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1.
Simen Gjelseth Antonsen Arne Joakim C. Bunkan Tomas Mikoviny Yngve Stenstrøm Armin Wisthaler 《Molecular physics》2020,118(15)
The kinetics of the O3, OH and NO3 radical reactions with diazomethane were studied in smog chamber experiments employing long-path FTIR and PTR-ToF-MS detection. The rate coefficients were determined to be k CH2NN+O3?=?(3.2?±?0.4)?×?10?17 and k CH2NN+OH?=?(1.68?±?0.12)?×?10?10 cm3 molecule?1 s?1 at 295?±?3?K and 1013?±?30 hPa, whereas the CH2NN?+?NO3 reaction was too fast to be determined in the static smog chamber experiments. Formaldehyde was the sole product observed in all the reactions. The experimental results are supported by CCSD(T*)-F12a/aug-cc-pVTZ//M062X/aug-cc-pVTZ calculations showing the reactions to proceed exclusively via addition to the carbon atom. The atmospheric fate of diazomethane is discussed. 相似文献
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Ozonolysis of a Series of Methylated Alkenes: Reaction Rate Coefficients and Gas‐Phase Products 下载免费PDF全文
Tristan Braure Véronique Riffault Alexandre Tomas Romeo Iulian Olariu Cecilia Arsene Yuri Bedjanian Patrice Coddeville 《国际化学动力学杂志》2015,47(9):596-605
The gas‐phase ozonolysis of three methylated alkenes, i.e., trans‐2,2‐dimethyl‐3‐hexene (22dM3H), trans‐2,5‐dimethyl‐3‐hexene (25dM3H), and 4‐methyl‐1‐pentene (4M1P), has been investigated in the presence of sufficient hydroxyl radical scavenger in a laminar flow reactor at ambient temperature (296 ± 2 K) and P = 1 atm of dry air (RH ≤ 5%). Ozone levels in the reactor were monitored by an automatic analyzer. Alkene and gas‐phase product concentrations were determined via online sampling either on three‐bed adsorbent cartridges followed by thermodesorption and GC/FID‐MS analysis or on 2,4‐dinitrophenylhydrazine (DNPH) cartridges for subsequent HPLC/UV analysis. Reaction rate coefficients of (3.38 ± 0.12) × 10?17 for 22dM3H and (2.71 ± 0.26) × 10?17 for 25dM3H, both in cm3 molecule?1 s?1 units, have been obtained under pseudo–first‐order conditions. Primary carbonyl products have been identified for the three investigated alkenes, and branching ratios are reported. In the case of 4M1P ozonolysis, the yield of a Criegee intermediate was indirectly determined. Kinetics and product study results are compared to those of literature when available. This work represents the first investigation of reaction products in the ozonolysis of 22dM3H, 25dM3H, and 4M1P in a flow reactor. 相似文献
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In this paper, a generalized anti–maximum principle for the second order differential operator with potentials is proved. As an application, we will give a monotone iterative scheme for periodic solutions of nonlinear second order equations. Such a scheme involves the Lp norms of the growth, 1 ≤ p ≤ ∞, while the usual one is just the case p = ∞. 相似文献
6.
Twelve-membered ring pseudopeptidic cyclic disulfides have been prepared by iodine oxidation of the parent dithiols. However, oxidation of N,N′-(1,2-phenylene)bis(2-mercapto-2-methylpropanamide) afforded a 25/75 mixture of cyclic mono- and bis-disulfides that were separated by selective precipitation in CHCl3. The cyclic bis-disulfide was selectively prepared by iodine oxidation of the Ni complex of this dithiol and crystallized. Its crystal structure was solved by X-ray diffraction. All these cyclic mono- or bis-disulfides were selectively converted to cyclic mono- and bis-thiosulfinates upon stoichiometric oxidation with dimethyldioxirane at low temperature. 1H NMR of the cyclic bis-thiosulfinate revealed the presence of four isomers, two couples of stereoisomers, as expected from the insertion of two oxygen atoms in this compound, one on each disulfide bond. The two couples of cis/trans isomers were separated by preparative TLC and identified after alkaline cleavage of the two S(O)-S bonds and metalation with Ni(II). As HO− attack is selective for the sulfinyl sulfur, the nature of the Ni complexes obtained is a signature of each couple of stereoisomers. 相似文献
7.
A fictitious domain approach to the numerical solution of PDEs in stochastic domains 总被引:1,自引:0,他引:1
We present an efficient method for the numerical realization of elliptic PDEs in domains depending on random variables. Domains
are bounded, and have finite fluctuations. The key feature is the combination of a fictitious domain approach and a polynomial
chaos expansion. The PDE is solved in a larger, fixed domain (the fictitious domain), with the original boundary condition
enforced via a Lagrange multiplier acting on a random manifold inside the new domain. A (generalized) Wiener expansion is
invoked to convert such a stochastic problem into a deterministic one, depending on an extra set of real variables (the stochastic
variables). Discretization is accomplished by standard mixed finite elements in the physical variables and a Galerkin projection
method with numerical integration (which coincides with a collocation scheme) in the stochastic variables. A stability and
convergence analysis of the method, as well as numerical results, are provided. The convergence is “spectral” in the polynomial
chaos order, in any subdomain which does not contain the random boundaries. 相似文献
8.
A noncooperative game governed by a distributed-parameter predator-prey system is considered, assuming that two players control
initial conditions for predator and prey, respectively. Existence of a Nash equilibrium is shown under the condition that
the desired population profiles and the environmental carrying capacity for the prey are sufficiently small. A conceptual
approximation algorithm is proposed and analyzed. Finally, numerical simulations are performed, too. 相似文献
9.
The paper is devoted to statistical nonparametric estimation of multivariate distribution density. The influence of data pre-clustering
on the estimation accuracy of multimodal density is analyzed by means of the Monte Carlo method. It is shown that the soft
clustering is more advantageous than the hard one. While a moderate increase in the number of clusters also increases the
calculation time, it considerably reduces the estimation error. 相似文献
10.
Dimensional analysis is presented as a powerful tool in the study of the paste boriding process. In particular, a dimensional method is used to study the growth kinetics of the boride layers FeB and Fe2B. Experiments were performed in AISI 1045 steel and AISI M2 steel, to test the suggested model. Samples of 1045 steel were prepared and treated using boron paste thickness of 3-5 mm, at temperatures of 1193, 1223 and 1273 K, with 2, 4 and 6 h of treatment time. The M2 specimens had boron paste thickness of 3 and 4 mm and temperatures of 1223, 1253 and 1273 K for 2 and 6 h. Results indicate that the growth of boron layers obeys power laws of the form y = αxβ, where α and β constants are a function of the material and the interface of interest. Validation of the model was carried out using experimental data with an average error percentage of 7.6% for Fe2B in 1045 steel, 15.8% for FeB and 3.4% for Fe2B in M2 steel. 相似文献