Ozonolysis of geraniol-trans, 6-methyl-5-hepten-2-one, and 6-hydroxy-4-methyl-4-hexenal: kinetics and mechanisms

A combined density functional theory and transition-state theory study of the mechanisms and reaction coefficients of gas-phase ozonolysis of geraniol-trans, 6-methyl-5-hepten-2-one, and 6-hydroxy-4-methyl-4-hexenal is presented. The geometries, energies, and harmonic vibrational frequencies of each stationary point were determined by B3LYP/6-31(d,p), MPW1K/cc-pVDZ, and BH&HLYP/cc-pVDZ methods. According to the calculations, the ozone 6-methyl-5-hepten-2-one reaction is faster than the ozone 6-hydroxy-4-methyl-4-hexenal reaction, but both are slower than the ozone geraniol-trans reaction. By using the BH&HLYP/cc-pVDZ data, a global rate coefficient of 5.9 x 10(-16) cm(3) molecule(-1) s(-1) was calculated, corresponding to the sum of geraniol-trans, 6-methyl-5-hepten-2-one, and 6-hydroxy-4-methyl-4-hexenal reactions with the ozone. These results are in good agreement with the experimental studies.     

CH2 CHF与臭氧反应机理的量子化学研究

用量子化学MP2方法,在6-311+ +G(d,p)基组水平上研究了烯烃CH2CHF与臭氧反应的机理,对氟代乙烯臭氧化反应Criegee机理进行了系统的计算,全参数优化了反应过程中反应物、中间体、过渡态和产物的几何构型,在QCISD(T)/6-311+ +G(d,p)水平上计算了它们的能量.并对它们进行了频率分析,以确定中间体和过渡态的真实性.研究结果表明,氟代乙烯与臭氧反应沿Criegee机理是可信的、合理的.同时研究还发现,就氟代乙烯与臭氧反应活性而言,其控制步骤的位垒较低,可以说氟代乙烯与臭氧反应活性较强,也就是说氟代乙烯对臭氧的损耗较大.     

Ozone generation on the lead dioxide electrodes in a sulfuric acid solution at potentials of 2 to 3 V

The electrochemical synthesis of ozone is studied on lead dioxide electrodes in sulfuric acid solutions. The two maximums of the current efficiency for ozone (CEO) observed at 2–3.5 V are largely due to the participation of various chemisorbed particles in the ozone synthesis. In the vicinity of the first CEO maximum at lead dioxide, ozone forms only in a discharge of water molecules with the participation of adsorbed oxygen-containing radicals. In the potential range of the second maximum, the adsorbed anion radicals, e.g., ·HSO₄ and ·SO₄, also take part in the reaction of ozone generation. At the electrode not subjected to anodic polarization, CEO is considerably higher than that on the preliminarily polarized electrode. On the basis of the experimental data, schemes for the ozone evolution at PbO₂ in sulfuric acid at 2 to 3 V are proposed.     

Heterogeneous reactions of linoleic acid and linolenic acid particles with ozone: reaction pathways and changes in particle mass, hygroscopicity, and morphology

In this study, an electrodynamic balance (EDB) and a single particle Raman spectroscopic system were used to investigate the heterogeneous reactions of linoleic acid and linolenic acid with ozone under ambient temperatures (22-24 degrees C) and dry conditions (RH<5%). Raman characterizations provide evidence that ozone-induced autoxidation, in addition to direct ozonolysis, is a plausible pathway in the reactions between ozone and linoleic acid and linolenic acid particles. Furthermore, the significance of this specific oxidation pathway depends on the ozone concentrations used in the experiment. A low ozone concentration (approximately 200-250 ppb) with a longer exposure period (20 h) favors autoxidation but an extremely high ozone concentration (approximately 10 ppm) favors ozonolysis and forces most unsaturated fatty acids to react with ozone in a relatively short period of time. In the low ozone concentration experiments, the mass of the ozone-processed linoleic acid and linolenic acid particles increased by about 2-3% and 10-13%, respectively. In addition, the mass ratios (particle mass at RH approximately 85% to particle mass at RH<5%) of the ozone-processed linoleic acid and linolenic acid particles increased by about 2-3% and 3-4%, respectively. The morphology of the pure and ozone-processed linoleic acid and linolenic acid particles are compared, based on imagining and their light scattering patterns.     

Dynamics of the reaction of ozone with humic and fulvic acids in lake water,and the structures of fragments of their molecules

The rates of ozone absorption during bubbling of an ozone-oxygen mixture through a sample of lake water with high contents of humic and fulvic acids were measured. Three characteristic sections were distinguished on the kinetic curve. The corresponding effective rate constants of ozone reactions with the substrate are 5.1 - 10⁴, 1.4 - 10², and 7.6 L mol^?1 s^?1. Structures of the reacting fragments and their contents in the system were suggested.     

Chemiluminescent reactions of E-2-hydroxy-4′-substituted stilbenes with ozone

The reaction of seven E-2-hydroxy-4′-substituted stilbenes with ozone is chemiluminescent, the quantum yields depending on Hammett's σ constant for the 4′-substituent. The primary emitter is the salicylaldehyde anion in all cases. The apparent rate constants derived from chemiluminescence decay measurements are a linear function of Hammett's σ constants. Mechanistic implications are discussed for the ozonolysis reaction of these compounds.     

Some Transformations of (-)-(1S,4R)-1-Vinyl-7,7-dimethyl-bicyclo[2.2.1]heptan-2-one

Reactions were studied of (-)-(1S,4R)-1-vinyl-7,7-dimethylbicyclo[2.2.1]heptan-2-one with ethyl acetate lithium derivative, potassium acetylide, ozone, with a system OsO₄-N-methylmorpholine N-oxide, and some subsequent transformations of the products obtained.     

Iodoxybenzene. A remarkably close ozone equivalent

Iodoxybenzene is isoelectronic to ozone and several of its reactions proceed via pathways remarkably similar to that of ozone. An attractive feature of iodoxybenzene mediated reactions is the direct formation of products and the transformation of the reagent to iodobenzene. The formation of benzil and iodobenzene in good yields from diphenylacetylene provides support for the anticipated intermediate arising from π⁴s+π²s addition. Iodoxybenzene transforms phenanthrene to phenanthrenequinone as a result of the initially formed 4 + 2 adduct undergoing C-H rupture, in preference to the C-C rupture. This change is parallel to the transformation of phenanthrene 9-carboxylic acid to phenanthrenequinone with ozone. The expected C-C rupture of the initially formed adduct does take place with acenaphthylene leading to naphthalic anhydride. The reaction of pyrene with iodoxybenzene leads to nearly equal amounts of the 4-5, 1-6 and 3-6 quinones involving attack on the bond of the lowest bond localisation energy and the atom of the lowest atom localization energy. This behaviour is similar to the action of ozone on benzopyrene. iodoxybenzene transforms anthracene, just like ozone, to anthraquinone, in good yields. The involvement of transannular addition of iodoxybenzene, as is partly the case with ozone, is proved unlikely by reaction with 9, 10 dimethylanthracene which gave 10-methyl 9-anthraldehyde and 10-carboxy 9-anthraldehyde, involving the insertion of elements of iodoxybenzene to the aryl C-H bond. This tendency of iodoxybenzene has been further demonstrated by the following changes: diphenylmethane→ benzophenone; fluorene→fluorenone and tetralin→α-tetralone. Several of the transformations brought about with iodoxybenzene provide attractive synthetic routes, particularly to phenanthrenequinone, pyrenequinones and tetralone. Finally, just like the 2O₃→3O₂ change, iodoxybenzene, and even more so, 4-iodoxybiphenyl, thermally fragment to iodobenzene and 4-iodobiphenyl.     

磷酸根修饰的Mn掺杂介孔TiO2在VUV-PCO体系高效催化氧化甲苯性能

Vacuum ultraviolet irradiation coupled with photocatalytic oxidation (VUV-PCO) is an efficient and promising method for eliminating pollutants at room temperature; it involves three processes: vacuum ultraviolet (VUV) photolysis, photocatalytic oxidation (PCO), and ozone catalytic oxidation. Herein, toluene was chosen as the representative volatile organic compound (VOC), which is one of the most important precursors to form fine particulate matter and photochemical smog, because of its high toxicity and extensive existence in industries. All experiments were performed in a fixed-bed continuous-flow reactor that contained units for VUV photolysis and PCO. Mesoporous P-Mn-TiO₂ was prepared by one-step hydrolysis and used as a catalyst for the oxidation of gaseous toluene under VUV irradiation through the VUV-PCO process. The as-prepared P-Mn-TiO₂ samples were characterized by scanning electron microscope (SEM), transmission electron microscope (TEM), ultraviolet-visible light (UV-Vis) spectroscopy, and X-ray diffraction (XRD) analysis to determine the physicochemical properties of the catalysts and to determine the mechanisms of Mn doping and phosphoric acid modification and the effects of these processes on photocatalytic activity, ozone catalytic activity, and adsorption performance. The results indicated that the synergistic effect of phosphoric acid modification and Mn doping can improve the ozone catalytic activity and photocatalytic performance by increasing the number of oxygen active sites, completely eliminating the outlet ozone, and simultaneously promoting the efficient degradation of toluene. Moreover, doping TiO₂ with Mn³⁺ significantly enhanced light harvesting, and numerous oxygen vacancies can be generated on the catalyst surface because of the presence of doped Mn³⁺ in the lattice, which adsorbs and transforms the oxygen species for toluene degradation. In addition, modification with an appropriate amount of phosphate groups can facilitate O₂ and O₃ adsorption on the TiO₂ surface that can favor photo-induced charge carrier separation, thereby significantly improving the photocatalytic and ozone catalytic activities. The excellent catalytic performance of mesoporous P-Mn-TiO₂ for toluene degradation and outlet ozone elimination was ascribed to the formation of highly reactive oxidizing species such as O(1D), O(3P), and ·OH via the catalytic decomposition of O₃ adsorbed on the oxygen vacancy sites containing Mn and phosphate groups on the catalyst surface. In the VUV-PCO process, toluene was first destructed via VUV photolysis and oxidized by residual O₃ generated from VUV photolysis and the active oxygen species formed in the presence of the catalyst. Finally, toluene and the generated intermediate products were oxidized and degraded to CO₂ and H₂O through VUV-PCO. In addition, the outlet ozone byproduct was simultaneously eliminated by the multifunctional catalyst.      

铜和铝离子/UV催化臭氧降解偶氮二异丁腈废水研究

利用多相催化臭氧(O3)工艺处理偶氮二异丁腈(AIBN)废水,探讨不同催化O3体系(Cu2+、Al3+、Cu2++Al3+/UV催化O3)对AIBN废水中氰类污染物的降解特性,并对不同催化O3体系的动力学特性进行研究。结果表明,金属离子对催化O3工艺的处理效率具有明显影响,不同催化O3工艺对CN-去除作用都呈现起始去除速率较高而后减弱的特点,其中Cu2+和Al3+共同催化O3工艺的整体去除率较高,优于单独Cu2+和Al3+的催化性能。这可能是由于p H变化、金属离子与CN-配合作用、金属离子和O3作用的综合影响结果。动力学研究结果表明,不同催化O3体系降解AIBN废水中的CN-污染物的氧化反应符合准一级动力学反应,表观反应速率常数k在0.0245~0.00301 min-1之间。     

Ozone production and losses in N<Subscript>2</Subscript>/O<Subscript>2</Subscript> mixtures in an ozone generator

Nonunique ozone concentrations at the output of an ozone generator under identical external conditions of barrier discharge activation of N₂/O₂ mixtures but with different prehistories of operating practice and employed gas mixtures are investigated theoretically. An analytical approach is developed to determine the ozone yield with regard for its heterogeneous loss. Plasma-chemical and electron kinetics in the N₂/O₂-mixtures are calculated numerically. The results of numerical calculations are compared to experimental data obtained by the authors. It is noted that the heterogeneous loss of ozone is the probable reason for the observed variety of behavior of О₃ concentrations, depending on prehistory of ozone generator operation, along with the N₂ and O₂ gas flow rates and the specific active power.     

3d Metal complexes with 2-hydroxy-3-methoxybenzaliminopropyl and 4-hydroxy-3-methoxybenzaliminopropyl immobilized on aerosil as catalysts of ozone decomposition

The composition and structure of M(II) (Mn, Co, Cu) complexes with Schiff bases (L1 = 2-hydroxy-3-methoxybenzaliminopropyl, L2 = 4-hydroxy-3-methoxybenzaliminopropyl) immobilized on Aerosil and their catalytic activity in ozone decomposition were studied. The formation of pseudotetrahedral bisligand complexes M(L1)₂ and pseudooctahedral complexes M(L2)₂ on the modified surface of Aerosil was confirmed by IR and ESR spectroscopy and by diffuse reflectance spectroscopy (DSR). The catalytic activity of isostructural complexes in ozone decomposition varies in the order Mn > Co > Cu, and M(L₂)₂ complexes are more active than M(L1)₂.     

Nonstatistical behavior of reactive scattering in the (18)O+(32)O(2) isotope exchange reaction

The recombination of oxygen atoms with oxygen molecules to form ozone exhibits several strange chemical characteristics, including unusually large differences in formation rate coefficients when different isotopes of oxygen participate. Purely statistical chemical reaction rate theories cannot describe these isotope effects, suggesting that reaction dynamics must play an important role. We investigated the dynamics of the 18O + 32O2 --> O3(*) --> 16O + 34O2 isotope exchange reaction (which proceeds on the same potential energy surface as ozone formation) using crossed atomic and molecular beams at a collision energy of 7.3 kcal mol(-1), providing the first direct experimental evidence that the dissociation of excited ozone exhibits significant nonstatistical behavior. These results are compared with quantum statistical and quasi-classical trajectory calculations in order to gain insight into the potential energy surface and the dynamics of ozone formation.     

五氧化二氮和水反应的从头算研究

在臭氧空洞形成过程中,极地云是一个重要的条件。为了理解极地云的形成和性质,采用不同水平的从头计算方法对N~2O~5+H~2O→2HNO~3反应进行了理论研究。在QCISD(T)//MP2/6-311G(d,p)理论水平上,该气相反应的焓变△H^0=-39.5kJ·mol^-^1,自由能变化△G^0=-36.1kJ/mol,活化能E~a=88.2kJ·mol^-^1(298K)。计算的结果与五氧化二氮易潮解的性质相符。     

Isomeric structures of protonated ozone: A theoretical study

Ab initio molecular orbital calculations have been used to determine the structure of protonated ozone. Four stable minima were found on the O₃H⁺ singlet potential energy surface. Three forms correspond to ozone protonated at the central oxygen (C_2v) or at the terminal oxygen (two C_s isomers, E and Z). The fourth isomer (C_s) is a derivative of trioxirane. The most stable structure is the planar E form I. The proton affinity of ozone (to give I) is given as 123.6 kcal/mole (MP2/6-31G*//4-31G). The energy difference between I and protonated trioxirane VI is greater than that between ozone and trioxirane.     

Surface Modification of (001) Facets Dominated TiO2 with Ozone for Adsorption and Photocatalytic Degradation of Gaseous Toluene

This study investigated the positive effect of surface modification with ozone on the photocatalytic performance of anatase TiO₂ with dominated (001) facets for toluene degradation. The performance of photocatalyst was tested on a home-made volatile organic compounds degradation system. The ozone modi cation, toluene adsorption and degradation mechanism were established by a combination of various characterization methods, in situ diffuse reflectance infrared fourier transform spectroscopy, and density functional theory calculation. The surface modi cation with ozone can significantly enhance the photocatalytic degradation performance for toluene. The abundant unsaturated coordinated 5c-Ti sites on (001) facets act as the adsorption sites for ozone. The formed Ti-O bonds reacted with H₂O to generate a large amount of isolated Ti_5c-OH which act as the adsorption sites for toluene, and thus significantly increase the adsorption capacity for toluene. The outstanding photocatalytic performance of ozone-modified TiO₂ is due to its high adsorption ability for toluene and the abundant surface hydroxyl groups, which produce very reactive OH radicals under irradiation. Furthermore, the O₂ generated via ozone dissociation could combine with the photogenerated electrons to form superoxide radicals which are also conductive to the toluene degradation.     

Thinking out of the black box: accurate barrier heights of 1,3-dipolar cycloadditions of ozone with acetylene and ethylene

Accurate barriers for the 1,3-dipolar cycloadditions of ozone with acetylene and ethylene have been determined via the systematic extrapolation of ab initio energies within the focal point approach of Allen and co-workers. Electron correlation has been accounted for primarily via coupled cluster theory, including single, double, and triple excitations, as well as a perturbative treatment of connected quadruple excitations [CCSD, CCSD(T), CCSDT, and CCSDT(Q)]. For the concerted [4 + 2] cycloadditions, the final recommended barriers are DeltaH(0K) = 9.4 +/- 0.2 and 5.3 +/- 0.2 kcal mol(-1) for ozone adding to acetylene and ethylene, respectively. These agree with recent results of Cremer et al. and Anglada et al., respectively. The reaction energy for O3 + C2H2 exhibits a protracted convergence with respect to inclusion of electron correlation, with the CCSDT/cc-pVDZ and CCSDT(Q)/cc-pVDZ values differing by 2.3 kcal mol-1. Recommended enthalpies of formation (298 K) for cycloadducts 1,2,3-trioxole and 1,2,3-trioxolane are +32.8 and -1.6 kcal mol(-1), respectively. Popular composite ab initio approaches [CBS-QB3, CBS-APNO, G3, G3B3, G3(MP2)B3, G4, G4(MP3), and G4(MP2)] predict a range of barrier heights for these systems. The CBS-QB3 computed barrier for ozone and acetylene, DeltaH(0K) = 4.4 kcal mol(-1), deviates by 5 kcal mol(-1) from the focal point value. CBS-QB3 similarly underestimates the barrier for the reaction of ozone and ethylene, yielding a prediction of only 0.7 kcal mol(-1). The errors in the CBS-QB3 results are significantly larger than mean errors observed in application to the G2 test set. The problem is traced to the nontransferability of MP2 basis set effects in the case of these reaction barriers. The recently published G4 and G4(MP2) approaches perform substantially better for O3 + C2H2, predicting enthalpy barriers of 9.0 and 8.4 kcal mol(-1), respectively. For the prediction of these reaction barriers, the additive corrections applied in the majority of the composite approaches considered lead to worse agreement with the reference focal point values than would be obtained relying only on single point energies evaluated at the highest level of theory utilized within each composite method.     

Study on the Physical and Chemical Characteristics of DBD: The Effect of N2/O2 Mixture Ratio on the Product Regulation

Plasma Chemistry and Plasma Processing - The chemical product behaviors of dielectric barrier discharge (DBD) in N2/O2 gas mixtures are investigated. Besides ozone mode and nitrogen oxides mode, a...     

Identification of oxidation products of solanesol produced during air sampling for tobacco smoke by electrospray mass spectrometry and HPLC

Solanesol, a 45-carbon, trisesquiterpenoid alcohol found in tobacco leaves and tobacco smoke, has been used as a quantitative marker for tobacco smoke for years. However, solanesol appears to be unreliable as a quantitative marker for tobacco smoke during environmental air sampling because it can be degraded substantially when present as a component of tobacco smoke and by as much as 100% when present as pure solanesol on fortified filters during air sampling. Since there is strong evidence that ozone is the agent responsible for the degradation, solanesol appears to be unreliable as a quantitative marker during indoor air sampling when indoor levels of ozone are greater than about 15 ppb. The degree of loss of pure solanesol is directly proportional to the concentration of ozone and the length of the sampling period and depends on the type of 37 mm membrane filter used for air sampling (PTFE or quartz fiber). While the degree of loss of solanesol is inversely proportional to the relative humidity of the air at a sampling rate of 1.7 L min(-1), the degree of loss is virtually independent of relative humidity at a lower sampling rate; i.e., 0.25 L min(-1). A curve of loss of solanesol on a filter versus concentration of ozone from an ozone generator is virtually identical to a curve segment based on atmospheric ozone under the same conditions of air sampling. Oxidation of solanesol by ozone to approximately 25 to 60% completion produces at least three series of products for a total of at least 26 compounds: (1) isoprenoid acetones, (2)omega-hydroxyisoprenoid acetaldehydes, and (3) isoprenoid oxoaldehydes. All products in each series were tentatively identified as their derivatives with 2-(p-aminophenyl)ethanol (APE) by electrospray mass spectrometry (ES-MS). Ten ozonation products were detected as their 2,4-dinitrophenylhydrazine derivatives by HPLC at 360 nm: 4-oxopentanal and nine isoprenoid acetones (acetone, 6-methyl-5-hepten-2-one, geranylacetone, farnesylacetone, tetraprenylacetone, geranylfarnesylacetone, farnesylfarnesylacetone, farnesylgeranylgeranylacetone and bombiprenone.     

The rate of reaction of methyl radicals with ozone

The absolute rate constant for the reaction of methyl radicals with ozone has been measured as a function of temperature. Small concentrations of CH₃ were generated by flash photolyzing CH₃NO₂ at 193 nm with an ArF laser. A photoionization mass spectrometer was used to follow the rate of decay of CH₃ at various ozone concentrations. The resulting rate constants could be fit by the expressions over the temperature range of 243–384 K. These rate constants can be modeled by simple transition state theory using reasonable parameters for the activated complex. Use of this rate constant shows that less than 1% of the methyl radicals formed in the stratosphere react with ozone.