Kinetics of radical reactions involved in the gas-phase thermal decomposition of nitrobenzene

The performance of a method for analyzing complex kinetic processes is demonstrated by the example of the thermal decomposition of nitrobenzene in the gas phase. A gradual increase in the number of reactions, determination of the parameters involved, and comparison with experimental data made it possible to construct a minimum mechanism capable of describing the experimental data within the selected pressure range. The rate constants for a number of reactions of radicals with the initial reactant and reaction products were determined.     

Sonochemical and photochemical reactions of bromotrichloromethane in the presence and absence of 1-alkene

Comparison between sonolysis and photolysis of bromotrichloromethane in the presence and absence of 1-alkenes was performed to elucidate the characteristics of homogeneous sonochemistry. Results indicate that the photolysis of BrCCl3 generates radicals in a homogeneous and dispersed state, while sonolysis generates them in a heterogeneous and localized state. In the photochemical reaction the BrCCl3-adduct was obtained over a wide range of mole fractions of BrCCl3, whereas in the sonochemical reaction the yield of the BrCCl3-adduct showed a sharp maximum in a range of high mole fractions of BrCCl3. This may be attributed to the large variation in surface tension.     

On the redox reactions between allyl radicals and NOx

NO_x mitigation is a central focus of combustion technologies with increasingly stringent emission regulations. NO_x can also enhance the autoignition of hydrocarbon fuels and can promote soot oxidation. The reaction between allyl radical (C₃H₅) and NO_x plays an important role in the oxidation kinetics of propene. In this work, we measured the absolute rate coefficients for the redox reaction between C₃H₅ and NO_x over the temperature range of 1000–1252 K and pressure range of 1.5–5.0 bar using a shock tube and UV laser absorption technique. We produced C₃H₅ by shock heating of C₃H₅I behind reflected shock waves. Using a Ti:Sapphire laser system with frequency quadrupling, we monitored the kinetics of C₃H₅ at 220 nm. Unlike low-temperature chemistry, the two target reactions, C₃H₅ + NO → products (R1) and C₃H₅ + NO₂ → products (R2), exhibited a strong positive temperature dependence for this radical-radical type reaction. However, these reactions did not show any pressure dependence over the pressure range of 1.5–5.0 bar, indicating that the measured rate coefficients are close to the high-pressure limit. The measured values of the rate coefficients resulted in the following Arrhenius expressions (in unit of cm³/molecule/s):$k_1\left({\mathrm{C}}_3{\mathrm{H}}_5+\text{NO}\right)=1.49\times {10}^{?10}\exp \left(?6083.6\frac{\mathrm{K}}{T}\right)\left(1017?1252K\right)$$k_2\left({\mathrm{C}}_3{\mathrm{H}}_5+\mathrm{N}{\mathrm{O}}_2\right)=1.71\times {10}^{?10}\exp \left(?3675.7\frac{\mathrm{K}}{T}\right)\left(1062?1250K\right)$To our knowledge, these are the first high-temperature measurements of allyl + NO_x reactions. The reported data will be highly useful in understanding the interaction of NO_x with resonantly stabilized radicals as well as the mutual sensitization effect of NO_x on hydrocarbon fuels.     

Sonochemical reactions at 640 kHz using an efficient reactor. Oxidation of potassium iodide

Ultrasound can be used to oxidize aqueous pollutants. However, due to economic reasons higher oxidation/destruction rates and higher energy efficiency are needed. Recent studies suggest that the higher ultrasound frequencies provide better oxidation rates than the conventional 20 kHz. Another area for improvement is reactor configuration. We have tested two new reactor configurations with proper focusing and reflection of ultrasound for maximum utilization. Reactor configuration plays an important role in the overall efficiency. In the new reactors, transducers and reaction mixture are separated by a polymer acoustic window which allows efficient transfer of ultrasound energy and not the heat from the transducer to the reaction mixture. One reactor at 640 kHz provides a 100% enhancement over the best reported rate for the oxidation of potassium iodide, on a per-Watt basis. Experiments conducted at varying initial KI concentrations show interesting behavior. Increasing the KI concentration by over eight fold merely increases the iodine production rate by two fold. This suggests that in the oxidation region surrounding the bubble, the KI concentration is much different than in the bulk. It is proposed that the hydrophobic bubble region has lower and near saturation KI concentration.     

Spin density distribution and stereochemistry of triphenylmethyl radical in solution

¹³C-E.S.R. coupling constants of triphenylmethyl radical are readily obtained from the model compound tris-(3,5-di-t-butylphenyl)-methyl. Twisting of the phenyl substituents in solution is proven for the first time by the observation of a considerable contribution from hyperconjugation to ac_ortho ^C. This twisting causes the unusually large a _meta ^H by π-σ interaction as proposed by Pople for twisted benzyl radicals. Two different sets of spin densities are obtained for C₁ and C₂ by employing ac₂ ^C, coupling constants of the ring protons and , depending on whether the σ-π parameters of Karplus and Fraenkel or those recently proposed by Strom, Underwood and Jurkowitz are used. The comparison of ac₁ ^C calculated from these spin densities with the experimental carbon-13 splitting at C₁ indicates some deviation from trigonal planarity at C₁ in solution when the σ-π-parameters of Karplus and Fraenkel are used. Use of the Strom, Underwood and Jurkowitz parameters, on the other hand, lead to pure sp² hybridization at C₁. The latter result is in contrast to the deviations from trigonal planarity observed previously for the central carbon atoms of triphenylmethyl radical in the gas phase and of tris-(p-nitrophenyl)-methyl in the solid state.     

Influence of ultrasound on the kinetic parameters of electrochemical redox reactions

The aim of this work is to determine the Tafel parameters with and without ultrasound. The total overvoltage has been corrected for diffusion by using rotating disk technique and potentiostatic extrapolation to infinite rotating speed. Three well known redox systems have been selected regardless to their different electrochemical behaviour: the quinone-hydroquinone, the Fe(II)Fe(III) chlorides and Fe(II)-Fe(III) cyanide systems. This work shows that the reversibility is higher with ultrasound only in the case of the quinone-hydroquinone system.     

Homogeneous and heterogeneous asymmetric reactions: Part 11. Sonochemical enantioselective hydrogenation of trifluoromethyl ketones over platinum catalysts

Enantioselective sonochemical hydrogenation of alpha,alpha,alpha-trifluoromethyl ketones, namely, 1,1,1-trifluoroacetophenone and 1,1,1-trifluoro-phenylacetone was carried out over various platinum catalysts modified by cinchonidine in different solvents. Both compounds yielded the (R)-alcohol as major product. The reaction rates and the enantiomeric excesses were determined over Pt/C, Pt/SiO2, Pt/K-10 and Pt/Al2O3 catalysts under conventional conditions. Since Pt/Al2O3 exhibited the best catalytic performance the effect of ultrasound on the catalytic activity and enantioselectivity was tested using this catalyst applying different sonochemical pretreatments. These methods included a pretreatment before the reaction in hydrogen and oxygen or both. The ultrasonic irradiation was found to be highly advantageous in the case of trifluoroacetophenone, whereas only moderate changes were observed using trifluoro-phenylacetone. After insonation of the catalyst, the enantioselectivity was considerably improved. Both the aerobic and anaerobic sonochemical pretreatments resulted in significant improvement in optical yield (up to 49% and 17% ee, at room temperature under 10 bar in 1,2-dichlorobenzene). In parallel, the hydrogenation rates increased to a small extent (1.1-1.2-fold increase) after hydrogenative ultrasonic pretreatment, whereas the rates decreased by a factor of 1.5-2 after aerobic insonation. To obtain more insight into the process, the effect of insonation time on the activity and enantioselectivity and actual changes of the catalyst were also studied.     

Rates of redox reactions in basaltic melts determined by Mössbauer spectroscopy

Mössbauer spectroscopy has been widely used for determining the ferric/ferrous ratio in amorphous rock samples to reveal the oxygen pressure in the melt. In the present investigation, Mössbauer spectroscopy in conjunction with melting experiments at controlled oxygen pressures was used to determine the rates of redox reactions in basaltic melts at 1300°C. The samples were kept at a fixed oxygen pressure long enough to reach equilibrium at a well established ferric/ferrous ratio. Then, the oxygen fugacity in the furnace was changed abruptly and the samples were kept for different lengths of time, from 15 min, to 4 hrs, at the new condition. At the end of each run the samples were quenched and the ferric/ferrous ratio analyzed by Mössbauer spectroscopy. A geological corollary of our results is that natural volcanic glasses, representing quenched melts, retain and reflect the oxidation state in the melt immediately prior to eruption, and hence the oxygen fugacity in the magma.     

Sonochemical and sonocatalytic degradation of monolinuron in water

The degradation of the phenylurea monolinuron (MLN) by ultrasound irradiation alone and in the presence of TiO(2) was investigated in aqueous solution. The experiments were carried out at low and high frequency (20 and 800 kHz) in complete darkness. The degradation of MLN by ultrasounds occurred mainly by a radical pathway, as shown the inhibitory effect of adding tert-butanol and bicarbonate ions to scavenge hydroxyl radicals. However, CO(3)(-) radicals were formed with bicarbonate and reacted in turn with MLN. In this study, the degradation rate of MLN and the rate constant of H(2)O(2) formation were used to evaluate the oxidative sonochemical efficiency. It was shown that ultrasound efficiency was improved in the presence of nanoparticles of TiO(2) and SiO(2) only at 20 kHz. These particles provide nucleation sites for cavitation bubbles at their surface, leading to an increase in the number of bubbles when the liquid is irradiated by ultrasound, thereby enhancing sonochemical reaction yield. In the case of TiO(2), sonochemical efficiency was found to be greater than with SiO(2) for the same mass introduced. In addition to the increase in the number of cavitation bubbles, activated species may be formed at the TiO(2) surface that promote the formation of H(2)O(2) and the decomposition of MLN.     

Sonochemical degradation of chlorophenols in water

Sonochemical degradation of dilute aqueous solutions of 2-, 3- and 4-chlorophenol and pentachlorophenol has been investigated under air or argon atmosphere. The degradation follows first-order kinetics in the initial state with rates in the range 4.5-6.6 microM min-1 under air and 6.0-7.2 microM min-1 under argon at a concentration of 100 microM of chlorophenols. The rate of OH radical formation from water is 19.8 microM min-1 under argon and 14.7 microM min-1 under air in the same sonolysis conditions. The sonolysis of chlorophenols is effectively inhibited, but not completely, by the addition of t-BuOH, which is known to be an efficient OH radical scavenger in aqueous sonolysis. This suggests that the main degradation of chlorophenols proceeds via reaction with OH radicals; a thermal reaction also occurs, although its contribution is small. The addition of appropriate amounts of Fe(II) ions accelerates the degradation. This is probably due to the regeneration of OH radicals from hydrogen peroxide, which would be formed from recombination of OH radicals and which may contribute a little to the degradation. The ability to inhibit bacterial multiplication of pentachlorophenol decreases with ultrasonic irradiation.     

Sonochemical degradation of triclosan in water and wastewater

The sonochemical degradation of 5 μg l⁻¹ triclosan, a priority micro-pollutant, in various environmental samples (seawater, urban runoff and influent domestic wastewater) as well as in model solutions (pure and saline water) was investigated. Experiments were conducted with a horn-type sonicator operating at 80 kHz frequency and a nominal applied power of 135 W, while solid-phase microextraction coupled with gas chromatography–electron capture detector (SPME/GC–ECD) was employed to monitor triclosan degradation. The latter followed pseudo-first order kinetics with the rate constant being (min⁻¹): 0.2284 for seawater > 0.1051 for 3.5% NaCl in deionised water > 0.0597 for centrifuged urban runoff  0.0523 for untreated urban runoff > 0.0272 for deionised water > 0.0063 for wastewater influent. SPME/GC–ECD and SPME coupled with gas chromatography–mass spectrometry (SPME/GC–MS) were also used to check for the formation of chlorinated and other toxic by-products; at the conditions in question, the presence of such compounds was not confirmed.     

Sonochemical formation of nitrate and nitrite in water

The formation of nitrite and nitrate ions in water under irradiation with 900 kHz ultrasound was studied as a function of time, temperature and gas (oxygen/nitrogen) composition. The rate decreases as temperature increases, and is below the detection limit when there is no O2 gas present. The absolute rate of formation of NOx- ions obtained (about 30 x 10(-9) mol min-1 W-1) agrees well with previous similar studies. The differences in the NO2-/NO3- ratio found between various studies can be satisfactorily explained though a mechanism where HNO2 and HNO3 are formed in the gas phase of the imploding cavity, and then dissolve in the water and dissociate to ions. The NO2- species is initially substantially favoured, as considerably more NO is formed than NO2. Thermodynamic calculations indicate that at the 'hot spot' temperature of about 5000 K believed to be present, there would very large amounts of NO and OH radicals present, and at such high temperatures, thermodynamics would be a good approximation of the situation, since the rates of reactions would be very rapid. The reaction needs O2 in order to proceed to a significant degree; no NOx- was detected in the absence of oxygen gas.     

混响场中超声化学效应的研究

本文借助荧光光谱分析法,使用815kHz超声波对小尺度混响场中声化学产额进行了研究。研究发现混响场中的声化学效应有两个特点:一是声空化的阈值声强下降到约0.3W/cm²(行波场为0.7W/cm²);二是声强大于阈值时,声化学产额随声强而增加,随后(声强约为1.69—2.13w/cm²)出现陡然上升的拐点(行波场则趋向饱和)。理论分析表明,阈值下降是由于混响场的声能密度增大;声化学产额随声强变化的拐点则来自于声波辐射压力对液体表面的干扰.为此,本文从实验与理论上证明,为使声化学获得尽可能高的产额应在声化学反应器内建立混响声场。     

Sonochemical and photochemical oxidation of organic matter

Recent developments in sonochemistry have led us to study its use to treat water and wastewater. The effects of ultrasound wave in hydrophilic chemical oxidations are mainly due to hydroxyl radical production during the cavitation-induced water decomposition. Currently, the sonochemical destruction of aromatic compounds in water solution is obtained with low rates. The aim of this work is to evaluate the efficiency of the sonochemical effect in conjunction with a photochemical irradiation. Taking phenol as an example, the combined action of sonochemistry and photochemistry has been considered in a ‘sonuv’ reactor. An important enhancement of the degradation rate of phenol has been observed. It may be the result of three different oxidative processes: direct photochemical action, high frequency sonochemistry and reaction with ozone (produced by UV irradiation of air). The process has been successfully tested to lower the chemical oxygen demand of a municipal wastewater.     

Mass spectrometric characterization of phosphorylated peptides using MALDI in-source decay via redox reactions

Matrix-assisted laser desorption/ionization in-source decay (MALDI-ISD) has been used for characterization of a phosphorylated peptides and proteins because labile phosphate group is not lost during the MALDI-ISD process. The conventional MALDI-ISD is initiated by the hydrogen transfer from reducing matrix molecules to peptide backbone, leading to c'- and z'-series ions. In contrast, when an oxidizing chemical 5-nitrosalicylic acid (5-NSA) is served as the MALDI-ISD matrix, a- and x-series ions are specifically generated by hydrogen abstraction from peptide backbone to matrix molecule. The 5-NSA provides useful complementary information to the conventional MALDI-ISD for the analysis of amino acid sequencing and site localization of phosphorylation in peptides. The MALDI-ISD with reducing and oxidizing matrix could be a useful method for the de novo peptide sequencing.     

Sonochemical and photosonochemical degradation of 4-chlorophenol in aqueous media

The degradation of 4-chlorophenol (4-CP) in aqueous media by 516 kHz ultrasonic irradiation was investigated in order to clarify the degradation mechanism. The degradation of concentrated 4-CP solution by means of ultrasound, UV irradiation and their combined application was also studied. The obtained results indicate that *OH radical are the primary reactive species responsible for 4-CP ultrasonic degradation. Very little 4-CP degradation occurs if the sonolysis is carried out in the presence of the *OH radical scavenger tert-butyl alcohol, also indicating that little or no pyrolysis of the compound occurs. The dominant degradation mechanism is the reaction of substrate with *OH radicals at the gas bubble-liquid interface rather than high temperature direct pyrolysis in ultrasonic cavities. This mechanism can explain the lower degradation rate of the ionic form of 4-CP that is partly due to the rapid dissociation of *OH radicals in alkaline solutions. The sonochemical destruction of concentrated 4-CP aqueous solution is obtained with low rate. Coupling photolysis with ultrasound irradiation results in increased efficiency compared to the individual processes operating at common conditions. Interestingly, the photosonochemical decomposition rate constant is greater than the additive rate constants of the two processes. This may be the result of three different oxidative processes direct photochemical action, high frequency sonochemistry and reaction with ozone produced by UV irradiation of air, dissolved in liquid phase because of the geyser effect of ultrasound streaming. Additionally, the photodecomposition, at 254 nm, of hydrogen peroxide produced by ultrasound generating *OH radical can partly explain the destruction enhancement.     

Sonochemical degradation of cyclic nitroxides in aqueous solution

The sonochemical degradation of eight five- and six-membered nitroxides has been studied by EPR spectroscopy after exposure to ultrasound at a frequency of 354 kHz in argon-saturated aqueous solution. Concentration vs. time profiles do not follow a simple rate law. Octanol/water partition functions have been determined for all eight nitroxides, and an excellent linear correlation has been found between initial decomposition rates and hydrophobicity (log K(octanol/water)). Variation of initial rate with concentration was investigated for one compound (TEMPONE) and is largely consistent with an equilibrium distribution of substrate between bulk solution and the gas/liquid interface.     

Sonochemical production of intermetallic coatings in heterogeneous media

The production of 5–10 μm fused particles and agglomerates occurs when metal powders in hydrocarbon solvents are exposed to high-intensity ultrasound. The principle mechanism of particle fusion is believed to be interparticle collision caused by the rapid movement of particles propelled by shock waves generated at cavitation sites. An energy-dispersive X-ray (EDX) study of the agglomerates produced during the sonication of mixed-metal powders in decane indicates that not only are the metal particles fused by the action of ultrasound but that intermetallic coatings are also developed. By examination of mixed-metal systems (Ni/Co and Cu/Mo) with substantially different tribological characteristics, it has been determined that the coatings are generated by both adhesive wear and direct impact. The mechanisms of ultrasound-induced coatings are discussed.