Choice of a suitable hetero-aromatic nitrogen base as promoter for chromic acid oxidation of dl-mandelic acid in aqueous media at room temperature

Chromic acid oxidation of dl-mandelic acid in the presence and absence of different promoters has been studied in aqueous media under the kinetic conditions [mandelic acid]_T ? [Cr(VI)]_T and [promoter]_T ? [Cr(VI)]_T at 30 °C. The promoters used in this oxidation reaction, picolinic acid (PA), 2,2′-bipyridine (bpy), and 1,10-phenanthroline (phen), are strong chelating ligands which form complexes with most transition metal ions. The reaction is first-order with regard to [H⁺], [mandelic acid]_T, and [Cr(VI)]_T and also has first-order dependence on [promoter]_T. HCrO₄ ^? was found to be kinetically active in the absence of promoters; in the presence of promoters the Cr(VI)–promoter complexes were believed to be the active oxidants. In this path the Cr(VI)-promoter complex in each case undergoes nucleophilic attack by the mandelic acid to form a ternary complex which subsequently undergoes redox decomposition involving 3e transfer as the rate-determining step. Among the three promoters oxidation is much faster with 1,10-phenanthroline.     

Micellar effect on the reaction of picolinic acid catalyzed chromium(VI) oxidation of dimethyl sulfoxide in aqueous acidic media: A kinetic study

The kinetics and mechanism of picolinic acid (PA) catalyzed oxidation of dimethyl sulfoxide (DMSO) to dimethyl sulfone by chromium(VI) in both aqueous H₂SO₄ and HClO₄ media have been studied in the absence and presence of surfactants at different temperatures. Cr(VI)–PA complex formed in preequilibrium steps is the active oxidant that experiences the nucleophilic attack by DMSO to form a positively charged intermediate ternary complex. Within the proposed ternary complex, an oxygen transfer or a ligand coupling or both occurs to generate the product, dimethyl sulfone. Cr(VI) is ultimately converted to Cr(III)–PA complex. Under the experimental conditions, the process shows a first‐order dependence on each of the reactants (i.e., [Cr(VI)]_T, [PA]_T, [DMSO]_T, and [H⁺]). HCrO₄⁻ has been found kinetically active. The reaction is catalyzed by sodium dodecyl sulfate (SDS, a representative anionic surfactant) monotonically, while cetylpyridinium chloride (CPC, a representative cationic surfactant) retards the reaction continuously. The observed micellar effects have been explained by considering the hydrophobic and electrostatic interaction between the surfactants and reactants. A pseudo‐phase ion exchange (PIE) model has been applied to explain the micellar effect. The Piszkiewicz cooperative model has been applied to determine the kinetic parameters, and it indicates the existence of catalytically productive submicellar aggregates. Because of this reactant‐promoted micellization of the surfactant before or below the cmc value, the present systems do not show any discontinuity at the respective reported cmc values of the surfactants. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 173–181, 2001     

Cooxidation of anilides and oxalic acid by chromic acid: A one‐step,three‐electron oxidation

The chromic acid oxidation of a mixture of oxalic acid and anilides proceeds much faster than that of either of the two substrates alone. The oxidation kinetics of acetanilide, p‐methyl‐, p‐chloro‐, and p‐nitroacetanilides by Cr(VI) in the presence of oxalic acid in aqueous acetic acid medium follows first‐order, zero‐order, and second‐order dependence in [oxidant], [substrate], and in [oxalic acid], respectively, while the oxidation kinetics of benzanilide, p‐methyl‐, p‐chloro‐, and p‐nitrobenzanilides follow first order in [oxidant] and fractional order each in [substrate] and [oxalic acid] and yields corresponding azobenzenes and benzaldehydes in the case of benzanilide and substituted benzanilides as the main products of oxidation. Aluminium ions suppress the reaction. The intermediate is believed to be formed from the anilide and a chromic acid‐oxalic acid complex. In the proposed mechanism, the rate‐limiting step involves the direct reduction of Cr(VI) to Cr(III). © 2000 John Wiley & Sons, Inc. Int J Chem Kinet 33: 21–28, 2001     

Micellar catalysis on picolinic acid promoted hexavalent chromium oxidation of glycerol

Under pseudo-first-order conditions, monomeric Cr(VI) was found to be kinetically active in the absence of picolinic acid (PA), whereas in the PA-promoted path, the Cr(VI)–PA complex undergoes nucleophilic attack by the substrate to form a ternary complex which subsequently experiences redox decomposition, leading to glyceraldehydes and Cr(IV)–PA complex. The uncatalyzed path shows a second-order dependence on [H⁺], whereas the PA-catalyzed path shows zero-order dependence on [H⁺]. Both the uncatalyzed and PA-catalyzed path show a first-order dependence on [glycerol]_T and [Cr(VI)]_T. The PA-catalyzed path is first order in [PA]_T. All these observations remain unaltered in the presence of externally added surfactants. The effect of the cationic surfactant cetyl pyridinium chloride (CPC) and anionic surfactant sodium dodecyl sulfate (SDS) on the PA-catalyzed path have been studied. CPC inhibits, whereas SDS accelerates the reaction. Here, SDS is a catalyst for glyceraldehydes production and at the same time reduction of carcinogenic hexavalent chromium to nontoxic trivalent chromium. The reaction proceeds simultaneously in both aqueous and micellar phase. Micellar effects have been explained by considering the preferential partitioning of reactants between the micellar and aqueous phase. The Menger–Portnoy model, Piszkiewicz cooperative model, and pseudo-phase ion exchange model have been tested to explain the observed micellar effect.     

Micellar catalysis of chromium(VI) oxidation of ethane-1,2-diol in the presence and absence of 2,2′-bipyridine in aqueous acid media

The kinetics and mechanism of the Cr(VI) oxidation of ethane-1,2-diol in the presence and absence of 2,2′-bipyridine (bipy) in aqueous acid media were studied under the conditions [ethane-1,2-diol]_T ? [Cr(VI)]_T. Under the kinetic conditions, monomeric Cr(VI) was found to be kinetically active in the absence of bipy, whereas in the bipy-catalyzed path the Cr(VI)-bipy complex was the active oxidant. In this path, the Cr(VI)-bipy complex undergoes nucleophilic attack by the substrate to form a ternary complex which subsequently undergoes redox decomposition (through 2e transfer) leading to hydroxyethanol and the Cr(IV)-bipy complex. The Cr(IV)-bipy complex then participates further in oxidation of organic substrate, ultimately converted into inert Cr(III)-bipy complex. The uncatalyzed path shows a second-order dependence on [H⁺], while the bipy-catalyzed path shows a first-order dependence on [H⁺]. Both the uncatalyzed and bipy-catalyzed paths show first-order dependence on [ethane-1,2-diol]_T and on [Cr(VI)]_T. The bipy-catalyzed path is first-order in [bipy]_T. All these patterns remain unaltered in the presence of externally added surfactants. The effects of a cationic surfactant, N-cetylpyridinium chloride (CPC), and an anionic surfactant, sodium dodecyl sulfate (SDS), on both the uncatalyzed and bipy-catalyzed paths were studied. CPC inhibits both the uncatalyzed and bipy-catalyzed paths, whereas SDS catalyzes the reactions. The observed micellar effects are explained by considering a distribution pattern of the reactants between the micellar and aqueous phases.     

Ruthenium(III)-catalyzed and uncatalyzed kinetic studies on the oxidation of sulfanilic acid by chloramine-T in perchloric acid medium: a mechanistic approach

The kinetics of the oxidation of sulfanilic acid (SAA) by sodium N-chloro-p-toluenesulfonamide (CAT) in the presence and absence of ruthenium(III) chloride have been investigated at 303 K in perchloric acid medium. The reaction shows a first-order dependence on [CAT]_o and a non-linear dependence on both [SAA]_o and [HClO₄] for both the ruthenium(III)-catalyzed and uncatalyzed reactions. The order with respect to [Ru^III] is unity. The effects of added p-toluenesulfonamide, halide, ionic strength, and dielectric constant have been studied. Activation parameters have been evaluated. The rate of the reaction increases in the D₂O medium. The stoichiometry of the reaction was found to be 1:1 and the oxidation product of SAA was identified as N-hydroxyaminobenzene-4-sulfonic acid. The ruthenium(III)-catalyzed reactions are about four-fold faster than the uncatalyzed reactions. The protonated conjugate acid (CH₃C₆H₄SO₂NH₂Cl⁺) is postulated as the reactive oxidizing species in both the cases.     

Micellar catalysis on 1,10-phenanthroline promoted hexavalent chromium oxidation of ethanol

The kinetics and mechanism of Cr(VI) oxidation of ethanol in the presence and absence of 1,10-phenanthroline in aqueous acid media have been carried out. Monomeric species of Cr(VI) are kinetically active in the absence of phen, while in the phen catalyzed path, the Cr(VI)-phen complex has been suggested as the active oxidant. In the catalyzed path, the Cr(VI)-phen complex participates in the oxidation of ethanol and ultimately is converted into the Cr(III)-phen complex. In the uncatalyzed path, the Cr(VI)-substrate ester experiences an acid catalyzed redox decomposition in the rate-determining step. The uncatalyzed path shows a second-order dependence on [H⁺], while the phen catalyzed path shows a first-order dependence on [H⁺]. Both the uncatalyzed and phen-catalyzed paths show first-order dependence on [ethanol]_T and [Cr(VI)]_T. The phen-catalyzed path is first order in [phen]_T. These observations remain unaltered in the presence of externally added surfactants. CPC inhibits the reactions while SDS catalyzes the reactions. The observed miceller effects have been explained by considering partitioning of the reactants between the miceller and aqueous phase.     

Micellar Effect on the Reaction of Chromium(VI) Oxidation of L‐Sorbose in the Presence and Absence of Picolinic Acid in Aqueous Acid Media: A Kinetic Study

The kinetics and mechanism of chromic acid oxidation of L‐sorbose in the presence and absence of picolinic acid (PA) have been studied under the conditions, [L‐sorbose]_T » [PA]_T » [Cr(VI)]_T, at different temperatures. In the absence of PA, the monomeric chromic acid undergoes esterification with the substrate followed by the acid catalysed redox decomposition of the Cr(VI)‐substrate ester through glycol splitting to formaldehyde and the lactone of C₅‐aldonic acid and Cr(IV) which subsequently participates in the faster reactions. In the presence of PA, the Cr(VI)‐PA complex produced in a pre‐equilibrium step experiences a nucleophilic attack by the substrate to produce a ternary complex which decomposes through glycol splitting giving rise to the organic products and Cr(IV)‐PA complex. Both the uncatalysed and PA‐catalysed paths show the first‐order dependence on [L‐sorbose]_T and [Cr(VI)]_T. The PA‐catalysed path is first‐order in [PA]_T and it shows a fractional order in [H⁺]. The uncatalysed path shows a second‐order dependence on [H⁺]. In the presence of the surfactants like N‐cetylpyridinium chloride (CPC, a cationic surfactant) and sodium dodecyl sulfate (SDS, an anionic sulfate), the reaction orders remain unchanged. CPC has been found to inhibit both the uncatalysed and PA‐catalysed paths while SDS shows the rate accelerating effect for both the uncatalysed and PA‐catalysed paths. The observed micellar effects have been rationalised by considering the distribution of the reactants between the micellar and aqueous phases in terms of the proposed reaction mechanism.     

Solvent extraction studies of radioisotopic exchange of36Cl with Chloramine-B in strong acid medium

Exchange studies with³⁶Cl and Chloramine-B in strong acid medium revealed that the extent of exchange is less than that occurs at pH 3.3 indicating the formation of a new species of Chloramine-B which is not participating in the exchange reaction and this has been confirmed by conductometric titration of Chloramine-B with dilute solutions of H₂SO₄, HCl, HClO₄ and CH₃COOH.     

Dibenz [b,f]-1, 4-oxazepin-11 (10 H)-one und Dibenz [b,e]-1, 4-oxazepin-11 (5 H)-one. 12. Mitteilung über siebengliedrige Heterocyclen

The syntheses of dibenzo [b, f]-1, 4-oxazepin-11 (10 H)-ones (I) with electron-attracting substituents in position 2 by ring closure of the sodium salts of 2-halogeno-2′-hydroxy-benzanilides (II) are described. The reaction of II (R = SO₂·N(CH₃)₂) in N-methylpyrrolidone also led, by SMILES rearrangement, to the isomeric minor product dibenzo [b, e]-1, 4-oxazepin-11 (5 H)-one (III; R = SO₂·N(CH₃)₂), whose constitution was proven by synthesis from VI. In the case of II (R = SO₂·CH₃), the 5-methylsulfonyl-2-(2-hydroxyanilino)-benzoic acid (VI; R = SO₂·CH₃) was obtained directly after hydrolysis. The lactam I (R = NO₂) was rearranged to the corresponding acid VI by heating with dilute caustic soda.     

A kinetic study of electron transfer from L-Ascorbic acid to sodium perborate and potassium peroxy disulphate in aqueous acid and micellar media

Kinetics of oxidation of L-ascorbic acid (H₂A) by sodium perborate (SPB) and peroxy disulphate (PDS) have been investigated in aqueous acid and micellar media. Reaction kinetics indicated first-order dependence on both |oxidant| and |H₂A|. Increase in ionic strength (μ) increased reaction rate only in H₂SO₄ media. Rate of SPB oxidation of H₂A has been accelerated by acidity in HNO₃ and HCl media while a decreasing trend is observed in HClO₄ and H₂SO₄ media. The results are interpreted by various theories of acidity functions. Reaction rate is enhanced by the addition of added |H₂O₂| indicating a H₂O₂ coordinated boron species to be active in the present system. In the absence of micelle, increase in |acid| altered the PDS(SINGLEBOND)H₂A reaction rate marginally (a very small positive effect with HClO₄ and negative effect with H₂SO₄). Most plausible mechanisms have been proposed on the basis of experimental results. Activation parameters evaluated for specific kinetic constants are in accord with outer sphere electron transfer mechanism. In SPB(SINGLEBOND)H₂A system, addition of anionic micelle (Sodium lauryl sulfate) increased the rate, stabilizing the cationic species in the transition state in all the acid media. Although rate of PDS oxidation of H₂A was catalyzed by TX and inhibited by SDS at critical micellar concentration (CMC) increase in |acid| (both HClO₄ and H₂SO₄) beyond 9.6 × 10⁻⁴ M decreased the rate of oxidation. This trend was explained due to the repulsive interaction of coanion, HA⁻, and negatively charged micellar species. © 1996 John Wiley & Sons, Inc.     

Kinetic study of the Ce(iii)- or Mn(ii)-catalyzed Belousov–Zhabotinsky reactions with mixed organic acid/ketone substrates

In a stirred batch reactor, the Ce(III)- or Mn(II)-catalyzed Belousov–Zhabotinsky reaction with mixed organic acid/ketone substrates exhibits oscillatory behavior. The organic acids studied here are: dl-mandelic acid (MDA), dl-4-bromomandelic acid (BMDA), and dl-4-hydroxymandelic acid (HMDA), and the ketones are: acetone (Me₂CO), methyl ethyl ketone (MeCOEt), diethyl ketone (Et₂CO), acetophenone (MeCOPh), and cyclohexanone ((CH₂)₅CO). The effects of bromate ion, organic acid, ketone, metal-ion catalyst, and sulfuric acid concentrations on the oscillatory patterns are investigated. Both conventional and stopped-flow methods are applied to study the kinetics of the oxidation reactions of the above organic acids by Ce(IV) or Mn(III) ion. The order of relative reactivities of the oxidation reactions of organic acids in 1 M H₂SO₄ is Mn(III)(SINGLEBOND)HMDA reaction>Ce(IV)(SINGLEBOND)HMDA reaction>Mn(III)(SINGLEBOND)BMDA, reaction>Mn(III)(SINGLEBOND)MDA reaction>Ce(IV)(SINGLEBOND)BMDA reaction>Ce(IV)(SINGLEBOND)MDA reaction. Spectrophotometric study of the bromination reactions of the above ketones shows that these reactions are zero-order with respect to bromine and first-order with respect to ketone and that ketone enolization is the rate-determining step. The order of relative rates of bromination or enolization reactions of ketones in 1 M H₂SO₄ is (CH₂)₅CO≫(MeCOEt, Et₂CO, Me₂CO)>MeCOPh. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet:30: 595–604, 1998     

Kinetics of isotope exchange between [3-(iodophenyl)methyl]guanidine (mIBG) and [131I]-iodide

The reaction of isotope exchange between [3-(iodophenyl)methyl]guanidine, mIBG, and [¹³¹]-iodide in relatively concentrated solutions, in the presence of different ammonium salts, in a closed system, over the temperature range from 130 to 150°C, has been investigated. The reaction occurs either with (NH₄)₂SO₄ or CH₃COOH, which indicates that the reaction goes through some intermediate stages. Kinetic studies show the influence of the additives. The activation energies for the reaction with (NH₄)₂SO₄/H₂O, (NH₄)₂SO₄/CH₃COOH and CH₃COOH are 121.1, 115.1 and 84.5 kJ·mol^–1, respectively.     

Extraction of some elements of the groups IV b and VI b with 1-phenyl-3-methyl-4-caproyl-pyrazolone-5 (PMCP) from aqueous mineral acid solutions

Solvent extraction of Cr(VI), Mo(VI), W(VI) and Hf(IV) with 1-phenyl-3-methyl-4-caproyl-pyrazolone-5 (PMCP) in methyl isobutylketone (MIBK), xylene and chloroform (CHCl₃) from mineral acid solutions was studied. Chromium(VI) is not extracted from any of the acids studied (HCl, H₂SO₄ and HClO₄). Molybdenum(VI) is quantitatively extracted by the reagent in xylene and CHCl₃ from HClO₄ and HNO₃ solutions. It is also extracted quantitatively by the reagent in MIBK from HCl, HNO₃ and H₂SO₄ solutions but the participation of the diluent as extractant is considerable. Tungsten(VI) is quantitatively extracted in xylene from 9M HClO₄ solution. MIBK used as diluent also affects its extraction with PMCP. Hafnium(IV) is not extracted from H₂SO₄ solutions while it extracts more than 99% at 3M HNO₃ and above. The extracted species likely are: MoO₂(PMCP)₂, WO₂(PMCP)₂ and Hf(PMCP)₄, respectively.     

Equilibrium and kinetic studies of electron transfer reactions involving quinolinium dichromate and aminoalcohols in aqueous acid media

Summary Oxidation of the aminoalcohols (AA) such as ethanolamine, diethanolamine and triethanolamine by quinolinium dichromate (QDC) yielded formaldehyde as the main product in aqueous H₂SO₄ and HClO₄ media. The reaction kinetics exhibited a first-order dependence on [QDC]. Plots of 1/k versus 1/[AA] indicated the formation of a QDC-A A adduct prior to the rate limiting step. The equilibrium constants, K, for the formation of QDC-AA adducts were evaluated by kinetic and spectroscopic (Ardon's) methods. The reaction was found to be catalysed by HClO₄ and H₂SO₄. The results were analysed in terms of various acidity function theories.     

Kinetics of the Formation of the Blue Complex CrO(O2)2 Formed by Dichromate and H2O2 in Acid Solutions. A Stopped-Flow Investigation Using Rapid-Scan UV-VIS Detection

 The kinetics of the CrO(O₂)₂ formation by H₂O₂ and Cr₂O₇ ²⁻ in aqueous acidic media was measured at 293 ± 2 K in a pH range between 2.5 and 3.3. Using the stopped-flow method with rapid scan UV-VIS detection, the rate law of the formation of CrO(O₂)₂ was determined. For the media HClO₄, HNO₃ and CH₃COOH, the reaction order in the Cr₂O₇ ²⁻ concentration was found to be 0.5. For [H₂O₂] as well as for [H⁺], the reaction was first order in all acids used. In HCl and H₂SO₄ media the reaction was first order in Cr₂O₇ ²⁻. At T = 293 ± 2 K the rate constant for the formation of Cr(O)(O₂)₂ was found to be (7.3 ± 1.9) · 10² M^−3/2 s⁻¹ in HClO₄.     

Kinetics and mechanism of the reaction between dimethylformamide and chromium(VI)

The kinetics of oxidation of N,N‐dimethylformamide by chromium(VI) has been studied spectrophotometrically in aqueous perchloric acid media at 20°C. The rate showed a first‐order dependence on both [Cr(VI)] and [DMF], and increased markedly with increasing [H⁺]. The order with respect to [HClO₄] was found to lie between 1 and 2. The rate was found to be independent of ionic strength as well as of any inhibition effect of Mn(II). The formation of superoxochromium(III) ion was detected in an aerated solution of chromium(VI), DMF and HClO₄. The proposed mechanism, involving two reaction pathways, leads to the rate law, rate = K_a1 [HCrO₄⁻] [DMF] (k_I K_a2 [H⁺]²+k_II[H⁺]). The first pathway, with rate constant k_I, involves the formation of chromium(V) and a free radical. The second pathway, with rate constant k_II, involves the formation of Cr(IV), CO₂ and dimethylamine. © 1999 John Wiley & Sons, Inc. Int J Chem Kinet 31: 409–415, 1999     

Electron transfer reaction in the chromium(VI)-manganese(II) system in the presence of ethylenediaminetetraacetic acid (EDTA)

Upon addition of Cr ^VI to a solution of ethylenediaminetetraacetic acid (EDTA) and Mn ^II, a transient species appears which has an absorption maximum at 500 nm. Kinetic studies of the outer-sphere oxidation of the Mn ^II-EDTA complex with the Cr ^VI-EDTA complex have been investigated by visible spectrophotometry at 25 °C. The formation of a transient species has been characterized spectrophotometrically and the encounter complex formation constants have been determined (K_OS = 1.75 × 10² and 1.66 × 10³ mol^-2 dm⁶ for [EDTA] and [Mn^II] variations, respectively). The effect of total [EDTA], [Mn^II], [Cr ^VI] and [HClO₄] on the rate of the reaction was determined. On addition of HClO₄, there is a decrease in the rate constants. The reaction product is the Cr^III-EDTA complex with λ_max = 400 and 550 nm. On the basis of the various observations and product characterization a most plausible outer-sphere mechanism has been envisaged.     

(Liquid + liquid) phase equilibria of 1-alkyl-3-methylimidazolium methylsulfate with alcohols,or ethers,or ketones

Solubilities of binary mixtures that contain a room-temperature ionic liquid and an organic solvent – namely, 1,3-dimethylimidazolium methylsulfate, [mmim][CH₃SO₄], or 1-butyl-3-methylimidazolium methylsulfate, [bmim][CH₃SO₄] with an alcohol (hexan-1-ol, or octan-1-ol, or nonan-1-ol, or decan-1-ol), or an ether (dipropyl ether, or dibutyl ether, or methyl-1,1-dimethylethyl ether, or methyl-1,1-dimethylpropyl ether), or a ketone (pentan-2-one, or pentan-3-one, or hexan-2-one, or heptan-4-one, or cyclopentanone) – have been measured by a visual method from T = 270 K to the boiling temperature of the solvent. The (liquid + liquid) equilibria curves were predicted by the COSMO-RS method. For [bmim][CH₃SO₄], the COSMO-RS predictions correspond better with experimental results than do the predictions for [mmim][CH₃SO₄].Complete miscibility has been observed in the systems of [mmim][CH₃SO₄] with water and with alcohols ranging from methanol to octan-1-ol and that of [bmim][CH₃SO₄] with water and with alcohols ranging from methanol to decan-1-ol at the temperature T = 310 K.