Formation of hydrogen peroxide upon oxidation of oxalic acid in presence and absence of oxygen-II Oxygen as oxidant

Hydrogen peroxide, m a mixture that is 0.1M in manganese(II) sulphate and sulphuric add and exposed to light from a tungsten lamp, decomposes slowly at room temperature in a nitrogen atmosphere. At 75 degrees the reaction is fairly rapid in the dark (about 20-25% in 4 hr) and about 60% faster in light. Presence of oxalic add has little effect on the rate of disappearance of peroxide, the overall reaction corresponding to H(2)C(2)O(4) + H(2)O(2) --> 2CO(2) + 2H(2)O. In the presence of oxygen [and manganese(II)] this reaction does not take place; instead, hydrogen peroxide is formed and oxalic add disappears in equimolar amounts. The extent of all reactions greatly increases with increasing concentration of manganese. Acrylonitrilc acts as a retarder. Conditions m the presence of mangancse(II) are described, under which oxalic add can be oxidized quantitatively by oxygen to carbon dioxide with formation of an amount of hydrogen peroxide equimolar to the oxalic add oxidized. Reaction mechanisms are proposed to account for the fact that in the absence of oxygen 1 mole of peroxide disappears and in the presence of oxygen 1 mote of peroxide is formed for each mole of oxalic add reacted.     

On the effect of copper (II) and chloride ions on the iodate-hydrogen peroxide reaction in the presence and absence of manganese (II)

The effect of copper (II) and chloride ions on the manganese (II) catalyzed iodate-peroxide reaction has been examined with reference to the hydrogen peroxide-iodic acid-manganese (II)-organic species oscillatory reaction. The observations are considered to provide evidence for iodine dioxide as the key intermediate in the manganese (II) catalyzed reaction. Kinetic data for the copper (II) catalyzed reaction are reported.     

Enhanced degradation of 2,4-dinitrotoluene by ozonation in the presence of manganese(II) and oxalic acid

Manganese catalytic ozonation of 2,4-dinitrotoluene (DNT) in the presence of oxalic acid was studied. The addition of manganese ion (Mn²⁺) or oxalic acid alone in ozonation process did not enhance DNT degradation, but the addition of Mn²⁺ coupled with oxalic acid accelerated degradation of DNT. The DNT degradation efficiency was influenced by carbonate in the catalytic ozonation process. Kinetics study showed that Mn²⁺ catalytic ozonation significantly promoted the decomposition of ozone. Experimental results of electron spin resonance (ESR) demonstrated that addition of Mn²⁺ and oxalic acid produced much hydroxyl radicals in catalytic ozonation system than that in single ozonation system. These results suggested that catalytic ozonation followed hydroxyl radical-type mechanism. Mn²⁺ promoted decomposition of ozone to produce hydroxyl radical and it was oxidized into manganese oxide. Manganese oxide was reduced into Mn²⁺ by oxalic acid, which is the key step of catalytic process. Based on above results, a cycle catalytic mechanism of Mn²⁺ was proposed. Intermediates were determined by HPLC and GC–MS, and they mainly included aromatic organics and aliphatic carboxylic acids.     

Kinetics and mechanism of chromic acid oxidation of oxalic acid in absence and presence of different acid media. A kinetic study

Kinetics and mechanism of the reaction of Cr(VI) with oxalic acid have been studied in presence and absence of H₂SO₄, HClO₄, and CH₃COOH by monitoring the formation of Cr(III)-oxalic acid complex at 560 nm. The effect of total [oxalic acid], [Cr(VI)], [H₂SO₄], [HClO₄], and [CH₃COOH] on the reaction rate was determined at 30°C. Formation of carbon dioxide was also confirmed. The oxidation rate increases with [oxalic acid] and [CH₃COOH] while it decreases with [H₂SO₄], [HClO₄], and pH. The rate law governing the oxidation of oxalic acid over a wide range of conditions is rate=k₁ K_es1 [oxalic acid]_T [Cr(VI)]_T 1+K_es1 [oxalic acid]_T, where only undissociated oxalic acid is kinetically active. Kinetic evidence for the formation of a Cr(VI)(SINGLEBOND)oxalic acid 1:1 complex has been obtained and the equilibrium constant for their formation has been determined. The 1:1 complex exists most likely in an open chain form. The rate-limiting step of the oxidation reaction involves the breaking of the C(SINGLEBOND)C bond in the 1:2 complex. Oxidizing ability of Cr(VI) species have been discussed. Mechanism with the associated reaction kinetics is assigned. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 335–340, 1998     

Palladium(II) catalyzed oxidation of allyl alcohol by manganese(III) in aqueous sulfuric acid

The palladium(II) catalyzed oxidation of allyl alcohol by manganese(III) in acid medium is assumed to go via substrate-catalyst complex formation followed by the interaction of oxidant and complex in the rate-determining step. The rates exhibit fractional order in allyl alcohol and first order each in [Mn(III)] and [Pd(II)]. The reaction constants involved in the mechanism are determined.     

One-step three-electron oxidation of tartaric and glyoxylic acids by chromium(VI) in the absence and presence of manganese(II)

Kinetics of the initial stages of oxidation of tartaric acid (TA) in the absence and presence of manganese(II) ions have been studied spectrophotometrically. The rate of the induction was slow and then gradually increased with increasing [TA] and/or [HClO₄]. The reaction followed third-order kinetics; first-order with respect to each of [TA], [HClO₄] and [Cr^VI]. The kinetic and manganese(II) effect studies are consistent with a one-step three-electron mechanism (Cr^VI Cr^III without passing through Cr^IV as an intermediate) in which a termolecular complex is formed between TA, Mn^II and HCrO₄ ^–. In order to obtain further insight, oxidation of glyoxylic acid (GA), an oxidation product of TA, was also studied under the similar conditions. Details of the process are discussed.     

氯离子存在下四苯基卟啉合锰的电化学和现场光谱电化学II. 氧化过程

本文研究了氯离子滴定过程中四苯基卟啉合锰氧化过程的常规循环伏安、薄层循环伏安及现场紫外-可见光谱电化学行为。发现在1摩尔比的Cl^-存在下, 四苯基卟啉合锰经历了Mn(III)/Mn(III)环阳离子自由基及进一步氧化为环两价阳离子的过程, 并伴随有异卟啉生成的后行化学反应, 当2摩尔比的Cl^-存在时, 反应机理转变为Mn(III)/Mn(IV), Mn(IV)/Mn(IV)环阳离子自由基并伴随有异卟啉生成反应的两个氧化步骤。提出了与这一滴定过程相关的氧化还原反应机理。     

Kinetics and mechanism of benzene oxidation by peroxymonosulfate catalyzed with a binuclear manganese(IV) complex in the presence of oxalic acid

It is established that Oxone (peroxymonosulfate, 2KHSO₅ · KHSO₄ · K₂SO₄) oxidizes benzene to p-quinone very efficiently and selectively in a homogeneous solution in aqueous acetonitrile in the presence of a catalyst, i.e., dimeric manganese(IV) complex [LMn(O)₃MnL](PF₆)₂ where L is 1,4,7-trimethyl-1,4,7-triazacyclononane, and a cocatalyst, i.e., oxalic acid. The dependences of the maximum rate of quinone accumulation on the initial concentrations of reagents are studied. It is proposed that benzene is oxidized by the manganyl particle containing the Mn(V)=O fragment that forms upon the reaction of the reduced form of the starting dimeric manganese complex with Oxone.     

Kinetics and mechanism of oxidation of manganese(III) acidoporphyrin complexes with hydrogen peroxide

The reactions of manganese(III) acidotetraphenylporphyrin complexes with hydrogen peroxide in an aqueous-organic medium at 288–308 K are studied by spectrophotometry. The reaction is the oxidation of the manganese(III) complex. The spectral and kinetic data correspond to a multistep mechanism including the step of coordination of a hydrogen peroxide molecule by the central manganese atom. A possibility of formation of oxidized complexes without macrocycle destruction upon the reaction with H₂O₂ makes manganese(III) porphyrins quite promising for use as models of natural catalases.     

Oxidation of manganese(II) by ozone and reduction of manganese(III) by hydrogen peroxide in acidic solution

Manganese(II) is oxidized by ozone in acid solution, k=(1.5±0.2)×10³ M⁻¹ s⁻¹ in HClO₄ and k=(1.8±0.2)×10³M⁻¹ s⁻¹ in H₂SO₄. The plausible mechanism is an oxygen atom transfer from O₃ to Mn²⁺ producing the manganyl ion MnO²⁺, which subsequently reacts rapidly with Mn²⁺ to form Mn(III). No free OH radicals are involved in the mechanism. The spectrum of Mn(III) was obtained in the wave length range 200–310 nm. The activation energy for the initial reaction is 39.5 kJ/mol. Manganese(III) is reduced by hydrogen peroxide to Mn(II) with k(Mn(III)+H₂O₂)=2.8×10³M⁻¹ s⁻¹ at pH 0–2. The mechanism of the reaction involving formation of the manganese(II)-superoxide complex and reaction of H₂O₂ with Mn(IV) species formed due to reversible disproportionation of Mn(III), is suggested. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 207–214, 1998.     

Hydrogen peroxide oxidation of di(hydroxo)platinum(II) species in carboxylic acids

A facile procedure for synthesizing the mono(hydroxo)tris(carboxylato)platinum(IV) species has been achieved. The reaction of [Pt^II(OH)₂(dmpda)] (dmpda=2,2-dimethyl-1,3-propanediamine) with a 30% aqueous solution of H₂O₂ in the presence of a carboxylic acid produces a stable [Pt^IV(OOCR)₃(OH)(dmpda)] (R=Me, Et) complex in high yield. The crystal structures of [Pt^IV(OOCMe)₃(OH)(dmpda)] . H₂O (triclinic P1 bar, a=8.761(2) Å, b=9.245(3) Å, c=10.659(2) Å, =106.25(2)°, =93.90(2)°, =98.92(2)°, V=813.1(3) ų, Z=2, R= 0.0474) and [Pt^IV(OOCEt)₃(OH)(dmpda)] (monoclinic P2₁/c, a=12.777(4) Å, b=10.514(2) Å, c=14.971(3) Å, =107.40(2)°, V=1919.2(8) ų, Z=4, R=0.0611) show that the hydroxyl group has been selectively positioned at an axial site. The intramolecular hydrogen bond between the OH and C=O moiety exists (O(H)...=C, 2.83 Å for [Pt^IV(OOCMe)₃(OH)(dmpda)] · H₂O; 2.72 Å for [Pt^IV(OOCEt)₃(OH)(dmpda)]. Formation of the axial-mono(hydroxo)tris(carboxylato)platinum(IV) species may be ascribed to a combination of `reactive-equatorial effects' with `cis-addition' in the carboxylic acid.     

Kinetics and mechanism of decomposition of hydrogen peroxide in the presence of manganese(III) porphyrins

The kinetics of homogeneous decomposition of hydrogen peroxide in the presence of manganese complexes with anionic ligands and various aromatic macrocycles were studied by the volumetric method. Ionmolecular mechanism was proposed on the basis of spectrophotometric data for catalytic decomposition of hydrogen peroxide with participation of manganese(III) porphyrins. The catalytic activity of the porphyrin complexes was higher by a factor of 1.5–3 than the activity of the corresponding solvate complexes with anionic ligands. The catalytic activity of porphyrin manganese complexes can be controlled by variation of the electronic structure of the macroring and the nature of anionic ligand coordinated at the apical position.     

Metal compounds in free-radical processes. III. Polymerization of acrylonitrile initiated by copper (II) nitrate in presence or absence of triphenylphosphine

The bulk polymerization of acrylonitrile (AN) initiated by copper (II) nitrate, Cu(II), in the absence of light has been studied. The rate of the AN polymerization may be expressed in the Cu(II) concentration range from 5 × 10^?4 to 1 × 10^?1 mole 1.^?1 by the equation, R_p = k₅[Cu(II)]^0.68, where k₅ = K_AN[AN]/(1 + K_AN[AN]). From the spectrophotometric measurements the values of 0.70 l./mole and 0.08 l, mole were obtained for the equilibrium constant at 20 and 60°C, respectively, K_AN = [C]/[AN]-[Cu(II)], corresponding to the formation of the complex C from acrylonitrile and copper (II) nitrate. An addition of triphenylphosphine (C₆H₅)₃P into the polymerization system reduces R_p, and no polymerization takes place at all provided [(C₆H₅)₃P]/[Cu-(II)] ≧ 5. The retardation effect of (C₆H₅)₃P on the polymerization of AN initiated by Cu(II) is attributed to a competitive reaction of Cu(II) with (C₆H₅)₃P in which Cu(II) is reduced and the product of this reduction CuNO₃·2(C₆H₅)₃P is inactive with respect to the polymerization of AN.     

Manganese(III,IV) and manganese(III) oxide clusters trapped by copper(II) complexes

Reactions of quinquedentate Schiff base ligands with Mn and Cu ions afforded icosa- and hexadecanuclear mixed-metal clusters in which dinuclear CuII complexes trapped oxo-bridged [MnIII8MnIV4O12] and [MnIII6O6] cores, respectively. Maximum entropy method analysis for synchrotron X-ray diffraction data was used to determine the oxidation states of the Mn ions.     

Ruthenium(III) and ruthenium(III)-aminopolycarboxylic acid chelate-catalyzed oxidation of ascorbic acid by molecular oxygen

The kinetics of Ru(III) ion, Ru(III)-EDTA (1:1) and Ru(III)-IMDA (1:1) catalyzed oxidation of ascorbic acid by molecular oxygen are investigated at 25°C, μ = 0.1 M KNO₃, in the pH range 1.50 to 2.75. First-order kinetics were observed with respect to the concentrations of Ru(III) ion, Ru(III)-EDTA, Ru(III)-IMDA and ascorbic acid. The rate of oxidation was found to be inversely proportional to the hydrogen ion concentration. One-half-order and zero-order dependences with respect to the concentration of molecular oxygen were found in the cases of Ru(III) ion and Ru(III)-amino-polycarboxylic acid chelate-catalyzed oxidations, respectively. An inverse relationship was found between the stability and catalytic activity of the Ru(III) chelates of aminopolycarboxylic acids. The catalytic activities of Ru(III) ion and its chelates increase in the order Ru(III)-EDTA < Ru(III)-IMDA < Ru(III). The mechanistic implications of the oxidations catalyzed by Ru(III) ion and its chelates are discussed.     

Synthesis and spectroscopic study of copper(II) and manganese(II) complexes with pipemidic acid

The interaction of copper(II) and manganese(II) with pipemidic acid, Hpipem, afforded the complexes [Cu(pipem)(2)(H(2)O)] x 2H(2)O, 1 and [Mn(pipem)(2)(H(2)O)], 2. The new complexes have been characterised by elemental analyses, infrared, UV-vis and X-band EPR spectroscopy in the temperature range from 4 to 300 K. The monoanion, pipem, exhibits O,O ligation through the carbonyl and carboxylato oxygen atoms. Five coordinate square-pyramid configuration has been proposed for 1 and 2, and the fifth apical position is occupied by a coordinated water molecule.     

Determination of hydrogen peroxide by thallium(III) in the presence of iron(II)

A method for estimating hydrogen peroxide by oxidation with excess of thallium(III) in the presence of iron(II) and iodometric determination of excess of thallium(III) is described. Nitrate, sulphate, manganese(II) and copper(II) have no effect. Chloride interferes.