Elna J.K. Nilsson

On the performance of quantum chemical methods to predict solvatochromic effects: The case of acrolein in aqueous solution

The performance of the Hartree-Fock method and the three density functionals B3LYP, PBE0, and CAM-B3LYP is compared to results based on the coupled cluster singles and doubles model in predictions of the solvatochromic effects on the vertical n-->pi* and pi-->pi* electronic excitation energies of acrolein. All electronic structure methods employed the same solvent model, which is based on the combined quantum mechanics/molecular mechanics approach together with a dynamical averaging scheme. In addition to the predicted solvatochromic effects, we have also performed spectroscopic UV measurements of acrolein in vapor phase and aqueous solution. The gas-to-aqueous solution shift of the n-->pi* excitation energy is well reproduced by using all density functional methods considered. However, the B3LYP and PBE0 functionals completely fail to describe the pi-->pi* electronic transition in solution, whereas the recent CAM-B3LYP functional performs well also in this case. The pi-->pi* excitation energy of acrolein in water solution is found to be very dependent on intermolecular induction and nonelectrostatic interactions. The computed excitation energies of acrolein in vacuum and solution compare well to experimental data.

Endogenous free fatty acids repel and attract Collembola

We used video recording of the movement pattern of Protaphorura armata (Collembola) to test whether its avoidance of the odor of dead conspecifics extends to related species. P. armata was repelled by the odor of dead individuals of Onychiurus scotarius and Onychiurus circulans, but not by live individuals. Free palmitic, oleic, and linoleic acids were present in extracts of the three repellent species, but only free palmitic acid was detected in extracts of a fourth nonrepellent species, Folsomia candida. Synthetic palmitic acid was attractive to P. armata, linoleic acid was repellent, and oleic acid gave no response. O. scotarius and O. circulans also contained 2,3-dimethoxy-pyrido[2,3-b]pyrazine, known as a defense substance. We discuss the role of free fatty acids in predator avoidance, conspecifics attraction, and food recognition in P. armata.

Atmospheric chemistry of two biodiesel model compounds: methyl propionate and ethyl acetate.

The atmospheric chemistry of two C(4)H(8)O(2) isomers (methyl propionate and ethyl acetate) was investigated. With relative rate techniques in 980 mbar of air at 293 K the following rate constants were determined: k(C(2)H(5)C(O)OCH(3) + Cl) = (1.57 ± 0.23) × 10(-11), k(C(2)H(5)C(O)OCH(3) + OH) = (9.25 ± 1.27) × 10(-13), k(CH(3)C(O)OC(2)H(5) + Cl) = (1.76 ± 0.22) × 10(-11), and k(CH(3)C(O)OC(2)H(5) + OH) = (1.54 ± 0.22) × 10(-12) cm(3) molecule(-1) s(-1). The chlorine atom initiated oxidation of methyl propionate in 930 mbar of N(2)/O(2) diluent (with, and without, NO(x)) gave methyl pyruvate, propionic acid, acetaldehyde, formic acid, and formaldehyde as products. In experiments conducted in N(2) diluent the formation of CH(3)CHClC(O)OCH(3) and CH(3)CCl(2)C(O)OCH(3) was observed. From the observed product yields we conclude that the branching ratios for reaction of chlorine atoms with the CH(3)-, -CH(2)-, and -OCH(3) groups are <49 ± 9%, 42 ± 7%, and >9 ± 2%, respectively. The chlorine atom initiated oxidation of ethyl acetate in N(2)/O(2) diluent gave acetic acid, acetic acid anhydride, acetic formic anhydride, formaldehyde, and, in the presence of NO(x), PAN. From the yield of these products we conclude that at least 41 ± 6% of the reaction of chlorine atoms with ethyl acetate occurs at the -CH(2)- group. The rate constants and branching ratios for reactions of OH radicals with methyl propionate and ethyl acetate were investigated theoretically using transition state theory. The stationary points along the oxidation pathways were optimized at the CCSD(T)/cc-pVTZ//BHandHLYP/aug-cc-pVTZ level of theory. The reaction of OH radicals with ethyl acetate was computed to occur essentially exclusively (∼99%) at the -CH(2)- group. In contrast, both methyl groups and the -CH(2)- group contribute appreciably in the reaction of OH with methyl propionate. Decomposition via the α-ester rearrangement (to give C(2)H(5)C(O)OH and a HCO radical) and reaction with O(2) (to give CH(3)CH(2)C(O)OC(O)H) are competing atmospheric fates of the alkoxy radical CH(3)CH(2)C(O)OCH(2)O. Chemical activation of CH(3)CH(2)C(O)OCH(2)O radicals formed in the reaction of the corresponding peroxy radical with NO favors the α-ester rearrangement.

Experimental Uncertainties of the Heat Flux Method for Measuring Burning Velocities

ABSTRACT The laminar burning velocity is a fundamental property of combustible mixtures important for kinetic model validation as well as for practical applications. Many efforts are directed towards its accurate determination. The heat flux method is one of the commonly recognized methods for measuring laminar burning velocity, however, the information on the accuracy of the method is scattered in the literature. In the present work, an attempt was made to summarize and extend the available information on the different factors contributing to the experimental uncertainty of the heat flux method. Experimental setup of the Lund University group, typical for the heat flux community, and the procedures used to determine the burning velocity are described. Furthermore, the influence of different uncertainty factors, originating from each part of the setup, is analyzed. Asymmetric heat fluxes and the method for determining flame surface area were found to give an important contribution to the total error. As a result of this, some of the previously published data have been re-evaluated. Finally, recommendations are presented on how to control or reduce the uncertainties in the heat flux measurements, and possible directions for future research, aimed at improvement of the accuracy and understanding of the method, are outlined.

Gas-phase advanced oxidation for effective, efficient in situ control of pollution

In this article, gas-phase advanced oxidation, a new method for pollution control building on the photo-oxidation and particle formation chemistry occurring in the atmosphere, is introduced and characterized. The process uses ozone and UV-C light to produce in situ radicals to oxidize pollution, generating particles that are removed by a filter; ozone is removed using a MnO2 honeycomb catalyst. This combination of in situ processes removes a wide range of pollutants with a comparatively low specific energy input. Two proof-of-concept devices were built to test and optimize the process. The laboratory prototype was built of standard ventilation duct and could treat up to 850 m(3)/h. A portable continuous-flow prototype built in an aluminum flight case was able to treat 46 m(3)/h. Removal efficiencies of >95% were observed for propane, cyclohexane, benzene, isoprene, aerosol particle mass, and ozone for concentrations in the range of 0.4-6 ppm and exposure times up to 0.5 min. The laboratory prototype generated a OH(•) concentration derived from propane reaction of (2.5 ± 0.3) × 10(10) cm(-3) at a specific energy input of 3 kJ/m(3), and the portable device generated (4.6 ± 0.4) × 10(9) cm(-3) at 10 kJ/m(3). Based on these results, in situ gas-phase advanced oxidation is a viable control strategy for most volatile organic compounds, specifically those with a OH(•) reaction rate higher than ca. 5 × 10(-13) cm(3)/s. Gas-phase advanced oxidation is able to remove compounds that react with OH and to control ozone and total particulate mass. Secondary pollution including formaldehyde and ultrafine particles might be generated, depending on the composition of the primary pollution.

Relative Tropospheric Photolysis Rates of Acetaldehyde and Formaldehyde Isotopologues Measured at the European Photoreactor Facility

The photolysis rates of HCHO, DCDO, CH(3)CHO, and CH(3)CDO are studied by long-path FTIR spectroscopy in natural tropospheric conditions at the European Photoreactor Facility (EUPHORE) in Valencia, Spain. Average relative photolysis rates j(HCHO)/j(DCDO) = 3.15 +/- 0.08 and j(CH(3)CHO)/j(CH(3)CDO) = 1.26 +/- 0.03 are obtained from three days of experiments for each reaction in the period June 17 to July 7, 2006.

Isotope Effects in the Reactions of Chloroform Isotopologues with Cl, OH, and OD

The kinetic isotope effects in the reactions of CHCl(3), CDCl(3), and (13)CHCl(3) with Cl, OH, and OD radicals have been determined in relative rate experiments at 298 +/- 1 K and atmospheric pressure monitored by long path FTIR spectroscopy. The spectra were analyzed using a nonlinear least-squares spectral fitting procedure including line data from the HITRAN database and measured infrared spectra as references. The following relative reaction rates were determined: k(CHCl(3)+Cl)/k(CDCl(3)+Cl) = 3.28 +/- 0.01, k(CHCl(3)+Cl)/k((13)CHCl(3)+Cl) = 1.000 +/- 0.003, k(CHCl(3)+OH)/k(CDCl(3)+OH) = 3.73 +/- 0.02, k(CHCl(3)+OH)/k((13)CHCl(3)+OH) = 1.023 +/- 0.002, k(CHCl(3)+OD)/k(CDCl(3)+OD) = 3.95 +/- 0.03, and k(CHCl(3)+OD)/k((13)CHCl(3)+OD) = 1.032 +/- 0.004. Larger isotope effects in the OH reactions than in the Cl reactions are opposite to the trends for CH(4) and CH(3)Cl reported in the literature. The origin of these differences was investigated using electronic structure calculations performed at the MP2/aug-cc-PVXZ (X = D, T, Q) level of theory and are compared with previously calculated values for the other methane derivatives. The Born-Oppenheimer barrier heights to H abstraction are 12.2 and 17.0 kJ mol(-1) at the CCSD(T)/aug-cc-pVTZ level of theory for OH and Cl, respectively. The reaction rate coefficients of the two elementary vapor phase reactions including the (2)H and (13)C kinetic isotope effects were calculated using improved canonical variational theory with small curvature tunneling (ICVT/SCT) and the results compared with experimental data.

Atmospheric Chemistry of Tetrahydrofuran, 2-Methyltetrahydrofuran, and 2,5-Dimethyltetrahydrofuran: Kinetics of Reactions with Chlorine Atoms, OD Radicals, and Ozone

FTIR smog chamber techniques were used to study the kinetics of the gas-phase reactions of Cl atoms, OD radicals, and O3 with the five-membered ring-structured compounds tetrahydrofuran (C4H8O, THF), 2-methyltetrahydrofuran (CH3C4H7O, 2-MTHF), 2,5-dimethyltetrahydrofuran ((CH3)2C4H5O, 2,5-DMTHF), and furan (C4H4O). The rate coefficients determined using relative rate methods were kTHF+Cl = (1.96 ± 0.24) × 10(-10), kTHF+OD = (1.81 ± 0.27) × 10(-11), kTHF+O3 = (6.41 ± 2.90) × 10(-21), k2-MTHF+Cl = (2.65 ± 0.43) × 10(-10), k2-MTHF+OD = (2.41 ± 0.51) × 10(-11), k2-MTHF+O3 = (1.87 ± 0.82) × 10(-20), k2,5-DMTHF+OD = (4.56 ± 0.68) × 10(-11), k2,5-DMTHF+Cl = (2.84 ± 0.34) × 10(-10), k2,5-DMTHF+O3 = (4.58 ± 2.18), kfuran+Cl = (2.39 ± 0.27) × 10(-10), and kfuran+O3 = (2.60 ± 0.31) × 10(-18) molecules cm(-3) s(-1). Rate coefficients of the reactions with ozone were also determined using the absolute rate method under pseudo-first-order conditions. OD radicals, in place of OH radicals, were produced from CD3ONO to avoid spectral overlap of isopropyl and methyl nitrite with the reactants. The kinetics of OD radical reactions are expected to resemble the kinetics of OH radical reactions, and the rate coefficients of the reactions with OD radicals were used to calculate the atmospheric lifetimes with respect to reactions with OH radicals. The lifetimes of THF, 2-MTHF, and 2,5-DMTHF are approximately 15, 12, and 6 h, respectively.

Reactions of Three Lactones with Cl, OD, and O3: Atmospheric Impact and Trends in Furan Reactivity

Lactones, cyclic esters of hydroxycarboxylic acids, are interesting biofuel candidates as they can be made from cellulosic biomass and have favorable physical and chemical properties for distribution and use. The reactions of γ-valerolactone (GVL), γ-crotonolactone (2(5H)-F), and α-methyl-γ-crotonolactone (3M-2(5H)-F) with Cl, OD, and O3 were investigated in a static chamber at 700 Torr and 298 ± 2 K. The relative rate method was used to determine kGVL+Cl = (4.56 ± 0.51) × 10-11, kGVL+OD = (2.94 ± 0.41) × 10-11, k2(5H)-F+Cl = (2.94 ± 0.41) × 10-11, k2(5H)-F+OD = (4.06 ± 0.073) × 10-12, k3M-2(5H)-F+Cl = (16.1 ± 1.8) × 10-11, and k3M-2(5H)-F+OD = (12.6 ± 0.52) × 10-12, all rate coefficients in units of cm3 molecule-1 s-1. An absolute rate method was used to determine k2(5H)-F+O3 = (6.73 ± 0.18) × 10-20 and k3M-2(5H)-F+O3 = (5.42 ± 1.23) × 10-19 in units of cm3 molecule-1 s-1. Products were identified for reactions of the lactones with Cl. In the presence of O2 the products are formic acid (HCOOH), formyl chloride (CHClO), and phosgene (CCl2O), and also maleic anhydride (C2H2(CO)2O) for 2(5H)-F. In addition both reactions produced a number of unidentified products that likely belong to molecules with the ring-structure intact. A review of literature data for reactions of other furans show that the reactivity of the lactones are generally lower compared to that of corresponding compounds without the carbonyl group.

Investigations of microwave stimulation of turbulent flames with implications to gas turbine combustors

Efficient and clean production of electrical energy and mechanical (shaft) energy for use in industrial and domestic applications, surface- and ground transportation and aero-propulsion is currently of significant general concern. Fossil fuels are mainly used for transportation and aero-propulsion, but also for power generation. Combustion of fossil fuels typically give rise to undesired emissions such as unburned hydrocarbons, carbon dioxide, carbon monoxide, soot and nitrogen oxides. The most widespread approach to minimize these is to apply various lean-burn technologies, and sometimes also dilute the fuel with hydrogen. Although efficient in reducing emissions, lean-burn often results in combustion instabilities and igniteon issues, and thus become challenging itself. Another desired aspect of today’s engines is to increase the fuel flexibility. One possible technique that may be useful for circumventing these issues is plasma-assisted combustion, i.e. to supply a small amount of electric energy to the flame to stimulate the chemical kinetics. Although not new, this approach has not yet been fully explored, partly because of it’s complexity, and partly because of apparent sufficiency. Recently, however, several research studies of this area have emerged. This paper attempts to provide a brief summary of microwave-assisted combustion, in which microwaves are utilized to supply the electrical energy to the flame, and to demonstrate that this method is useful to enhance flame stabilization, delay lean blow-off, and to increase combustion efficiency. The main effect of microwaves (or electrical energy) is to enhance the chemical kinetics, resulting in increased reactivity and laminar and turbulent flame speeds. Here we will demonstrate that this will improve the performance of gas turbine combustors. (Less)