Photochemical sources of organic acids. 2. Formation of C5-C9 carboxylic acids from alkene ozonolysis under dry and humid conditions

The dependence of organic acid generation by alkene ozonolysis on relative humidity, thermalized Criegee intermediate scavengers, and alkene structure is investigated. Carboxylic acids generated from the ozonolysis of 1-hexene, 1-octene, 1-decene, trans-3-octene, and 1-methylcyclohexene were analyzed as trimethylsilyl (TMS) derivatives. Experiments were performed under dry (relative humidity (RH) < 1%) and humid (RH = 65%) conditions with cyclohexane or n-butyl ether as an OH scavenger. Pentanoic acid is produced from 1-hexene and trans-3-octene with yields 8.5 +/- 2.6 and 5.0 +/- 1.5% under dry conditions and 5.1 +/- 1.5 and 2.8 +/- 0.8% under humid conditions, respectively. Heptanoic acid yields from 1-octene are 8.3 +/- 2.5 and 4.4 +/- 1.3% under dry and humid conditions, respectively. Ozonolysis of 1-methylcyclohexene produced six C5-C7 multifunctional carboxylic acids, with a total yield of 7%. Several other acids and aldehydes were also monitored and quantified. An additional set of experiments with added stabilized Criegee intermediate (SCI) scavengers was performed for 1-octene ozonolysis under dry conditions. The results indicate that SCIs and their reaction with water are minor contributors to acid formation in the atmosphere and suggest that many of the acids are formed directly.     

On the use of CO as scavenger for OH radicals in the ozonolysis of simple alkenes and isoprene

The OH radical yields generated in the ozonolysis of ethene (ET), propene (PR), cis-2-butene (CB), trans-2-butene (TB), 2,3-dimethyl-2-butene (TME), and isoprene (ISP) in the presence of 20 Vol.% O₂ have been determined in a darkened glass reactor at 1 bar total pressure. The hydroxyl radicals formed were scavenged by an excess of CO added to the systems. The O₂ present converted H atoms formed in this reaction into HO₂. From measurements of the increase in CO₂ generation by FTIR the OH formation yields were determined to be 0.08 (ET), 0.18 (PR), 0.17 (CB), 0.24 (TB), 0.36 (TME), and 0.19 (ISP), respectively, per molecule of reacted ozone. The combined error in the OH determinations is estimated to be <10%. © 1997 John Wiley & Sons, Inc.     

Kinetics, products, and stereochemistry of the reaction of chlorine atoms with cis- and trans-2-butene in 10-700 Torr of N2 or N2/O2 diluent at 297 K

The reactions of Cl atoms with cis- and trans-2-butene have been studied using FTIR and GC analyses. The rate constant of the reaction was measured using the relative rate technique. Rate constants for the cis and trans isomers are indistinguishable over the pressure range 10-900 Torr of N2 or air and agree well with previous measurements at 760 Torr. Product yields for the reaction of cis-2-butene with Cl in N2 at 700 Torr are meso-2,3-dichlorobutane (47%), DL-2,3-dichlorobutane (18%), 3-chloro-1-butene (13%), cis-1-chloro-2-butene (13%), trans-1-chloro-2-butene (2%), and trans-2-butene (8%). The yields of these products depend on the total pressure. For trans-2-butene, the product yields are as follows: meso-2,3-dichlorobutane (48%), dl-2,3-dichlorobutane (17%), 3-chloro-1-butene (12%), cis-1-chloro-2-butene (2%), trans-1-chloro-2-butene (16%), and cis-2-butene (2%). The products are formed via addition, addition-elimination from a chemically activated adduct, and abstraction reactions. These reactions form (1) the stabilized 3-chloro-2-butyl radical, (2) the chemically activated 3-chloro-2-butyl radical, and (3) the methylallyl radical. These radicals subsequently react with Cl2 to form the products via a proposed chemical mechanism, which is discussed herein. This is the first detailed study of stereochemical effects on the products of a gas-phase Cl+olefin reaction. FTIR spectra (0.25 cm(-1) resolution) of meso- and DL-2,3-dichlorobutane are presented. The relative rate technique was used (at 900 Torr and 297 K) to measure: k(Cl + 3-chloro-1-butene) = (2.1 +/- 0.4) x 10(-10), k(Cl + 1-chloro-2-butene) = (2.2 +/- 0.4) x 10(-10), and k(Cl + 2,3-dichlorobutane) = (1.1 +/- 0.2) x 10(-11) cm3 molecule(-1) s(-1).     

Gas-phase kinetics of hydroxyl radical reactions with C3H6 and C4H8: product branching ratios and OH addition site-specificity

Products of the reaction of OH radicals with propene, trans-2-butene, and 1-butene have been investigated in a fast flow reactor, coupled with time-of-flight mass spectrometry, at pressures between 0.8 and 3.0 Torr. The product determination includes H atom abstraction channels as well as site-specific OH addition. The OH radicals are produced by the H + NO(2) → OH + NO reaction or by the F + H(2)O → OH + HF reaction, the H or F atoms being produced in a microwave discharge. The gas mixture is ionized using single photon ionization (SPI at 10.54 eV), and products are detected using time-of-flight mass spectrometry (TOF-MS). The H atom abstraction channels are measured to be <2% for OH + propene, 8 ± 3% for OH + 1-butene, and 3 ± 1% for OH + trans-2-butene. Analysis of ion fragmentation patterns leads to 72 ± 16% OH addition to the propene terminal C atom and 71 ± 16% OH addition to the 1-butene terminal C atom. The errors bars represent 95% confidence intervals and include estimated uncertainties in photoionization cross sections.     

2,3-Dimethyl-2-butene (TME) ozonolysis: pressure dependence of stabilized Criegee intermediates and evidence of stabilized vinyl hydroperoxides

We present measurements of the pressure dependence of stabilized Criegee intermediate (SCI) formation utilizing a hexafluoroacetone scavenger. SCI yields in the ozonolysis of 2,3-dimethyl-2-butene (TME) were measured in a high pressure flow reactor within a range of 50-710 Torr. Within this pressure range, SCI yields increase linearly with pressure. A zero pressure intercept of about 15% indicates that a significant fraction of CI are formed below the barrier to isomerization. By comparison of our results of the pressure dependence of SCI formation and both prompt and long-time OH yields, our results indicate that OH formation from ozonolysis proceeds via at least two intermediates, the SCI and presumably a vinylhydroperoxide (VHP).     

Vinyl hydrogen acidities of two stereoisomers

The gas-phase acidities of the vinyl hydrogens of cis- and trans-2-butene were measured by the silane kinetic method in a Fourier-transform ion cyclotron resonance spectrometer. The acidities of ethene and the secondary vinyl hydrogen of propene were measured by the same method. The method was calibrated using the known acidities of methane and benzene. The vinyl hydrogens of trans-2-butene are more acidic than the vinyl hydrogens of cis-2-butene by 4.5 kcal/mol; the acidities of ethene and the secondary vinyl hydrogen of propene are between those of the two butenes. The acidity of cis-2-butene is 409 +/- 2 kcal/mol, and the acidity of trans-2-butene is 405 +/- 2 kcal/mol. Density functional theory calculations are in good agreement with the experiments. The results are discussed in terms of steric interactions, polarizabilities, dipole-dipole interactions, and charge-dipole interactions.     

Pressure dependence of stabilized Criegee intermediate formation from a sequence of alkenes

Ozonolysis is a key reaction in atmospheric chemistry, although important details of the behavior of the ozonolysis intermediates are not known. The key intermediate in ozonolysis, the Criegee intermeiate (CI), is known to quickly isomerize, with the favored unimolecular pathway depending on the relative barriers to isomerization. Stabilized Criegee intermediates (SCI), those with energy below any barriers to isomerization, may result from initial formation with low energy or collisional stabilization of high energy CI. Bimolecular reactions of SCI have been proposed to play a role in OH formation and nucleation of new particles, but unimolecular reactions of SCI may well be too fast for these to be significant. We present measurements of the pressure dependence of SCI formation for a set of alkenes utilizing a hexafluoroacetone scavenger. We studied four alkenes (2,3-dimethyl-2-butene (TME), trans-5-decene, cyclohexene, α-pinene) to characterize how size and cyclization (endo vs exo) affect the stability of Criegee intermediates formed in ozonolysis. SCI yields in ozonolysis were measured in a high pressure flow reactor within a range of 30-750 Torr. The linear alkenes show considerable stabilization with trans-5-decene showing 100% stabilization at ～400 Torr and TME having 65% stabilization at 710 Torr. Extrapolation of the yields for linear alkenes to 0 Torr shows yields significantly above zero, indicating that a fraction of their CI are formed below the barrier to isomerization. CI from endocyclic alkenes show little to no stabilization and appear to have neglible stabilization at 0 Torr. Cyclohexene derived CI showed no stabilization even at 650 Torr, while α-pinene CI had ～15% stabilization at 740 Torr. Our results show a strong dependence of SCI formation on carbon number; adding just 2 to 3 CI carbons in linear alkenes increases stabilization by a factor of 10. Stabilization for endocyclic alkenes, at atmospheric pressure, begins to occur at a carbon number of 10, with only modest yields of SCI.     

Kinetic and product yield study of the heterogeneous gas-surface reaction of anthracene and ozone

Little quantitative information exists regarding the products of the heterogeneous reaction of polycyclic aromatic hydrocarbons (PAHs) and ozone. We have, therefore, performed the first quantitative study investigating the kinetics and products of the heterogeneous gas-surface reaction of anthracene and ozone as a function of ozone concentration and relative humidity (RH). The reaction exhibited pseudo-first-order kinetics for anthracene loss under dry conditions (RH < 1%) and the pseudo-first-order rate coefficients displayed a Langmuir-Hinshelwood dependence on the gas-phase ozone concentration, which yielded the following fitting parameters: the equilibrium constant for ozone adsorption, K(O3) = (2.8 +/- 0.9) x 10(-15) cm3 and the maximum pseudo-first-order rate coefficient, k(I)max = (6.4 +/- 1.8) x 10(-3) s(-1). The kinetics were unchanged when experiments were performed at approximately 50% and 60% RH. In the product study, a nonlinear dependence, similar to a Langmuir adsorption plot, of the anthraquinone product yield as a function of ozone concentration was observed and resulted in the following fitting parameters: K(O3) = (3.4 +/- 1.5) x 10(-15) cm3 and the maximum anthraquinone yield, ANQmax % = 30 +/- 18%. Experiments performed under higher relative humidity conditions ( approximately 50% and 60% RH) revealed that the anthraquinone yield was unaffected by the presence of gas-phase water. It is noteworthy that both the anthracene loss kinetics and the anthraquinone yields have a similar dependence on the degree of ozone partitioning to the surface. This can be understood in terms of a mechanism whereby the rate-determining steps for anthracene loss and anthraquinone formation are both driven by the amounts of ozone adsorbed on the surface. Our results suggest that at atmospherically relevant ozone concentrations (100 ppb) the anthraquinone yield from the ozonolysis of anthracene under dry and high relative humidity conditions would be less than 1%.     

Heterogeneous reactions of linoleic acid and linolenic acid particles with ozone: reaction pathways and changes in particle mass, hygroscopicity, and morphology

In this study, an electrodynamic balance (EDB) and a single particle Raman spectroscopic system were used to investigate the heterogeneous reactions of linoleic acid and linolenic acid with ozone under ambient temperatures (22-24 degrees C) and dry conditions (RH<5%). Raman characterizations provide evidence that ozone-induced autoxidation, in addition to direct ozonolysis, is a plausible pathway in the reactions between ozone and linoleic acid and linolenic acid particles. Furthermore, the significance of this specific oxidation pathway depends on the ozone concentrations used in the experiment. A low ozone concentration (approximately 200-250 ppb) with a longer exposure period (20 h) favors autoxidation but an extremely high ozone concentration (approximately 10 ppm) favors ozonolysis and forces most unsaturated fatty acids to react with ozone in a relatively short period of time. In the low ozone concentration experiments, the mass of the ozone-processed linoleic acid and linolenic acid particles increased by about 2-3% and 10-13%, respectively. In addition, the mass ratios (particle mass at RH approximately 85% to particle mass at RH<5%) of the ozone-processed linoleic acid and linolenic acid particles increased by about 2-3% and 3-4%, respectively. The morphology of the pure and ozone-processed linoleic acid and linolenic acid particles are compared, based on imagining and their light scattering patterns.     

Ab initio and microcalorimetric investigations of alkene adsorption on phosphotungstic acid

The adsorption of ethene, propene, 1-butene, trans-2-butene, and isobutene on phosphotungstic acid has been characterized by density functional theory (DFT) calculations and microcalorimetric experiments. The DFT-calculated chemisorption energies to form the corresponding alkoxides for ethene, propene, 1-butene, trans-2-butene, and isobutene were -86.8, -90.3, -102.6, -79.9, and -91.4 kJ mol(-1), respectively (for their most-favorable binding modes). The relative chemisorption energies to form the alkoxides are dictated by the strength of interaction of the acidic proton with the carbon atom of the double bond that becomes protonated. The activation barrier for chemisorption was greatest for alkenes with primary (1 degrees) carbenium-like transition states followed by secondary (2 degrees) and tertiary (3 degrees) transition states. The adsorption enthalpy established from microcalorimetric experiments with propene and isobutene was approximately -100 kJ mol(-1), which is close to the DFT-calculated values. Chemisorption of ethene on phosphotungstic acid during microcalorimetric experiments was minimal, presumably because of the large activation barrier associated with a 1 degrees carbenium-like transition state. The results from this study are compared with those in the literature for the adsorption of alkenes on zeolites, which have a similar adsorption mechanism. Our results suggest that alkene adsorption is stronger on phosphotungstic acid than on zeolites, as supported by the more exothermic chemisorption energies. Additionally, activation barriers for alkene adsorption are lower over phosphotungstic acid than over zeolites.     

Gas-phase ozonolysis of alkenes: formation of OH from anti carbonyl oxides

Gas-phase ozone-alkene reactions are known to produce the hydroxyl radical (OH) in high yields. Most mechanistic studies to date have focused on the role of syn carbonyl oxides; however, OH production from ethene ozonolysis indicates a second, poorly understood OH-forming channel, which may contribute to OH production in the ozonolysis of substituted alkenes as well. Using laser-induced fluorescence, we have measured OH and OD yields from the ozonolysis of two partially deuterated alkenes, cis- and trans-3-hexene-3,4-d2. OD is formed from both alkenes, indicating a pathway of hydroxyl-radical formation involving vinylic hydrogens, accounting for one-third of total OH formation from cis-3-hexene. The lack of a significant kinetic isotope effect suggests this pathway is the "hot acid" channel, arising from rearrangement of anti carbonyl oxides. Measured yields also allow for the estimation of syn:anti carbonyl oxide ratios, approximately 50:50 for trans-3-hexene and approximately 20:80 for cis-3-hexene, qualitatively consistent with our understanding of ozonide decomposition pathways.     

Synthesis of E- and Z-o-Methoxy-Substituted 2,3-Diphenyl Propenoic Acids and Its Methyl Esters

A series of stereoisomeric o-methoxy-substituted 2,3-diphenyl propenoic acids and their methyl esters have been synthesized. The E isomers were prepared by a modified Perkin condensation (substituted benzaldehyde, phenylacetic acid, Et₃N/acetic anhydride). The difficult to access Z isomers were obtained conveniently in good yields when the appropriate coumarin derivatives were allowed to react with KOH and CH₃I in DMSO.     

Mechanism of the OH-initiated oxidation of hydroxyacetone over the temperature range 236-298 K

The mechanism of the gas-phase reaction of OH radicals with hydroxyacetone (CH3C(O)CH2OH) was studied at 200 Torr over the temperature range 236-298 K in a turbulent flow reactor coupled to a chemical ionization mass-spectrometer. The product yields and kinetics were measured in the presence of O2 to simulate the atmospheric conditions. The major stable product at all temperatures is methylglyoxal. However, its yield decreases from 82% at 298 K to 49% at 236 K. Conversely, the yields of formic and acetic acids increase from about 8% to about 20%. Other observed products were formaldehyde, CO2 and peroxy radicals HO2 and CH3C(O)O2. A partial re-formation of OH radicals (by approximately 10% at 298 K) was found in the OH + hydroxyacetone + O2 chemical system along with a noticeable inverse secondary kinetic isotope effect (k(OH)/k(OD) = 0.78 +/- 0.10 at 298 K). The observed product yields are explained by the increasing role of the complex formed between the primary radical CH3C(O)CHOH and O2 at low temperature. The rate constant of the reaction CH3C(O)CHOH + O2 --> CH3C(O)CHO + HO2 at 298 K, (3.0 +/- 0.6) x 10(-12) cm3 molecule(-1) s(-1), was estimated by computer simulation of the concentration-time profiles of the CH3C(O)CHO product. The detailed mechanism of the OH-initiated oxidation of hydroxyacetone can help to better describe the atmospheric oxidation of isoprene, in particular, in the upper troposphere.     

Rate constants for the reaction of OH radicals with a series of alkanes and alkenes at 299 ± 2 K

Using methyl nitrite photolysis in air as a source of hydroxyl radicals, relative rate constants for the reaction of OH radicals with a series of alkanes and alkenes have been determined at 299 ± 2 K. The rate constant ratios obtained are: relative to n-hexane = 1.00, neopentane 0.135 ± 0.007, n-butane 0.453 ± 0.007, cyclohexane 1.32 ± 0.04; relative to cyclohexane = 1.00, n-butane 0.341 ± 0.002, cyclopentane 0.704 ± 0.007, 2,3-dimethylbutane 0.827 ± 0.004, ethene 1.12 ± 0.05; relative to propene = 1.00, 2-methyl-2-butene 3.43 ± 0.13, isoprene 3.81 ± 0.17, 2,3-dimethyl-2-butene 4.28 ± 0.21. These relative rate constants are placed on an absolute basis using previous absolute rate constant data and are compared and discussed with literature data.     

Formation of O(3P) atoms and epoxides from the gas- phase reaction of O3 with isoprene

The formation yields of 1,2-epoxy-2-methyl-3-butene and 1,2-epoxy-3-methyl-3-butene have been measured from the reaction of O₃ with isoprene at room temperature and one atmosphere total pressure of N₂ and air diluents, with and without cyclohexane to scavenge the OH radicals formed in this reaction system. In addition, a relative rate method was used to determine a rate constant for the gas-phase reaction of O₃ with 1,2-epoxy-2-methyl-3-butene of (2.5 ± 0.7) x 10^-18 cm³ molecules^-1 s^-1 at 296 ± 2 K. Our data show that the epoxide yields in N₂ and air diluents are the same, with formation yields of 1,2-epoxy-2-methyl-3-butene of 0.028 ± 0.007 and of 1,2-epoxy-3-methyl-3-butene of 0.011 ± 0.004. These data further show that the epoxides arise from the primary O₃ reaction with isoprene, and not via the formation of O(³P) atoms from the O₃ - isoprene reaction followed by reaction of these O(³P) atoms with isoprene.     

Heterogeneous uptake and reactivity of formic acid on calcium carbonate particles: a Knudsen cell reactor, FTIR and SEM study

The heterogeneous uptake and reactivity of formic acid (HCOOH), a common gas-phase organic acid found in the environment, on calcium carbonate (CaCO(3)) particles have been investigated using a Knudsen cell reactor, Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM). FTIR measurements show that the adsorption of formic acid on the surface of calcium carbonate results in the formation of calcium formate. Besides calcium formate, carbonic acid is also a reaction product under dry conditions (<1% RH). Under dry conditions and at low pressures, the initial uptake coefficient of formic acid on CaCO(3) particles is measured to be 3 +/- 1 x 10(-3) and decreases as the surface saturates with adsorbed products. The maximum surface coverage of formic acid under dry conditions is determined to be (3 +/- 1)x 10(14) molecules cm(-2). Under humidified conditions (RH >10%), adsorbed water on the surface of the carbonate particles participates in the surface reactivity of these particles, which results in the enhanced uptake kinetics and extent of reaction of this organic acid on CaCO(3) as well as opens up several new reaction pathways. These reaction pathways include: (i) the water-assisted dissociation of carbonic acid to CO(2) and H(2)O and (ii) the formation of calcium formate islands and crystallites, as evident by SEM images. The results presented here show that adsorbed water plays a potentially important role in the surface chemistry of gas-phase organic acids on calcium carbonate particles.     

在H3PO4存在下2,3-二甲基-2-丁烯与乙酐的酰化反应

在H3PO4存在下进行了2，3－二甲基－2－丁烯与乙酐的酰化反应，结果表明，H3PO4是室温下催化2，3－二甲基－2－丁烯与乙酐酰化反应的有效催化剂，在H3PO4存在下，酰化产物的收率主要取决于：（a)H3PO4的用量，（b)乙酐的用量；（c)反应温度和（d)反应时间，在适宜反应条件下，所得3，3，4－三甲基－4－戊烯－2－酮（TMP）约为99％，另外还发现，反应体系中加入少量乙酸，不会明显减少酰化产物的收率，乙酐的纯度，反应物的加入顺序对该反应几乎没有任何影响，在有和没有溶剂CH2Cl2的条件下所得酰化产物的收率是可比的。     

Interaction of formic and acetic acid with ice surfaces between 187 and 227 K. Investigation of single species- and competitive adsorption

The physical adsorption of formic (HC(O)OH) and acetic (CH(3)C(O)OH) acid on ice was measured as a function of concentration and temperature. At low concentrations, the gas-ice interaction could be analysed by applying Langmuir adsorption isotherms to determine temperature dependent partition constants, K(Lang). Using temperature independent saturation coverages (N(max)) of (2.2 +/- 0.5) x 10(14) molecule cm(-2) and (2.4 +/- 0.6) x 10(14) molecule cm(-2) for HC(O)OH and CH(3)C(O)OH, respectively, we derive K(Lang)(HC(O)OH) = 1.54 x 10(-24) exp (6150/T) and K(Lang)(CH(3)C(O)OH) = 6.55 x 10(-25) exp (6610/T) cm(3) molecule(-1). Via a van't Hoff analysis, adsorption enthalpies were obtained for HC(O)OH and CH(3)C(O)OH. Experiments in which both acids or HC(O)OH and methanol interacted with the ice surface simultaneously were adequately described by competitive adsorption kinetics. The results are compared to previous measurements and used to calculate the equilibrium partitioning of these trace gases to ice surfaces under conditions relevant to the atmosphere.     

Rate constants for the gas-phase reactions of O3 with a series of alkenes at 296 ± 2 K

The kinetics of the gas-phase reactions of O₃ with a series of alkenes have been investigated at atmospheric pressure (ca. 740 torr) of air and 296 ± 2 K, using a relative rate method in the presence of sufficient n-octane to scavenge any OH radicals generated in these reactions. Relative to k(O₃ + propene) = 1.00, the rate constants obtained were: 1-butene, 0.975 ± 0.030; 2-methylpropene, 1.14 ± 0.04; 2-methyl-1,3-butadiene (isoprene), 1.21 ± 0.02; 1,4-cyclohexadiene, 4.75 ± 0.23; cyclohexene, 7.38 ± 0.48; cis-2-butene, 12.8 ± 0.8; trans-2-butene, 21.5 ± 1.5; 2-methyl-2-butene, 42.1 ± 2.8; cyclopentene, 64.9 ± 4.3; and 2,3-dimethyl-2-butene, 123 ± 11. These relative rate constants have been placed on an absolute basis using a rate constant for the reaction of O₃ with propene of 1.01 × 10^?17 cm³ molecule^?1 s^?1 at 296 K derived from an analysis of the available literature data. The resulting rate constants then lead to a self-consistent set of room temperature data for the reactions of O₃ with these alkenes. © John Wiley & Sons, Inc.     

Laser pyrolysis studies of OH reaction rates with several butenes at 1200 K

Using a laser pyrolysis/laser fluorescence method, we have measured the rate constants for OH reacting with 1-butene, t-2-butene, isobutene, and 2,3-dimethyl-2-butene near 1200 K. The butene rate constants are large, ranging from 2.0–3.7 × 10^?11 cm^?3 s^?1, and increase with the number of allylic hydrogens. Transition-state theory considerations indicate these allylic hydrogens are easily abstracted, in contrast to prior observations on propene.