NO2 lifetimes by hanle effect measurements

We explain controversial results of previous Hanle effect (zero magnetic field level crossing) experiments on NO₂. It is shown that the magnetic resonance signal is in general associated with two characteristic times, the radiative lifetime τ_R ≳ 40 μs and an intramolecular decay time τ₀ ≈ 3 μs. The contributions of both times to the magnetic resonance signal have to beclearly separated to give reliable results. The two times τ_R and τ₀ are observed for all investigated absorption lines near 593 and 514 nm.     

A shock tube study of the pyrolysis of NO2

NO₂ concentration profiles in shock-heated NO₂/Ar mixtures were measured in the temperature range of 1350–2100 K and pressures up to 380 atm using Ar⁺ laser absorption at 472.7 nm, IR emission at 6.25±0.25 μm, and visible emission at 300–600 nm. In the course of this study, the absorption coefficient of NO₂ at 472.7 nm was measured at temperatures from 300 K to 2100 K and pressures up to 75 atm. Rate coefficients for the reactions NO₂+M→NO+O+M (1), NO₂+NO₂→2NO+O₂ (2a), and NO₂+NO₂→NO₃+NO (2b) were derived by comparing the measured and calculated NO₂ profiles. For reaction (1), the following low- and high-pressure limiting rate coefficients were inferred which describe the measured fall-off curves in Lindemann form within 15% [FORMULA] The inferred rate coefficient at the low- pressure limit, k_1o, is in good agreement with previous work at higher temperatures, but the energy of activation is lower by 20 kJ/mol than reported previously. The pressure dependence of k₁ observed in the earlier work of Troe [1] was confirmed. The rate coefficient inferred for the high pressure limit, k_1∞, is higher by a factor of two than Troe's value, but in agreement with data obtained by measuring specific energy-dependent rate coefficients. For the reactions (2a) and (2b), least-squares fits of the present data lead to the following Arrhenius expressions: [FORMULA] For reaction (2), the new data agree with previously recommended values of k_2a and k_2b, although the present study suggests a slightly higher preexponential factor for k_2a. © 1997 John Wiley & Sons, Inc. Int J Chem Kinet 29: 483–493, 1997.     

Molecular beam chemiluminescence. Collisional dissociation of tetramethyldioxetane by a fast xenon beam

The chemiluminescence arising from collisional dissociation of tetramethyldioxetane (TMD) by a supersonic xenon beam is recorded as function of collision energy (1–4.6 eV) and of TMD pressure. At TMD pressures as low as 5 × 10^?5 torr a third-order process is prominent, demonstrating the importance of secondary collisions which enhance the light yield. The energy dependence shows a threshold at E_O ≈ 30 ± 3 kcal/mol. Structure in the energy dependence is interpreted in terms of a rise with energy of the singlet/triplet acetone branching ratio.     

A study of product ratios in the direct (313 nm) and Hg-sensitized (254 nm) photodecomposition of 2-methylcyclohexanone in the gas phase

The photolysis of 2-methylcyclohexanone has been studied in the gas phase at 313 nm, mainly at 100°C, over a range of pressures. The Hg(6³P₁) photosensitized decomposition has also been investigated at 100°C. Under conditions of high excitation and/or little collisional quenching the major products are carbon monoxide and the hydrocarbons: 1-hexene, trans-and cis-2-hexene and methylcyclopentane, with minor aldehyde formation. The various product ratios are presented in tabular form. At lower excitation energies, and with increased collisional deactivation, trans- and cis-5-heptenal become important products, and the trans/cis aldehyde ratio is seen to be slightly pressure dependent when all the systems are compared. Similarly, there is a small pressure dependence for the Σ hexenes/methylcyclopentane ratio. From experiments at 250°C the temperature dependence of this ratio was established, and for thermalized hexane-1,5-diyl an activation energy difference (E_d ? E_c) = ?1.3 kcal mol^?1 has been determined for the disproportionation and combination of the biradical. The mechanism for the photolysis is discussed in terms of triplet state photochemistry and biradical intermediates as developed, in particular, by Frey and coworkers, this Journal, 16 , 1337 (1984).     

Ruby laser induced emission from NO2

Two different types of emission from excited NO₂ were observed using pulsed ruby laser light at 6943 Å. The first type of fluorescence was seen in the near-IR and results from the single photon excitation of NO₂ from the ground (²A₁) state. By observing the emission as a function of time an unexpected behavior was observed in the near IR and could be explained by a consecutive deactivation mechanism, wherein a secondary species is preferentially detected. A second type of emission recently observed in the blue spectral region is weaker and is due to a multiphoton process. The intensity of the blue emission is a function of the cube of the laser intensity at low pressures and approaches the square at high pressures. We attribute this variation to simultaneous deactivation of the NO₂^* intermediate by collision (square) and by anti-Stokes Raman scattering off of the NO₂^* (cube).     

Weak transverse magnetic field effect on the viscosity of Mn(NO3)2H2O solution at several temperature

Experiments show that transversally applied magnetic field H of strength 12 kG at 10, 15, 20, 25, 30, 40 and 60°C and the ambient pressure decreases the viscosity of high concentration Mn(NO₃)₂H₂O solution. The largest value of this decrease occurs at the temperature range of 20–25°C. On the other hand, at low paramagnetic ion concentrations, the applied magnetic field increases the viscosity of Mn(NO₃)₂H₂O solution in such a way that the observed effect value in the limit seems to approach the already measured viscosity increase of the pure water. However, the temperature dependence of the observed viscosity increase of the given dilute paramagnetic Mn(NO₃)₂H₂O solution appears to be more complex and at some temperature even opposite to that already shown viscosity—temperature behavior of the diamagnetic pure water.     

Kinetics of the reactions of isopropoxy radicals with NO,NO2, and O2

A fluorescence excitation spectrum of (CH₃)₂CHO (isopropoxy radical) is reported following photolysis of isopropyl nitrite at 355 nm. Rate constants for the reaction of isopropoxy with NO, NO₂, and O₂ have been measured as a function of pressure (1–50 Torr) and temperature (25–110°C) by monitoring isopropoxy radical concentrations using laser-induced fluorescence. We have obtained the following Arrhenius expressions for the reaction of isopropoxy with NO and O₂ respectively: (1.22±0.28)×10^?11 exp[(+0.62±0.14 kcal)/RT]cm²/s and (1.51±0.70)×10^?14 exp[(?0.39±0.28)kcal/RT]cm³/s where the uncertainties represent 2σ. The results with NO₂ are more complex, but indicate that reaction with NO₂ proceeds more rapidly than with NO contrary to previous reports. The pressure dependence of the thermal decomposition of the isopropoxy radical was studied at 104 and 133°C over a 300 Torr range using nitrogen as a buffer gas. The reaction is in the fall-off region over the entire range. Upper limits for the reaction of isopropoxy with acetaldehyde, isobutane, ethylene, and trimethyl ethylene are reported.We have performed the first LIF study of the isopropoxy radical. Arrhenius parameters were measured for the reaction of i-PrO with O₂, NO, NO₂, using direct radical measurement techniques. All reactions are in their high-pressure limits at a few Torr of pressure. The rate constant for the reactions of i-PrO with NO and NO₂ reactions exhibit a small negative activation energy. Studies of the i-PrO + NO₂ reaction produce data which indicate that O(³P) reacts rapidly with i-PrO. Unimolecular decomposition studies of i-PrO indicate that the reaction is in the fall-off region between 1 and 300 Torr of N₂ and the high-pressure limit is above 1 atmosphere of N₂.     

A simple model for the difference between coherence time and radiative lifetime in NO2

An intramolecular mechanism is proposed to reconcile the different lifetimes obtained from direct radiative decay measurements and from Hanle effect measurements on NO₂. This mechanism predicts a dependence of the coherence lifetime on the excited state rotational quantum number which is in good agreement with the previous experiments.     

Fluorescence lifetimes of formaldehyde (H2CO) in the A1A2 --> X1A2 band system at elevated temperatures and pressures

Fluorescence lifetimes of formaldehyde excited by picosecond laser radiation with a wavelength of 355 nm were determined in nitrogen gas in a cell using time-resolved laser-induced fluorescence spectroscopy. The measurements were conducted at temperatures between 295 and 770 K and pressures up to 10 bar (1 MPa). Detection was broadband in most cases. Temperature and pressure were found to have a quenching effect on the fluorescence. At 295 K and pressures between 1 and 5 bar, decay rates between 0.03 and 0.04 ns(-1) were observed. At 770 K, the decay rates increased from 0.11 to 0.17 ns(-1) as the pressure was raised from 1 to 10 bar. The dependence on pressure was not linear at 1 bar. At 10 bar the linearity is unclear. The dependence on temperature appeared to be exponential.     

Comparative Analysis of Indoor Levels of Suspended Particulates and Nitrogen Dioxide a Few Hours later after an Asthmatic Attack

Suspended particulates （TSP） and nitrogen dioxide （NO2） are known respiratory irritants linked to asthma aggravation. This pilot study was designed to investigate the role of these pollutants on the frequency of asthmatic attack on two of the inhabitants of a household. The surveillance of TSP and NO2 in this household commenced a few hours later, after one of the occupants suffered an attack. The TSP load determination was done using a High Volume Gravimetric sampler and a light scattering method via a Haz-Dust 10 μm particulate monitor. Palmes Diffusion tubes for NO2 and a portable Crowcon Gasman toxic gas detector were utilized for NO2 screening. In the first day of monitoring in the living room, the in situ particulate sampler （Haz-Dust） recorded a mean TSP level of 26,000 μg·m^-3. A confirmatory test with the eight hour average Gravimetric sampler gave 25,833 μg·m^-3. With the use of the Gasman toxic gas detector for NO2, the NO2 concentration for the first few hours of sampling was lower than 188 μg·m^-3, the detection limit of this instrument. However, the exact NO2 concentrations for the 7 day monitoring after the attack were 27.50 μg·m^-3 （kitchen） and 12.03 μg·m^-3 （living room） as recorded by the Palmes diffusion tubes.     

Microwave-Optical Double Resonance and Intermodulated Fluorescence Studies of Thioformaldehyde

Studies of the 4¹₀ band of the à ¹A₂ X?¹A₁ transition of thioformaldehyde by means of intermodulated fluorescence and microwave-optical double resonance have revealed numerous small perturbations in the excited state levels caused by high rovibronic levels of the ground state. Singlet-triplet perturbations have been studied by the same techniques and also by anticrossings produced in the presence of a magnetic field. The use of microwave-optical double resonance for studying collisional processes is discussed.     

Picosecond UV photolysis and laser-induced fluorescence probing of gas-phase nitromethane

Ground-state NO₂ radicals are formed in <5 ps with a quantum yield of ≈ 70% in 264 nm photolysis of low pressure nitromethane, as revealed by laser-induced fluorescence probing. Raman shifted photolyzing pulses indicate the NO₂ yield varies little with wavelength, although a small yield of excited state NO^*₂ produced at 264 nm increases significantly at 238 nm.     

Hanle effect measurement of the lifetime of the A 1II state of PN

Hanle effect spectra have been observed for A ¹II PN. PN is generated in a microwave discharge and flowed into a fluorescence cell where it is optically excited by a PN emission lamp. The Hanle effect signal for the ν′ = 0 band is fitted to a calculated signal, determining a radiative lifetime for the band of 227 ± 70 ns.     

Collisional depolarization of excited114Cd 5s5p 3 P 1 atoms by collisions with molecular gases

Depolarization of excited¹¹⁴Cd 5s5p ³ P ₁ atoms induced by collisions with various molecular gases (N₂, H₂, D₂, CO, CO₂, CH₄, C₂H₆, C₂H₄) has been investigated using polarized fluorescence spectroscopy. After pulsed optical excitation of the Cd 5³ P ₁ level with appropriately polarized light the temporal behaviour of Zeeman quantum beats has been observed showing the influence of collisional destruction of orientation and alignment. By analyzing the signal curves at different molecular gas pressures the corresponding depolarization cross sections for¹¹⁴Cd atoms in the 5³ P ₁ state have been obtained. With regard to a test of a nuclear spin decoupling model for the collisions the cross sections were compared with previously measured hyperfine structure transfer cross sections of¹¹³Cd 5s5p ³ P ₁ atoms.     

Validation of a thermal decomposition mechanism of formaldehyde by detection of CH2O and HCO behind shock waves

The thermal decomposition of formaldehyde was investigated behind shock waves at temperatures between 1675 and 2080 K. Quantitative concentration time profiles of formaldehyde and formyl radicals were measured by means of sensitive 174 nm VUV absorption (CH₂O) and 614 nm FM spectroscopy (HCO), respectively. The rate constant of the radical forming channel (1a), CH₂O + M → HCO + H + M, of the unimolecular decomposition of formaldehyde in argon was measured at temperatures from 1675 to 2080 K at an average total pressure of 1.2 bar, k_1a = 5.0 × 10¹⁵ exp(‐308 kJ mol^?1/RT) cm³ mol^?1 s^?1. The pressure dependence, the rate of the competing molecular channel (1b), CH₂O + M → H₂ + CO + M, and the branching fraction β = k_1a/(kA_1a + k_1b) was characterized by a two‐channel RRKM/master equation analysis. With channel (1b) being the main channel at low pressures, the branching fraction was found to switch from channel (1b) to channel (1a) at moderate pressures of 1–50 bar. Taking advantage of the results of two preceding publications, a decomposition mechanism with six reactions is recommended, which was validated by measured formyl radical profiles and numerous literature experimental observations. The mechanism is capable of a reliable prediction of almost all formaldehyde pyrolysis literature data, including CH₂O, CO, and H atom measurements at temperatures of 1200–3200 K, with mixtures of 7 ppm to 5% formaldehyde, and pressures up to 15 bar. Some evidence was found for a self‐reaction of two CH₂O molecules. At high initial CH₂O mole fractions the reverse of reaction (6), CH₂OH + HCO ? CH₂O + CH₂O becomes noticeable. The rate of the forward reaction was roughly measured to be k₆ = 1.5 × 10¹³ cm³ mol^?1 s^?1. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 157–169 2004     

High-pressure Raman study of vibrational relaxation in N2O

The vibrational widths of the ν₁ and ν₃ Raman bands of N₂O were determined at pressures ranging from 8 bar to 2 kbar and temperatures varied from 25 to 150°C. The different dephasing theories including motional narrowing collisional models and resonant vibrational energy transfer theory were tested. A comparison of the theoretical predictions with the experimental data indicates the resonance VV transfer represents the dominant broadening mechanism. The observed frequency shifts between isotropic and anisotropic components of the bands were interpreted in terms of dipole-dipole interactions in dense N₂O.     

Molecular polarization and laser photopredissociation in the presence of a magnetic field

The theory of the angular distribution of the photofragment resulting from weak predissociation in a diatomic molecule is worked out in the density matrix formalism. Special attention is given to the relationship between photofragment anisotropy, molecular polarization and fluorescence light polarization. The effect of a steady applied magnetic field is discussed and compared with classical Hanle effect. Application to the case of O₂⁺, b⁴σ_R^? state studied by fast ion beam laser spectroscopy (FIBLAS) is presented. Zeeman effect of the low J levels is observed in good agreement with theory and the angular distribution of the photofragments arising from a few selected Zeeman sublevels offers qualitative experimental confirmation of the theoretically predicted behavior.     

A kinetics study of the reaction of Cl with NO2

The third order rate coefficients for the addition reaction of Cl with NO₂, Cl + NO₂ + M → ClNO₂ (ClONO) + M; k₁, were measured to be k₁(He) = (7.5 ± 1.1) × 10^?31 cm⁶ molecule^?2 s^?1 and k₁(N₂) = (16.6 ± 3.0) × 10^?31 cm⁶ molecule^?2 s^?1 at 298 K using the flash photolysis-resonance fluorescence method. The pressure range of the study was 15 to 500 torr He and 19 to 200 torr N₂. The temperature dependence of the third order rate coefficients were also measured between 240 and 350 K. The 298 K results are compared with those from previous low pressure studies.     

N2O5 photolysis products investigated by fluorescence and optoacoustic techniques

Pulsed laser photolysis of N₂O₅ near 290 nm coupled with fluorescence detection (calibrated by NO₂ photolysis) showed that the O(³P) quantum yield is ≤0.1. A pulsed laser optoacoustic technique in a flow tube (ca. 6 torr of N₂) was tested by photolysis of NO₂ and then applied to N₂O₅. Nitric oxide was added to react with NO₃ free radical and the resulting increase in the optoacoustic signal confirmed the presence of NO₃ free radicals. Based on the relative optoacoustic signals observed for NO₂ and N₂O₅, the quantum yield for NO₃ production is 0.8 ± 0.2.     

An experimental and modeling study of the oxidation of n-heptane,ethylbenzene, and n-butylbenzene in a jet-stirred reactor at pressures up to 10 bar

In the context of better understanding pollutant formation from internal combustion engines, new experimental speciation data were obtained in a high-pressure jet-stirred reactor for the oxidation of three molecules, which are considered in surrogates of diesel fuel, n-heptane, ethylbenzene, and n-butylbenzene. These experiments were performed at pressures up to 10 bar, at temperatures ranging from 500 to 1 100 K, and for a residence time of 2 s. Based on results previously obtained close to the atmospheric pressure for the same molecules, the pressure effect on fuel conversion and product selectivity was discussed. In addition, for the three fuels, the experimental temperature dependence of species mole fractions was compared with simulations using recent literature models with generally a good agreement. For n-heptane, the obtained experimental data, at 10 bar for stoichiometric mixtures, included the temperature dependence of the mole fractions of the reactants and those of 21 products. Interestingly, the formation of species previously identified as C₇ diones was found significantly enhanced at 10 bar compared with lower pressures. The oxidation of ethyl- and n-butylbenzenes was investigated at 10 bar for equivalence ratios of 0.5, 1, and 2. The obtained experimental data included the temperature dependence of the mole fractions of the reactants and those of 13 products for the C₈ fuels and of 19 products for the C₁₀ one. For ethylbenzene under stoichiometric conditions, the pressure dependence (from 1 to 10 bar) of species mole fraction was also recorded and compared with simulations with more deviations obtained than for temperature dependence. For both aromatic reactants, a flow rate analysis was used to discuss the main pressure influence on product selectivities.