Natural radioactivity and human exposure by raw materials and end product from cement industry used as building materials

During the manufacturing process in the cement industry, raw materials of different levels of natural radioactivity are utilized. In this study we present the radiological impact of cements as a building material and the different raw materials used in their manufacture. A total of 218 samples of raw materials and their end product cements were collected from the cement industry of Macedonia (The Former Yugoslav Republic) during the period 2005–2007. The specific activities, evaluated by gamma spectrometry analysis, showed the highest mean specific activity in fly ash (²²⁶Ra, 107 ± 45 Bq kg^?1; ²³²Th, 109 ± 30 Bq kg^?1; ⁴⁰K, 685 ± 171 Bq kg^?1), which is used as a raw material. However, the final cement product usually has relatively lower activity compared with the activity of the raw material and the mean specific activity of the final cement products were lower (²²⁶Ra, 42 ± 10 Bq kg^?1; ²³²Th, 28 ± 6 Bq kg^?1; ⁴⁰K, 264 ± 50 Bq kg^?1). The radium equivalent activity and the hazard index were calculated for each sample to assess the radiation hazard. The mean annual effective dose originating from the cements was found to be 111 ± 22 μSv y^?1, which is below the recommended EC limit of 300 μSv y^?1.     

Measuring radon flux across active faults: Relevance of excavating and possibility of satellite discharges

Searching for gas exhalation around major tectonic contacts raises important methodological issues such as the role of the superficial soil and the possible long distance transport. These effects have been studied on the Xidatan segment of the Kunlun Fault, Qinghai Province, China, using measurement of the radon-222 and carbon dioxide exhalation flux. A significant radon flux, reaching up to 538 ± 33 mBq m^?2 s^?1 was observed in a 2–3 m deep trench excavated across the fault. On the soil surface, the radon flux varied from 7 to 38 mBq m^?2 s^?1, including on the fault trace, with an average value of 14.1 ± 1.0 mBq m^?2 s^?1, similar to the world average. The carbon dioxide flux on the soil surface, with an average value of 12.9 ± 3.3 g m^?2 day^?1, also remained similar to regular background values. It showed no systematic spatial variation up to a distance of 1 km from the fault, and no clear enhancement in the trench. However, a high carbon dioxide flux of 421 ± 130 g m^?2 day^?1 was observed near subvertical fractured phyllite outcrops on a hill located about 3 km north of the fault, at the boundary of the large-scale pull-apart basin associated with the fault. This high carbon dioxide flux was associated with a high radon flux of 607 ± 35 mBq m^?2 s^?1. These preliminary results indicate that, at the fault trace, it can be important to measure gas flux at the bottom of a trench to remove superficial soil layers. In addition, gas discharges need to be investigated also at some distance from the main fault, in zones where morphotectonics features support associated secondary fractures.     

A highly luminescent complexes of Eu(III) and Tb(III) with norfloxacin and gatifloxacin doped in sol–gel matrix: A comparable approach of using silica doped Tb(III) and Eu(III) as optical sensor

Highly luminescent complexes of Eu and Tb ions with norfloxacin (NFLX) and gatifloxacin (GFLX) were prepared in sol–gel matrix. The red and green emissions of Eu and Tb ions were obtained by the energy transfer from the triplet state of (NFLX) and (GFLX) to the excited emitting states (⁵D₀ and ⁵D₄) of Eu and Tb, respectively. The intensity of the electric field emission bands (⁵D₀→⁷F₂, 617 nm and ⁵D₄→⁷F₅, 545 nm) of Eu and Tb ions were proportional to the concentration of (NFLX at pH 6.0) and (GFLX at pH 3.5) in acetonitrile with excitation wavelengths (λ_ex) (340 and 395) and (370 and 350 nm) for Eu and Tb ions, respectively. The monitored luminescence intensity of the system showed a good linear relationship with the concentration of NFLX within a range of 5×10^?9–5.8×10^?6 and 5×10^?8–1.0×10^?6 mol L^?1 with a correlation coefficient of 0.990, and for GFLX within a range of 2.4×10^?9–3.2×10^?5 and 5×10^?8–8.0×10^?6 mol L^?1 with a correlation coefficient of 0.995. The detection limit (LOD) was determined as 3.0×10^?9 and 1.0×10^?8 mol L^?1 for NFLX and 1.6×10^?10 and 2.0×10^?8mol L^?1 for GFLX. The limit of quantification (LOQ) is 9×10^?9 and 3.0×10^?8 and 4.8×10^?10 and 6.0×10^?8 in case of Eu and Tb, respectively.     

Instant controlled pressure drop technology and ultrasound assisted extraction for sequential extraction of essential oil and antioxidants

The instant controlled pressure drop (DIC) technology enabled both the extraction of essential oil and the expansion of the matrix itself which improved solvent extraction. The sequential use of DIC and Ultrasound Assisted Extraction (UAE) triggered complementary actions materialized by supplementary effects. We visualized these combination impacts by comparing them to standard techniques: Hydrodistillation (HD) and Solvent Extraction (SE). First, the extraction of orange peel Essential Oils (EO) was achieved by HD during 4 h and DIC process (after optimization) during 2 min; EO yields was 1.97 mg/g dry material (dm) with HD compared to 16.57 mg/g dm with DIC. Second, the solid residue was recovered to extract antioxidant compounds (naringin and hesperidin) by SE and UAE. Scanning electron microscope showed that after HD the recovered solid shriveled as opposite to DIC treatment which expanded the product structure. HPLC analyses showed that the best kinetics and yields of naringin and hesperidin extraction was when DIC and UAE are combined. Indeed, after 1 h of extraction, DIC treated orange peels with UAE were 0.825 ± 1.6 × 10^?2 g/g of dry material (dm) for hesperidin and 6.45 × 10^?2 ± 2.3 × 10^?4 g/g dm for naringin compared to 0.64 ± 2.7 × 10^?2 g/g of dry material (dm) and 5.7 × 10^?2 ± 1.6 × 10^?3 g/g dm, respectively with SE. By combining DIC to UAE, it was possible to enhance kinetics and yields of antioxidant extraction.     

Dissociation of dimethyl ether at high temperatures

The decomposition of dimethyl ether (CH₃OCH₃) has been investigated behind incident shock waves in a diaphragmless shock tube using laser schlieren densitometry, LS (T = 1500–2450 K, P = 57 ± 4, 125 ± 5 and 253 ± 12 Torr). The LS density gradient profiles were simulated and excellent agreement was found between the simulations and experimental profiles. Rate coefficients for CH₃OCH₃ → CH₃O + CH₃ were obtained. They showed strong fall-off, and at the lower end of the experimental temperature range are close to the low pressure limit. First order rate coefficient expressions were determined over 1500 < T < 2450 K. k_57Torr = (3.10 ± 1.0) × 10⁷⁹T^?19.03 exp(?54417/T) s^?1, k_125Torr = (1.12 ± 0.3) × 10⁸³T^?19.94 exp(?55554/T) s^?1and k_253Torr = (1.02 ± 0.3) × 10⁷³T^?17.09 exp(?51500/T) s^?1. The effect of a roaming channel for decomposition of dimethyl ether was assessed and the best agreement was obtained with 1% dissociation of DME via the roaming path.     

The inactivation kinetics of polyphenol oxidase in mushroom (Agaricus bisporus) during thermal and thermosonic treatments

The effect of thermal and thermosonic treatments on the inactivation kinetics of polyphenol oxidase (PPO) in mushroom (Agaricus bisporus) was studied in 55–75 °C temperature range. In both the processes, the inactivation kinetics of PPO followed a first-order kinetics (R² = 0.941–0.989). The D values during thermal inactivation varied from 112 ± 8.4 min to 1.2 ± 0.07 min while they varied from 57.8 ± 6.1 min to 0.88 ± 0.05 min during thermosonic inactivation at the same temperature range. The activation energy during thermal inactivation was found to be 214 ± 17 kJ/mol, while it was 183 ± 32 kJ/mol during thermosonic inactivation. The inactivating effect of combined ultrasound and heat was found to synergistically enhance the inactivation kinetics of PPO. The D values of PPO decreased by 1.3–3 times during thermosonic inactivation compared to the D values of PPO during thermal inactivation at the temperature range. Therefore, thermosonication can be further developed as an alternative to “hot break” process of mushroom.     

Refinements of the WKMC empirical line lists (5852–7919 cm−1) for methane between 80 K and 296 K

During the last 4 years, empirical line lists for methane at room temperature and at 80 K were constructed from spectra recorded by (i) differential absorption spectroscopy (DAS) in the high energy part of the tetradecad (5852?6195 cm^?1) and in the icosad (6717–7589 cm^?1) and (ii) high sensitivity CW-Cavity Ring Down Spectroscopy (CRDS) in the 1.58 μm and 1.28 μm transparency windows (6165–6750 cm^?1 and 7541–7919 cm^?1, respectively). We have recently constructed the global line lists for methane in “natural” isotopic abundance, covering the spectral region from 5854 to 7919 cm^?1 (Campargue A, Wang L, Kassi S, Mondelain D, Bézard B, Lellouch E, et al., An empirical line list for methane in the 1.26–1.71 μm region for planetary investigations (T=80–300 K). Application to Titan, Icarus 219 (2012) 110–128). These WKMC (Wang, Kassi, Mondelain, Campargue) empirical lists include about 43,000 and 46,420 lines at 80±3 K and 296±3 K, respectively. The “two temperature method” provided lower state energy values, E_emp, for about 24,000 transitions allowing us to account satisfactorily for the temperature dependence of the methane absorption over the considered region. The obtained lists have been already successfully applied in a large range of temperature conditions existing on Titan, Uranus, Pluto, Saturn and Jupiter.In the present contribution, we provide some improvements to our lists by using literature data to extend the set of lower state energy values and by correcting the distortion of the high E_emp values (J>10) due to the temperature gradient existing in the cryogenic cell used for the recordings. The proposed refinements are found to have an overall limited impact but they may be significant in some spectral intervals below 6500 cm^?1.The new version of our lists at 80 K and 296 K is provided as Supplementary Material: the WKMC@80K+ and WKMC@296K lists are adapted for planetary and atmospheric applications, respectively. The WKMC@80K+ list is made applicable over a wider range of temperatures and shows satisfactory extrapolation capabilities up to room temperature. It was obtained by transferring to the 80 K list the 27,580 single lines present only in the 296 K list, with corresponding lower state energy values chosen to make them below the detectivity limit at 80 K.In the discussion, the different line lists and databases available for methane in the near infrared are compared and some suggestions are given.     

Thermo,Iono and photoluminescence properties of 100 MeV Si7+ ions bombarded CaSiO3:Eu3+ nanophosphor

This paper reports on the thermo (TL), iono (IL) and photoluminescence (PL) properties of nanocrystalline CaSiO₃:Eu³⁺ (1–5 mol %) bombarded with 100 MeV Si⁷⁺ ions for the first time. The effect of different dopant concentrations and influence of ion fluence has been discussed. The characteristic emission peaks ⁵D₀→⁷F_J (J=0, 1, 2, 3, 4) of Eu³⁺ ions was recorded in both PL (1×10¹¹–1×10¹³ ions cm^?2) and IL (4.16×10¹²–6.77×10¹² ions cm^?2) spectra. It is observed that PL intensity increases with ion fluence, whereas in IL the peaks intensity increases up to fluence 5.20×10¹² ions cm^?2, then it decreases. A well resolved TL glow peak at ～304 °C was recorded in all the ion bombarded samples at a warming rate of 5 °C s^?1. The TL intensity is found to be maximum at 5 mol% Eu³⁺ concentration. Further, TL intensity increases sub linearly with shifting of glow peak towards lower temperature with ion fluence.     

Hydrothermal synthesis of functionalized CdS nanoparticles and their application as fluorescence probes in the determination of uracil and thymine

A novel, sensitive, and convenient method for the determination of uracil and thymine by functionalized CdS nanoparticles (NPs) was proposed. CdS NPs were prepared by hydrothermal process and modified with thioglycollic acid (TGA) in aqueous solution. The fluorescence intensity of functionalized CdS NPs was quenched in the presence of uracil or thymine. Under optimal conditions, the relative fluorescence intensity (F₀/F) was proportional to the concentration in the range of 9.0×10^?6–1.0×10^?4 mol/L for uracil (r=0.9985) and 8.8×10^?7–1.5×10^?4 mol/L for thymine (r=0.9960). The corresponding detection limits were 9.6×10^?7 mol/L and 3.2×10^?7 mol/L, respectively. In addition, the possible quenching mechanism was also discussed.     

Hydrogen permeation of tungsten phosphate glass thin films

Thin films of tungsten phosphate glasses were deposited on a Pd substrate by a pulsed laser deposition method and the flux of hydrogen passed thorough the glass film was measured with a conventional gas permeation technique in the temperature range 300–500 °C. The glass film deposited at low oxygen pressure was inappropriate for hydrogen permeation because of reduction of W ions due to oxygen deficiency. The membrane used in the hydrogen permeation experiment was a 3-layered membrane and consisted of Pd film (~ 20 nm), the glass film (≤ 300 nm) and the Pd substrate (250 µm). When the pressure difference of hydrogen and thickness of the glass layer were respectively 0.2 MPa and ~ 100 nm, the permeation rate through the membrane was 2.0 × 10^? 6 mol cm^? 2 s^? 1 at 500 °C. It was confirmed that the protonic and electronic mixed conducting glass thin film show high hydrogen permeation rate.     

Differentiation of central gland prostate cancer from benign prostatic hyperplasia using monoexponential and biexponential diffusion-weighted imaging

PurposeTo investigate biexponential apparent diffusion parameters of prostate central gland (CG) cancer, stromal hyperplasia (SH), and glandular hyperplasia (GH) and compare with monoexponential apparent diffusion coefficient (ADC) value for discriminating prostate cancer from benign hyperplasia.Materials and MethodsTwenty-one CG cancer foci, 23 SH and 26 GH nodules in the CG were analyzed in 39 patients (19 with CG cancer, 20 with peripheral zone cancer but no CG cancer) who underwent preoperative conventional DWI (b-value 0, 1000 s/mm²) and a 10 b-value (range 0 to 3000 s/mm²) DWI. All of the cancer and hyperplastic foci on MR images were localized on the basis of histopathologic correlation. The ADC value of the monoexponential DWI, and the fast apparent diffusion coefficient (ADCf), slow apparent diffusion coefficient (ADCs) value and the fraction of ADCf (f) of the biexponential DWI were calculated for all of the lesions. Receiver operating characteristic (ROC) analysis was performed for the differentiation of CG cancer from SH and GH.ResultsThe ADC values (× 10^? 3 mm²/s) were 0.87 ± 0.11, 1.06 ± 0.15, and 1.61 ± 0.27 in CG cancer, SH and GH foci, respectively, and differed significantly, yielding areas under the ROC curve (AUCs) of 1.00 and 0.80 for the differentiation of carcinoma from GH and SH, respectively. The ADCf (× 10^? 3 mm²/s), ADCs (× 10^? 3 mm²/s) and f for cancer were 1.92 ± 0.38, 0.53 ± 0.17, and 47.7 ± 6.1%, respectively, which were lower than the same values for GH (3.43 ± 0.65, 1.12 ± 0.21, 61.1 ± 8.7%) (all p < 0.01). The ADCf and ADCs for cancer were also lower than those for SH (3.11 ± 0.30, 0.79 ± 0.21) (all p < 0.01). The ADCf yielded AUCs (1.00, p > 0.01) that were comparable to those from ADC for the differentiation of cancer from GH, while ADCf yielded higher AUCs (0.92) compared with ADC (p < 0.01) for the differentiation of cancer from SH. ADCs and f revealed AUCs of 0.97 and 0.90, respectively, for the differentiation of cancer from GH, and the ADCs offered relatively lower AUCs (0.68) for differentiating cancer from SH.ConclusionBiexponential DWI could potentially improve the differentiation of prostate cancer in CG, and the ADCf of the biexponential model offers better accuracy than ADC.     

Structural and electrochemical properties of layered lithium nitridocuprates Li3 − xCuxN

We report a systematic study of the layered lithium nitridocuprates Li_3 ? xCu_xN with 0.1 ≤ x ≤ 0.39. The structural data obtained from experimental XRD patterns, Rietveld refinements and unit cell parameters calculation vs x, indicate that copper (I) substitute interlayer lithium ions in the parent nitride Li₃N to form the Li_3 ? xCu_xN compound without any Li vacancy in the Li₂N^? layer. Electrochemical results report Li insertion into the corresponding layered structures cannot take place in the 1.2/0.02 V voltage range as in the case of lithium into nitridonickelates and nitridocobaltates. However, in the initial charge process of Li_3 ? xCu_xN at 1.4 V leading to a specific capacity higher than 1000 mA h/g, the oxidation of copper and nitride ions is probably involved inducing a strong structural disordering process. As a consequence a new rechargeable electrochemical system characterized by discharge–charge potential of ≈ 0.3 V/1.2 V appears from the second cycle. Cycling experiments 0.02 V voltage/0.02 V range induce a complete destruction of the layered host lattice and the presence of Cu₃N in the charge state suggests a conversion reaction. The capacity recovered in the 1.4/0.02 V range practically stabilizes around 500 mA h/g after 20 cycles.     

Thermodynamics and kinetics of CO and benzene adsorption on Pt(111) studied with pulsed molecular beams and microcalorimetry

The adsorption and desorption of the system CO/Pt(111) and C₆H₆/Pt(111) at 300 K has been investigated with a pulsed molecular beam method in combination with a microcalorimeter. For benzene the sticking probability has been measured in dependence of the coverage θ. For coverages θ > 0.8 transient adsorption is observed. From an analysis of the time-dependence of the molecular beam pulses the rate constant for desorption is determined to be 5.6 s^? 1. With a precursor-mediated kinetic adsorption model this allows to obtain also the hopping rate constant of 95.5 s^? 1. The measured adsorption enthalpies could be best described by (199 ? 77θ ? 51θ²) kJ/mol, in good agreement with the literature values. For CO on Pt(111) also transient adsorption has been observed for θ > 0.95 at 300 K. The kinetic analysis yields rate constants for desorption and hopping of 20 s^?1 and 51 s^?1, respectively. The heats of adsorption show a linear dependence on coverage (131 ? 38θ) kJ/mol between 0 ≤ θ ≤ 0.3, which is consistent with the desorption data from the literature. For higher coverage (up to θ = 0.9ML) a slope of ?63 kJ/mol describes the decrease of the differential heat of adsorption best. This result is only compatible with desorption experiments, if the pre-exponential factor decreases strongly at higher coverage. We found good agreement with recent quantum chemical calculations made for (θ = 0.5ML).     

Electrochemical redox supercapacitors using PVdF-HFP based gel electrolytes and polypyrrole as conducting polymer electrode

Electrochemical redox supercapacitors have been fabricated using polymeric gel electrolytes polyvinylidene fluoride co-hexafluoropropylene (PVdF-HFP)–ethylene carbonate (EC)–propylene carbonate (PC)–MClO₄: M = Li, Na, (C₂H₅)₄N and electrochemically deposited polypyrrole as conducting polymer electrode. The performance of the capacitors have been characterized using a.c impedance spectroscopy, cyclic linear sweep voltammetry and galvanostatic charge–discharge techniques. The capacitors shows larger values of overall capacitance of about 14–25 mF cm^− 2 (equivalent to a single electrode specific capacitance of 78–137 F g^− 1 of polypyrrole), which corresponds to the energy density of 11–19 W h kg^− 1 and power density of 0.22–0.44 kW kg^− 1. The values of capacitance have been found to be almost stable up to 5000 cycles and even more. A comparison indicates that the capacitive behaviour and the capacitance values are not much affected with the size of cations of the salts incorporated in gel electrolytes, rather predominant role of anions is possible at the electrode–electrolyte interfaces. Furthermore the coulombic efficiencies of all the cells were found to be nearly 100% that is comparable to the liquid electrolytes based capacitors.     

High resolution emission spectroscopy of the E2Π–X2Σ+ transition of SrH and SrD

Emission spectra of SrH and SrD have been studied at high resolution using a Fourier transform spectrometer. The molecules have been produced in a high temperature furnace from the reaction of strontium metal vapor with H₂/D₂ in the presence of a slow flow of Ar gas. The spectra observed in the 18 000–19 500 cm^?1 region consist of the 0–0 and 1–1 bands of the E²Π–X²Σ⁺ transition of the two isotopologues. A rotational analysis of these bands has been obtained by combining the present measurements with previously available pure rotation and vibration–rotation measurements for the ground state, and improved spectroscopic constants have been obtained for the E²Π state. The present analysis provides spectroscopic constants for the E²Π state as ΔG(½) = 1166.1011(15) cm^?1, B_e = 3.805503(32) cm^?1, α_e = 0.098880(47) cm^?1, r_e = 2.1083727(89) Å for SrH, and ΔG(½) = 839.1283(23) cm^?1, B_e = 1.918564(15) cm^?1, α_e = 0.034719(23) cm^?1, r_e = 2.1121943(83) Å for SrD.     

Preparation of carbon nanoparticles from electrolysis of molten carbonates and use as anode materials in lithium-ion batteries

The electrochemical reduction of molten Li–Na–K carbonates at 450 °C provides “quasi-spherical” carbon nanoparticles with size comprised between 40 and 80 nm (deduced from AFM measurements). XRD analyses performed after washing and heat-treatment at various temperatures have revealed the presence of graphitised and amorphous phases. The d₀₀₂ values were close to the ideal one obtained for pure graphite. Raman spectroscopy has pointed out surface disordering which increases with increasing temperature of the heat-treatment. The presence of Na and Li on the surface of the carbon powder has been evidenced by SIMS. The maximum Na and Li contents were observed for carbon samples heat-treated at 400 °C. Their electrochemical performances vs. the insertion/deinsertion of lithium cations were studied in 1 M LiPF₆–EC : DEC : DMC (2 : 1 : 2). The first charge–discharge cycle is characterised by a high irreversible capacity as in the case of hard-disordered carbon materials. However, the potential profile in galvanostatic mode is intermediate between that usually observed for graphite and amorphous carbon: rather continuous charge–discharge curves sloping between 1.5 and 0.3 V vs. Li / Li⁺, and successive phase transformations between 0.3 and 0.02 V vs. Li / Li⁺. The best electrochemical performances were obtained with carbon powders heat-treated at 400 °C which exhibits a reversible capacity value of 1080 mAh g^− 1 (composition of Li_2.9C₆). This sample has also both the lowest surface disordering (deduced from Raman spectroscopy), and the highest Na and Li surface contents (deduced from SIMS).     

Analysis of Tb3+- and melittin-binding with the C-terminal domain of centrin in Euplotes octocarinatus

Centrin is a low molecular mass (20 KDa) protein that belongs to the EF-hand superfamily. In this work, the interaction between the Tb³⁺-saturated C-terminal domain of Euplotes octocarinatus centrin (Tb₂-C-EoCen) and 2-p-toluidinylnaphthalene-6-sulfonate (TNS) was investigated using difference UV–vis spectra and the fluorescence spectra methods. In 100 mM N-2-hydroxy-ethylpiperazine-N-2-ethanesulfonic acid (Hepes) at pH 7.4, with the addition of Tb₂-C-EoCen, four new peaks were observed at 265 nm, 278 nm, 317 nm and 360 nm by absorptivity compared with blank solution of TNS. At the same time, the reaction could be measured by fluorescence spectra. The fluorescence emission of TNS was shifted from 480 nm to 445 nm in the presence of Tb₂-C-EoCen. Meanwhile, its fluorescence intensity was increased markedly. The 1:1 stoichiometric ratio of C-EoCen to TNS was confirmed by fluorescence titration curves. The conditional binding constants of TNS with C-EoCen and Tb₂-C-EoCen were calculated to be log K_{(C-EoCen-TNS)}=5.32±0.04  M^?1 and log K_{(Tb2-C-EoCen-TNS)}=5.58±0.12 M^?1, respectively. In addition, the protein of Tb₂-C-EoCen binding with melittin was also studied. Based on the fluorescence titration curves, the 1:1 stoichiometric ratio of Tb₂-C-EoCen to melittin was confirmed. And the conditional binding constant of C-EoCen with melittin was calculated to be log Ka′=6.79±0.17 M^?1.     

The reaction of 2,5-dimethylfuran with hydrogen atoms – An experimental and theoretical study

The kinetics of the reaction of hydrogen atoms with 2,5-dimethylfuran (25DMF), a promising liquid transport biofuel, was experimentally studied in a shock tube at temperatures between 970 and 1240 K and pressures of 1.6 and 4.8 bar. The hydrogen atoms were produced by pyrolysis of ethyl iodide and monitored by atom resonance absorption spectrometry. From the hydrogen atom concentration–time profiles, overall rate coefficients for the reaction H + 25DMF → products (R1) were inferred. The results can be expressed by the Arrhenius equation k₁ = 4.4 × 10^?11 exp(?1180 K/T) cm^?3 s^?1 with an estimated uncertainty of ±30%. A significant pressure dependence was not observed. The results were analyzed in terms of statistical rate theory with molecular and transition state data from quantum chemical calculations. Three different compound methods were used to characterize the potential energy surface: CBS-QB3, CBS-APNO, and G3. It is found that reaction (R1) mainly (>75%) proceeds via an addition–elimination mechanism to yield 2-methylfuran + CH₃. Kinetic parameters for the most important competing channels of the net reaction (R1) were calculated.     

Photo-absorption studies on carbonyl sulphide in 30,000–91,000 cm−1 region using synchrotron radiation

Photo-absorption spectrum of carbonyl sulphide (OCS) is recorded in 30,000–91,000 cm^?1 (3300–1050 Å) region at an average resolution of 1.2 Å using Photo-physics beamline on the 450 MeV Indus-1 synchrotron radiation source at RRCAT Indore, India. Owing to significant absorption cross section dependence, spectra of OCS are recorded at various pressures (0.001–5 mbar) to optimize the S/N ratio for band systems appearing at different energy regions. The spectral region below 70,000 cm^?1 has contributions from dissociation mechanism of the ground state of OCS and three valence band systems arising from promotion of a 3π electron to 4π and 10σ orbital. Improved S/N ratio helped in unambiguous assignment of the valence band progressions at 42,000–48,000 cm^?1, 53,000–62,000 cm^?1 and 63,500–70,000 cm^?1 regions to the ¹Δ←X¹Σ⁺ transition, the relatively intense and sharp bands of ¹Π←X¹Σ⁺ transition and intense but broad bands of ¹Σ⁺←X¹Σ⁺ transition, respectively, and obtain the vibrational frequencies. Above 70,000 cm^?1 Rydberg series arising from s, p, d and f orbitals converging to the ionic ground state X²Π of OCS⁺ (90,121 cm^?1) are identified. Long progression in the first few members of the Rydberg series is suggestive of mixed valence character. Quantum defects are evaluated and used to discuss the nature of the molecular orbital. The present study provides a unifying picture of the VUV photo-absorption spectrum of OCS up to its first ionization limit.     

Multi-species time-history measurements during high-temperature acetone and 2-butanone pyrolysis

High-temperature acetone and 2-butanone pyrolysis studies were conducted behind reflected shock waves using five species time-history measurements (ketone, CO, CH₃, CH₄ and C₂H₄). Experimental conditions covered temperatures of 1100–1600 K at 1.6 atm, for mixtures of 0.25–1.5% ketone in argon. During acetone pyrolysis, the CO concentration time-history was found to be strongly sensitive to the acetone dissociation rate constant k₁ (CH₃COCH₃ → CH₃ + CH₃CO), and this could be directly determined from the CO time-histories, yielding k₁(1.6 atm) = 2.46 × 10¹⁴ exp(?69.3 [kcal/mol]/RT) s^?1 with an uncertainty of ±25%. This rate constant is in good agreement with previous shock tube studies from Sato and Hidaka (2000) [3] and Saxena et al. (2009) [4] (within 30%) at temperatures above 1450 K, but is at least three times faster than the evaluation from Sato and Hidaka at temperatures below 1250 K. Using this revised k₁ value with the recent mechanism of Pichon et al. (2009) [5], the simulated profiles during acetone pyrolysis show excellent agreement with all five species time-history measurements. Similarly, the overall 2-butanone decomposition rate constant k_tot was inferred from measured 2-butanone time-histories, yielding k_tot(1.5 atm) = 6.08 × 10¹³ exp(?63.1 [kcal/mol]/RT) s^?1 with an uncertainty of ±35%. This rate constant is approximately 30% faster than that proposed by Serinyel et al. (2010) [11] at 1119 K, and approximately 100% faster at 1412 K. Using the measured 2-butanone and CO time-histories and an O-atom balance analysis, a missing removal pathway for methyl ketene was identified. The rate constant for the decomposition of methyl ketene was assumed to be the same as the value for the ketene decomposition reaction. Using the revised k_tot value and adding the methyl ketene decomposition reaction to the Serinyel et al. mechanism, the simulated profiles during 2-butanone pyrolysis show good agreement with the measurements for all five species.