Free-field propagation of high intensity noise

Observed spectral data from supersonic jet aircraft are known to contain much more high frequency energy than can be explained by linear acoustic propagation theory. It is believed that the high frequency energy is an effect of nonlinear distortion due to the extremely high acoustic levels generated by the jet engines. The objective, to measure acoustic waveform distortion for spherically diverging high intensity noise, was reached by using an electropneumatic acoustic source capable of generating sound pressure levels in the range of 140 to 160 decibels (re 20 micro Pa). The noise spectrum was shaped to represent the spectra generated by jet engines. Two microphones were used to capture the acoustic pressure waveform at different points along the propagation path in order to provide a direct measure of the waveform distortion as well as spectral distortion. A secondary objective was to determine that the observed distortion is an acoustic effect. To do this an existing computer prediction code that deals with nonlinear acoustic propagation was used on data representative of the measured data. The results clearly demonstrate that high intensity jet noise does shift the energy in the spectrum to the higher frequencies along the propagation path. In addition, the data from the computer model are in good agreement with the measurements, thus demonstrating that the waveform distortion can be accounted for with nonlinear acoustic theory

Laserspektroskopische Untersuchungen und molekularkinetische Modellierung der Kinetik von Radikalreaktionen in der Gasphase

In der vorliegenden Arbeit wurde der thermische Zerfall des Cyclohexoxyradikals sowie die Reaktion von NCN mit NO über einen breiten Parameterbereich untersucht. Es wurden Experimente in quasi-statischen Reaktoren mit Laserphotolyse-/LIF-Technik durchgeführt. Die experimentellen Ergebnisse wurden mit statistischer Reaktionstheorie analysiert. Besondere Bedeutung kam der adäquaten Beschreibung von gehinderten inneren Rotatoren zu, wofür Methoden programmiert, implementiert und getestet wurden

Laserspektroskopische Untersuchungen und molekularkinetische Modellierung der Kinetik von Radikalreaktionen in der Gasphase

In der vorliegenden Arbeit wurde der thermische Zerfall des Cyclohexoxyradikals sowie die Reaktion von NCN mit NO über einen breiten Parameterbereich untersucht. Es wurden Experimente in quasi-statischen Reaktoren mit Laserphotolyse-/LIF-Technik durchgeführt. Die experimentellen Ergebnisse wurden mit statistischer Reaktionstheorie analysiert. Besondere Bedeutung kam der adäquaten Beschreibung von gehinderten inneren Rotatoren zu, wofür Methoden programmiert, implementiert und getestet wurden

Observations of aerosol, cloud, turbulence, and radiation properties at the top of the Marine Boundary Layer over the Eastern North Atlantic Ocean

We report on the Azores Stratocumulus Measurements of Radiation, Turbulence and Aerosols (ACORES) campaign, which took place around Graciosa and Pico Islands/Azores in July 2017. The main objective was to investigate the vertical distribution of aerosol particles, stratocumulus microphysical and radiative properties, and turbulence parameters in the eastern North Atlantic. The vertical exchange of mass, momentum, and energy between the free troposphere (FT) and the cloudy marine boundary layer (MBL) was explored over a range of scales from submeters to kilometers. To cover these spatial scales with appropriate measurements, helicopterborne observations with unprecedented high resolution were realized using the Airborne Cloud Turbulence Observation System (ACTOS) and Spectral Modular Airborne Radiation Measurement System–Helicopter-Borne Observations (SMART-HELIOS) instrumental payloadsPostprint (published version

VUV Photoionization Cross Sections of HO_2, H_2O_2, and H_2CO

The absolute vacuum ultraviolet (VUV) photoionization spectra of the hydroperoxyl radical (HO_2), hydrogen peroxide (H_2O_2), and formaldehyde (H_2CO) have been measured from their first ionization thresholds to 12.008 eV. HO_2, H_2O_2, and H_2CO were generated from the oxidation of methanol initiated by pulsed-laser-photolysis of Cl_2 in a low-pressure slow flow reactor. Reactants, intermediates, and products were detected by time-resolved multiplexed synchrotron photoionization mass spectrometry. Absolute concentrations were obtained from the time-dependent photoion signals by modeling the kinetics of the methanol oxidation chemistry. Photoionization cross sections were determined at several photon energies relative to the cross section of methanol, which was in turn determined relative to that of propene. These measurements were used to place relative photoionization spectra of HO_2, H_2O_2, and H_2CO on an absolute scale, resulting in absolute photoionization spectra

Direct kinetics study of CH2OO + methyl vinyl ketone and CH2OO + methacrolein reactions and an upper limit determination for CH2OO + CO reaction

Methyl vinyl ketone (MVK) and methacrolein (MACR) are important intermediate products in atmospheric degradation of volatile organic compounds, especially of isoprene. This work investigates the reactions of the smallest Criegee intermediate, CH2OO, with its co-products from isoprene ozonolysis, MVK and MACR, using multiplexed photoionization mass spectrometry (MPIMS), with either tunable synchrotron radiation from the Advanced Light Source or Lyman-alpha (10.2 eV) radiation for photoionization. CH2OO was produced via pulsed laser photolysis of CH(2)l(2) in the presence of excess O-2. Time-resolved measurements of reactant disappearance and of product formation were performed to monitor reaction progress; first order rate coefficients were obtained from exponential fits to the CH2OO decays. The bimolecular reaction rate coefficients at 300 K and 4 Torr are k(CH2OO + MVK) = (5.0 +/- 0.4) x 10(-13) cm(3) s(-1) and k(CH2OO + MACR) = (4.4 +/- 1.0) x 10(-13) cm(3) s(-1), where the stated +/- 2 sigma uncertainties are statistical uncertainties. Adduct formation is observed for both reactions and is attributed to the formation of a secondary ozonides (1,2,4-trioxolanes), supported by master equation calculations of the kinetics and the agreement between measured and calculated adiabatic ionization energies. Kinetics measurements were also performed for a possible bimolecular CH2OO + CO reaction and for the reaction of CH2OO with CF3CHCH2 at 300 K and 4 Torr. For CH2OO + CO, no reaction is observed and an upper limit is determined: k(CH2OO + CO) <2 x 10(-16) cm(3) s(-1). For CH2OO + CF3CHCH2, an upper limit of k(CH2OO + CF3CHCH2) <2 x 10(-14) cm(3) s(-1) is obtained.Peer reviewe

Проектирование расписания движения городского пассажирского транспорта на основе одноприборной задачи теории расписания

The branched C alcohol isopentanol (3-methylbutan-1-ol) has shown promise as a potential biofuel both because of new advanced biochemical routes for its production and because of its combustion characteristics, in particular as a fuel for homogeneous-charge compression ignition (HCCI) or related strategies. In the present work, the fundamental autoignition chemistry of isopentanol is investigated by using the technique of pulsed-photolytic Cl-initiated oxidation and by analyzing the reacting mixture by time-resolved tunable synchrotron photoionization mass spectrometry in low-pressure (8 Torr) experiments in the 550-750 K temperature range. The mass-spectrometric experiments reveal a rich chemistry for the initial steps of isopentanol oxidation and give new insight into the low-temperature oxidation mechanism of medium-chain alcohols. Formation of isopentanal (3-methylbutanal) and unsaturated alcohols (including enols) associated with HO production was observed. Cyclic ether channels are not observed, although such channels dominate OH formation in alkane oxidation. Rather, products are observed that correspond to formation of OH via β-C-C bond fission pathways of QOOH species derived from β- and γ-hydroxyisopentylperoxy (RO ) radicals. In these pathways, internal hydrogen abstraction in the RO QOOH isomerization reaction takes place from either the -OH group or the C-H bond in α-position to the -OH group. These pathways should be broadly characteristic for longer-chain alcohol oxidation. Isomer-resolved branching ratios are deduced, showing evolution of the main products from 550 to 750 K, which can be qualitatively explained by the dominance of RO chemistry at lower temperature and hydroxyisopentyl decomposition at higher temperature

Direct Measurements of Unimolecular and Bimolecular Reaction Kinetics of the Criegee Intermediate (CH 3 ) 2 COO

The Criegee intermediate acetone oxide, (CH3)2COO, is formed by laser photolysis of 2,2-diiodopropane in the presence of O2 and characterized by synchrotron photoionization mass spectrometry and by cavity ring-down ultraviolet absorption spectroscopy. The rate coefficient of the reaction of the Criegee intermediate with SO2 was measured using photoionization mass spectrometry and pseudo-first-order methods to be (7.3 ± 0.5) × 10–11 cm3 s–1 at 298 K and 4 Torr and (1.5 ± 0.5) × 10–10 cm3 s–1 at 298 K and 10 Torr (He buffer). These values are similar to directly measured rate coefficients of anti-CH3CHOO with SO2, and in good agreement with recent UV absorption measurements. The measurement of this reaction at 293 K and slightly higher pressures (between 10 and 100 Torr) in N2 from cavity ring-down decay of the ultraviolet absorption of (CH3)2COO yielded even larger rate coefficients, in the range (1.84 ± 0.12) × 10–10 to (2.29 ± 0.08) × 10–10 cm3 s–1. Photoionization mass spectrometry measurements with deuterated acetone oxide at 4 Torr show an inverse deuterium kinetic isotope effect, kH/kD = (0.53 ± 0.06), for reactions with SO2, which may be consistent with recent suggestions that the formation of an association complex affects the rate coefficient. The reaction of (CD3)2COO with NO2 has a rate coefficient at 298 K and 4 Torr of (2.1 ± 0.5) × 10–12 cm3 s–1 (measured with photoionization mass spectrometry), again similar to rate for the reaction of anti-CH3CHOO with NO2. Cavity ring-down measurements of the acetone oxide removal without added reagents display a combination of first- and second-order decay kinetics, which can be deconvolved to derive values for both the self-reaction of (CH3)2COO and its unimolecular thermal decay. The inferred unimolecular decay rate coefficient at 293 K, (305 ± 70) s–1, is similar to determinations from ozonolysis. The present measurements confirm the large rate coefficient for reaction of (CH3)2COO with SO2 and the small rate coefficient for its reaction with water. Product measurements of the reactions of (CH3)2COO with NO2 and with SO2 suggest that these reactions may facilitate isomerization to 2-hydroperoxypropene, possibly by subsequent reactions of association products