Kinetics and mechanism of Oxidation of Diaqua(nitrilotriacetato)cobaltate(II) by Peroxodisulfate ion in aqueous acidic solutions

Kinetik und mechanismus der oxydation von diaqua(nitrilotriacetato)-cobaltat(II) durch peroxodisulfat in wäßrigsauren lösungen Die Kinetik der Oxydation von Co^II-NTA durch Peroxodisulfat (S₂O) in saurem Medium photometrisch untersucht. Die Stöchiometrie der Reaktion ist: 2Co^II-NTA^? + S₂O → 2Co^III?NTA + 2SO. Im pH-Bereich 4,2—5,4 folgt die Reaktion dem Geschwindigkeitsgesetz [H⁺] und [S₂O] sind die Wasserstoff- bzw. Peroxodisulfationen-Konzentration, K_H ist die Dissoziationskonstante des Co^II(NTA)H und k_H ist die Geschwindigkeitskonstante für den Elektronenübergang. Die Aktivierungsparameter werden mitgeteilt und der mögliche Mechanismus für den Elektronenübergang wird diskutiert.     

Oxidation kinetics of crystal violet by potassium permanganate in acidic medium

The oxidation kinetics of crystal violet (a triphenylmethane dye) by potassium permanganate was focused in an acidic medium by the spectrophotometric method at 584 nm. The oxidation reaction of crystal violet by potassium permanganate is carried out in an acidic medium at different temperatures ranging within 298–318 K. The kinetic study was carried out to investigate the effect of the concentration, ionic strength and temperature. The reaction followed first order kinetics with respect to potassium permanganate and crystal violet and the overall rate of the reaction was found to be second order. Thermodynamic activation parameters like the activation energy (E_a), enthalpy change (ΔH*), free energy change (ΔG*), and entropy change (ΔS*) have also been evaluated.     

Oxidation of benzene by ozone in aqueous solutions

The rates of reaction between benzene and ozone were measured at temperatures varying from 5 to 35 °C in aqueous solutions in the pH range 3–7 utilizing the stopped-flow technique. The ozonation reaction was one-half order with respect to the concentration of both ozone and benzene in acidic solutions. In neutral solutions, however, the reaction was first order in ozone concentration and nearly independent of benzene concentration. At 25 °C the half-life of the reaction decreased from about 20 to less than 0.2 s and the first-order rate constant increased from 0.012 to 12.2 s⁻¹ as the pH value of the solutions increased from 3 to 7.Both benzoquinone (p-quinone) and hydroquinone (1,4-dihydroxybenzene) were formed in the neutral solutions as detected with a gas chromatograph. In the acidic solutions, however, only benzoquinone was found. The activation energies at pH values of 3 and 7 respectively were estimated to be 20.9 and 3.3 kcal mol⁻¹. A shift in the mechanism of the reaction is suggested by the results.     

Solubilization of methacrylic acid based polymers by surfactants in acidic solutions

The effect of various surfactants on the solubility of methacrylic acid based polyelectrolytes that are insoluble in water at low pH, i.e. isotactic poly(methacrylic acid), i-PMA, Luviflex Soft and Luviflex Silk, was studied by surface tension, fluorescence spectroscopy, potentiometric titration and dynamic light scattering, DLS, measurements. Results show that Luviflex Silk and Luviflex Soft form polymeric micelles in aqueous solutions above a well-defined concentration, whereas both i-PMA and Luviflex Soft undergo a pH-induced conformational transition. The critical association concentration values for each surfactant in the presence of completely ionized polyions were determined. Potentiometric and DLS measurements show that the addition of an anionic and a nonionic surfactant significantly increases the solubility of the polymers at low pH, while the presence of a cationic surfactant results in a formation of an insoluble polymer-surfactant aggregate. The present results could help in regulating the removal of hair-setting polymers by water.     

Preconcentration of trace metals from acidic solutions by coprecipitation with dithizone

Traces of Ag, Bi, Cd, Cu, Hg, Pb, Pd and Zn are separated by carrier precipitation with dithizone from diluted HNO₃ and HCl solutions. The separated trace elements are determined by flame AAS and/or by spectrophotometry. The preconcentration recovery is dependent on the acid concentration of the sample solution. The amount of dithizone precipitated is optimized. The detection limits (ng/ml) are 15.0 (Pb, Zn), 12.0 (Pd), 10.0 (Bi), 6.0 (Ag), 5.0 (Hg), 2.0 (Cu) and 1.0 (Cd). Aluminium, aluminium sulfate and gallium are analyzed with the method. The accuracy of the results was checked by differential pulse voltammetry.     

Oxidation with manganate solutions

Summary Manganate solutions prepared by the reduction of permanganate with formic acid in 1 M NaOH are fairly stable in a concentration of 0.015 M in presence of 1 M NaOH. They can be titrated successfuly with arsenite in the presence of telluric acid but not in its absence owing to the sluggishness of the reaction. Titration of arsenite with manganate yields always lower results deviating by 0.77% from the theoretical values in presence of telluric acid and 0.1–0.2 M NaOH. Much earlier end points with errors amounting to – 17 or – 38% are obtained in the absence of telluric acid.This work was started during 1957. Since that time the reactions of manganate with arsenite, tellurite, bivalent manganese and hydrogen peroxide were studied in our laboratory. While this work was prepared for publication den Boef et al. published their first investigation in the same line in 1959.     

Oxidation with manganate solutions

Summary The reaction between Tl⁺ solutions and manganate is sluggish. In the titration of Tl⁺ with manganate solution the end points are always attained earlier than the theoretical. When the reaction is accelerated by NaCl and heating to 45–50° C the end points were found to be concordant with the theoretical values. Titration of manganate with Tl⁺ solutions gives accurate results in presence of telluric acid but not in its absence. It is also possible to determine Tl⁺ by oxidation with an excess of K₂MnO₄ using arsenite as a back titrant for excess oxidant.Part III: Issa, I. M., and M. G. E. Allam: Z. analyt. Chem. 175, 103 (1960).     

Oxidation with manganate solutions

Summary The reaction of tellurite with manganate solution is not rapid in 0.2–0.5 N NaOH but is enhanced at higher alkalinities. Titration of tellurite with manganate gives accurate results. The titration of manganate with quadrivalent tellurium gives good results both in the presence or absence of telluric acid but the accuracy is better in the presence of telluric acid than in its absence. In the titration curve of manganate the step corresponding to hypomanganate is observed only in the presence of telluric acid and above 1 N NaOH.Part I cf. Z. analyt. Chem. 172, 21 (1960).     

S-oxygenation of thiocarbamides I: Oxidation of phenylthiourea by chlorite in acidic media

The oxidation of 1-phenyl-2-thiourea (PTU) by chlorite was studied in aqueous acidic media. The reaction is extremely complex with reaction dynamics strongly influenced by the pH of reaction medium. In excess chlorite concentrations the reaction stoichiometry involves the complete desulfurization of PTU to yield a urea residue and sulfate: 2ClO2- + PhN(H)CSNH2 + H2O --> SO4(2-) + PhN(H)CONH2 + 2Cl- + 2H+. In excess PTU, mixtures of sulfinic and sulfonic acids are formed. The reaction was followed spectrophotometrically by observing the formation of chlorine dioxide which is formed from the reaction of the reactive intermediate HOCl and chlorite: 2ClO2- + HOCl + H+ --> 2ClO2(aq) + Cl- + H2O. The complexity of the ClO2- - PTU reaction arises from the fact that the reaction of ClO2 with PTU is slow enough to allow the accumulation of ClO2 in the presence of PTU. Hence the formation of ClO2 was observed to be oligooscillatory with transient formation of ClO2 even in conditions of excess oxidant. The reaction showed complex acid dependence with acid catalysis in pH conditions higher than pKa of HClO2 and acid retardation in pH conditions of less than 2.0. The rate of oxidation of PTU was given by -d[PTU]/dt = k1[ClO2-][PTU] + k2[HClO2][PTU] with the rate law: -d[PTU]/dt = [Cl(III)](T)[PTU]0/K(a1) + [H+] [k1K(a1) + k2[H+]]; where [Cl(III)]T is the sum of chlorite and chlorous acid and K(a1) is the acid dissociation constant for chlorous acid. The following bimolecular rate constants were evaluated; k1 = 31.5+/-2.3 M(-1) s(-1) and k2 = 114+/-7 M(-1) s(-1). The direct reaction of ClO2 with PTU was autocatalytic in low acid concentrations with a stoichiometric ratio of 8:5; 8ClO2 + 5PhN(H)CSNH2 + 9H2O --> 5SO4(2-) + 5PhN(H)CONH2 + 8Cl- + 18H+. The proposed mechanism implicates HOCl as a major intermediate whose autocatalytic production determined the observed global dynamics of the reaction. A comprehensive 29-reaction scheme is evoked to describe the complex reaction dynamics.     

Oxidation of atrazine by photoactivated potassium persulfate in aqueous solutions

General laws of the photochemical oxidation of atrazine by inorganic peroxo compounds under the impact of solar radiation are studied. It is found that almost complete conversion of atrazine can be achieved via photochemical oxidation with persulfate after 120 min, but no deep mineralization is observed. The effect an aqueous matrix has on the processes of atrazine degradation in combined oxidation systems is considered.     

Enhanced stability of ZnTPPS by polymeric gold nanoparticles in acidic aqueous solutions

Novel kind of core-shell corona complex micelles were prepared, which enhanced both the hydrolytic stability and the photostability of water-soluble zinc tetrakis(4-sulfonatophenyl) porphyrin (ZnTPPS) in acidic aqueous solutions. The core-shell gold nanoparticles (AuNPS) were synthesized by reducing HAuCl₄ and di-thioester terminated block copolymer, poly(Nisopropylacrylamide)-block-poly(4-vinylpyridine) (PNIPAM-b-P4VP). The complex micelles with gold core, P4VP/ZnTPPS shell and PNIPAM corona were formed by simple mixing of gold nanoparticles and ZnTPPS. The photochemical properties of the complex micelles were studied by UV–Visiblespectroscopy and fluorescence spectroscopy. The results showed trapping of ZnTPPS in the positively charged micellar shell that effectively prevented demetallation of the ZnTPPS that would occur in acidic aqueous solutions. Furthermore, with appropriate concentration of gold nanoparticles, ZnTPPS in the complex micelle had excellent photostability by suppression of generation of reactive oxygen species (ROS). The enhanced stability of ZnTPPS in acidic aqueous media could be extensively used for photocatalysis and in solar cells.     

Oxidation rate of saturated hydrocarbons by permanganate in aqueous solutions

Conclusions The reaction for the oxidation of alkanes in aqueous permanganate solutions is first order in both substrate and oxidizing agent. The reaction rate constants were measured for a number of C₃-C₇ normal, iso-, and cycloalkanes. The normal type of selectivity is fulfilled: the tertiary C-H bonds are more active, while the primary C-H bonds are less active than the secondary C-H bonds.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1654–1656, July, 1982.     

Oxidation of azo dyes in aqueous solutions by combined methods

Fundamental aspects of the oxidative destruction of Orange III azo dye in aqueous solutions by integrated methods combining UV irradiation and iron-peroxide treatment were studied.     

Enhanced protonation of cresol red in acidic aqueous solutions caused by freezing

The protonation degree of cresol red (CR) in frozen aqueous solutions at 253 or 77 K, containing various acids (HF, HCl, HNO3, H2SO4, and p-toluenesulfonic acid), sodium hydroxide, NaCl, or NH4Cl, was examined using UV/Vis absorption spectroscopy. CR, a weak organic diacid, has been selected as a model system to study the acid-base interactions at the grain boundaries of ice. The multivariate curve resolution alternating least-squares method was used to determine the number and abundances of chemical species responsible for the overlaying absorption visible spectra measured. The results showed that the extent of CR protonation, enhanced in the solid state by 2-4 orders of magnitude in contrast to the liquid solution, is principally connected to an increase in the local concentration of acids. It was found that this enhancement was not very sensitive to either the freezing rate or the type of acid used and that CR apparently established an acid-base equilibrium prior to solidification. In addition, the presence of inorganic salts, such as NaCl or NH4Cl, is reported to cause a more efficient deprotonation of CR in the former case and an enhanced protonation in the latter case, being well explained by the theory of Bronshteyn and Chernov. CR thus served as an acid-base indicator at the grain boundaries of ice samples. Structural changes in the CR molecule induced by lowering the temperature and a presence of the constraining ice environment were studied by the absorption and 1H NMR spectroscopies. Cryospheric and atmospheric implications concerning the influence of acids and bases on composition and reactivity of ice or snow contaminants were examined.     

Oxidation of thiol compounds by molecular oxygen in aqueous solutions

Side self-oxidation of thiols was studied. It was found that these reactions in neutral and alkaline solutions are induced by impurities of variable-valence metals. The ability of transition metals to catalyze oxidation of thiols changes in the order Cu > Mn > Fe > Ni Co. The plot of the self-oxidation rate vs. pH passes through a maximum whose position on the pH scale depends on both the nature of metal and the structure of the thiol oxidized. For thiols having different structures, the kinetic orders in reactions catalyzed by copper ions differently vary with pH, which is apparently associated with the formation of complexes possessing different catalytic activity.     

Oxidation of 2-amino-4-methylphenol in acidic medium

The oxidation of 2-amino-4-methylphenol 1 , by ferricyanide, in acetic acid yields benzoquinonimine 2 , phenoxazinonimine 3 and 4 , triphenodioxazines 5 and phenoxazinone 6 . The reaction mechanism seems to start with an electrophilic substitution of the quinonimine, from 1 , on the electron rich 1 , rather than with a nucleophilic attack of 1 on the arising quinonimine.     

The first step of oxidation of alkylbenzenes by permanganates in acidic aqueous solutions

Data on the kinetics, kinetic isotope effects, substrate selectivety, and activation parameters for the first step of oxidation of alkylbenzenes by permanganante in acidic aqueous solutions are surveyed. The MnO₄ ⁻, HMnO₄, and MnO₃ ⁺ species serve as oxidants at different acidities. The increase in the positive charge in this series enhances the electrophilicity of the reagent, which manifests itself as an increase in the reaction rate and a change in the site of attack on the alkylbenzene molecule (either the aromatic ring or C−H bond in the alkyl group). The oxidation of the alkyl C−H bonds in alkylbenzenes and in alkanes follows similar mechanisms, while the attack on the aromatic ring proceedsvia the electrophilic aromatic substitution mechanism with a transition state intermediate between the charge transfer complex and σ-complex. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 765–780, May, 2000.