Kinetics and mechanisms of the reaction of chromium(III) and 2,4-hexanedione in aqueous solution

1989 ◽  
Vol 67 (8) ◽  
pp. 1305-1307 ◽  
Author(s):  
Carlos Blanco ◽  
José M. Hernando ◽  
Manuel Mateo
Keyword(s):  
Aqueous Solution ◽  
Concentration Dependence ◽  
Rate Constants ◽  
Metal Ion ◽  
Reversible Reaction ◽  
First Order ◽  
Pseudo First Order ◽  
Enol Tautomer ◽  
Metallic Species ◽  
Mechanism Of The Reaction

The kinetics and mechanism of the reaction between Cr(III) and 2,4-hexanedione in aqueous solution have been studied. Complexation occurs by coordination of both oxygen atoms of the ligand to the chromium(III) center, with concomitant loss of a proton yielding 1:1 complex of the type [Cr(CH3COCHCOC2H5)(H2O)4]2+. When the metal ion is in pseudo first-order excess the concentration dependence of the observed rate constants agrees with a mechanism involving reversible reaction between the enol tautomer of 2,4-hexanedione and the metallic species Cr(H2O)63+ and Cr(H2O)5OH2+, with rate constants of 8.0 × 10−4 and 3.5 × 10−2 dm3 mol−1 s−1, respectively. Keywords: chromium(III), β-diketones, β-diketonates, kinetics, complexation.

Aminolysis of naphthyl acetates catalyzed by cyclodextrins

1999 ◽  
Vol 77 (5-6) ◽  
pp. 950-959 ◽  
Author(s):  
Oswald S Tee ◽  
Michael J Boyd
Keyword(s):  
Aqueous Solution ◽  
Transition State ◽  
Rate Constants ◽  
Nucleophilic Attack ◽  
Reactivity Ratios ◽  
Aryl Group ◽  
First Order ◽  
Free Amine ◽  
Transition State Stabilization ◽  
Pseudo First Order

The effects of cyclodextrins (CDs) on the rate of nucleophilic attack on 1- and 2-naphthyl acetates (1-NA and 2-NA) in aqueous solution have been investigated. Analysis of the variation of the pseudo-first-order rate constants with [nucleophile] and [CD] affords rate constants for reaction of the nucleophiles with free ester (kN) and with ester bound to the CD (kcN). The reaction of 1-NA and 2-NA with the trifluoroethoxide anion is slowed down by β-CD as the ratios kcN/kN are 0.11 and 0.30, respectively. For reaction with the anion of 2-mercaptoethanol in the presence of α-CD, β-CD, "hydroxypropyl-β-CD" (hp-β-CD) and γ-CD, the reactivity ratios kcN/kN vary between 0.04 and 2.4, ranging from strong retardation to modest catalysis; the retardations arise with β-CD and hp-β-CD, which bind the esters strongly. By contrast, the attack of primary alkylamines is generally accelerated, and in many cases substantially so. For the aminolysis of 1-NA in the presence of β-CD, values of kcN/kN range from 7 to 460, assuming that free amine reacts with CD-bound ester. Alternatively, if the CD-catalyzed reaction involves free ester reacting with CD-bound amine, with rate constant kNc, the ratios kNc/kN vary from 43 to 140. Either way, there is appreciable catalysis of the aminolysis of 1-NA by β-CD. For the aminolysis of 2-NA, the effects are less dramatic: the ratios kcN/kN range from 0.19 to 17, and values of kNc/kN vary from 17 to 110. The reaction of 1-NA with n-hexylamine is also catalyzed by γ-CD. The variations of kinetic parameters with alkylamine chain length suggest that the CD-catalyzed aminolysis basically takes place by the attack of CD-bound amine on the free ester. However, there must be some stabilizing interactions between the aryl group of the ester and the CD during the reaction, since the transition state stabilization is different for 1-NA and 2-NA, as well for other esters.Key words: aminolysis, catalysis, cyclodextrin, ester cleavage, kinetics.

scholarly journals Evaluation of Cd(II) Ion Removal from Aqueous Solution by a Low-Cost Adsorbent Prepared from White Yam (Dioscorea rotundata) Waste Using Batch Sorption

2018 ◽  
Vol 2 (3) ◽  
pp. 35 ◽  
Author(s):  
Edidiong Asuquo ◽  
Alastair Martin ◽  
Petrus Nzerem
Keyword(s):  
Aqueous Solution ◽  
Langmuir Isotherm ◽  
Metal Ion ◽  
Aqueous System ◽  
Ion Concentration ◽  
Dioscorea Rotundata ◽  
First Order ◽  
White Yam ◽  
Pseudo First Order ◽  
Adsorbent Dose

An agricultural residue, white yam (Dioscorea rotundata) tuber peel (YTBS), was used for the removal of Cd(II) ion from an aqueous solution using a batch method. The adsorbent was characterized using FTIR, TGA, SEM, EDX, N2 BET, XRD, and XRF. The optimization of sorption variables such as pH, contact time, adsorbent dose, and initial metal ion concentration at 25 °C were also carried out. The results indicated the dependence of sorption on the adsorbate pH and adsorbent dose, while the adsorption system reached equilibrium in 180 min. The sorption kinetics was fitted to three models (pseudo first order, pseudo second order, and Elovich) to validate the kinetics, and the pseudo first order was the best model for the description of Cd(II) uptake. Equilibrium isotherm modelling was also carried out using the Langmuir, Freundlich, and Temkin models, with the Langmuir isotherm giving the best fitting to the experimental results. The maximum loading capacity (qmax) of the adsorbent for Cd(II) obtained from the Langmuir isotherm model was 22.4 mg∙g−1 with an isotherm constant (KL) of 3.46 × 10−3 L·mg−1 and r2 value of 0.99. This result indicates that the YTBS residue was a good adsorbent for the removal of Cd(II) ion from aqueous system.

scholarly journals Efficient degradation of naproxen by persulfate activated with zero-valent iron: performance, kinetic and degradation pathways

2020 ◽  
Vol 81 (10) ◽  
pp. 2078-2091
Author(s):  
Shuyu Dong ◽  
Xiaoxue Zhai ◽  
Ruobing Pi ◽  
Jinbao Wei ◽  
Yunpeng Wang ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Hydroxyl Radical ◽  
Rate Constants ◽  
Zero Valent Iron ◽  
Degradation Pathways ◽  
First Order ◽  
First Order Kinetics ◽  
Degradation Rates ◽  
Initial Ph ◽  
Pseudo First Order

Abstract Degradation of naproxen (NAP) by persulfate (PS) activated with zero-valent iron (ZVI) was investigated in our study. The NAP in aqueous solution was degraded effectively by the ZVI/PS system and the degradation exhibited a pseudo-first-order kinetics pattern. Both sulfate radical (SO4•−) and hydroxyl radical (HO•) participate in the NAP degradation. The second-order rate constants for NAP reacting with SO4•− and HO• were (5.64 ± 0.73) × 109 M−1 s−1 and (9.05 ± 0.51) × 109 M−1 s−1, respectively. Influence of key parameters (initial pH, PS dosage, ZVI dosage, and NAP dosage) on NAP degradation were evaluated systematically. Based on the detected intermediates, the pathways of NAP degradation in ZVI/PS system was proposed. It was found that the presence of ammonia accelerated the corrosion of ZVI and thus promoted the release of Fe2+, which induced the increased generation of sulfate radicals from PS and promoted the degradation of NAP. Compared to its counterpart without ammonia, the degradation rates of NAP by ZVI/PS were increased to 3.6–17.5 folds and 1.2–2.2 folds under pH 7 and pH 9, respectively.

Kinetics and mechanism of the decarboxylation of pyrimidine-2-carboxylic acid in aqueous solution

1977 ◽  
Vol 55 (13) ◽  
pp. 2478-2481 ◽  
Author(s):  
Gerald E. Dunn ◽  
Edward A. Lawler ◽  
A. Brian Yamashita
Keyword(s):  
Carbon Dioxide ◽  
Aqueous Solution ◽  
Carboxylic Acid ◽  
Rate Constants ◽  
Kinetics And Mechanism ◽  
First Order ◽  
Order Rate ◽  
Pseudo First Order ◽  
Positively Charged

Pseudo-first-order rate constants for the decarboxylation of pyrimidine-2-carboxylic acid have been determined at 65 °C in aqueous solution over the acidity range pH = 2 to H0 = −9.5. Rate constants increase rapidly from pH = 2 to H0 = −3, then remain constant. This behaviour can be accounted for by a Hammick-type mechanism in which monoprotonated pyrimidine-2-carboxylic acid loses carbon dioxide to form an ylide (stabilized by the adjacent positively charged nitrogens) which rapidly converts to pyrimidine.

Effect of β-cyclodextrin on the reaction of α-amino acid anions with p-nitrophenyl acetate and p-nitrophenyl hexanoate

1997 ◽  
Vol 75 (1) ◽  
pp. 83-91 ◽  
Author(s):  
Oswald S. Tee ◽  
Timothy A. Gadosy ◽  
Javier B. Giorgi
Keyword(s):  
Aqueous Solution ◽  
Amino Acids ◽  
Data Analysis ◽  
Amino Acid ◽  
Rate Constants ◽  
First Order ◽  
Yield Rate ◽  
Pseudo First Order ◽  
Rate Ratios ◽  
Kinetics Of

The effects of β-cyclodextrin (β-CD) on the kinetics of the reaction of α-amino acid anions with p-nitrophenyl acetate (pNPA) and p-nitrophenyl hexanoate (pNPH) have been investigated. Pseudo-first-order rate constants obtained with various concentrations of nucleophile and β-CD, in aqueous solution at pH 9.88, were analyzed to yield rate constants for reaction of the nucleophiles with free ester (kN) and with ester bound to β-CD (kcN). For pNPA reacting with amino acids that bind weakly to β-CD, if at all, the ratio kcN/kN is very close to one, but for amino acids that bind appreciably to β-CD this ratio is greater than one (up to 3.5). Generally similar behaviour is observed for reactions with pNPH, but the rate ratios are smaller and all less than one. These findings are comparable to those obtained in this laboratory for the CD-mediated reactions of p-nitrophenyl alkanoate esters with other nucleophiles, including simple alkylamines that bind quite strongly to CDs, but they differ from those reported in an earlier study of the reaction of pNPA with amino acid anions (Can. J. Chem. 69, 1124 (1991)) where the data analysis suggested more substantial catalysis by cyclodextrins. Key words: amino acids, cyclodextrin, ester cleavage, kinetics, catalysis.

Kinetics and mechanism of the reaction of iron(III) with 6-methyl-2,4-heptanedione and 3,5-heptanedione

1990 ◽  
Vol 55 (8) ◽  
pp. 1984-1990 ◽  
Author(s):  
José M. Hernando ◽  
Olimpio Montero ◽  
Carlos Blanco
Keyword(s):  
Aqueous Solution ◽  
Metal Ion ◽  
Activation Parameters ◽  
Enol Form ◽  
Kinetics And Mechanism ◽  
Kinetic Constants ◽  
Steric Factors ◽  
Kinetics Of ◽  
Mechanism Of The Reaction

The kinetics of the reactions of iron(III) with 6-methyl-2,4-heptanedione and 3,5-heptanedione to form the corresponding monocomplexes have been studied spectrophotometrically in the range 5 °C to 16 °C at I 25 mol l-1 in aqueous solution. In the proposed mechanism for the two complexes, the enol form reacts with the metal ion by parallel acid-independent and inverse-acid paths. The kinetic constants for both pathways have been calculated at five temperatures. Activation parameters have also been calculated. The results are consistent with an associative activation for Fe(H2O)63+ and dissociative activation for Fe(H2O)5(OH)2+. The differences in the results for the complexes of heptanediones studied are interpreted in terms of steric factors.

A kinetic standard for precise calibration of spectrophotometer cell temperature.

1981 ◽  
Vol 27 (5) ◽  
pp. 753-755 ◽  
Author(s):  
P A Adams ◽  
M C Berman
Keyword(s):  
Temperature Dependence ◽  
Rate Constants ◽  
Cell Temperature ◽  
First Order ◽  
Order Rate ◽  
Acid Catalyzed ◽  
Pseudo First Order ◽  
Hydrolysis Of

Abstract We describe a simple, highly reproducible kinetic technique for precisely measuring temperature in spectrophotometric systems having reaction cells that are inaccessible to conventional temperature probes. The method is based on the temperature dependence of pseudo-first-order rate constants for the acid-catalyzed hydrolysis of N-o-tolyl-D-glucosylamine. Temperatures of reaction cuvette contents are measured with a precision of +/- 0.05 degrees C (1 SD).

scholarly journals Kinetics and mechanism of sol-gel transformation between some trivalent- and tetravalent-metal ions and Sodium alginate Anionic polyelectrolyte with formation of coordination Biopolymeric structure polymembranes Hydrogels of Capillary Structures Ex

2007 ◽  
Vol 3 (1) ◽  
pp. 133-142 ◽  
Author(s):  
Ishaq Abdullah Zaafarany
Keyword(s):  
Sodium Alginate ◽  
Metal Ion ◽  
Sol Gel ◽  
Coordination Geometry ◽  
Large Excess ◽  
First Order ◽  
Pseudo First Order ◽  
The Stability ◽  
Kinetics Of ◽  
Overall Kinetics

Abstract          The kinetics of sol-gel transformation between A13+, La 3+ and Th4+ metal ion electrolytes and sodium alginate sol have been studied complexometrically at various  temperatures. In the presence of a large excess of sodium alginate sol concentration over that of metal ion electrolyte, the pseudo first–order plots of exchange showed sigmoidal curves with two distinct stages. The initial part was relatively fast and curved significantly at early times, followed by a slow decrease in the rates of exchange over longer time periods. The rate constants of gelation showed second-order overall kinetics which was first order in the concentration of both reactants. The thermodynamic parameters have been evaluated and tentative gelation mechanisms consistent with the kinetic results of gelation are suggested. The stability of these ionotropic metal-alginate complexes has been discussed in terms of the coordination geometry and strength of chelated bonds.

scholarly journals Photocatalytic degradation of sulfamethazine in aqueous solution using ZnO with different morphologies

2018 ◽  
Vol 5 (4) ◽  
pp. 171457 ◽  
Author(s):  
Zhigang Yi ◽  
Juan Wang ◽  
Tao Jiang ◽  
Qiong Tang ◽  
Ying Cheng
Keyword(s):  
Aqueous Solution ◽  
Photocatalytic Degradation ◽  
Reaction System ◽  
Degradation Pathway ◽  
Order Reaction ◽  
Pseudo First Order Reaction ◽  
First Order ◽  
Different Shapes ◽  
Pseudo First Order ◽  
Release Ratio

In this study, photocatalytic experiments of 20 mg l −1 sulfamethazine (SMN) in aqueous solution containing ZnO with different morphologies, tetra-needle-like ZnO (T-ZnO), flower-like ZnO (F-ZnO) and nanoparticles ZnO (P-ZnO), were performed. The results indicated that photocatalytic degradation of SMN was effective and followed the pseudo-first-order reaction, but the degree of SMN mineralization showed obvious differences using ZnO with different shapes. After 12 h irradiation, 86%, 71% and 50% of the initial total organic carbon was eliminated in SMN suspension containing T-ZnO, F-ZnO and P-ZnO, respectively. The release ratio of sulfur was close to 100% in the presence of T-ZnO, but reached to 86% and 67% in the presence of F-ZnO and P-ZnO, respectively. The release ratio of nitrogen was about 76%, 63% and 40% using T-ZnO, F-ZnO and P-ZnO as photocatalyst, respectively. The morphology of ZnO played an important role in determining its catalytic activity. Seven intermediates were observed and identified in the UV/T-ZnO reaction system by LC-MS/MS analysis, and a possible degradation pathway was proposed.

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