Mbar Total Pressure Research Articles

Gas-Phase Kinetic Investigation of the OH-Initiated Oxidation of a Series of Methyl-Butenols under Simulated Atmospheric Conditions.

Five biogenic unsaturated alcohols have been investigated under simulated atmospheric conditions regarding their gas-phase OH reactivity. The gas-phase rate coefficients of OH radicals with 2-methyl-3-buten-2-ol (k1), 3-methyl-2-buten-1-ol (k2), 3-methyl-3-buten-1-ol (k3), 2-methyl-3-buten-1-ol (k4), and 3-methyl-3-buten-2-ol (k5) at 298 ± 2 K and 1000 ± 10 mbar total pressure of synthetic air were determined under low- and high-NOx conditions using the relative kinetic technique. The present work provides for the first time the rate coefficients of gas-phase reactions of hydroxyl radicals with 2-methyl-3-buten-1-ol and 3-methyl-3-buten-2-ol. The following rate constants were measured (in 10-11 cm3 molecule-1 s-1): k1 = 6.32 ± 0.49, k2 = 14.55 ± 0.93, k3 = 10.04 ± 0.78, k4 = 5.31 ± 0.37, and k5 = 11.71 ± 1.29. No significant differences in the measured rate coefficients were obtained when either 365 nm photolysis of CH3ONO in the presence of NO or 254 nm photolysis of H2O2 was used as a source of OH radicals. Reactivity toward other classes of related compounds such as alkenes and saturated alcohols is discussed. A comparison of the structure-activity relationship (SAR) estimates derived from the available accepted methodologies with experimental data available for unsaturated alcohols is provided. Atmospheric lifetimes for the investigated series of alkenols with respect to the main atmospheric oxidants are given and discussed.

Mars' atmosphere, volatiles, and climate as the sun heats up over the next 6 billion years

As the solar luminosity continues to increase over the next 6 billion years, the Martian surface will heat up to above the melting temperature of water ice. Water ice currently in the polar caps and ground ice will melt, potentially repopulating crater lakes or a very small ocean, with the abundance possibly enhanced due to diffusion upward of water currently locked in the deep crust. CO2 adsorbed in the regolith and locked up in the south-polar ice cap will diffuse into the atmosphere, providing up to 50 mbar total pressure; this will further increase the temperature via greenhouse warming. There are two end-member scenarios for the climate under these conditions: (i) Surface water could drive an atmospheric water cycle somewhat analogous to present-day Earth's, which would create a global clement climate conducive to the existence of widespread surface life. (ii) The widespread presence of liquid water could cause CO2 to form carbonate minerals and H2O to hydrate surface/subsurface minerals (or allow H released from water to escape to space), and CO2 and H2O could be lost to space, leaving Mars with a dry environment. The climate could end up between these end-members and also could vary with time. This uncertain climate end state informs our view that exoplanet evolution and habitability can be driven by endogenous processes associated with a terrestrial planet as well as by the ability of EUV and a stellar wind from the host star to strip away atmosphere.

Customized boron-doped diamond electrodes for efficient water treatment via HF-CVD parameter optimization

Among the Design of Experiments (DoE) approaches available, the Taguchi method offers a methodical and effective way to optimize designs with fewer experimental trials. The effects of deposition conditions on the final properties of boron-doped diamond (BDD) films for water treatment applications deposited in a Hot Filament Chemical Vapor Deposition (HF-CVD) reactor were evaluated by applying a Taguchi Matrix. Methane to hydrogen (CH4/H2) ratio, argon mass flow, and total gas pressure were the controllable factors, each in three different levels. Diamond quality was affected by a combination of the three considered factors. A 0.02 CH4/H2 ratio was found as the optimal value to yield films with reduced non-diamond carbon inclusions in our CVD system. Resistivity, residual stress, double-layer capacitance, and surface roughness were mainly affected by total pressure and argon content. The methane content and the total pressure significantly influenced growth rate and grain size. The latter was primarily responsible for changes in the electrochemical potential window and the electron transfer process of the BDD films. Within the studied range of deposition conditions, the optimal deposition parameters to obtain BDD films for water treatment applications were: 0.02 CH4/H2 ratio, 25 mbar total gas pressure, and 30 sccm argon mass flow.

Spectroscopic investigation of a Co(0001) model catalyst during exposure to H2 and CO at near-ambient pressures.

Cobalt catalysts, although already used industrially for Fischer-Tropsch synthesis, are prone to a number of deactivation mechanisms such as oxidation of the active phase, and the deposition of carbon and reaction products. We have performed near-ambient-pressure X-ray photoelectron spectroscopy on Co(0001) model catalysts during exposure to gases relevant to Fischer-Tropsch synthesis, i.e., CO and H2, at 0.25 mbar total pressure. At this pressure, CO seems to be more efficient at keeping the Co(0001) surface metallic than H2, which is the opposite behavior as reported in the literature for other pressure ranges. We offer an interpretation of these differences based on the preferred adsorption and dissociation sites of CO and H2 compared to the oxidizing agent water (present as impurity in the gas feed and one of the products of the reaction). Additionally, detailed carbon spectra measured at the HIPPIE beamline of MAX IV allow for the distinction of different adsorbed species: CO and COx species are present in correlation to the presence of oxygen on the surface. Carbidic carbon and graphitic carbon can both be removed by hydrogen, whereas adsorbed hydrocarbons possibly poison the surface.

Time-Sensitive Aspects of Mars Sample Return (MSR) Science.

Time-Sensitive Aspects of Mars Sample Return (MSR) Science.

Stroboscopic operando spectroscopy of the dynamics in heterogeneous catalysis by event-averaging

Heterogeneous catalyst surfaces are dynamic entities that respond rapidly to changes in their local gas environment, and the dynamics of the response is a decisive factor for the catalysts’ action and activity. Few probes are able to map catalyst structure and local gas environment simultaneously under reaction conditions at the timescales of the dynamic changes. Here we use the CO oxidation reaction and a Pd(100) model catalyst to demonstrate how such studies can be performed by time-resolved ambient pressure photoelectron spectroscopy. Central elements of the method are cyclic gas pulsing and software-based event-averaging by image recognition of spectral features. A key finding is that at 3.2 mbar total pressure a metallic, predominantly CO-covered metallic surface turns highly active for a few seconds once the O2:CO ratio becomes high enough to lift the CO poisoning effect before mass transport limitations triggers formation of a √5 oxide.

How Surface Species Drive Product Distribution during Ammonia Oxidation: An STM and Operando APXPS Study

The oxidation of ammonia is a key reaction for the production of artificial fertilizers and for environmental protection. Depending on the area of application, the catalytic reaction needs to be tuned toward the production of either N2 or NO, and this selectivity is controlled by temperature, pressure, reactant ratio, and the type of catalyst. PtRh alloys are highly useful catalytic materials for the oxidation of ammonia, and they can be employed at different reaction conditions. In contrast to pure Pt and Rh catalysts, for which a large number of studies of ammonia oxidation reaction mechanism are available, for PtRh alloys, direct spectroscopic evidence for structure–performance relationship is still lacking. To understand the behavior of PtRh alloys, namely, what is their active phase under reaction conditions and how the alloy composition leads to a particular product distribution, we study the oxidation of ammonia over PtRh/Pt(111) surfaces by simultaneous operando ambient pressure X-ray photoelectron spectroscopy and mass spectrometry at 1 mbar total reaction pressure. These data are complemented by a catalyst surface characterization by scanning tunneling microscopy in ultrahigh vacuum. We establish that the predominant surface structure during NH3 oxidation strongly depends on the degree of Pt enrichment and the O2/NH3 mixing ratio. At the nanoscale, the selectivity toward N2 or NO production is driven by the surface populations of N and O species. These, in turn, are controlled by the nature of the alloying of Pt with Rh.

Formation of CN Radical from Nitrogen and Carbon Condensation and from Photodissociation in Femtosecond Laser-Induced Plasmas: Time-Resolved FT-UV-Vis Spectroscopic Study of the Violet Emission of CN Radical.

Exploring the formation of diatomic radicals in femtosecond plasmas is important to establish the most dominant kinetic pathways following ionization and dissociation of small molecules. In this work, cyano radical formation has been studied from bromoform, acetonitrile, and methanol in nitrogen and argon plasmas created with a focused femtosecond laser beam operating at 100 kHz repetition rate and 1030 nm wavelength with 43 fs pulse length and 250 μJ pulse energy. Time-resolved Fourier transform fluorescence spectroscopy was applied in the ultraviolet-visible (UV-vis) spectral range for the characterization of the rotational and vibrational temperatures of the CN(B) radicals via fitting the experimental data. The high repetition rate of the laser allows efficient coupling with the step-scan Fourier transform spectroscopy method. Coulomb explosion at the very high intensity (∼1016 W/cm2) resulted in the formation of nascent atoms, ions, and electrons. The condensation reactions of carbon and reactive nitrogen species resulted in the formation of CN(B2Σ+) radicals and C2(d3Πg) dicarbon molecules/radicals. The CN(B) radicals were formed at the highest concentration in the case of bromoform because the weak carbon-bromine bonds resulted in reactive carbon atoms and CH radicals, which are reactive precursors for the CN(B) radical formation. In the case of acetonitrile, immediate production of CN(B) is observed with nanosecond resolution, which suggests that the CN is formed either via photodetachment or via roaming reaction associated with the Coulomb explosion of the parent molecule. The nascent rotational temperature was very high (∼6000-8500 K) and rapidly decreased in all instances within 40 ns with bromoform and acetonitrile. The highest vibrational temperature (∼7800 K) was observed in an acetonitrile/Ar mixture that decreased in about 30 ns and then increased in the observed time window. The vibrational temperature increased in all samples between 30 and 200 ns. The time dependence of fluorescence is described with a monoexponential decay in the case of acetonitrile/Ar and with biexponential decays in all other instances in the 0-250 mbar total pressure range. The shorter time constant is close to the radiative lifetime of CN(B) emission (∼60-80 ns), which can be attributed to the CN(B) radicals produced in the first few collisions at lower pressures. The longer CN(B) emission is from CN(B) created by slower chemical reactions involving carbon atoms, C2 radicals, and reactive nitrogen-containing species.

Influence of Rf plasma carbonitriding on AISI304L, SSMn6Ni and SSMn10Ni for nuclear applications

The present study aims to examine the effect of rf plasma surface carbonitriding on austenite stainless steel AISI304L, SSMn6Ni and SSMn10Ni for pressurized water reactors application. All samples were fabricated at Central Metallurgical Research & Devolopment Institute (CMRDI), Egypt. They were also carbonitrided by rf plasma in a mixture of nitrogen and acetylene gases (85% N2 + 15% C2H2) at 500 W plasma power and 7.5 × 10−2 mbar total gas pressure. In addition, the mechanical, tribological and corrosion resistance of the treated steels revealed strenghthening in the surface properties compared with that of the untreated samples. Furthermore, nuclear properties were investigated using different radioactive sources of neutron and gamma rays at different energies. Gamma ray measurements compared between the experimental and theoretical (μ and σ) shielding parameters of all carbonitrided steel samples at various energies ranging between 300.63 and 2614.51 keV. Moreover, a slight increase occurred in the macroscopic cross section of the total slow neutrons of all carbonitrided samples.

Temperature‐dependent rate constant for the reaction of F atoms with HNO3

AbstractThe kinetics of the reaction of F atom with HNO3, source of NO3 radicals widely used in laboratory studies, has been investigated at nearly 2.7 mbar total pressure of helium over a wide temperature range, T = 220‐700 K, using a low‐pressure discharge flow reactor combined with an electron impact ionization quadrupole mass spectrometer. The rate constant of the reaction F + HNO3 → NO3 + HF (1) was determined using both relative rate method and absolute measurements under pseudo–first‐order conditions, monitoring the kinetics of F‐atom consumption in excess of HNO3, k1 = (8.2 ± 0.4) × 10−12 exp((315 ± 15)/T) cm3 molecule−1 s−1 (where the uncertainties represent precision at the 2σ level, the estimated total uncertainty on k1 being 15% at all temperatures). The reaction rate constant was found to be in excellent agreement with the only previous temperature‐dependent study. Experiments on detection of the reaction product, HF, have shown that NO3 and HF forming channel of the title reaction is the dominant, if not unique, on the whole temperature range of the study.

A rotational Raman study under non-thermal conditions in pulsed CO2–N2 and CO2–O2 glow discharges

This work employs in situ rotational Raman spectroscopy to study the effect of N2 and O2 addition to CO2 in pulsed glow discharges in the mbar range. The spatiotemporally resolved measurements are performed in CO2 and 25%, 50% and 75% of N2 or O2 admixture, in a 5–10 ms on-off cycle, 50 mA plasma current and 6.7 mbar total pressure. The rotational temperature profile is not affected by adding N2, ranging from 400 to 850 K from start to end of the discharge pulse, while the addition of O2 decreases the temperature at corresponding time points. Molecular number densities of CO2, CO, O2 and N2 are determined, showing the spatial homogeneity along the axis of the reactor and uniformity during the cycle. The measurements in the N2 containing mixtures show that CO2 conversion factor α increases from 0.15 to 0.33 when the content of N2 is increased from 0% to 75%, demonstrating the potential of N2 addition to enhance the vibrational pumping of CO2 and its beneficial effect on CO2 dissociation. Furthermore, the influence of admixtures on CO2 vibrations is examined by analysing the vibrationally averaged nuclear spin degeneracy. The difference between the fitted odd averaged degeneracy and the calculated odd degeneracy assuming thermal conditions increases with the addition of N2, demonstrating the growth of vibrational temperatures in CO2. On the other hand, the addition of O2 leads to a decrease of α, which might be attributed to quenched vibrations of CO2, and/or to the influence of the back reaction in the presence of O2.

An intercomparison of HO<sub>2</sub> measurements by fluorescence assay by gas expansion and cavity ring-down spectroscopy within HIRAC (Highly Instrumented Reactor for Atmospheric Chemistry)

Abstract. The HO2 radical was monitored simultaneously using two independent techniques in the Leeds HIRAC (Highly Instrumented Reactor for Atmospheric Chemistry) atmospheric simulation chamber at room temperature and total pressures of 150 and 1000 mbar of synthetic air. In the first method, HO2 was measured indirectly following sampling through a pinhole expansion to 3 mbar when sampling from 1000 mbar and to 1 mbar when sampling from 150 mbar. Subsequent addition of NO converted it to OH, which was detected via laser-induced fluorescence spectroscopy using the FAGE (fluorescence assay by gas expansion) technique. The FAGE method is used widely to measure HO2 concentrations in the field and was calibrated using the 185 nm photolysis of water vapour in synthetic air with a limit of detection at 1000 mbar of 1.6 × 106 molecule cm−3 for an averaging time of 30 s. In the second method, HO2 was measured directly and absolutely without the need for calibration using cavity ring-down spectroscopy (CRDS), with the optical path across the entire ∼ 1.4 m width of the chamber, with excitation of the first O-H overtone at 1506.43 nm using a diode laser and with a sensitivity determined from Allan deviation plots of 3.0 × 108 and 1.5 × 109 molecule cm−3 at 150 and 1000 mbar respectively, for an averaging period of 30 s. HO2 was generated in HIRAC by the photolysis of Cl2 using black lamps in the presence of methanol in synthetic air and was monitored by FAGE and CRDS for ∼ 5–10 min periods with the lamps on and also during the HO2 decay after the lamps were switched off. At 1000 mbar total pressure the correlation plot of [HO2]FAGE versus [HO2]CRDS gave an average gradient of 0.84 ± 0.08 for HO2 concentrations in the range ∼ 4–100 × 109 molecule cm−3, while at 150 mbar total pressure the corresponding gradient was 0.90 ± 0.12 on average for HO2 concentrations in the range ∼ 6–750 × 108 molecule cm−3.For the period after the lamps were switched off, the second-order decay of the HO2 FAGE signal via its self-reaction was used to calculate the FAGE calibration constant for both 150 and 1000 mbar total pressure. This enabled a calibration of the FAGE method at 150 mbar, an independent measurement of the FAGE calibration at 1000 mbar and an independent determination of the HO2 cross section at 1506.43 nm, σHO2, at both pressures. For CRDS, the HO2 concentration obtained using σHO2, determined using previous reported spectral data for HO2, and the kinetic decay of HO2 method agreed to within 20 and 12 % at 150 and 1000 mbar respectively. For the FAGE method a very good agreement (difference within 8 %) has been obtained at 1000 mbar between the water vapour calibration method and the kinetic decay of the HO2 fluorescence signal method. This is the first intercomparison of HO2 between the FAGE and CRDS methods, and the good agreement between HO2 concentrations measured using the indirect FAGE method and the direct CRDS method provides validation for the FAGE method, which is used widely for field measurements of HO2 in the atmosphere.

Transient Structures of PdO during CO Oxidation over Pd(100)

In situ high-energy surface X-ray diffraction was employed to determine the surface structure dynamics of a Pd(100) single crystal surface acting as a model catalyst to promote CO oxidation. The measurements were performed under semirealistic conditions, i.e., 100 mbar total gas pressure and 600 K sample temperature. The surface structure was studied in detail both in a steady gas flow and in a gradually changing gas composition with a time resolution of 0.5 s. The experimental technique allows for rapid reciprocal space mapping providing the complete information on structural changes of a surface with unprecedented time resolution in harsh conditions. Our results show that the (√5 × √5)R27°-PdO(101) surface oxide forms in a close to stoichiometric O2 and CO gas mixture as the mass spectrometry indicates a transition to a highly active state with the reaction rate limited by the CO mass transfer to the Pd(100) surface. Using a low excess of O2 in the gas stoichiometry, islands of bulk oxide grow epitaxial...

Atmospheric Fate of a Series of Carbonyl Nitrates: Photolysis Frequencies and OH-Oxidation Rate Constants

Multifunctional organic nitrates are potential NO(x) reservoirs whose atmospheric chemistry is somewhat little known. They could play an important role in the spatial distribution of reactive nitrogen species and consequently in ozone formation and distribution in remote areas. In this work, the rate constants for the reaction with OH radical and the photolysis frequencies of α-nitrooxyacetone, 3-nitrooxy-2-butanone, and 3-methyl-3-nitrooxy-2-butanone have been determined at room temperature at 1000 mbar total pressure of synthetic air. The rate constants for the OH oxidation were measured using the relative rate technique, with methanol as reference compound. The following rate constants were obtained for the reaction with OH: k(OH) = (6.7 ± 2.5) × 10(-13) cm(3) molecule(-1) s(-1) for α-nitrooxyacetone, (10.6 ± 4.1) × 10(-13) cm(3) molecule(-1) s(-1) for 3-nitrooxy-2-butanone, and (2.6 ± 0.9) × 10(-13) cm(3) molecule(-1) s(-1) for 3-methyl-3-nitrooxy-2-butanone. The corresponding photolysis frequencies extrapolated to typical atmospheric conditions for July first at noon at 40° latitude North were (4.8 ± 0.3) × 10(-5) s(-1), (5.7 ± 0.3) × 10(-5) s(-1), and (7.4 ± 0.2) × 10(-5) s(-1), respectively. The data show that photolysis is a major atmospheric sink for these organic nitrates.

Formation and stability of bulk carbonic acid (H2CO3) by protonation of tropospheric calcite.

Organic acids play an important role in the acidification of our atmosphere. These weak acids can contribute up to 60 % of the free airborne acidity. By far the most abundant organic acids are the C1 and C2 monocarboxylic acids, formic acid (HCOOH) and acetic acid (CH3COOH), which show mixing ratios in the gas phase ranging up to 20 ppb over land1,2 and down to 0.2 ppb in the remote oceanic boundary layer or troposphere.3,4 These acids are partitioned between the gas phase and the particulate phase, where roughly one half to two thirds can be found in particulate matter (PM2.5).2 The most important removal mechanism is dry deposition, which accounts for more than 90 % of the total organic acid deposition budget. The remaining fraction is removed by rain as particulate-phase acids, whereas removal by chemical reactions is negligible.1,5 In addition to the two most important organic acids, C3–C10 aliphatic monocarboxylic acids1 and C2–C11 aliphatic dicarboxylic acids1,2,6–11 as well as aromatic carboxylic acids1 have also been observed in air. The water-soluble fraction of organic carbon can on average consist of 35 % mono- and dicarboxylic acids.12 While the C2-dicarboxylic acid, oxalic acid (COOH)2, is commonly observed in all field studies, the C1-dicarboxylic acid, carbonic acid (H2CO3), has barely received any attention, mainly because it is thought that it immediately decomposes to water and carbon dioxide. However, it has previously been shown that gaseous, water-free carbonic acid is surprisingly stable,13 that amorphous and crystalline solids of pure carbonic acid can be produced and stored without decomposition at temperatures up to 230 K even in the presence of water14 and that this solid can be sublimed at, for example, 220 K and recondensed in vacuo at surfaces of lower temperature.15

Atmospheric Chemistry of Ethyl Propionate

Ethyl propionate is a model for fatty acid ethyl esters used as first-generation biodiesel. The atmospheric chemistry of ethyl propionate was investigated at 980 mbar total pressure. Relative rate measurements in 980 mbar N(2) at 293 ± 0.5 K were used to determine rate constants of k(C(2)H(5)C(O)OC(2)H(5) + Cl) = (3.11 ± 0.35) × 10(-11), k(CH(3)CHClC(O)OC(2)H(5) + Cl) = (7.43 ± 0.83) × 10(-12), and k(C(2)H(5)C(O)OC(2)H(5) + OH) = (2.14 ± 0.21) × 10(-12) cm(3) molecule(-1) s(-1). At 273-313 K, a negative Arrhenius activation energy of -3 kJ mol(-1) is observed.. The chlorine atom-initiated oxidation of ethyl propionate in 980 mbar N(2) gave the following products (stoichiometric yields): ClCH(2)CH(2)C(O)OC(2)H(5) (0.204 ± 0.031), CH(3)CHClC(O)OC(2)H(5) (0.251 ± 0.040), and C(2)H(5)C(O)OCHClCH(3) (0.481 ± 0.088). The chlorine atom-initiated oxidation of ethyl propionate in 980 mbar of N(2)/O(2) (with and without NO(x)) gave the following products: ethyl pyruvate (CH(3)C(O)C(O)OC(2)H(5)), propionic acid (C(2)H(5)C(O)OH), formaldehyde (HCHO), and, in the presence of NO(x), PAN (CH(3)C(O)OONO(2)). The lack of acetaldehyde as a product suggests that the CH(3)CH(O)C(O)OC(2)H(5) radical favors isomerization over decomposition. From the observed product yields, we conclude that H-abstraction by chlorine atoms from ethyl propionate occurs 20.4 ± 3.1%, 25.1 ± 4.0%, and 48.1 ± 8.8% from the CH(3)-, -CH(2)-, and -OCH(2)- groups, respectively. The rate constant and branching ratios for the reaction between ethyl propionate and the OH radical were investigated theoretically using quantum mechanical calculations and transition state theory. The stationary points along the reaction path were optimized using the CCSD(T)-F12/VDZ-F12//BH&HLYP/aug-cc-pVTZ level of theory; this model showed that OH radicals abstract hydrogen atoms primarily from the -OCH(2)- group (80%).

Enhanced performance of a wide-aperture copper vapour laser with hydrogen additive in neon buffer gas

A wide-aperture copper vapour laser was demonstrated at ∼10 kHz rep-rate with hydrogen additive in its buffer gas. Maximum power in excess of ∼50 W (at 10 kHz) was achieved by adding 1.96% hydrogen to the neon buffer gas at 20 mbar total gas pressure. This increase in output power was about 70% as compared to ∼30 W achieved with pure neon at 5.5 kHz rep-rate. The 70% enhancement achieved was significantly higher than the maximum reported value of 50% so far in the literature. The enhancement was much higher (about 150%) as compared to its 20 W power at 10 kHz rep-rate using pure neon as the standard CVL operation.

Propane dissociation in a non-thermal high-pressure nitrogen plasma

The removal and the conversion processes of propane in N2/C3H8 mixtures (concentration of hydrocarbon molecules up to 5500 ppm) energized by a photo-triggered discharge (homogeneous plasma) are studied at 460 mbar total pressure, both experimentally and theoretically. A self-consistent 0D discharge and kinetic model is used to interpret chromatographic measurements of propane and some by-products' concentrations (hydrogen and hydrocarbons with two or three carbon atoms). It is suggested, from the comparison between measurements and model predictions, that quenching processes of nitrogen metastable states by C3H8 lead to the dissociation of the hydrocarbon molecule, and are the most important processes for the removal of propane. Such a result is obtained using the quenching coefficient value previously determined by Callear and Wood (1971 Trans. Faraday Soc. 67 272) for the state, whereas the coefficient for collisions of the singlet states with C3H8 is estimated to be 3.0 × 10−10 cm3 s−1 in order to explain the measured propane disappearance in the N2/C3H8 mixture excited by the photo-triggered discharge. The hydrogen molecule is the measured most populated by-product and, also from the comparison between experimental results and model predictions, the most probable dissociation products of propane appear to be H2 and C3H6. The propene molecule is also efficiently dissociated by the quenching processes of N2 states, and probably leads to the production of hydrogen atoms and methyl radicals with equivalent probabilities. The kinetic model predicts that the carbon atom is distributed amongst numerous molecules, including HCN, CH4, C2H2, C2H4, C2H6 and C3H6.

Thermal decomposition of trifluoromethoxycarbonyl peroxy nitrate, CF3OC(O)O2NO2

AbstractThe thermal decomposition of trifluoromethoxycarbonyl peroxy nitrate, CF3OC(O)O2NO2, has been studied between 278 and 306 K at 270 mbar total pressure using He as a diluent gas. The pressure dependence of the reaction was also studied at 292 K between 1.2 and 270 mbar total pressure. The rate constant reaches its high‐pressure limit at 70 mbar. The first step of the decomposition leads to CF3OC(O)O2 and NO2 formation, that is, CF3OC(O)O2NO2 + M ⇆ CF3OC(O)O2 + NO2 + M (k1, k−1). Reaction (−1) was prevented by adding an excess of NO that reacts with the peroxy radical intermediate and leads to carbonyl fluoride (CF2O), carbon dioxide (CO2), nitrogen dioxide (NO2), and small quantities of CF3OC(O)O2C(O)OCF3. The kinetics of reaction (1) was determined by following the loss of CF3OC(O)O2NO2 via IR spectroscopy. The temperature dependence of the decomposition follows the equation k1(T) = 1.0 × 1016 e−((111±3)/(RT)) for the exponential term expressed in kJ mol−1. The values obtained for the kinetic parameters such as k1 at 298 K, the activation energy (Ea), and the preexponential factor (A) are compared with literature data for other acyl peroxy nitrates. The atmospheric thermal stability of CF3OC(O)O2NO2 and its dependence with altitude is discussed. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 831–838, 2008

Effect Of Propene, n-Decane, and Toluene Plasma Kinetics on NO Conversion in Homogeneous Oxygen-Rich Dry Mixtures at Ambient Temperature

A photo-triggered discharge is used to study the influence of three hydrocarbons (HCs), propene (C3H6), n-decane (C10H22), and toluene (C6H5CH3) on NO conversion in N2/O2/NO/HC mixtures, with 18.5% O2 concentration, 700 ppm of NO, and an hydrocarbon concentration ranging between 190 ppm and 2,700 ppm. The electrical system generates a transient homogeneous plasma, working under 400 mbar total pressure, with a 50 ns short current pulse at a repetition frequency up to a few Hz. The NO concentration at the exit of the reactor is quantified using absolute FTIR spectroscopy measurements, as a function of the specific deposited energy in the discharge and the mixture composition. Owing to the plasma homogeneity, the experimental results can be compared to predictions of a self-consistent 0-D discharge and kinetic model based on available data in the literature about reactions and their rate constants. It is shown that the addition of either propene (as for DBD or corona discharges) or n-decane to N2/O2/NO leads to an improvement of the NO removal as compared to the mixture without hydrocarbon molecules. The adopted kinetic schemes explain this effect for the two mixture types. On the other hand, both the experiments and model predictions emphasize that the addition of toluene does not lead to the improvement of NO conversion. Moreover, compounds that are useful for NOx reduction catalysis, such as aldehydes, are less produced in the mixture with toluene.