scholarly journals Temperature-(208–318 K) and pressure-(18–696 Torr) dependent rate coefficients for the reaction between OH and HNO<sub>3</sub>

2018 ◽  
Vol 18 (4) ◽  
pp. 2381-2394 ◽  
Author(s):  
Katrin Dulitz ◽  
Damien Amedro ◽  
Terry J. Dillon ◽  
Andrea Pozzer ◽  
John N. Crowley
Keyword(s):  
Cross Sections ◽  
Pressure Dependence ◽  
Low Temperatures ◽  
Room Temperature ◽  
Rate Coefficients ◽  
Title Reaction ◽  
Data Set ◽  
Dependent Rate ◽  
Temperature And Pressure

Abstract. Rate coefficients (k5) for the title reaction were obtained using pulsed laser photolytic generation of OH coupled to its detection by laser-induced fluorescence (PLP–LIF). More than 80 determinations of k5 were carried out in nitrogen or air bath gas at various temperatures and pressures. The accuracy of the rate coefficients obtained was enhanced by in situ measurement of the concentrations of both HNO3 reactant and NO2 impurity. The rate coefficients show both temperature and pressure dependence with a rapid increase in k5 at low temperatures. The pressure dependence was weak at room temperature but increased significantly at low temperatures. The entire data set was combined with selected literature values of k5 and parameterised using a combination of pressure-dependent and -independent terms to give an expression that covers the relevant pressure and temperature range for the atmosphere. A global model, using the new parameterisation for k5 rather than those presently accepted, indicated small but significant latitude- and altitude-dependent changes in the HNO3 ∕ NOx ratio of between −6 and +6 %. Effective HNO3 absorption cross sections (184.95 and 213.86 nm, units of cm2 molecule−1) were obtained as part of this work: σ213.86  =  4.52−0.12+0.23  ×  10−19 and σ184.95  =  1.61−0.04+0.08  ×  10−17.

scholarly journals Temperature (208–318 K) and pressure (18–696 Torr) dependent rate coefficients for the reaction between OH and HNO<sub>3</sub>

2017 ◽  
Author(s):  
Katrin Dulitz ◽  
Damien Amedro ◽  
Terry J. Dillon ◽  
Andrea Pozzer ◽  
John N. Crowley
Keyword(s):  
Cross Sections ◽  
Pressure Dependence ◽  
Low Temperatures ◽  
Room Temperature ◽  
Rate Coefficients ◽  
Title Reaction ◽  
Dependent Rate ◽  
Temperature And Pressure ◽  
Entire Dataset

Abstract. Rate coefficients (k5) for the title reaction were obtained using pulsed laser photolytic generation of OH coupled to its detection by laser-induced fluorescence (PLP-LIF). More than eighty determinations of k5 were carried out in nitrogen or air bath gas at various temperatures and pressures. The accuracy of the rate coefficients obtained was enhanced by in-situ measurement of the concentrations of both HNO3 reactant and NO2 impurity. The rate coefficients show both temperature and pressure dependence with a rapid increase in k5 at low temperatures. The pressure dependence was weak at room temperature but increased significantly at low temperatures. The entire dataset was combined with selected literature values of k5 and parameterised using a combination of pressure dependent and independent terms to give an expression that covers the relevant pressure and temperature range for the atmosphere. A global model, using the new parameterisation for k5 rather than those presently accepted, indicated small but significant latitude and altitude dependent changes in the HNO3 / NOx ratio of between −6 % and +6 %. Effective HNO3 absorption cross sections (184.95 and 213.86 nm, units of cm2 molecule−1) were obtained as part of this work: σ213.86 = 4.52+0.23−0.12 × 10−19 and σ184.95 = 1.61+0.08−0.04 × 10−17.

scholarly journals Kinetics of the OH + NO<sub>2</sub> reaction: rate coefficients (217–333 K, 16–1200 mbar) and fall-off parameters for N<sub>2</sub> and O<sub>2</sub> bath gases

2019 ◽  
Vol 19 (16) ◽  
pp. 10643-10657 ◽  
Author(s):  
Damien Amedro ◽  
Arne J. C. Bunkan ◽  
Matias Berasategui ◽  
John N. Crowley
Keyword(s):  
Pressure Range ◽  
Great Influence ◽  
Rate Coefficients ◽  
Atmospheric Conditions ◽  
Collision Efficiency ◽  
Title Reaction ◽  
Temperature And Pressure ◽  
Kinetics Of ◽  
Lower Collision

Abstract. The radical terminating, termolecular reaction between OH and NO2 exerts great influence on the NOy∕NOx ratio and O3 formation in the atmosphere. Evaluation panels (IUPAC and NASA) recommend rate coefficients for this reaction that disagree by as much as a factor of 1.6 at low temperature and pressure. In this work, the title reaction was studied by pulsed laser photolysis and laser-induced fluorescence over the pressure range 16–1200 mbar and temperature range 217–333 K in N2 bath gas, with experiments at 295 K (67–333 mbar) for O2. In situ measurement of NO2 using two optical absorption set-ups enabled generation of highly precise, accurate rate coefficients in the fall-off pressure range, appropriate for atmospheric conditions. We found, in agreement with previous work, that O2 bath gas has a lower collision efficiency than N2 with a relative collision efficiency to N2 of 0.74. Using the Troe-type formulation for termolecular reactions we present a new set of parameters with k0(N2) = 2.6×10-30 cm6 molecule−2 s−1, k0(O2) = 2.0×10-30 cm6 molecule−2 s−1, m=3.6, k∞=6.3×10-11 cm3 molecule−1 s−1, and Fc=0.39 and compare our results to previous studies in N2 and O2 bath gases.

scholarly journals Temperature dependent rate coefficients for the reactions of the hydroxyl radical with the atmospheric biogenics isoprene, <i>α</i>-pinene and Δ-3-carene

2017 ◽  
Author(s):  
Terry J. Dillon ◽  
Katrin Dulitz ◽  
Christoph M. B. Gross ◽  
John N. Crowley
Keyword(s):  
Cross Sections ◽  
Room Temperature ◽  
Relative Rate ◽  
Gas Pressure ◽  
Rate Coefficients ◽  
Absorption Cross ◽  
Temperature Dependent ◽  
Degradation Reactions ◽  
Dependent Rate ◽  
Accuracy And Precision

Abstract. Abstract. Pulsed laser methods for OH generation and detection were used to study atmospheric degradation reactions for three important biogenic gases: OH + isoprene (R1); OH + α-pinene (R2); and OH + Δ-3-carene (R3). Gas-phase rate coefficients were characterised by non-Arrhenius kinetics for all three reactions. For (R1), k1 (241–356 K) = (1.93 ± 0.08) × 10−11 exp (466 ± 12)/T cm3 molecule−1 s−1 was determined, with a room temperature value of k1 (297 K) = (9.3 ± 0.4) × 10−11 cm3 molecule−1 s−1, independent of bath-gas pressure (5–200 Torr) and composition (M = N2 or air). Accuracy and precision were enhanced by online optical monitoring of isoprene, with absolute concentrations obtained via an absorption cross-section, σisoprene = (1.28 ± 0.06) × 10−17 cm2 molecule−1 at λ = 184.95 nm, determined in this work. These results indicate that significant discrepancies between previous absolute and relative rate determinations of k1 result in part from σ values used to derive the isoprene concentration. Similar methods were used to determine rate coefficients (in 10−11 cm3 molecule−1 s−1) for (R2–R3): k2 (238–357 K) = (1.83 ± 0.04) × exp (330 ± 6)/T; and k3 (235–357 K) = (2.48 ± 0.14) × exp (357 ± 17)/T. This is the first temperature-dependent dataset for (R3) and enables the calculation of reliable atmospheric lifetimes with respect to OH removal for e.g. boreal forest springtime conditions. Room temperature values of k2 (296 K) = (5.4 ± 0.2) × 10−11 cm3 molecule−1 s−1 and k3 (297 K) = (8.1 ± 0.3) × 10−11 cm3 molecule−1 s−1 were independent of bath-gas pressure (7–200 Torr, N2 or air), and in good agreement with previously reported values. In the course of this work, 184.95 nm absorption cross-sections were determined: σ = (1.54 ± 0.08) × 10−17cm 2 molecule−1 for α-pinene and (2.40 ± 0.12) × 10−17  cm2 molecule−1 for Δ-3-carene.

DYNAMICS OF THE N(2D)+H2 REACTION ON THE $\tilde{X}^2 A^{\prime\prime}$ SURFACE, PROPAGATING REAL WAVE PACKETS WITH AN ARCCOS MAPPING OF THE HAMILTONIAN

2003 ◽  
Vol 02 (04) ◽  
pp. 547-551 ◽  
Author(s):  
PAOLO DEFAZIO ◽  
CARLO PETRONGOLO
Keyword(s):  
Rate Constant ◽  
Cross Sections ◽  
Room Temperature ◽  
Wave Packets ◽  
Flux Analysis ◽  
Title Reaction ◽  
Angular Momentum Quantum Number ◽  
Insertion Mechanism ◽  
Temperature Rate ◽  
Good Agreement

We have investigated the dynamics of the title reaction with the Gray and Balint-Kurti approach, which propagates real wave packets (WP) under an arccos mapping of a scaled and shifted Hamiltonian. We have considered H 2 rotational quanta j=0 and 1 and obtained reaction probabilities using reactant coordinates and the flux analysis. We have calculated accurate reaction probabilities for total angular momentum quantum number J=0, centrifugal-sudden probabilities for J>0, cross sections, and the room temperature rate constant. The present cross sections are in good agreement with previous quasiclassical trajectory (QCT) results and the theoretical rate constant compares rather well with that observed. WP snapshots show that the reaction occurs via a C2v insertion mechanism, confirming previous QCT calculations.

scholarly journals Structure determination from in situ diffraction with the Rigaku PlateMate

2014 ◽  
Vol 70 (a1) ◽  
pp. C1152-C1152
Author(s):  
Pierre Le Magueres ◽  
Angela Criswell ◽  
Joseph Ferrara
Keyword(s):  
Room Temperature ◽  
Data Set ◽  
X Ray ◽  
The Past ◽  
Large Numbers ◽  
Structure Solution ◽  
Crystal Properties ◽  
Manual Handling ◽  
In Situ Diffraction

As crystallographers face increasing problems with crystallizing new proteins, in-situ screening in crystallization trays at room temperature is experiencing a renaissance. It saves a lot of time when screening large numbers of crystallization hits and it helps avoid crystal damage caused by human manipulation error (harsh manual handling, bad freezing) or changes in crystal properties (dehydration, wrong cryo-conditions). In certain cases, it is also possible to go beyond screening and collect enough data for structure solution, especially on an X-ray home source where a less intense beam helps minimize the devastations of radiation damage occurring at room temperature. The Rigaku PlateMate has proved itself as an efficient and easy-to-use in-situ screening tool on the field for the past two years. It is as easily mounted on a goniometer as a regular goniometer head and thanks to a plate adapter with SBS footprints, it accommodates most 96-wells plate types, from sitting and hanging drop to LCP plates. In addition, thanks to its narrow dimensions and aided by software to prevent collisions with the detector and the crystal viewing camera, the PlateMate can be used to easily collect data from crystals in situ. In this work, we present structure solution results obtained from data collected with the PlateMate on crystals from various proteins (native crystals or containing gold or iodine) and using one or multiple crystals to make up a complete data set.

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