The kinetics and reactivity of several polyatomic free radicals in reactions with NO2, O2, Cl2, and HCl

In this thesis, the kinetics of several alkyl, halogenated alkyl, and alkenyl free radical reactions with NO2, O2, Cl2, and HCl reactants were studied over a wide temperature range in time resolved conditions. Laser photolysis photoionisation mass spectrometer coupled to a flow reactor was the experimental method employed and this thesis present the first measurements performed with the experimental system constructed. During this thesis a great amount of work was devoted to the designing, building, testing, and improving the experimental apparatus. Carbon-centred free radicals were generated by the pulsed 193 or 248 nm photolysis of suitable precursors along the tubular reactor. The kinetics was studied under pseudo-first-order conditions using either He or N2 buffer gas. The temperature and pressure ranges employed were between 190 and 500 K, and 0.5 45 torr, respectively. The possible role of heterogeneous wall reactions was investigated employing reactor tubes with different sizes, i.e. to significantly vary the surface to volume ratio. In this thesis, significant new contributions to the kinetics of carbon-centred free radical reactions with nitrogen dioxide were obtained. Altogether eight substituted alkyl (CH2Cl, CHCl2, CCl3, CH2I, CH2Br, CHBr2, CHBrCl, and CHBrCH3) and two alkenyl (C2H3, C3H3) free radical reactions with NO2 were investigated as a function of temperature. The bimolecular rate coefficients of all these reactions were observed to possess negative temperature dependencies, while pressure dependencies were not noticed for any of these reactions. Halogen substitution was observed to moderately reduce the reactivity of substituted alkyl radicals in the reaction with NO2, while the resonance stabilisation of the alkenyl radical lowers its reactivity with respect to NO2 only slightly. Two reactions relevant to atmospheric chemistry, CH2Br + O2 and CH2I + O2, were also investigated. It was noticed that while CH2Br + O2 reaction shows pronounced pressure dependence, characteristic of peroxy radical formation, no such dependence was observed for the CH2I + O2 reaction. Observed primary products of the CH2I + O2 reaction were the I-atom and the IO radical. Kinetics of CH3 + HCl, CD3 + HCl, CH3 + DCl, and CD3 + DCl reactions were also studied. While all these reactions possess positive activation energies, in contrast to the other systems investigated in this thesis, the CH3 + HCl and CD3 + HCl reactions show a non-linear temperature dependency on the Arrhenius plot. The reactivity of substituted methyl radicals toward NO2 was observed to increase with decreasing electron affinity of the radical. The same trend was observed for the reactions of substituted methyl radicals with Cl2. It is proposed that interactions of frontier orbitals are responsible to these observations and Frontier Orbital Theory could be used to explain the observed reactivity trends of these highly exothermic reactions having reactant-like transition states.Tässä opinnäytteessä tutkittiin neljän alkyyli-radikaalin (esim. CH3, C2H5), kahdeksan halogenoidun alkyyli-radikaalin (esim. CH2Cl, CH2Br, CHBrCl) sekä kahden alkenyyli-radikaalin (C2H3, C3H3) reaktioita typpidioksidin (NO2), hapen (O2), kloorin (Cl2) ja vetykloridin (HCl) kanssa kaasufaasissa. Tutkittavat radikaalit tuotettiin sopivasta lähtöaineesta 193:n tai 248:n nm laserpulssilla reaktoriputkessa virtaavaan kaasuseokseen, joka koostui pääosin puskurikaasusta (heliumista (He) tai typestä (N2)) sekä radikaalin lähtöaineesta ja reaktantti-kaasusta (esim. NO2), joita oli yhteensä alle neljä prosenttia kaasun kokonaismäärästä. Kaasuseoksessa tapahtuvia reaktioita tutkittiin aika-erotteisesti pseudo-ensimmäisen-kertaluvun-olosuhteissa ottamalla jatkuvasti pieni näyte valoionisaatio-massaspektrometrille. Mittauksiin käytetty laitteisto rakennettiin merkittävältä osin tämän työn aikana. Huomattava osa tähän opinnäytteeseen käytetystä ajasta kului laitteiston osien suunnitteluun, rakentamiseen, testaamiseen ja edelleen kehittämiseen. Esitetyt mittaustulokset ovat ensimmäiset uudella laitteistolla, jolla reaktioita tutkittiin tässä työssä noin 190 500 K (-85 230 °C) lämpötiloissa ja noin 0.5 45 torr (0.0007 0.06 bar) paineissa. Tämä työ antaa merkittävästi uutta tietoa hiilikeskisten vapaiden radikaalien reaktioista typpidioksidin kanssa. Haitallisten typen oksidien (NO, NO2) pääasiallinen lähde on liikenne (polttomoottorit) ja vähäisemmässä määrin myös energiantuotanto (voimalaitokset). Kaikkiaan tässä työssä tutkittiin kahdeksan substituoidun alkyyli-radikaalin (CH2Cl, CHCl2, CCl3, CH2I, CH2Br, CHBr2, CHBrCl ja CHBrCH3) ja kahden alkenyyli-radikaalin (C2H3, C3H3) reaktioita typpidioksidin kanssa lämpötilan funktiona. Kaikkien tutkittavien reaktioiden havaittiin nopeutuvan lämpötilaa alennettaessa eikä yhdellekään reaktiolle havaittu paineriippuvuutta. Halogeenisubstituution havaittiin alentavan alkyyli-radikaalin reaktiivisuutta typpidioksidia kohtaan merkittävästi, kun taas resonanssi-stabilisaation huomattiin vähentävän radikaalin reaktiivisuutta NO2:a kohtaan vain vähän. Työssä tutkittiin myös kahta ilmakehässä tärkeätä CH2Br + O2 ja CH2I + O2 reaktiota. Ensin mainitun reaktion nopeuden havaittiin riippuvan kaasuseoksen paineesta, joka on ominaista peroksi-radikaalin (CH2BrOO) muodostumiselle, kun taas paineriippuvuutta ei havaittu jälkimmäiselle reaktiolle. Tämän reaktion (CH2I + O2) primäärituotteiksi havaittiin jodi-atomi (I) ja IO-radikaali. Myös CH3 + HCl, CD3 + HCl, CH3 + DCl ja CD3 + DCl reaktioiden kinetiikkaa tutkittiin. Kaikkien näiden reaktioiden havaittiin nopeutuvan lämpötilaa nostettaessa, päinvastoin kuin muiden tässä työssä tutkittavien reaktioiden tapauksessa. Substituoitujen metyyliradikaalien reaktiivisuuden havaittiin lisääntyvän typpidioksidia kohtaan radikaalin elektroniaffiniteetin pienentyessä. Sama havainto tehtiin näiden radikaalien reaktioille Cl2:n kanssa. Tässä työssä ehdotetaan, että nämä havainnot voidaan merkittävässä määrin selittää radikaalin ja molekyylin valenssi-orbitaalien vuorovaikutuksella. Näissä hyvin eksotermisissa radikaali-reaktioissa siirtymätila on hyvin lähtöaineiden kaltainen, jolloin raja-orbitaali teoriaa (Frontier Orbital Theory) voidaan hyödyntää selittämään havaitut reaktiivisuuksien käyttäytymiset

Time-resolved, broadband UV-absorption spectrometry measurements of Criegee intermediate kinetics using a new photolytic precursor : unimolecular decomposition of CH2OO and its reaction with formic acid

We present a time-resolved broadband cavity-enhanced UV-absorption spectrometer apparatus that we have constructed and utilized for temperature- and pressure-dependent kinetic measurements of formaldehyde oxide (CH2OO) reactions. We also introduce and utilize a new photolytic precursor, bromoiodomethane (CH2IBr), which photolysis at 213 nm in presence of O2 produces CH2OO. Importantly, this precursor appears to be free from secondary reactions that may regenerate CH2OO in kinetic experiments. The unimolecular decomposition rate coefficient of CH2OO has been measured over wide pressure (5–400 Torr) and temperature (296–600 K) ranges and master equation simulations of the decomposition kinetics have been performed using MESMER program. The MESMER simulations of the experimental data with the calculated zero-point energy corrected transition state energy 85.9 kJ mol−1 for decomposition required no adjustment and returned 〈ΔE〉down = 123.2 × (T/298 K)0.74 cm−1 for temperature-dependent exponential-down model of the collisional energy transfer in He. A very good agreement between results of simulations and experiments is obtained. The results are compared with the previously reported unimolecular decomposition study by Stone et al. (Phys. Chem. Chem. Phys., 2018, 20, 24940–24954). Current master equation simulations suggest about 61% decomposition yield for the predominant H2 + CO2 channel, whereas the yields of two other channels, H2O + CO, and HCO + OH, are sensitive on the parameters involved in the simulations. The kinetics of CH2OO reaction with formic acid has also been investigated as function of pressure (5–150 Torr) and temperature (296–458 K). The bimolecular rate coefficient for CH2OO + HCOOH reaction shows a negative temperature dependency, decreasing from (1.0 ± 0.03) × 10−10 cm3 molecule−1 s−1 at 296 K to (0.47 ± 0.05) × 10−10 cm3 molecule−1 s−1 at 458 K with an Arrhenius activation energy of −4.9 ± 1.6 kJ mol−1, where statistical uncertainties shown are 2σ. Estimated overall uncertainty in the measured rate coefficients is about ±20%. Current bimolecular rate coefficient at room temperature agrees with the previously reported rate coefficients from the direct kinetic experiments. The reaction is found to be pressure independent over the range between 5 and 150 Torr at 296 K in He.We present a time-resolved broadband cavity-enhanced UV-absorption spectrometer apparatus that we have constructed and utilized for temperature- and pressure-dependent kinetic measurements of formaldehyde oxide (CH2OO) reactions. We also introduce and utilize a new photolytic precursor, bromoiodomethane (CH2IBr), which photolysis at 213 nm in presence of O-2 produces CH2OO. Importantly, this precursor appears to be free from secondary reactions that may regenerate CH2OO in kinetic experiments. The unimolecular decomposition rate coefficient of CH2OO has been measured over wide pressure (5-400 Torr) and temperature (296-600 K) ranges and master equation simulations of the decomposition kinetics have been performed using MESMER program. The MESMER simulations of the experimental data with the calculated zero-point energy corrected transition state energy 85.9 kJ mol(-1) for decomposition required no adjustment and returned (down) = 123.2 x (T/298 K)(0.74) cm(-1) for temperature-dependent exponential-down model of the collisional energy transfer in He. A very good agreement between results of simulations and experiments is obtained. The results are compared with the previously reported unimolecular decomposition study by Stone et al. (Phys. Chem. Chem. Phys., 2018, 20, 24940-24954). Current master equation simulations suggest about 61% decomposition yield for the predominant H-2 + CO2 channel, whereas the yields of two other channels, H2O + CO, and HCO + OH, are sensitive on the parameters involved in the simulations. The kinetics of CH2OO reaction with formic acid has also been investigated as function of pressure (5-150 Torr) and temperature (296-458 K). The bimolecular rate coefficient for CH2OO + HCOOH reaction shows a negative temperature dependency, decreasing from (1.0 +/- 0.03) x 10(-10) cm(3) molecule(-1) s(-1) at 296 K to (0.47 +/- 0.05) x 10(-10) cm(3) molecule(-1) s(-1) at 458 K with an Arrhenius activation energy of -4.9 +/- 1.6 kJ mol(-1), where statistical uncertainties shown are 2 sigma. Estimated overall uncertainty in the measured rate coefficients is about +/- 20%. Current bimolecular rate coefficient at room temperature agrees with the previously reported rate coefficients from the direct kinetic experiments. The reaction is found to be pressure independent over the range between 5 and 150 Torr at 296 K in He.Peer reviewe

Kinetics of the Reactions of CH2Cl, CH3CHCl, and CH3CCl2 Radicals with Cl2 in the Temperature Range 191-363 K

Peer reviewe

Solving the discrepancy between the direct and relative-rate determinations of unimolecular reaction kinetics of dimethyl- substituted Criegee intermediate (CH3)2COO using a new photolytic precursor

We have performed direct kinetic measurements of thermal unimolecular reaction of (CH3)2COO in the temperature 243– 340 K and pressure 5–350 Torr ranges using time-resolved UV-absorption spectroscopy. We have utilized a new photolytic precursor, 2-bromo-2-iodopropane ((CH3)2CIBr), which photolysis at 213 nm in presence of O2 produces acetone oxide, (CH3)2COO. The results show that the thermal unimolecular reaction is more important main loss process of (CH3)2COO in the atmosphere than direct kinetic studies hitherto suggest. The current experiments show that the unimolecular reaction rate of (CH3)2COO at 296 K and atmospheric pressure is 899 ± 42 s-1. Probably more importantly, current measurements bring the direct and relative rate measurements of thermal unimolecular reaction kinetics of (CH3)2COO in quantitative agreement.Peer reviewe

An Experimental and Master Equation Investigation of Kinetics of the CH2OO+RCN Reactions (R = H, CH3, C2H5) and Their Atmospheric Relevance

We have performed direct kinetic measurements of the CH2OO + RCN reactions (R = H, CH3, C2H5) in the temperature range 233-360 K and pressure range 10-250 Torr using time-resolved UV-absorption spectroscopy. We have utilized a new photolytic precursor, chloroiodomethane (CH2ICl), whose photolysis at 193 nm in the presence of O2 produces CH2OO. Observed bimolecular rate coefficients for CH2OO + HCN, CH2OO + CH3CN, and CH2OO + C2H5CN reactions at 296 K are (2.22 +/- 0.65) x 10-14 cm3 molecule-1 s-1, (1.02 +/- 0.10) x 10-14 cm3 molecule-1 s-1, and (2.55 +/- 0.13) x 10-14 cm3 molecule-1 s-1, respectively, suggesting that reaction with CH2OO is a potential atmospheric degradation pathway for nitriles. All the reactions have negligible temperature and pressure dependence in the studied regions. Quantum chemical calculations (omega B97X-D/aug-cc-pVTZ optimization with CCSD(T)-F12a/VDZ-F12 electronic energy correction) of the CH2OO + RCN reactions indicate that the barrierless lowest-energy reaction path leads to a ring closure, resulting in the formation of a 1,2,4-dioxazole compound. Master equation modeling results suggest that following the ring closure, chemical activation in the case of CH2OO + HCN and CH2OO + CH3CN reactions leads to a rapid decomposition of 1,2,4-dioxazole into a CH2O + RNCO pair, or by a rearrangement, into a formyl amide (RC(O)NHC(O)H), followed by decomposition into CO and an imidic acid (RC(NH)OH). The 1,2,4-dioxazole, the CH2O + RNCO pair, and the CO + RC(NH)OH pair are atmospherically significant end products to varying degrees.Peer reviewe

Effect of Methyl Group Substitution on the Kinetics of Vinyl Radical + O-2 Reaction

The kinetics of (CH3)(2)CCH + O-2 (1) and (CH3)(2)CCCH3 + O-2 (2) reactions have been measured as a function of temperature (223-600 K) at low pressures (0.4-2 Torr) using a tubular laminar flow reactor coupled to a photoionization mass spectrometer (PIMS). These reactions are important for accurate modeling of unsaturated hydrocarbon combustion. Photolysis of a brominated precursor by a pulsed excimer laser radiation at 248 nm wavelength along the flow reactor axis was used for the production of radicals. The measured bimolecular rate coefficient of reaction 1 shows a negative temperature dependence over the temperature range 223-384 K and becomes temperature independent at higher temperatures. The bimolecular rate coefficient of reaction 2 exhibits a negative temperature dependence throughout the experimental temperature range. The bimolecular rate coefficients of reactions 1 and 2 are expected to be at the high-pressure limit under the current experimental conditions, and the following values are obtained at 298 K: k(1)(298 K) = (4.5 +/- 0.5) x 10(-12) cm(3) s(-1) and k(2)(298 = (8.9 +/- 1.0) x 10(-12) cm(3) s(-1). The observed products for reactions 1 and 2 were CH3COCH3 and CH3 + CH3COCH3, respectively. Substituting both beta-hydrogens in the vinyl radical (CH2CH) with methyl groups decreases the rate coefficient of the CH2CH + O-2 reaction by about 50%. However, the rate coefficient of the triply substituted (CH3)(2)CCCH3 radical reaction with O-2 is almost identical to the CH2CH + O-2 rate coefficient under the covered temperature range.Peer reviewe

Temperature and Pressure Dependence of the Reaction between Ethyl Radical and Molecular Oxygen : Experiments and Master Equation Simulations

Funding Information: We thank Stephen Klippenstein for providing us with the geometries, harmonic frequencies, and relative energies of the stationary points from his recent CH + O publication as well as the state sum for the loose recombination transition state. T.T.P. acknowledges support from the Doctoral Programme in Chemistry and Molecular Sciences of the University of Helsinki and the Magnus Ehrnrooth Foundation for funding. Project K129140 for G.L. was implemented with the support provided by the Ministry of Innovation and Technology of Hungary from the National Research, Development and Innovation Fund, financed under the OTKA funding scheme. T.T.P., E.A.R., and A.J.E. acknowledge support from the Academy of Finland (Grants 325250 and 346374). The authors also acknowledge CSC IT Center for Science in Finland for computational resources. 2 5 • 2 Publisher Copyright: © 2023 The Authors.We have used laser-photolysis - photoionization mass-spectrometry to measure the rate coefficient for the reaction between ethyl radical and molecular oxygen as a function of temperature (190-801 K) and pressure (0.2-6 Torr) under pseudo first-order conditions ([He] >> [O2] >> [C2H5 center dot]). Multiple ethyl precursor, photolysis wavelength, reactor material, and coating combinations were used. We reinvestigated the temperature dependence of the title reaction's rate coefficient to resolve inconsistencies in existing data. The current results indicate that some literature values for the rate coefficient may indeed be slightly too large. The experimental work was complemented with master equation simulations. We used the current and some previous rate coefficient measurements to optimize the values of key parameters in the master equation model. After optimization, the model was able to reproduce experimental falloff curves and C2H4 + HO2 center dot yields. We then used the model to perform simulations over wide temperature (200-1500 K) and pressure (10-4-102 bar) ranges and provide the results in PLOG format to facilitate their use in atmospheric and combustion models.Peer reviewe

Kinetics and thermochemistry of the reaction of 3-methylpropargyl radical with molecular oxygen

We have measured the kinetics and thermochemistry of the reaction of 3-methylpropargyl radical (but-2-yn-1-yl) with molecular oxygen over temperature (223-681 K) and bath gas density (1.2 - 15.0 x 10(16)cm(-3)) ranges employing photoionization mass-spectrometry. At low temperatures (223-304 K), the reaction proceeds overwhelmingly by a simple addition reaction to the -CH2 end of the radical, and the measured CH3CCCH2 center dot+O-2 reaction rate coefficient shows negative temperature dependence and depends on bath gas density. At intermediate temperatures (340-395 K), the addition reaction equilibrates and the equilibrium constant was determined at different temperatures. At high temperatures (465-681 K), the kinetics is governed by O-2 addition to the third carbon atom of the radical, and rate coefficient measurements were again possible. The high temperature CH3CCCH2 center dot +O(2 )rate coefficient is much smaller than at low T, shows positive temperature dependence, and is independent of bath gas density. In the intermediate and high temperature ranges, we observe a formation signal for ketene (ethenone). The reaction was further investigated by combining the experimental results with quantum chemical calculations and master equation modeling. By making small adjustments (2 - 3 kJ mol(-1)) to the energies of two key transition states, the model reproduces the experimental results within uncertainties. The experimentally constrained master equation model was used to simulate the CH3CCCH2 center dot+ O-2 reaction system at temperatures and pressures relevant to combustion. (C) 2018 The Combustion Institute. Published by Elsevier Inc. All rights reserved.Peer reviewe

Kinetics and thermochemistry of the reaction of 1-methylpropargyl radicals with oxygen molecules : Experiments and computations

We have used laser-photolysis/photoionization mass spectrometry to measure the kinetics of the reaction of 1-methylpropargyl (but-3-yn-2-yl, CH C=CH-CH3) radicals with oxygen molecules as a function of temperature (T = 200 - 685 K) and bath gas density (1.2 - 15 x 10(16) cm(-3)). The low temperature (TPeer reviewe