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Absorption spectra of benzene and perfluorobenzene at high temperatures - kinetics of benzene pyrolysis
Benzene, benzene-d sub 6 and sulfur dioxide radiative lifetime measurement comparison, investigating internal conversion behavior
The Cassini Ion and Neutral Mass Spectrometer (Waite, Jr., et al., 2007) and the Composite Infrared Spectrometer (Coustenis, A., et al., 2007) have detected benzene in the upper atmosphere and stratosphere of Titan. Photochemical reactions involving benzene in Titan's atmosphere may influence polycyclic aromatic hydrocarbon formation, aerosol formation, and the radiative balance of Titan's atmosphere. We measure the effect of benzene on the optical properties of Titan analog particles in the laboratory. Using cavity ring-down aerosol extinction spectroscopy, we determine the real and imaginary refractive index at 532 nm of particles formed by benzene photolysis and Titan analog particles formed with ppm-levels of benzene. These studies are compared to the previous study by Hasenkopf, et a1. (2010) of Titan analog particles formed by methane photolysis.
Context. Saturn's polar upper atmosphere exhibits significant auroral activity; however, its impact on stratospheric chemistry (i.e. the production of benzene and heavier hydrocarbons) and thermal structure remains poorly documented. Aims. We aim to bring new constraints on the benzene distribution in Saturn's stratosphere, to characterize polar aerosols (their vertical distribution, composition, thermal infrared optical properties), and to quantify the aerosols' radiative impact on the thermal structure. Methods. Infrared spectra acquired by the Composite Infrared Spectrometer (CIRS) on board Cassini in limb viewing geometry are analysed to derive benzene column abundances and aerosol opacity profiles over the 3 to 0.1 mbar pressure range. The spectral dependency of the haze opacity is assessed in the ranges 680-900 and 1360-1440 cm(exp −1). Then, a radiative climate model is used to compute equilibrium temperature profiles, with and without haze, given the haze properties derived from CIRS measurements. Results. On Saturn's auroral region (80 deg S), benzene is found to be slightly enhanced compared to its equatorial and mid-latitude values. This contrasts with the Moses & Greathouse (2005, J. Geophys. Res., 110, 9007) photochemical model, which predicts a benzene abundance 50 times lower at 80◦S than at the equator. This advocates for the inclusion of ion-related reactions in Saturn's chemical models. The polar stratosphere is also enriched in aerosols, with spectral signatures consistent with vibration modes assigned to aromatic and aliphatic hydrocarbons, and presenting similarities with the signatures observed in Titan's stratosphere. The aerosol mass loading at 80 deg S is estimated to be 1−4 × 10(exp −5) g cm(exp −2), an order of magnitude less than on Jupiter, which is consistent with the order of magnitude weaker auroral power at Saturn.We estimate that this polar haze warms the middle stratosphere by 6 K in summer and cools the upper stratosphere by 5 K in winter. Hence, aerosols linked with auroral activity can partly account for the warm polar hood observed in Saturn's summer stratosphere.
The International Space Station (ISS) Air Quality Monitors (AQMs) have provided targeted in-flight analysis of volatile organic compounds (VOCs) in the ISS atmosphere since early 2013. During their initial half decade of use covering multiple sets of units, the AQMs performed well, meeting their validation criteria and showing excellent accuracy compared to archival samples. In addition to routine environmental monitoring, the AQMs have also been used during a number of contingency situations and investigations related to Environmental Control and Life Support Systems (ECLSS). These include a potential ammonia leak, increases in atmospheric ethanol, and efforts to locate potential sources of polydimethylsiloxanes that lead to the production of dimethylsilanediol (DMSD) in the US Water Processor Assembly (WPA). As the fleet of AQMs has aged, several issues have arisen. These have ranged from pervasive problems on electronics boards to loss of sensitivity due to operating in an elevated CO2 environment. The most notable issue encountered during on-orbit operations was incorrect identification of compounds. This initially occurred in mid-2020, when AQM1 reported the presence of benzene. While the AQM team questioned the validity of these results, the concentration of the “benzene” continued to increase and eventually exceeded the 30- and 180-day Spacecraft Maximum Allowable Concentration (SMAC). This led to wide-ranging efforts by a number of groups aimed at understanding the situation and identifying the source of the “benzene.” AQM1 failed after being relocated to the Russian Segment as part of the investigation, and the unit was returned for evaluation. When archive samples collected while the AQM was measuring elevated benzene showed no detectable benzene, the focus of the investigation shifted to determining the cause of the false positive readings. Here, we will discuss the results of this investigation by the AQM team, potential causes of the interference, and subsequent reporting of AQM1 results.
The International Space Station (ISS) Air Quality Monitors (AQMs) have provided targeted in-flight analysis of volatile organic compounds (VOCs) in the ISS atmosphere since early 2013. During their initial half decade of use covering multiple sets of units, the AQMs performed well, meeting their validation criteria and showing excellent accuracy compared to archival samples. In addition to routine environmental monitoring, the AQMs have also been used during a number of contingency situations and investigations related to Environmental Control and Life Support Systems (ECLSS). These include a potential ammonia leak, increases in atmospheric ethanol, and efforts to locate potential sources of polydimethylsiloxanes that lead to the production of dimethylsilanediol (DMSD) in the US Water Processor Assembly (WPA). As the fleet of AQMs has aged, several issues have arisen. These have ranged from pervasive problems on electronics boards to loss of sensitivity due to operating in an elevated CO2 environment. The most notable issue encountered during on-orbit operations was incorrect identification of compounds. This initially occurred in mid-2020, when AQM1 reported the presence of benzene. While the AQM team questioned the validity of these results, the concentration of the “benzene” continued to increase and eventually exceeded the 30- and 180-day Spacecraft Maximum Allowable Concentration (SMAC). This led to wide-ranging efforts by a number of groups aimed at understanding the situation and identifying the source of the “benzene.” AQM1 failed after being relocated to the Russian Segment as part of the investigation, and the unit was returned for evaluation. When archive samples collected while the AQM was measuring elevated benzene showed no detectable benzene, the focus of the investigation shifted to determining the cause of the false positive readings. Here, we will discuss the results of this investigation by the AQM team, potential causes of the interference, and subsequent reporting of AQM1 results.
The International Space Station (ISS) Air Quality Monitors (AQMs) have provided targeted in-flight analysis of volatile organic compounds (VOCs) in the ISS atmosphere since early 2013. During their initial half decade of use covering multiple sets of units, the AQMs performed well, meeting their validation criteria and showing excellent accuracy compared to archival samples. In addition to routine environmental monitoring, the AQMs have also been used during a number of contingency situations and investigations related to Environmental Control and Life Support Systems (ECLSS). These include a potential ammonia leak, increases in atmospheric ethanol, and efforts to locate potential sources of polydimethylsiloxanes that lead to the production of dimethylsilanediol (DMSD) in the US Water Processor Assembly (WPA). As the fleet of AQMs has aged, several issues have arisen. These have ranged from pervasive problems on electronics boards to loss of sensitivity due to operating in an elevated CO2 environment. The most notable issue encountered during on-orbit operations was incorrect identification of compounds. This initially occurred in mid-2020, when AQM1 reported the presence of benzene. While the AQM team questioned the validity of these results, the concentration of the “benzene” continued to increase and eventually exceeded the 30- and 180-day Spacecraft Maximum Allowable Concentration (SMAC). This led to wide-ranging efforts by a number of groups aimed at understanding the situation and identifying the source of the “benzene.” AQM1 failed after being relocated to the Russian Segment as part of the investigation, and the unit was returned for evaluation. When archive samples collected while the AQM was measuring elevated benzene showed no detectable benzene, the focus of the investigation shifted to determining the cause of the false positive readings. Here, we will discuss the results of this investigation by the AQM team, potential causes of the interference, and subsequent reporting of AQM1 results.
The vibrational dephasing of the 656/cm mode (nu1, a1g) of CS2 and the 991/cm mode (nu2, a1g) of benzene have been studied as a function of concentration in mixtures with a number of solvents using a ps time-resolved CARS technique. This technique employs two tunable synchronously-pumped mode-locked dye lasers in a stimulated Raman pump, coherent anti-Stokes Raman probe time-resolved experiment. Results are obtained for CS2 in carbon tetrachloride, benzene, nitrobenzene, and ethanol and for benzene nu2 in CS2. The dephasing rates of CS2 nu1 increase on dilution with the polar solvents and decrease or remain constant on dilution with the nonpolar solvents. The CS2/benzene solutions show a contrasting behavior, with the CS2 nu1 dephasing rate being nearly independent of concentration whereas the benzene nu2 dephasing rate decreases on dilution. These results are compared to theoretical models for vibrational dephasing of polyatomic molecules in solution.
An expanded and improved version of a previously published benzene oxidation mechanism is presented and shown to model published experimental data fairly successfully. This benzene submodel is coupled to a modified version of a toluene oxidation submodel from the recent literature. This complete mechanism is shown to successfully model published experimental toluene oxidation data for a highly mixed flow reactor and for higher temperature ignition delay times in a shock tube. A comprehensive sensitivity analysis showing the most important reactions is presented for both the benzene and toluene reacting systems. The NASA Lewis toluene mechanism's modeling capability is found to be equivalent to that of the previously published mechanism which contains a somewhat different benzene submodel.
Polycyclic aromatic hydrocarbons and related species have been suggested to play a key role in the astrochemical evolution of the interstellar medium, but the formation mechanism of even their simplest building block-the aromatic benzene molecule-has remained elusive for decades. Here we demonstrate in crossed molecular beam experiments combined with electronic structure and statistical calculations that benzene (C6H6) can be synthesized via the barrierless, exoergic reaction of the ethynyl radical and 1,3- butadiene, C2H + H2CCHCHCH2 --> C6H6, + H, under single collision conditions. This reaction portrays the simplest representative of a reaction class in which aromatic molecules with a benzene core can be formed from acyclic precursors via barrierless reactions of ethynyl radicals with substituted 1,3-butadlene molecules. Unique gas-grain astrochemical models imply that this low-temperature route controls the synthesis of the very first aromatic ring from acyclic precursors in cold molecular clouds, such as in the Taurus Molecular Cloud. Rapid, subsequent barrierless reactions of benzene with ethynyl radicals can lead to naphthalene-like structures thus effectively propagating the ethynyl-radical mediated formation of aromatic molecules in the interstellar medium.
The oxidation of stoichiometric mixtures of benzene and toluene behind incident shock waves was studied for a temperature range from 1700 to 2800 K and a pressure range from 1.1 to 1.7 atm. The concentration of CO and CO2 produced were measured as well as the product of the oxygen atom and carbon monoxide concentrations. Comparisons between the benzene experimental data and results calculated by use of a reaction mechanism published in the open literature were carried out. With some additional reactions and changes in rate constants to reflect the pressure-temperature range of the experimental data, a good agreement was achieved between computed and experimental results. A reaction mechanism was developed for toluene oxidation based on analogous rate steps from the benzene mechanism. Measurements of NOx levels in an actual flame device, a jet-stirred combustor, were reproduced successfully by use of the reaction mechanism developed from the shock-tube experiments on toluene. These experimental measurements of NOx levels were reproduced from a computer simulation of a jet-stirred combustor.
The ignition delay times of benzene and toluene with oxygen diluted in argon were investigated over a wide range of conditions. For benzene the concentration ranges were 0.42 to 1.69 percent fuel and 3.78 to 20.3 percent oxygen. The temperature range was 1212 to 1748 K and the reflected shock pressures were 1.7 to 7.89 atm. Statistical evaluation of the benzene experiments provided an overall equation which is given. For toluene the concentration ranges were 0.5 to 1.5 percent fuel and 4.48 to 13.45 percent oxygen. The temperature range was 1339 to 1797 K and the reflected shock pressures were 1.95 to 8.85 atm. The overall ignition delay equation for toluene after a statistical evaluation is also given. Detailed experimental information is provided.
A detailed mechanism for the oxidation of toluene in both argon and nitrogen dilutents is presented. The mechanism was used to compute experimentally ignition delay times for shock-heated toluene-oxygen-argon mixtures with resonably good success over a wide range of initial temperatures and pressures. Attempts to compute experimentally measured concentration profiles for toluene oxidation in a turbulent reactor were partially successful. An extensive sensitivity analysis was performed to determine the reactions which control the ignition process and the rates of formation and destruction of various species. The most important step was found to be the reaction of toluene with molecular oxygen, followed by the reactions of hydroperoxyl and atomic oxygen with benzyl radicals. These findings contrast with the benzene oxidation, where the benzene-molecular oxygen reaction is quite unimportant and the reaction of phenyl with molecular oxygen dominates. In the toluene mechanism the corresponding reaction of benzyl radicals with oxygen is unimportant. Two reactions which are important in the oxidation of benzene also influence the oxidation of toluene for several conditions. These are the oxidations of phenyl and cyclopentadienyl radicals by molecular oxygen. The mechanism presented successfully computes the decrease of toluene concentration with time in the nitrogen diluted turbulent reactor. This fact, in addition to the good prediction of ignition delay times, shows that this mechanism can be used for modeling the ignition and combustion process in practical, well-mixed combustion systems.
Soot formation in benzene-methanol and benzene-ethanol argon-diluted mixtures was studied behind reflected shock waves by monitoring the attenuation of an He-Ne laser beam. The experiments were performed at temperatures 1580-2250 K, pressures 2.0-3.0 bar, and total carbon atom concentrations (2.0-2.7) x 10 to the 17th atoms/cu cm. The results obtained indicate that the addition of alcohol suppresses the formation of soot from benzene at all temperatures, and that the reduction in soot yields is increased with the amount of alcohol added. The analysis of the results indicates that the suppression effect is probably due to the oxidation of soot and soot precursors by OH and the removal of hydrogen atoms by alcohol and water molecules.
High-resolution optical and microwave spectra of the gas-phase benzene-ammonia dimer were obtained, showing that the ammonia molecule resides above the benzene plane and undergoes free, or nearly free, internal rotation. To estimate the binding energy (De) and other global properties of the intermolecular potential, theoretical calculations were performed for the benzene-ammonia dimer, using the Gaussian 92 (Fritsch, 1992) program at the MP2/6-31G** level. The predicted De was found to be at the lowest end of the range commonly accepted for hydrogen bonding and considerably below that of C6H6-H2O, consistent with the gas-phase acidities of ammonia and water. The observed geometry greatly resembles the amino-aromatic interaction found naturally in proteins.
The continuous monitoring of changes on the quality of ambient air is a field of advantage of ion mobility spectrometry. Benzene, Toluene, and Xylene are substances of special interest because of their toxicity. We present an optimized drift tube for ion mobility spectrometers, which uses photo-ionization tubes to produce the ions to be analyzed. The actual version of this drift tube has a length of 45 mm, an electric field strength established within the drift tube of about 180 V/cm and a shutter-opening-time of 400 mus. With the hydrogen tube used for ionisation a mean flux of 10(exp 12) photons/sq cm s was established for the experiments described. We discuss the results of investigations on Benzene, Toluene, and Xylene in normal used gasoline SUPER. The detection limits obtained with the ion mobility spectrometer developed in co-operation are in the range of 10 ppbv in this case. Normally, charge transfer from Benzene ions to Toluene takes place. Nevertheless the simultaneous determination in mixtures is possible by a data evaluation procedure developed for this case. The interferences found between Xylene and others are rather weak. The ion mobility spectra of different concentrations of gasoline SUPER are attached as an example for the resolution and the detection limit of the instrument developed. Resolution and sensitivity of the system are well demonstrated. A hand-held portable device produced just now is to be tested for special environmental analytical problems in some industrial and scientific laboratories in Germany.
We report a theoretical study of the dissociative ionization (DI) and product distributions of benzene (C6H6) and pyridine (C5H5N) from their low-lying ionization channels. Our approach makes use of the fact that electronic motion is much faster than nuclear motion allowing DI to be treated as a two-step process. The first step is the electron-impact ionization resulting in an ion with the same nuclear geometry as the neutral molecule. In the second step, the nuclei relax from the initial geometry and undergo unimolecular dissociation. For the ionization process we use the improved binary-encounter dipole (iBED) model [W.M. Huo, Phys. Rev. A64,042719-I (2001)]. For the unimolecular dissociation, we use multiconfigurational self-consistent field (MCSCF) methods to determine the steepest descent pathways to the possible product channels. More accurate methods are then used to obtain better energetics of the paths which are used to determine unimolecular dissociation probabilities and product distributions. Our analysis of the dissociation products and the thresholds of their productions for benzene are compared with the recent dissociative photoionization meausurements of benzene by Feng et al. [R. Feng, G. Cooper, C.E. Brion, J. Electron Spectrosc. Relat. Phenom. 123,211 (2002)] and the dissociative photoionization measurements of pyridine by Tixier et al. [S. Tixier, G. Cooper, R. Feng, C.E. Brion, J. Electron Spectrosc. Relat. Phenom. 123,185 (2002)] using dipole (e,e+ion) coincidence spectroscopy.
Gaseous benzene-iodine and diethyl ether-iodine spectra, extinction coefficients, formation constants and enthalpies for charge transfer complexes of gaseous benzene-iodine and diethyl ether-iodine