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1.
Tartaric acid oxidation by vanadium(V) in sulfuric acid medium was investigated spectrophotometrically at 760 nm and 30°C by appearance of the vanadium(IV), as vanadyl. The reaction rate was determined under pseudo-first-order conditions with an excess of hydroxyacid over the oxidant concentration. The oxidation showed a first-order dependence with respect to vanadium(V) concentration and fractional orders with respect to tartaric acid and sulfuric acid concentrations, with no control and with constant ionic strength. The reaction rate is enhanced by an increase of ionic strength, and slightly reduced by a decrease of the dielectric constant of the medium. The activation parameters were calculated based on the rate constants determined in the 293 to 313 K interval. The proposed oxidation mechanisms and the derived rate laws are consistent with the experimental rate laws. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 55–61, 1998.  相似文献   

2.
The oxidation kinetics of malic acid by vanadium(V) in aqueous sulphuric acid was investigated at 303 K by monitoring the appearance of vanadium(IV) at 760 nm. The reaction showed first-order behavior with respect to vanadium(V), malic acid, and hydrogen ion concentration, respectively, regardless of the ionic strength. The reaction rate is enhanced by an increase in ionic strength and a decrease of the dielectric constant of the medium by addition of methanol. The activation parameters were estimated by varying the temperature in the range of 293 K to 313 K to 313 K. An oxidation mechanism is proposed, involving different vanadium(V) species produced in the presence of sulphuric acid. © 1995 John Wiley & Sons, Inc.  相似文献   

3.
The kinetics and mechanism of Ag(I)-catalyzed oxidation of l-alanine by cerium (IV) in sulfuric acid media have been investigated by titrimetric technique of redox in the temperature range of 298–313 K. It is found that the reaction is of first order with respect to Ce(IV) and l-alanine, and it is of a positive fractional order with respect to Ag(I). It is found that the pseudo first order ([l-alanine] ? [Ce(IV)] ? [Ag(I)]) rate constant k′ increases with the increase of[H+]. The major oxidation product of alanine has been identified as acetaldehyde by an 1H NMR and IR spectroscopy. Under the experimental conditions, the kinetically active species has been found to be Ce4+. Under nitrogen atmosphere, the reaction system can initiate the polymerization of acrylonitrile, indicating generation of free radicals. On the basis of the experimental results, a suitable mechanism has been proposed. The rate constants of the rate-determining step together with the activation parameters were evaluated.  相似文献   

4.
5.
The kinetics of oxidation of gallic acid with potassium bromate in the presence of vanadium(V) catalyst in aqueous acid medium has been studied under varying conditions. The active species of catalyst and oxidant in the reaction were understood to be HBrO3 and VO2+. The autocatalysis exhibited by one of the products, i.e. Br, was attributed to complex formation between bromide and vanadium(V). A composite scheme and rate law were possible, some reaction constants involved in the mechanism have been evaluated. © 1996 John Wiley & Sons, Inc.  相似文献   

6.
The IR and electronic absorption spectra of di-2-ethylhexyl hydrogen phosphate (HDEHP) extracts of vanadium(V) and sulfuric acid and of vanadium(V) solutions in sulfuric acid were studied. The composition of the extractable complex was determined, and the equation of vanadium(V) extraction with HDEHP was suggested. The equilibrium constant of vanadium(V) extraction from concentrated sulfuric acid solutions was found.  相似文献   

7.
The kinetics of oxidation of ethyldigol by vanadium(V) in aqueous acidic medium has been carried out. The reaction is first order with respect to vanadium(V) and the substrate and is acid catalysed.Hammett acidity function (H 0) andBunnett hypothesis have been applied. The formation of free radicals during the course of the reaction has been indicated. A probable reaction mechanism is proposed.
Die Kinetik der Oxidation von Ethyldigol mit Vanadium(V) in wäßrigem saurem Medium
Zusammenfassung Es wurde die Kinetik der Oxidation von Ethyldigol mittels Vanadium(V) in wäßriger saurer Lösung untersucht. Die Reaktion ist erster Ordnung bezüglich Vanadium(V) und Substrat und ist säurekatalysiert. Es wurden dieHammett-Aciditätsfunktion (H 0) und dieBunnett-Hypothese angewandt. Die Bildung von freien Radikalen während der Reaktion konnte bestätigt werden. Es wird ein Reaktionsmechanismus vorgeschlagen.
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8.
The kinetics of oxidation of vanadium(III) by hydroxylamine have been investigated at high acidities in the temperature range 25–30 °C. Rates decreased with increasing acidity of the medium. Both NH2OH and NH3OH+ are capable of oxidizing V(III) in parallel reactions, the order being unity each in oxidant and reductant.
(III) 25–30 °C. . NH2OH NH3OH+ V(III) , , .
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9.
The title reaction was studied in aqueous perchloric acid medium in the presence of 15% acetic acid by volume. It was observed that the reaction proceeds via an intermediate 11 oxidant-substrate complex. The reaction is inhibited by H+ ions. A mechanism consistent with the experimental results is proposed.
(V) - 15% . - - 11. , .
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10.
The kinetic and mechanistic studies of homogeneously Rh(III)-catalysed oxidation of D-xylose and L-sorbose by Nbromoacetamide (NBA) in perchloric acid medium were carried out at 40 °C. The reactions were first-order with respect to each of [NBA], [Rh(III)] and [H+] and zero-order in [sugar]. Variation of [Cl?] showed positive effect while variation of [Hg(OAc)2] showed negative effect on the rate of the reactions. Addition of acetamide (NHA) had a negative effect on the rate of the reaction. The rate of the reaction was unaffected by the change in ionic strength (??) of the medium. Various activation parameters were calculated with the help of pseudo-first-order rate constant, k1, obtained at four different temperatures. The mechanisms involving RhCl4(H2O)2 ?, as reactive species of rhodium(III), and H2OBr+, as reactive species of NBA, are proposed which find support from the spectrophotometric evidence and activation parameters, especially the entropy of activation.  相似文献   

11.
The kinetics of oxidation of alanine and phenylalanine by sodium N-chlorobenzene sulfonamide (CAB) has been investigated at 30°C in two ranges of acid concentrations. The reactions follow identical kinetics for both amino acids. At low acid concentration (0.03–0.10M), simultaneous catalysis by H+ and Cl? ions is noted. The rate shows a first-order dependence on [CAB], but is independent of [substrate]. A variation of the ionic strength or the dielectric constant of the medium or the presence of the added reaction product benzene sulfonamide (BSA) has no pronounced effect on the rate. At [HCl] > 0.2M, the rate is independent of [H+], but shows a first-order dependence on [CAB] and a fractional-order dependence on [amino acid]. The addition of BSA or Cl? ions, or a change in the ionic strength of the medium has no influence on the rate. Upon decreasing the dielectric constant of the medium, the rate increased, indicating positive ion–dipole interaction in the rate-determining step. The reaction was studied at different temperatures, and activation parameters have been computed. Rate laws in agreement with experimental results have been derived. Suitable mechanisms to account for the observed kinetics are proposed. The rate constants obtained from the derived rate laws as [H+], [Cl?], and [substrate] vary are in excellent agreement with the observed rate constants, thus justifying the proposed rate laws and hence the suggested mechanistic schemes.  相似文献   

12.
13.
The effect of La2O3, K2O and Li2O on the properties and catalytic performance of silica-supported nickel catalysts for the hydrogenation of m-dinitrobenzene was investigated. The catalysts promoted with La2O3, Li2O and K2O showed better catalytic performance than the catalyst without promotion, especially the ones co-promoted with La2O3 and K2O or Li2O.  相似文献   

14.
The oxidation of amino acids by chloramine-T (CAT) in HCl medium at 30°C indicates simultaneous catalysis by H+ and Cl ions in the HCl concentration range of 0.04–0.12 M. The reaction is first order with respect to concentrations [CAT], [H+] and [arginine], but zero order with respect to [histidine]. The rate depends also on Cl concentration following 0.7th order. At HCl concentrations >0.12 M, the rate equation is:w=k[CAT] [amino acid]0.6 and is independent of the [Cl]. A suitable mechanism has been suggested.
-T (CAT) HCl (30°C) H+, Cl [HCl]=0,04–0,12M. [CAT], [H+] [] []. [Cl]0,7. [HCl]>0,12M =k · [CAT][]0,6 [Cl]. .
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15.
The manganese(II) catalysed oxidation of glycerol by cerium(IV) in aqueous sulphuric acid has been studied spectrophotometrically at 25 °C and I = 1.60 mol dm−3. Stoichiometry analysis shows that one mole of glycerol reacts with two moles of cerium(IV) to give cerium(III) and glycolic aldehyde. The reaction is first order in both cerium(IV) and manganese(II), and the order with respect to glycerol concentration varies from first to zero order as the glycerol concentration increases. Increase in sulphuric acid concentration, added sulphate and bisulphate all decrease the rate. Added cerium(III) retards the rate of reaction, whereas glycolic aldehyde had no effect. The active species of oxidant and catalyst are Ce(SO4)2 and [Mn(H2O)4]2+. A mechanism is proposed, and the reaction constants and activation parameters have been determined.  相似文献   

16.
The kinetics of the reaction have been investigated in H2SO4 medium under different conditions. The observed bimolecular rate constant kobs, has been found to depend on [H+]?0.55 and to increase with the initial concentration ratio of the reactants R0 = [H2O2]0/[U (IV)]0 above 0.49. The activation energy of the overall reaction has been determined as 13.79 and 14.3 kcal/mol at R0 = 1 and 0.35, respectively. Consistent with experimental data, a detailed reaction mechanism has been proposed where the hydrolytic reaction (4) followed by the rate-controlling reaction (10) and subsequent fast reactions of U (V) and OH radicals are involved: A kinetic expression has been derived from which a graphical evaluation of (kK4)?1 and k?1 has been made at R0 = 1 as (12.30 ± 0.09) × 10?3 M min, (6.23 ± 2.19) × 10?4 M min; and at R0 = 0.35 as (12.63 ± 2.13) × 10?3 M min, (8.32 ± 6.62) × 10?4 M min, respectively. Indications of some participation of a chain reactionat R0 = 1 have been obtained without affecting thesecond-order kinetics as observed.  相似文献   

17.
The oxidation of D ‐mannitol by cerium(IV) has been studied spectrophotometrically in aqueous sulfuric acid medium at 25°C at constant ionic strength of 1.60 mol dm?3. A microamount of ruthenium(III) (10?6 mol dm?3) is sufficient to enhance the slow reaction between D ‐mannitol and cerium(IV). The oxidation products were identified by spot test, IR and GC‐MS spectra. The stoichiometry is 1:4, i.e., [D ‐mannitol]: [Ce(IV)] = 1:4. The reaction is first order in both cerium(IV) and ruthenium(III) concentrations. The order with respect to D ‐mannitol concentration varies from first order to zero order as the D ‐mannitol concentration increases. Increase in the sulfuric acid concentration decreases the reaction rate. The added sulfate and bisulfate decreases the rate of reaction. The active species of oxidant and catalyst are Ce(SO4)2 and [Ru(H2O)6]3+, respectively. A possible mechanism is proposed. The activation parameters are determined with respect to a slow step and reaction constants involved have been determined. © 2010 Wiley Periodicals, Inc. Int J Chem Kinet 42: 440–452, 2010  相似文献   

18.
The oxidation of tyrosine by chromium(VI) in aqueous perchloric acid medium has been studied spectrophotometrically at 30 °C and at a constant ionic strength I = 3.10 mol dm−3. The main reaction products were identified as chromium(III) and 4-hydroxyphenylacetaldehyde. The stoichiometry is 2:3, i.e., two moles of chromium(VI) react with three moles of tyrosine. The reaction is first order with respect to both chromium(VI) and tyrosine. Increase in perchloric acid concentration increased the rate of reaction. The order with respect to acid concentration was found to be two. Added products, ionic strength and dielectric constant of the medium did not have any significant effect on the reaction rate. A suitable mechanism is proposed. The activation parameters were determined with respect to the slow step of the mechanism. The thermodynamic quantities were also determined and discussed.  相似文献   

19.
Vanadium(V) oxidation ofL-arabinose has been found to be first order with respect to oxidant and substrate concentrations. It has been found that the order with respect to [H+] changes from one in 2.5M–4.5M acid concentration range to two in 5.0M–6.5M acid concentration range. The oxidation rate has been found to increase with ionic strength and decrease with dielectric constant of the medium. Thermodynamic parameters E, S and G have been evaluated as 22.63±0.19 kcal/mol,–3.00±0.65 e. u. and 23.59±±0.05 kcal/mol respectively. The reaction has been found to be initiated by the formation of free radical in a slow rate determining step.
Kinetik und mechanismus der oxidation von L-arabinose mit vanadium(V)
Zusammenfassung Die Vanadium(V)-Oxidation vonL-Arabinose verläuft bezüglich des Oxidationsmittels und Substrats erster Ordnung. Bezüglich der Änderung von [H+] zeigte sich für den Bereich 2,5M–4,5M eine Abhängigkeit erster, im Bereich 5,0M–6,5M eine von zweiter Ordnung. Die Oxidationsgeschwindigkeit steigt mit der Ionenstärke und fällt mit der Dielektrizitätskonstanten des Mediums. Es wurden die thermodynamischen Parameter E, S und G bestimmt: 22,63±0,19 kcal mol–1. –3,00±0,65 e. u. und 23,59±±0,05 kcal mol–1. Es wurde festgestellt, daß die Reaktion über die Bildung eines freien Radikals in einem langsamen, geschwindigkeitsbestimmenden Schritt initiiert wird.
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20.
Oxidation of sulfanilic acid to the corresponding azoxy derivative by peroxomonophosphoric acid (PMPA) has been studied in aqueous medium. The observed bell-shaped pH-rate profile has been rationalized on the basis of protonation of the amino group and ionization into different PMPA species and a suitable rate law has been proposed. The mechanism of oxidation involves the nucleophilic attack of nitrogen on the electrophilic peroxo oxygen.
- (PMPA) . pH— , PMPA . .
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