Kinetic analysis of the pathways to naphthalene formation from phenyl + 1,3-Butadiyne reaction

Having a better understanding of polycyclic aromatic hydrocarbon (PAH) formation under flame conditions contributes to optimizing the fuel reforming process, where soot poisons the downstream catalyst. In this work, the phenyl + 1,3-Butadiyne reaction is systematically investigated to examine its contribution to naphthalene formation. The reaction potential energy surfaces were calculated using DFT/M06–2X/cc-pvtz and G4 methods. The temperature- and pressure-dependent reaction rate constants were calculated using RRKM theory with solving master equation. The results revealed that 2-naphthyl could be directly formed by phenyl + 1,3-Butadiyne reaction. With H assistance, naphthalene could be formed by the pathway of phenyl + 1,3-Butadiyne → C₆H₅CHCCCH (+H) → C₆H₅CHCHCCH (+H) →naphthalene +H. The proposed pathway is kinetically favorable, and featured by relatively low energy barrier. The importance of the proposed pathway reaction was confirmed in a premixed and a diffusion C₂H₄/O₂/Ar flame simulations, where the enhancement of naphthalene by the investigated reactions is notable. The mole fraction of A₂ is promoted by a factor of 10% in premix C₂H₄/O₂/Ar flame and 30% in C₂H₄/O₂/Ar counterflow flame, bringing the prediction results closer to the experimental results. The relative contribution of different reaction route to A₂ formation is evaluated for HACA, cyclopentadienyl radical-cyclopentadienyl radical, phenyl-vinylacetylene[1], benzyl radical-propargyl radical, indene-CH₂ and phenyl-1,3-Butadiyne routes in premixed and diffusion C₂H₄/O₂/Ar flames. This work suggests that the PAH growth by 1,3-Butadiyne addition reaction is an effective pathway for A₂ formation, which should be considered in future PAH mechanism.     

Comprehensive visualization of detonation-diffraction structures and sizes in unstable and stable mixtures

The geometry and characteristic length of diffraction and re-initiation during a two-dimensional detonation propagation were revealed by visualization. C₂H₄ + 3O₂ (unstable), 2C₂H₂ + 5O₂ + 7Ar (stable) and 2C₂H₂ + 5O₂ + 21Ar (stable) were used as the test mixtures. Experiments were performed over the deviation angle range from 30° to 150° and the initial pressure range from 15.8 to 102.3 kPa. By self-emitting photography, we confirmed that the geometry and the characteristic length of diffraction are not different among test gases, with the exception of the fan-like structure of re-initiation that occurred regardless of whether the mixture was unstable or stable. We conducted a compensative experiment by changing the deviation angle and initial pressure, and summarized the detonation diffraction by shadowgraph. At deviation angles larger than 60°, we measured the distances from the vertex of the channel corner to the point where the transverse detonation wave reflected on the under wall (= wall reflection distance) and confirmed that wall reflection distances are approximately in the range of 10–15 times the cell width, whether the mixture is unstable or stable.     

Dielectric barrier discharge plasma torch treatment of pyrolysis fuel oil in presence of methane and ethane

For the first time, atmospheric-pressure low-temperature plasma treatment of pyrolysis fuel oil (PFO) was investigated in dielectric barrier discharge (DBD) plasma torch reactor. Main parameters including working gas flow rate and Ar/CH₄ ratio along with the effects of separate Ar/C₂H₆ on the cracking of PFO were studied. By increasing the flow of argon and methane, the production rate of hydrocarbons containing ethane, ethylene, acetylene, propane, propylene, C₄, and C₅ increased from 1.72 to 10.48 ml/min for 4000 ml/min argon plus 400 ml/min methane as the working gas. In this case, the production rate of hydrogen increases from 10.58 to 56.86. The production rate of hydrocarbons increased from 3.53 to 13.5 ml/min by decreasing Ar/CH₄ ratio from 40 to 5.6. By changing the type of working gas from methane to ethane, the production of hydrocarbons considerably increased from 6.47 to 17.75 ml/min.     

Enhancement of inner tube formation from peapods in de-pressurized inert gas environment

C₆₀ molecules encased in single-wall carbon nanotubes, so-called peapods, can be transformed into small-diameter tubes inside the host tubes after high-temperature heat treatment in vacuum at ∼1200 °C. Here, we report an experiment on high-temperature heat treatment of peapods in inert gas environment, and show the evidence of enhancing the formation rate of inner tubes, the rate being more than ∼6 times higher in Ar environment and ∼9 times higher in He than that in vacuum. This means that the inert gas atoms markedly accelerate the polymerization of C₆₀. In contrast to Ar and He, it is found that H₂ gas does not enhance the C₆₀ polymerization. PACS 61.46.Fg; 81.05.Tp; 82.60.Qr     

Spectroscopic investigations of microwave microplasmas in various gases at atmospheric pressure

In this paper results of the experimental investigations of a coaxial microwave (2.45 GHz) microplasma source (MMS) with graphite or tungsten inner conductor operated in Ar, N₂ and Ar/C₂H₂ mixture at atmospheric pressure are presented. The microwave power absorbed by the microplasmas and the intensity of UV-C emission from the microplasmas were measured. Using optical emission spectroscopy, the electron number density in Ar microplasma, and rotational and vibrational temperatures in N₂ and Ar/C₂H₂ microplasmas were determined. All experiments were performed with a gas flow rate from 0.3 to 8 l/min and absorbed microwave power from 5 to 300 W. The simplicity of the MMS, stability of its operation with atmospheric pressure gases, and parameters of the microplasmas allow concluding that the MMS can be used in various applications.     

On the direct formation of HO2 radicals after 248 nm irradiation of benzene C6H6 in the presence of O2

We present in this work the direct observation of HO₂ radicals after irradiation of benzene C₆H₆ at 248 nm in the presence of O₂. HO₂ radicals have been unambiguously identified using the very selective and sensitive detection of continuous wave cavity ring-down spectroscopy (cw-CRDS) coupled to a laser photolysis reactor. HO₂ radicals were detected in the first vibrational overtone of the OH stretch at 6638.20 cm^-1, using a DFB diode laser. This reaction might be important because 248 nm photolysis of H₂O₂ has often been used in the past for studying the OH^•-initiated degradation of C₆H₆, often using a large excess of C₆H₆ over H₂O₂. The possible importance of the title reaction with respect to these former laboratory studies has been quantified through comparison with HO₂ ^• signals obtained from 248 nm photolysis of H₂O₂: one obtains under our conditions (excess O₂ and total pressure of 6.6 kPa helium) from the 248 nm irradiation of identical initial concentrations [C₆H₆]=[H₂O₂] the following relative initial radical concentrations: [HO₂ ^•]=(0.28±0.05)×[OH^•]. Experiments with various O₂ concentrations have revealed that the origin of the HO₂ radicals is not the reaction of H-atoms with O₂, but must originate from the reaction of O₂ with excited C₆H₆ ^*. The quantum yield of C₆H₆ ^* formation has been deduced to ϕ=0.2±0.1. PACS  42.62.Fi; 82.20.Pm; 82.33.Tb     

Growth of multiwalled carbon nanotubes from acetylene over in situ formed Co nanoparticles on MgO support

The performance of Co catalysts supported on MgO at different Co loading (10%-75%) for the formation of carbon nanotubes through acetylene decomposition at 600 ^°C with H₂/C₂H₂ mixture for 1 h is investigated. The yield of MWNTs increases with an increase in Co loading (up to 50%). Starting from 1 g of catalyst precursor, about 8 g of MWNTs was obtained. The XRD patterns of catalyst precursor indicate the presence of cobalt in oxidic phase that eventually transformed into the catalytically active Co nanoparticles (12-18 nm) under the influence of acetylene and was responsible for the growth of coiled-like multi-walled CNTs as revealed by SEM and HRTEM images. It is suggested that bending in coil shaped MWNTs has the potential for functionalization for its biomedical applications.     

Synthesis of coiled carbon nanotubes on Co/Al2O3 catalysts in a fluidised-bed

Mixtures of regularly coiled and straight multi-walled carbon nanotubes (MWNTs) were synthesised on alumina supported Co catalysts prepared by pH controlled, wet impregnation. The synthesis reaction was performed under C₂H₂:H₂:N₂ at 750 °C in a fluidised-bed for 30 min. Scanning electron microscopy/energy dispersive X-ray spectroscopy shows good distribution of the active Co particles on the surface of the alumina support. Determined from 10 individual SEM images from the same product batch, the CNTs present are typically from 10 to 40 nm in diameter. Thermogravimetric analysis (TGA) and Raman spectroscopy indicate the total oxidative weight loss is independent of pH during catalyst preparation. This study is the first to report the use of a fluidised-bed for the synthesis of coiled MWNTs, using alumina supported Co catalysts.     

Comparison of CH4/H2 and C2H6/H2 inductively coupled plasma etching of ZnO

CH₄/H₂-based discharges are attractive for dry etching of single crystal ZnO because of their non-corrosive nature. We show that substitution of C₂H₆ for CH₄ increases the ZnO etch rate by approximately a factor of 2 both with and without any inert gas additive. The C₂H₆/H₂/Ar mixture provides a strong enhancement over pure Ar sputtering, in sharp contrast to the case of CH₄/H₂/Ar. The threshold ion energy for initiating etching is 42.4 eV for C₂H₆/H₂/Ar and 59.8 eV for CH₄/H₂/Ar. The etched surface morphologies were smooth, independent of the chemistry and the Zn/O ratio in the near-surface region was unchanged within experimental error after etching with both chemistries. The plasma etching improved the band-edge photoluminescence intensity and suppressed the deep level emission from the bulk ZnO under our conditions, due possibly to removal of surface contamination layer.     

Ultrahigh Electron Emissive Carbon Nanotubes with Nano-sized RuO2 Particles Deposition

Multi-wall carbon nanotubes (MWNTs) have a great commercial potential as electron field emitters, but suffer from fundamental problems such as stability and brightness. By depositing the MWNTs with nano-sized ruthenium dioxide (RuO₂) particles, a new high performance emitter has been developed. When compared to MWNTs, the MWNTs impregnated with 1–2 nm sized RuO₂ have superior and more efficient electrical characteristics. MWNTs supported by a silicon substrate showed a reduction in the onset voltage from 5.4 to 4 V/μm after RuO₂ impregnation. The long-term stability of the impregnated MWNTs is also demonstrated with only a 20% increase in applied voltage required after 700 h operation at 40 mA/cm².     

Formation of soot particles in pyrolysis and oxidation of aliphatic and aromatic hydrocarbons: Experiments and detailed kinetic modeling

Experiments on pyrolysis and oxidation of rich mixtures of various aliphatic and simple aromatic hydrocarbons in reflected shock waves have been performed. The mixtures C₂H₂/Ar, C₂H₆/Ar, C₂H₄/Ar, C₂H₄/O₂/Ar, CH₄/Ar, CH₄/O₂/Ar, C₃H₈/Ar, C₃H₆/Ar, toluene/Ar, and benzene/Ar were studied. The yield of soot and the temperature of soot particles were determined experimentally by the double-beam absorption emission method. The kinetic model of soot formation during the pyrolysis and oxidation of rich mixtures of aliphatic and aromatic hydrocarbons complemented with a set of nucleations of soot particles from both polyaromatic fragments and unsaturated aliphatic hydrocarbons was suggested. This kinetic model of soot formation was successfully tested. It describes the experimental literature data on the yield of the products of pyrolysis and oxidation of acetylene and diacetylene in a shock tube. The results of our experiments and kinetic calculations of the time, temperature, and concentration dependences are in good agreement for all hydrocarbons under study. All the kinetic parameters of the model remained strictly constant.     

Single-pulse shock-tube study on the pyrolysis of small esters (ethyl and propyl propanoate,isopropyl acetate) and methyl isopropyl carbonate

Single-pulse shock-tube experiments were used to study the thermal decomposition of selected oxygenated hydrocarbons: Ethyl propanoate (C₂H₅OC(O)C₂H₅; EP), propyl propanoate (C₃H₇OC(O)C₂H₅; PP), isopropyl acetate ((CH₃)₂HCOC(O)CH₃; IPA), and methyl isopropyl carbonate ((CH₃)₂HCOC(O)OCH₃; MIC) The consumption of reactants and the formation of stable products such as C₂H₄ and C₃H₆ were measured with gas chromatography/mass spectrometry (GC/MS). Depending on the considered reactant, the temperatures range from 716–1102 K at pressures between 1.5 and 2.0 bar. Rate-coefficient data were obtained from first-order analysis. All reactants primarily decompose by six-center eliminations: EP → C₂H₄ + C₂H₅COOH (propionic acid); PP → C₃H₆ + C₂H₅COOH; IPA → C₃H₆ + CH₃COOH (acetic acid); MIC → C₃H₆ + CH₃OC(O)OH (methoxy formic acid). Experimental rate-coefficient data can be well represented by the following Arrhenius expressions: k(EP → products) = 10^13.49±0.16 exp(−214.95±3.25 kJ/mol/RT) s⁻¹; k(PP → products) = 10^12.21±0.16 exp(–191.21±2.79 kJ/mol/RT) s⁻¹; k(IPA → products) = 10^13.10±0.31 exp(–186.38±5.10 kJ/mol/RT) s⁻¹; k(MIC → products) = 10^12.43±0.29 exp(–165.25±4.46 kJ/mol/RT) s⁻¹. The determination of rate coefficients was based on the amount of C₂H₄ or C₃H₆ formed. The potential energy surface (PES) of the thermal decomposition of these four reactants was determined with the G4 composite method. A master-equation analysis was conducted based on energies and molecular properties from the G4 computations. The results indicate that the length of a linear alkyl substituent does not significantly influence the rate of six-center eliminations, whereas the change from a linear to a branched alkyl substituent results in a significant reactivity increase. The comparison between rate-coefficient data also shows that alkyl carbonates have higher reactivity towards decomposition by six-center elimination than esters. The results are discussed in in the context of reactivity patterns of carbonyl compounds.     

Mössbauer spectroscopy studies of the preparation steps of unsupported Fe- and FeMo-sulfide hydrotreating catalysts

Both the gas atmosphere (Ar, 15% H₂S−H₂, H₂) and the temperature of treatment strongly affect the distribution of iron atoms among different phases (FeS₂-pyrite, Fe_1−x S-pyrrhotite, FeS-troilite, mixed Fe−Mo−S structure) in Fe- and FeMo sulfide catalysts. In FeMo sulfide catalysts FeS₂ (pyrite) and the Fe−Mo−S structure are stabilized by MoS₂.     

High-sensitivity CW Fabry–Pérot enhanced spectroscopy of CO2 and C2H2 using a 1064-nm Nd:YAG laser

2 (20⁰3←00⁰0) R(6), C₂H₂ (2100⁰1¹←0000⁰0⁰) R(12), and C₂H₂ (1200⁰3¹←0000⁰0⁰) P(6) near 1064 nm using CW cavity ring-down spectroscopy and CW cavity transmission. An effective interaction length of more than 30 km was achieved (cavity finesse ≈86000) and the sensitivity was ≈10^-8 cm^-1. Higher sensitivity of 3.3×10^-11 cm^-1/ was obtained by cavity-enhanced wavelength modulation spectroscopy. The absorption coefficients, pressure broadening coefficients, lineshapes, line strengths, and absolute wavelengths of those lines were determined, some of them for the first time. The measurements were carried out over a wide range of pressures from the strongly inhomogeneous to the strongly homogeneous region. Received: 25 May 1998/Revised version: 28 July 1998     

A new one-step synthesis method for coating multi-walled carbon nanotubes with iron oxide nanorods

A facile solution-chemical method has been developed to be capable of covering a multiwalled carbon nanotube (MWNTs) with iron oxide nanorods without using any bridging species. MWNTs in this composite were decorated randomly by α-Fe₂O₃ nanorods with diameters in the range of 3–5 nm and lengths of 15–30 nm. The formation route to anchor α-Fe₂O₃ nanorods onto MWNTs was proposed as the intercalation and adsorption of iron ions onto the wall of MWNTs, followed by the nucleation and growth of α-Fe₂O₃ nanorods. α-Fe₂O₃/MWNTs nanocomposites show specific high Brunauer–Emmett–Teller surface areas. The photocatalytic activity experiment indicated that the prepared α-Fe₂O₃/MWNTs nanocomposites exhibited a higher photocatalytic activity for the photocatalytic decolorization of rhodamine B aqueous solution under the visible-light illumination than the single phase α-Fe₂O₃ samples. This methodology made the synthesis of MWNTs-nanorods composites possible and may be further extended to prepare more complicated nanocomposites based on MWNTs for technological applications.     

Massive liquid Ar and Xe detectors for direct Dark Matter searches

A novel experiment for direct search for Dark Matter with liquid argon double-phase chamber with a mass of liquid Ar up to several hundred tons is proposed. To suppress the β, γ and n ₀ backgrounds, the comparison of scintillation and ionization signals for every event is suggested. The addition in liquid Ar of photosensitive Ge(CH₃)₄ or C₂H₄ and suppression of triplet component of scintillation signals ensures the detection of scintillation signals with high efficiency and provides a complete suppression of the electron background. For the detection of photoelectrons and ionization electrons, highly stable and reliable GEM detectors must be used.     

Oxidation of di-n-propyl ether: Characterization of low-temperature products

The oxidation of di-n-propyl-ether (DPE) was performed in a jet-stirred reactor at 1 and 10 atm, at residence times of 1 and 0.7 s, respectively, and initial fuel concentrations of 5000 and 1000 ppm at 1 and 10 atm, respectively. Atmospheric pressure experiments were used for characterization of cool flame products. The 10 atm experiment provided KHPs profile vs. temperature and mole fraction profiles of stable species which were obtained through sonic probe sampling, gas chromatography, Fourier transform infrared spectrometry analyses. High resolution mass spectrometry analyses (HRMS) with syringe direct injection or ultra-high-pressure liquid chromatography coupling was used to characterize hydroperoxides (C₃H₈O₂, C₆H₁₄O₃), diols (C₆H₁₄O₃), ketohydroperoxides (C₆H₁₂O₄), carboxylic acids, and highly oxygenated molecules (C₆H₁₂O₆, C₆H₁₂O₈) resulting from up to four O₂ additions on fuel's radicals. Heated electrospray and atmospheric pressure chemical ionizations (HESI and APCI) were used in positive and negative mode. Whereas the CH₂ groups neighboring the ether function are the most favorable sites for H-atom abstraction reactions, speciation indicated that other sites can react by metathesis forming a large pool of intermediates. Our kinetic reaction mechanism represents the experimental data for most of the stable species but need to be expended for simulating the formation of newly detected species.     

The research on the synthesis and structure of some new ferrocene derivatives

The reaction of C₅H₄RLi with FeCl₂ gave nine new compounds of Fe(C₅H₄R)₂ [R=C(CH₃)₂C₆H₄CH₃-p(-m,-o), C₆H₁₀C₆H₅, C(Me)₂C₆C₄OCH_3-o, C₆H₁₀C₆H₄CH₃-p(,-m,-o), C₆H₁₀C₆H₄OCH₃-p]. The compositions of compounds were determined through elementary analysis. The structural determination was made by IR and H²NMR. Mossbauer spectia were taken at room temperature. The IS and QS values are 0.41–0.45mm/s and 2.3–2.5mm/s., respectively. The solid state structure of the complex has been determined by a single crystal x-ray diffraction study, crystal data for Fe[C₅H₄C(CH₃)₂C₆H₅]₂: a=17.988(2)A, b=17. 411(2)A, c=7.496(1)A, α=β=90°, r=112.23°, Z=4, monoclinic form, space group C2/c. Our conclusions are: in π-acceptor ligand, the nucleophilic substituents decrease and the electrophilic substituts increase the metal to ligand electron cloud shift, which results in a decrease or an increase in the strength of the coordinate bonds and in the stabilization of the complexes by their steric effect.     

Evaluation of Sr- and Mn-substituted LaAlO3 as potential SOFC anode materials

Lanthanum–aluminate-based oxides, (La_0.8Sr_0.2)_1−yAl_1−xMn_xO_3−δ (x = 0, 0.3, 0.5; y = 0 or 0.06) (LSAM), were synthesized and evaluated in detail as potential anode materials for solid oxide fuel cells (SOFCs). The electrical conductivity of LSAM (Mn ≥ 30 mol%) is dominated by p-type electronic conduction and can be treated as a diluted system of lanthanum manganites, (La,Sr)MnO₃. At 810 °C, the electrical conductivity of (La_0.8Sr_0.2)_0.94Al_0.5Mn_0.5O_3−δ (LSAM8255b) reaches 12 S/cm in air and 2.7 S/cm in humidified Ar/4% H₂ (p(O₂) ≈ 10^− 18 bar). The thermal expansion coefficients of LSAM8255a and LSAM8255b match YSZ very well and no chemical reaction was observed between these two perovskite materials and YSZ up to at least 1400 °C. Fairly good electrochemical performance was observed for an LSAM8255b–YSZ composite anode. At 850 °C, the polarization resistances are only 0.34 and 0.50 Ω cm² in wet (∼3% H₂O) Ar/20% H₂ and wet Ar/20% CH₄, respectively. In addition, an exposure to Ar/20% CH₄/3% H₂O for 35 h did not cause any apparent carbon deposition on the electrode. However, the chemical stability of LSAM8255a and LSAM8255b in a typical anode environment under open circuit conditions does not seem sufficient, leading to performance degradation with time in wet Ar/20% H₂ or wet Ar/20% CH₄. Furthermore, relatively large chemical expansion (0.3–0.5%) was observed when the atmosphere was switched from air to wet Ar/4% H₂, which might cause intolerable stress on the thin film electrolyte layer for a large-area anode-supported planar SOFC, but which might be tolerable for small geometries or electrolyte-supported SOFCs.     

Kinetics for the reactions of phenyl with methanol and ethanol: Comparison of theory and experiment

The kinetics of the C₆H₅ reactions with CH₃OH and C₂H₅OH has been measured by pulsed-laser photolysis/mass-spectrometry (PLP/MS) employing acetophenone as the radical source. Kinetic modeling of the benzene formed in the reactions over the temperature range 306–771 K allows us to reliably determine the total rate constants for H-abstraction reactions. In order to improve our low temperature measurements down to 304 K we have also applied the cavity ring-down spectrometric technique using nitrosobenzene as the radical source. Both sets of data agree closely. A weighted least-squares analysis of the two complementary sets of data for the two reactions gave the total rate constants k(CH₃OH) = (7.82 ± 0.44) × 10¹¹ exp [?(853 ± 30)/T] and k(C₂H₅OH) = (5.73 ± 0.58) × 10¹¹ exp [?(1103 ± 44)/T] cm³ mol^?1 s^?1 for the temperature range studied. Theoretically, four possible product channels of the C₆H₅ + CH₃OH reaction producing C₆H₆ + CH₃O, C₆H₆ + CH₂OH, C₆H₅OH + CH₃ and C₆H₅OCH₃ + H and five possible product channels of the C₆H₅ + C₂H₅OH reaction producing C₆H₆ + C₂H₅O, C₆H₆ + CH₂CH₂OH, C₆H₆ + CH₃CHOH, C₆H₅OH + CH₃CH₂ and C₆H₅OCH₂CH₃ + H have been computed at the G2M//B3LYP/6?311+G(d, p) level of theory. The hydrogen abstraction channels were predicted to have lower energy barriers than those for the substitution reactions and their rate constants were calculated by the microcanonical variational transition state theory at 200–3000 K. The predicted rate constants are in good agreement with the experimental values. Significantly, the rate constant for the CH₃OH reaction with C₆H₅ was found to be greater than that for the C₂H₅OH reaction and both reactions were found computationally to be dominated by H-abstraction from the hydroxyl group attributable to the affinity of the phenyl toward the OH group and the predicted lower energy barriers for the OH attack.