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1
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A prospect for LiBH4 as on-board hydrogen storage

100%
Saldan I.
Open Chemistry
|
2011
|
vol. 9
|
issue 5
761-775
EN
In contrast to the traditional metal hydrides, in which hydrogen storage involves the reversible hydrogen entering/exiting of the host hydride lattice, LiBH4 releases hydrogen via decomposition that produces segregated LiH and amorphous B phases. This is obviously the reason why lithium borohydride applications in fuel cells so far meet only one requirement - high hydrogen storage capacity. Nevertheless, its thermodynamics and kinetics studies are very active today and efficient ways to meet fuel cell requirements might be done through lowering the temperature for hydrogenation/dehydrogenation and suitable catalyst. Some improvements are expected to enable LiBH4 to be used in on-board hydrogen storage.
2
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Kinetic investigation of oxidation of aromatic anils by magnesium monoperoxyphthalate in aqueous acidic medium

100%
Ramakrishnan V., Kulandaivelu K.
Polish Journal of Chemical Technology
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2013
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vol. 15
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issue 3
55-60
EN
The kinetics of oxidation of aromatic anils to benzaldehyde and azobenzene by magnesium monoperoxyphthalate (MMPP) has been studied in aqueous acetic acid medium. The low dielectric constant of the medium facilitates the reactivity. It has been found that ionic strength of the reaction has no significant effect on rate. The added acrylonitrile has no effect on the reaction rate indicating the absence of free radical mechanism. The added Mn(II) decreases the rate of the reaction, which indicates the involvement of two-electron transfer. Highly negative ΔS# values indicate a structured transition state. The deviation of Hammett plot is noted and a non-linear concave downward curve is obtained for the anils with substituents in the aniline moiety. The observed break in the log kobs versus σ is attributed to the transition state whereas the non-linear concave upward curve is observed for the substituents in the benzaldehyde moiety and a non-linear concacve upward curve is observed for the substituents in the combination of aniline and benzaldehyde moiety and a suitable mechanism is proposed
3
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Mechanistic aspects of oxidation on L-tyrosine by diperiodatocuprate(III) complex in alkali media: a kinetic model

100%
Shetti N., Hegde R., Nandibewoor S.
Open Chemistry
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2009
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vol. 7
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issue 4
929-937
EN
Oxidation of an amino acid, L-tyrosine (L-Tyr) by diperiodatocuprate(III) (DPC) in alkaline medium at a constant ionic strength of 0.1 mol dm−3 was studied spectrophotometrically at different temperatures (288.1–313.1 K). The reaction between DPC and L-Tyr in alkaline medium exhibits 1:4 stoichiometry (L-Tyr:DPC). Intervention of free radicals was observed in the reaction. Based on the observed orders and experimental evidence, a mechanism involving monoperiodatocuprate(III) (MPC) as the reactive oxidant species has been proposed. A suitable mechanism is proposed through the formation of a complex and free radical intermediate. The products were identified by spot test and characterized by spectral studies. The reaction constants involved in the different steps of the mechanism were calculated. The activation parameters with respect to slow step of the mechanism were computed and are discussed. The thermodynamic quantities were determined for different equilibrium steps. Isokinetic temperature was also calculated and found to be 252.3 K. [...]
4
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The study of cyclooctene oxidation with molecular oxygen catalyzed by VSi2

100%
Makota O., Trach Y., Leboda R., Skubiszewska-Zięba J.
Open Chemistry
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2009
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vol. 7
|
issue 4
731-738
EN
The catalytic effect of VSi2 on initial stages of the liquid-phase oxidation of cyclooctene by molecular oxygen was studied. The vanadium disilicide influences on the oxidation process in the presence of hydroperoxide. VSi2 takes part in a radical formation stage by catalysis of hydroperoxide decomposition reaction. The catalyst was investigated before and after reaction using FTIR spectroscopy. From the data obtained, the kinetic model of the catalytic oxidation process was proposed and the equation for the reaction rate was derived. The equation has described all observed dependences of reaction rate on the concentration of reactants and content of catalyst. [...]
5
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Stress degradation study of two oral antidiabetics, gliclazide and glipizide, and chemical analysis by LC and LC/MS methods

100%
Gumieniczek A., Berecka A., Pietraś R., Ślebioda M.
Open Chemistry
|
2014
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vol. 12
|
issue 1
80-89
EN
Kinetic study of degradation of two oral antidiabetics, gliclazide and glipizide, was performed using new HPLC method which was validated in terms of selectivity, sensitivity, linearity, precision and accuracy. The stress degradation was performed in 0.2 M HCl, 0.2 M NaOH as well as in acetate and phosphate buffers over the pH range 3.8–8.3 at 30 and 70°C. In strong acidic and alkaline media gliclazide was almost fully degraded while glipizide showed much higher stability. Generally, degradation processes of gliclazide and glipizide were observed as the first order reactions while the rates of decomposition for both drugs were smallest at pH 8.3. The samples of gliclazide and glipizide stressed in strong acid and alkali at 70°C were additionally analyzed using an LC/MS method and some products of decomposition were detected and identified. It was concluded that glipizide was more resistant to very high or very low pH and would have higher stability compared to gliclazide. Such comparisons have not been performed so far for these valuable drugs. Additional LC/MS study showed that during decomposition of sulfonylureas, different degradation pathways were possible. [...]
6
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Kinetic study of wood pyrolysis in presence of metal halides

100%
Beliy V., Udoratina E.
Open Chemistry
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2014
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vol. 12
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issue 12
1294-1303
EN
The purpose of this work was to study the kinetics of wood pyrolysis in the presence of inorganic salts, representatives of classes of alkali and alkaline earth metal halides (NaCl, KCl, KBr, CaCl2, BaCl2·2H2O) and Lewis acids (AlCl3·6H2O, FeCl3·6H2O, CuCl2, CuBr2, ZnCl2·1.5H2O, NiCl2·6H2O, SnCl2·2H2O) using TG-DSC. The activity of these catalysts was estimated by the temperature of the beginning of pyrolysis, charcoal yield and kinetic parameters, such as energy of activation and reaction order. Using the Lewis acids as catalysts for pyrolysis leads to a decrease in the temperature of the process beginning and the activation energy. In the presence of other catalysts activation energy does not significantly change. The increase of a seeming reaction order in the presence of Lewis acids possibly is a consequence of complication of the thermodestruction mechanism, with the appearance of new parallel competing stages.
7
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Content available

Oxidation of Distyryl Ketone by Quinaldinium Chlorochromate – A Kinetic Study

100%
Periyasamy S. K., Saravanakumar K.
World News of Natural Sciences
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2017
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vol. 13
113-121
EN
Oxidation of distyrylketone by quinaldinium chlorochromate [QnCC] in water and acetic acid medium has been studied under pseudo first order condition. The reaction shows unit order dependence each with respect to oxidant and hydrogen ion. The reaction with respect to substrate is found to be fractional order. The reaction rate decreases with increasing the concentration of Mn2+ ions. The reaction does not induce the polymerization of acrylonitrile. A possible mechanism has been proposed in the formation of cinnamic acid and Phenyl acetaldehyde.
8
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Kinetic studies for the esterification of acetic acid with epichlorohydrin over an anion exchange resin catalyst

100%
Muresan E., Oprea S., Hulea V., Malutan T., Vata M.
Open Chemistry
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2008
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vol. 6
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issue 3
419-428
EN
The kinetics of the esterification reaction between acetic acid and epichlorohydrin catalysed by Purolite A-520E strong basic anion exchange resin was studied. The effects of certain parameters such as stirring speed, particle diameter, temperature, catalyst amount and molar ratio between reactants were experimentally determined. It was found that the overall reaction rate is intrinsically kinetically controlled. The partial orders of reaction with respect to catalyst, acetic acid and epichlorohydrin were determined. A reaction mechanism is proposed. Based on chromatographic data and taking into account the partial orders of reaction, a more detailed kinetic model is suggested. [...]
9
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Activity and stereoselectivity of Ru-based catalyst bearing a fluorinated imidazolinium ligand

100%
Siano V., D’Auria I., Grisi F., Costabile C., Longo P.
Open Chemistry
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2011
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vol. 9
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issue 4
605-609
EN
Grubbs II generation catalyst (3), bearing a fluorinated imidazolinium ligand, was investigated in cross metathesis (CM), ring closing metathesis (RCM) and ring opening polymerization metathesis (ROMP) for a variety of substrates. Kinetic studies showed reduced stability of the catalyst in methylene chloride following the first 15 minutes of reaction preventing a higher efficiency despite the very high activity. Beneficial solvent effects on the catalyst stability were observed by performing RCM in C6F6. [...]
10
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Application of Box-Behnken design with response surface methodology for modeling and optimizing ultrasonic oxidation of arsenite with H2O2

100%
Qiu P., Cui M., Kang K., Park B., Son Y., Khim E., Jang M., Khim J.
Open Chemistry
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2014
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vol. 12
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issue 2
164-172
EN
A combined ultrasound (US)/H2O2 process was used to oxidize arsenite to arsenate, yielding a synergistic effect value of 1.26. This showed that the combined process could be an effective method of oxidizing arsenite, instead of using either ultrasonic or H2O2 oxidation processes. This combined process was successfully modeled and optimized using a Box-Behnken design with response surface methodology (RSM). The effects of the US power density, the initial concentration of arsenite, and the H2O2 concentration on the sonochemical oxidation efficiency of arsenite were investigated. Analysis of variance indicated that the proposed quadratic model successfully interpreted the experimental data with coefficients of determination of R 2 = 0.95 and adjusted R 2 = 0.91. Through this model, we can predict and control the oxidation efficiency under different conditions. Furthermore, the optimal conditions for the oxidation of arsenite were found to be a US power density of 233.26 W L−1, an initial arsenite concentration of 0.5 mg L−1, and an H2O2 concentration of 74.29 mg L−1. The predicted oxidation efficiency obtained from the RSM under the optimal conditions was 88.95%. A confirmation test of the optimal conditions verified the validity of the model, yielding an oxidation efficiency of 90.1%.
11
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Alkaline hydrolysis of brilliant green in mixed cationic surfactant systems

88%
Olanrewaju O., Ige J., Omopariola S.
Open Chemistry
|
2011
|
vol. 9
|
issue 1
106-111
EN
Kinetic measurements were performed for the alkaline hydrolysis of brilliant green - a triphenylmethane dye used as a model compound for probing micellar rate effects. This reaction was studied both in the presence of tetradecyltrimethylammonium bromide (TTAB) and tetradecyltriphenylphosphonium bromide (TTPPBr) and also in binary mixtures of these surfactants at different mole fractions of each. All rate surfactant profiles were analyzed using the pseudo-phase model in order to obtain the regression parameters, including binding constants and rate constants in the micellar pseudo-phase. The reaction was catalyzed by both surfactants. The catalytic factor increases from about 10 for pure TTPPBr to about 38 for pure TTAB. Binding of BG to micellar surface is greater in pure TTAB than in pure TTPPBr but significantly reduced in the surfactant mixtures than in pure components. Reduction of the binding constant becomes more significant as the mole fraction of TTAB is increased in the mixture. The kinetic data have been analyzed in terms of models of Piszkiewicz and Raghavan-Srinivasan which are in good agreement. [...]
12
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Kinetics studies and mechanism evolution of the epoxidation of styrene over nanoporous Au doped TS-1

88%
Saxena S., Dwivedi R., Bhadauria S., Chumbhale V., Prasad R.
Polish Journal of Chemical Technology
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2010
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vol. 12
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issue 4
72-78
EN
A kinetic investigation of the slurry phase epoxidation of styrene with hydrogen peroxide has been carried out, for the first time, over nanoporous Au doped TS-1 catalyst, in a batch reactor, in the temperature range of 313-333 K. It was found that product selectivity and the rate of reaction are greatly influenced by concentrations of styrene and hydrogen peroxide. Kinetics studies reveal that the mechanism of the reaction is of the "Redox" type. The rate equation, r = k1 k2 PO PH / (k1 PO + k2 PH) deduced, assuming a steady state involving two stage oxidation-reduction process, represent the data most satisfactorily for the conversion of styrene to styrene oxide. A tentative mechanism of the process has also been suggested.
13
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Mechanism and kinetics of glass-ceramics formation in the LiO2-SiO2-CaO-P2O5-CaF2 system

88%
Palou M., Kuzielová E., Vitkovič M., Noaman M.
Open Chemistry
|
2009
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vol. 7
|
issue 2
228-233
EN
Two glasses based on lithium disilicate (LS2), with and without fluorapatite (FA), were synthesised in the Li2O-SiO2-CaO-P2O5-CaF2 system with P2O5: CaO: CaF2 ratios corresponding to fluorapatite. Glass-ceramics have then been prepared by thermal treatment. The mechanism and kinetics of crystallization as functions of grain size and rate of heating were investigated using thermal analysis methods. The smaller particles crystallize preferentially by surface crystallization, which is replaced by volume crystallization at larger particle sizes. Inclusion of FA in the LS2 favours crystallization through the surface mechanism. The onset limit for volume crystallization replacing the surface mechanism is at about 0.3 mm for pure LS2 glass and 0.9 mm for glass containing FA. The calculated activation energies of the glasses (299 ± 1 kJ mol-1 for pure LS2 glass and 288 ± 7 kJ mol−1 for glass containing FA according to Kissinger, or 313 ± 1 kJ mol-1 for pure LS2 glass and 303 ± 8 kJ mol-1 for glass containing FA according to Ozawa) indicate that the tendency of the glasses to crystallize is supported by the FA presence. Bioactivity of all samples has been proved in vitro by the formation of new layers of apatite-like phases after soaking in SBF. [...]
14
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Catalytic degradation of methylene blue in aqueous solutions over Ni- and Co- oxide systems

88%
Stoyanova M., Christoskova S.
Open Chemistry
|
2011
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vol. 9
|
issue 6
1000-1007
EN
The oxidative catalytic degradation of the cationic dye methylene blue (MB) with NaOCl in aqueous solutions was studied using individual and iron modified Ni- and Co-oxide systems as catalysts. The adsorption extent and the contribution of the uncatalyzed oxidation on the overall degree of MB were determined. The results indicate that methylene blue-a representative of a class of dyestuffs resistant to biodegradation-could be successfully decolorized and degraded using nickel and cobalt oxide catalysts at room temperature. The highest catalytic activity manifests in the Co-oxide system which is consistent with the adsorption data. The oxidative degradation reaction proceeds via first-order kinetics. Temperature has a relatively small effect on the methylene blue degradation kinetics. The results obtained reveal that the catalysts investigated are suitable for oxidative destruction of methytlene blue dye in wastewaters. [...]
15
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A new specific mechanism for thioacid/azide amidation: electronic and solvent effects

88%
Gao Y.
Open Chemistry
|
2010
|
vol. 8
|
issue 2
308-319
EN
Detailed theoretical studies of azide/thioacid amidation are performed using density functional theory. The calculated results indicate that electronic properties of azide have significant effects on reaction pathways, which result in two distinct mechanisms for electron-rich and electron-poor azide coupling in the base-promoted amidation. For electron-rich azide amidation, after the concerted [3+2] cycloaddition of azide/thiocarboxylate, a new reaction channel is found challenging that recently mentioned, which follows two consecutive, unimolecular reactions with very low activation barriers (−1) to give an anionic amide and a nitrous sulfide (N2S). Distinct from electron-rich azide amidation, electron-poor azide first couples with thiocarboxylate to form a linear stable adduct, and then passes through the transition state of the rate-controlling step to afford the anionic amide, rather than the thiatrazoline. The free energy barrier of this step is 4.2 kcal mol−1 lower than that previously proposed. Comparatively, the azide/thioacid amidations undergo the concerted [3+2] cycloaddition and the subsequent retro-[3+2] cycloaddition process to give cis-enol form of the amide, which have higher activation barriers than those in the based-promoted amidation. Solvent effects investigated indicate that non-polar solvents, such as chloroform, are more preferable for the base-promoted thioacid/azide amidation. [...]
16
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Synthesis, characterization and adsorption properties of nanostructured hybrid materials modified by boron and zirconium

88%
Georgieva R., Vassileva P., Detcheva A., Voykova D., Gerganova T., Ivanova Y.
Open Chemistry
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2012
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vol. 10
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issue 5
1484-1494
EN
The adsorption properties of two new nanostructured hybrid materials containing B2O3 and ZrO2 were studied. The new organic-inorganic materials were synthesized via a sol-gel method. As a modifying agent, a quantity of 10 wt.% Zr(OPr)4 or B(OCH3)3 was added. The structure of the hybrid materials was investigated by means of (Fourier transform infrared spectroscopy (FTIR), x-ray diffractometry (XRD), scanning electron microscopy (SEM), (atomic force microscopy (AFM) and nuclear magnetic resonance spectroscopy (NMR). Based on the obtained data, the most probable cross-linking mechanism for the derived gels was proposed. The characterization of texture parameters of both materials was carried out with the use of low-temperature adsorption of nitrogen. Adsorption of Cu(II), Fe(III), Cr(III), Cd(II) and Pb(II) ions on both materials was investigated using multi-component solutions with different concentrations and acidity by means of the batch method. Kinetics of adsorption was also investigated. Pseudo-first order, pseudo-second order and intraparticle diffusion models were used to analyze kinetic data. The adsorption was significantly affected by the pH value. Equilibrium data were fitted to linear Langmuir, Freundlich and Dubinin-Radushkevich models and maximum adsorption capacities were calculated. [...]
17
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Biosorption of heavy metals by Streptomyces species - an overview

88%
Mosbah R., Sahmoune M.
Open Chemistry
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2013
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vol. 11
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issue 9
1412-1422
EN
Abstract Heavy metals, derived from industrial wastewater discharge, present a serious threat to human health and to natural water. Biosorption is regarded as a cost-effective biotechnology for the treatment of high volume and low concentration wastewaters containing heavy metal(s) in the order of 1 to 100 mg L−1. Among the biomaterials for heavy metal removal which have been researched during the past decades is the Streptomyces species, a by-product of an industrial antibiotic fermentation process. This paper describes the hazards posed by heavy metals effluents on the environment and use of various Streptomyces species to remove heavy metals from aqueous solution. Characterization of Streptomyces species, factors affecting biosorption, biosorption isotherms and biosorption kinetics is discussed. Graphical abstract [...]
18
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Multicomponent spectrometric analysis of riboflavin and photoproducts and their kinetic applications

88%
Sheraz M., Kazi S., Ahmed S., Qadeer K., Khan M., Ahmad I.
|
EN
Riboflavin (RF) is a light sensitive compound and is known to form a number of photoproducts. These photoproducts possess the same nucleus and may interfere in the analysis of RF by UV and visible spectrometry. Therefore, it is necessary to apply the methods of multicomponent spectrometric analysis to quantify the vitamin and its photoproducts accurately. Such methods are useful in the study of the kinetics of photodegradation reactions of RF to obtain accurate and reliable results. Any interference in these methods due to linear or nonlinear irrelevant absorption of the minor unknown products can be accounted for by the application of appropriate correction procedures prior to kinetic treatment. Various factors affecting the accuracy, precision and selectivity of these analytical procedures are also discussed. This review highlights the principles and applications of multicomponent spectrometric methods and their application to the simultaneous determination of RF and its major photoproducts in degraded solutions to evaluate the kinetics of degradation.
19
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Application of NRTL activity coefficient model to describe the kinetics of gas adsorption

88%
Nieszporek K., Banach T., Podkościelny P.
Open Chemistry
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2014
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vol. 12
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issue 2
185-193
EN
The Non-Random Two-Liquid activity coefficient model is applied to describe the kinetics of pure gas adsorption on energetically heterogeneous solid surfaces. The surface energetic heterogeneity has been represented by the Gaussian-like function of the adsorption energy distribution. Two different kinetic isotherms have been presented. One of them, determined by using the statistical rate theory, has been critically discussed. The applicability of the presented approach has been demonstrated by a quantitative analysis of two sets of experimental data previously reported in the literature.
20
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RETRACTED ARTICLE: Kinetic and anion degradation products study on photocatalytic degradation of reactive orange 5 solution with phosphotungstic acid

88%
Zhong J., Zhao H., Ma D., Lian A., Li M., Xie B., Li J.
Open Chemistry
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2008
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vol. 6
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issue 1
99-105
EN
Increasing environmental pollution caused by toxic dyes is a matter of great concern due to their hazardous nature. So it is crucial to develop processes which can destroy these dyes effectively. It has been generally agreed that reactive orange 5 (KGN) can be effectively degraded in aerated phosphotungstic acid (HPA) in a homogeneous reaction system using near-UV irradiation. In this paper, photocatalytic degradation of reactive orange 5 solutions with phosphotungstic acid was investigated, especially more attention was paid to the kinetic model and the anion degradation products. The results revealed that the photocatalytic degradation reaction of KGN with HPA in a homogenous solution can be described by Langmuir-Hinshelwood equation and Langmuir-Hinshewood kinetic model described it well. The reaction manifested the first order with lower concentration(⩽30 mg L−1) with the limiting rate constant and the adsorption constant in this case being 0.8098 mg L−1 min−1 and 4.359 10−2 L mg−1, respectively. The degradation mechanism of KGN with HPA is different from that with TiO2, the anion products of the two reaction systems are the same. The difference in degradation mechanism of KGN with HPA from that with TiO2 is caused by the nature of the photocatalyst. [...]
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