium. The Raman and IR spectra were useful to assess the relevant interaction of Querc with Cu(II) ions, which play an important role in the metal-catalysed generation of reactive oxygen species. Depending on pH and the metal-to-ligand ratio, the different chelating sites of Querc change their ability to complex copper ions. Under neutral conditions, the 5-OH group of ring A and CO-4 of ring C have a chelating power superior to that of the catechol group (ring B), whereas the complexation in alkaline medium occurs in the reverse order. In addition, experiments with Querc and Zn(II) ions, carried out at basic pH in order to verify the possible Cu(II)-catalysed oxidation of the ligand, indicated the absence of the above process. Copyright © 2005 John Wiley & Sons, Ltd. [source]
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