Luminescent chemical waves in the Cu(II)-catalyzed oscillatory oxidation of SCN- ions with hydrogen peroxide

The oscillatory oxidation of thiocyanate ions with hydrogen peroxide, catalyzed by Cu2+ ions in alkaline media, was so far observed as occurring simultaneously in the entire space of the batch or flow reactor. We performed this reaction for the first time in the thin-layer reactor and observed the spatiotemporal course of the above process, in the presence of luminol as the chemiluminescent indicator. A series of luminescent patterns periodically starting from the random reaction center and spreading throughout the entire solution layer was reported. For a batch-stirred system, the bursts of luminescence were found to correlate with the steep decreases of the oscillating Pt electrode potential. These novel results open possibilities for further experimental and theoretical investigations of those spatiotemporal patterns, including studies of the mechanism of this chemically complex process.     

Quantification of hydrogen peroxide during the low-temperature oxidation of alkanes

The first reliable quantification of hydrogen peroxide (H(2)O(2)) formed during the low-temperature oxidation of an organic compound has been achieved thanks to a new system that couples a jet stirred reactor to a detection by continuous wave cavity ring-down spectroscopy (cw-CRDS) in the near-infrared. The quantification of this key compound for hydrocarbon low-temperature oxidation regime has been obtained under conditions close to those actually observed before the autoignition. The studied hydrocarbon was n-butane, the smallest alkane which has an oxidation behavior close to that of the species present in gasoline and diesel fuels.     

Effect of water vapor on chemical transport of zinc oxide by hydrogen peroxide

The dependence of the mass transfer rate on the water vapor partial pressure for the chemical transport of ZnO assisted by hydrogen peroxide was studied. The effect of water on the rate of ZnO transport was demonstrated to be dual: positive at low [H₂O: H₂O₂] ratios and negative at high. The data obtained were discussed in terms of the unique properties of the structured-water layer adjacent to the solid surface.     

Reactions of hydrogen atom with hydrogen peroxide

Rate coefficients are calculated using canonical variational transition state theory with multidimensional tunneling (CVT/SCT) for the reactions H + H2O2 --> H2O + OH (1a) and H + H2O2 --> HO2 + H2 (1b). Reaction barrier heights are determined using two theoretical approaches: (i) comparison of parametrized rate coefficient calculations employing CVT/SCT to experiment and (ii) high-level ab initio methods. The evaluated experimental data reveal considerable variations of the barrier height for the first reaction: although the zero-point-exclusive barrier for (1a) derived from the data by Klemm et al. (First Int. Chem. Kinet. Symposium 1975, 61) is 4.6 kcal/mol, other available measurements result in a higher barrier of 6.2 kcal/mol. The empirically derived zero-point-exclusive barrier for (1b) is 10.4 kcal/mol. The electronic structure of the system at transition state geometries in both reactions was found to have "multireference" character; therefore special care was taken when analyzing electronic structure calculations. Transition state geometries are optimized by multireference perturbation theory (MRMP2) with a variety of one-electron basis sets, and by a multireference coupled cluster (MR-AQCCSD) method. A variety of single-reference benchmark-level calculations have also been carried out; included among them are BMC-CCSD, G3SX(MP3), G3SX, G3, G2, MCG3, CBS-APNO, CBS-Q, CBS-QB3, and CCSD(T). Our data obtained at the MRMP2 level are the most complete; the barrier height for (1a) using MRMP2 at the infinite basis set limit is 4.8 kcal/mol. Results are also obtained with midlevel single-reference multicoefficient correlation methods, such as MC3BB, MC3MPW, MC-QCISD/3, and MC-QCISD-MPWB, and with a variety of hybrid density functional methods, which are compared with high-level theory. On the basis of the evaluated experimental values and the benchmark calculations, two possible recommended values are given for the rate coefficients.     

Transformation of wood during ozonization in the presence of hydrogen peroxide

Samples of ozonized aspen wood pretreated with hydrogen peroxide solutions of various concentrations are investigated by UV diffuse reflectance spectroscopy, IR spectroscopy, and X-ray structural analysis. The general course of wood transformation under the action of the O₃/H₂O₂ system is associated with the destruction of lignin and oxidation of carbohydrates, raising the fraction of the crystalline phase in a lignocarbohydrate material. The possibility of varying the depth of the chemical and structural transformation of the substrate upon changing the hydrogen peroxide concentration in the O₃/H₂O₂ system is demonstrated.     

Determination of hydrogen peroxide concentration in THOR coolant during reactor operation

The concentrations of hydrogen peroxide formed in the coolant due to radiolysis were studied during THOR operation at 1 MW. The relation between doses and hydrogen peroxide formation in a neutron-gamma mixed field was investigated. The initial concentration was 2.3×10^–5 g/ml at the beginning of reactor operation, and then it was increased rather rapidly at the first 9 h. The increasing rate was slowed down till the end of 30 h operation. The maximum concentration of hydrogen peroxide was found to be 4.7×10^–5 g/ml, and its decrease followed the exponential curve.     

Quantum chemical modelling of ethene epoxidation with hydrogen peroxide: role of catalytic sites

Ethene epoxidation with hydrogen peroxide was studied on hydroxylated binuclear metal sites, using DFT calculations at the B3LYP/6-311+G(d,p) level of theory. A decrease of the activation enthalpy of approximately 100 kJ mol(-1) was observed compared to the gas phase reaction between hydrogen peroxide and ethene. It was previously shown that micro-solvation with water reduces the activation enthalpy by approximately 77 kJ mol(-1) and only the additional 24 kJ mol(-1) can be attributed to the binuclear site. Three different metal centres were tested, Ti(iv), Si(iv) and Ge(iv), in order to investigate any specific role of the metal centre on the activation enthalpy. The results clearly show that the activation enthalpy is independent on the nature of the metal centre. This emphasises the role of the hydrogen bonded network provided by the hydroxylated metal sites, on the stabilisation of the transitions state. In ref. 1 (A. Lundin, I. Panas and E. Ahlberg, J. Phys. Chem. A, 2007, 111, 9080) it was demonstrated that, at the transition state and upon micro-solvation, the hydrogen peroxide entity becomes polarized within the hydrogen bonding network, forming a negatively-charged fragment distant from the ethene molecule and a positively-charged fragment directly involved in the oxygen insertion step. The same mechanism was found to hold also for the reaction at the binuclear catalytic site, since the required hydrogen bonding is effectively provided by the hydroxylated metal centres. This mechanism is compared to the two-step pathway which employs a metal peroxide intermediate. Both reaction channels were found to be plausible in confined environments.     

Aluminum electrode modified with manganese hexacyanoferrate as a chemical sensor for hydrogen peroxide

A chemically modified electrode was fabricated based on manganese hexacyanoferrate (MnHCF) film. The MnHCF was used as a modifier immobilized onto an aluminum electrode. Stability of the electroactive film formed on the Al electrode surface indicated that MnHCF is a suitable material for the preparation of modified electrodes. The analytical applicability of the modified electrode for the determination of hydrogen peroxide was examined. A linear response in concentration range of 6.0x10(-7)-7.4x10(-3) M (r=0.9997) was obtained with detection limit of 2.0x10(-7) M for the determination of hydrogen peroxide. The modified electrode exhibited a good selectivity for H(2)O(2) in real samples. The mentioned electrode has advantages of being highly stable, sensitive, inexpensive, ease of construction and use.     

Novel type of oscillatory chemical reactions

Chemical oscillations occur during the uncatalyzed oxidation of a number of phenol and aniline derivatives by acidic bromate.

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Crosslink network evolution of BIIR/EPDM blends during peroxide vulcanization

Crosslink network evolution of brominated butyl rubber (BIIR)/ethylene–propylene–diene-monomer rubber (EPDM) blends during peroxide vulcanization is studied at a meso-scale level. In this work, EPDM is added as a co-agent to increase the crosslink density of BIIR vulcanization. With increasing EPDM content from 0 to 20 phr, the maximum torque of BIIR/EPDM compounds during vulcanization increases by 73%, reaching to 3.40 dNm. Vulcanization kinetic study shows that addition of EPDM favors to the crosslinking of BIIR compound. Meanwhile, the addition of 20 phr EPDM contributes to an increase in the crosslink density of BIIR/EPDM(80/20) vulcanizate, avoiding downward trend at post-cure period in comparison with BIIR only. Crosslink network evolution of BIIR/EPDM blends is divided into three periods during peroxide vulcanization at 150 °C. The role of EPDM in the crosslink network evolution is studied by proton nuclear magnetic resonance, and a “network patching” mechanism is proposed in which EPDM is implied to work as patch on damaged crosslink network resulted from the degradation nature of BIIR.     

Chemiluminescence determination of hydrogen peroxide

An overview of literature on the procedures for the chemiluminescence determination of hydrogen peroxide is presented.     

荧光光度法测定过氧化氢

在碱性介质中,以四羧基铁酞菁为过氧化物酶模拟催化H2O2氧化邻苯二胺,生成2,3-二氨基吩嗪,该产物在577 nm处产生荧光,其荧光强度随H2O2浓度的增大而增加,在1.6×10-7～9.7×10-6mol/L范围内呈良好的线性关系,相关系数r为0.9941,据此建立了一种测定痕量H2O2的新方法。方法的检出限为1.1×10-7mol/L,用于雨水中H2O2的测定,结果令人满意。     

Oscillatory reactions involving hydrogen peroxide and thiosulfate-kinetics of the oxidation of tetrathionate by hydrogen peroxide

The reaction between tetrathionate and hydrogen peroxide forms an important part of several pH oscillators based on the oxidation of thiosulfate. The kinetics of this reaction were examined in a batch reactor by measurement of the initial pH values in the range from 8 to 10.5. Experimental data were evaluated by the method of initial reaction rates combined with the assumption of instantaneously equilibrated acid-base reactions. The rate-determining step was found to be of the first order with respect to tetrathionate, hydrogen peroxide, and OH- ions with the value of rate constant k = (1.50 +/- 0.03) x 10(2) (M2 s)(-1) at 25 degrees C. In the alkaline solution, no distinct catalytic effect of Cu2+ was observed in contrast to earlier assumptions. The waveform of measured pH over the course of the reaction indicates that thiosulfate is probably an intermediate because characteristics of the curves are very similar to those for the oxidation of thiosulfate. We also measured the time evolution of concentrations of major components by the attenuated total internal reflectance infrared spectroscopy to further elucidate the underlying reaction mechanism. These measurements confirm the suspected role of thiosulfate as an intermediate in the studied reaction and provide valuable detailed information on the time evolution of thiosulfate, sulfite, sulfate, tetrathionate, and trithionate. These experimental observations are included in a simple mechanism that accurately simulates the reaction course in an alkaline solution. The results provide considerable new insights into the nature of autocatalysis in the hydrogen peroxide-thiosulfate-Cu2+ reaction and suggest that a new role for Cu2+ in the oscillatory dynamics observed in a flow-through reactor needs to be found.     

Flow-injection analysis of hydrogen peroxide based on carbon nanospheres catalyzed hydrogen carbonate-hydrogen peroxide chemiluminescent reaction

A flow-injection chemiluminescence (CL) system with high sensitivity, selectivity, rapidity, and reproducibility is proposed for the determination of hydrogen peroxide (H(2)O(2)) in water samples. The system is based on the reaction of hydrogen peroxide and hydrogen carbonate solution. Carbon nanospheres (CNSs) prepared from aqueous glucose solution are used to enhance the weak CL. The CL intensity was found to be directly proportional to the concentration of H(2)O(2) present in the sample solutions. The effects upon the CL of several physicochemical parameters, including the concentration of the reagents, the mixing order of the reagents, flow rate, pH, particle size of CNSs and other relevant variables, were studied and optimized. The proposed method exhibited advantages in a larger linear range of 5.0 × 10(-8) to 3.0 × 10(-6) mol L(-1) and a lower limit of detection of 1.0 × 10(-9) mol L(-1) (S/N = 3). This method has been successfully applied to the evaluation of H(2)O(2) in tap water and snow water with recoveries from 80 to 110%. The relative standard deviation (RSD) was less than 8% for intra- and inter-assay precision. Based on the kinetic curve, the CL spectrum, fluorescence spectrum, UV-visible spectrum, and electron spin resonance (ESR) spectrum of NaHCO(3)-H(2)O(2)-CNSs system, a possible CL mechanism was proposed. Superoxide ion radical (˙O(2)(-)) and hydroxide radical (˙OH) were generated during the reaction of NaHCO(3) and H(2)O(2). They were the key intermediates for the production of hole-injected and electron-injected CNSs in the CL process.     

Troilite oxidation by hydrogen peroxide

The kinetics and mechanism of troilite oxidation by H(2)O(2) was studied at temperatures of 25 and 45 degrees C. Solutions within the range 0.1-0.85 mol L(-1) H(2)O(2) in HClO(4) (0.01-0.1 mol L(-1)) were used as dissolution media. The experimental amount of dissolved iron was plotted versus t(n), with n ranging from 0.25 to 1.55. The theoretical interpretation of this dependence suggests that the troilite oxidation involves several processes: Both experimental results and theoretical considerations illustrate the importance of temperature, pH, and [H(2)O(2)] for the kinetics and mechanisms of troilite oxidation. The amounts of dissolved iron strongly increase with temperature and [H(+)], whereas an increase of H(2)O(2) concentration seems to reduce the troilite oxidation. The reaction orders with respect to [H(+)] are variable, pointing out notable modifications of reaction mechanism with experimental conditions. The estimated value E(a)=25.4+/-0.9 k J mol(-1) ([H(2)O(2)]=0.4 mol L(-1) and pH 1) points to dissolution kinetics controlled by a mix regime of surface reaction and diffusion.     

Physical and chemical evolution of PMDA-ODA during thermal imidization

The processing of poly(imide) films from poly(amic acid) solutions involves the simultaneous loss of solvent and chemical conversion, and may involve structural reorganization such as orientation or crystallization. Here, we describe weight loss, solvent sorption. Fourier transform infrared (FTIR), and wide-angle x-ray scattering (WAXS) studies during thermal imidization of the commercially important poly(imide) PMDA-ODA. The results indicate that imidization proceeds nearly to completion before significant crystallization occurs. The experimental data are interpreted in terms of a triangular phase diagram that makes it possible to plot the processing pathway during the conversion from poly(amic acid) solution to solid poly(imide). In constructing this triangular phase diagram the extent of imidization (i.e., the composition of the poly(amic acid-co-imide) copolymers during conversion) is treated as an independent thermodynamic variable. The form of the triangular phase diagram can be predicted from the Flory-Huggins lattice theory of mixing. There is inevitably a two-phase region present due to the relatively poor solubility of the poly(imide) in the poly(amic acid) solvent (NMP). The specific processing pathway taken depends on the relative amount of solvent loss and imidization during conversion. Further details about the triangular phase diagrams of poly(imides) will require such studies as solvent swelling at intermediate stages of conversion. © 1995 John Wiley & Sons, Inc.     

Calorimetry studies of a chemical oscillatory system

The effect of putrescine (PUT) on KSCN-H₂O₂-CuSO₄-NaOH oscillating system was investigated by calorimetric method. The oscillating reaction was monitored in a closed reactor with stirring, and the result showed that the oscillating period was linearly related with putrescine concentration and the numbers of oscillation decreased with increase in putrescine concentration. When [PUT]=2.83·10⁻⁴ M, no oscillation was observed. A possible mechanism is proposed that putrescine is a scavenger of the active-oxygen species. The result of numerical simulation by a simplified mechanism consisting of 18 kinetic steps and 16 variables is consistent with the experimental findings.