CF3CH(ONO)CF3: Synthesis,IR spectrum,and use as OH radical source for kinetic and mechanistic studies

The synthesis, IR spectrum, and first‐principles characterization of CF₃CH(ONO)CF₃ as well as its use as an OH radical source in kinetic and mechanistic studies are reported. CF₃CH(ONO)CF₃ exists in two conformers corresponding to rotation about the RCO? NO bond. The more prevalent trans conformer accounts for the prominent IR absorption features at frequencies (cm^?1) of 1766 (N?O stretch), 1302, 1210, and 1119 (C? F stretches), and 761 (O? N? O bend); the cis conformer contributes a number of distinct weaker features. CF₃CH(ONO)CF₃ was readily photolyzed using fluorescent blacklamps to generate CF₃C(O)CF₃ and, by implication, OH radicals in 100% yield. CF₃CH(ONO)CF₃ photolysis is a convenient source of OH radicals in the studies of the yields of CO, CO₂, HCHO, and HC(O)OH products which can be difficult to measure using more conventional OH radical sources (e.g., CH₃ONO photolysis). CF₃CH(ONO)CF₃ photolysis was used to measure k(OH + C₂H₄)/k(OH + C₃H₆) = 0.29 ± 0.01 and to establish upper limits of 16 and 6% for the molar yields of CO and HC(O)OH from the reaction of OH radicals with benzene in 700 Torr of air at 296 K. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 159–165, 2003     

The hydroxyl radical reaction rate constant and products of 3,5‐dimethyl‐1‐hexyn‐3‐ol

A bimolecular rate constant,k_DHO, of (29 ± 9) × 10^?12 cm³ molecule^?1 s^?1 was measured using the relative rate technique for the reaction of the hydroxyl radical (OH) with 3,5‐dimethyl‐1‐hexyn‐3‐ol (DHO, HC?CC(OH)(CH₃)CH₂CH(CH₃)₂) at (297 ± 3) K and 1 atm total pressure. To more clearly define DHO's indoor environment degradation mechanism, the products of the DHO + OH reaction were also investigated. The positively identified DHO/OH reaction products were acetone ((CH₃)₂C?O), 3‐butyne‐2‐one (3B2O, HC?CC(?O)(CH₃)), 2‐methyl‐propanal (2MP, H(O?)CCH(CH₃)₂), 4‐methyl‐2‐pentanone (MIBK, CH₃C(?O)CH₂CH(CH₃)₂), ethanedial (GLY, HC(?O)C(?O)H), 2‐oxopropanal (MGLY, CH₃C(?O)C(?O)H), and 2,3‐butanedione (23BD, CH₃C(?O)C(?O)CH₃). The yields of 3B2O and MIBK from the DHO/OH reaction were (8.4 ± 0.3) and (26 ± 2)%, respectively. The use of derivatizing agents O‐(2,3,4,5,6‐pentalfluorobenzyl)hydroxylamine (PFBHA) and N,O‐bis(trimethylsilyl)trifluoroacetamide (BSTFA) clearly indicated that several other reaction products were formed. The elucidation of these other reaction products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible DHO/OH reaction mechanisms based on previously published volatile organic compound/OH gas‐phase reaction mechanisms. © 2004 Wiley Periodicals, Inc. Int J Chem Kinet 36: 534–544, 2004     

Mechanism for the gas‐phase reaction between OH and 3‐methylfuran: A theoretical study

The mechanism for the OH + 3‐methylfuran reaction has been studied via ab initio calculations to investigate various reaction pathways on the doublet potential energy surface. Optimizations of the reactants, products, intermediates, and transition structures are conducted using the MP2 level of theory with the 6‐311G(d,p) basis set. The single‐point electronic energy of each optimized geometry is refined with G3MP2 and G3MP2B3 calculations. The theoretical study suggests that the OH + 3‐methylfuran reaction is dominated by the formation of HC(O)CH?C(CH₃)CHOH (P7) and CH(OH)CH?C(CH₃)C(O)H (P9), formed from two low‐lying adducts, IM1 and IM2. The direct hydrogen abstraction pathways and the S_N2 reaction may play a minor or negligible role in the overall reaction of OH with 3‐methylfuran. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008     

Versatile Reaction Pathways of 1,1,3,3,3-Pentafluoropropene at Rh(I) Complexes [Rh(E)(PEt3)3] (E=H,GePh3, Si(OEt)3, F,Cl): C-F versus C-H Bond Activation Steps

The reaction of the rhodium(I) complexes [Rh(E)(PEt₃)₃] (E=GePh₃ ( 1 ), H ( 6 ), F ( 7 )) with 1,1,3,3,3-pentafluoropropene afforded the defluorinative germylation products Z/E-2-(triphenylgermyl)-1,3,3,3-tetrafluoropropene and the fluorido complex [Rh(F)(CF₃CHCF₂)(PEt₃)₂] ( 2 ) together with the fluorophosphorane E-(CF₃)CH=CF(PFEt₃). For [Rh(Si(OEt)₃)(PEt₃)₃] ( 4 ) the coordination of the fluoroolefin was found to give [Rh{Si(OEt)₃}(CF₃CHCF₂)(PEt₃)₂] ( 5 ). Two equivalents of complex 2 reacted further by C−F bond oxidative addition to yield [Rh(CF=CHCF₃)(PEt₃)₂(μ-F)₃Rh(CF₃CHCF₂)(PEt₃)] ( 9 ). The role of the fluorido ligand on the reactivity of complex 2 was assessed by comparison with the analogous chlorido complex. The use of complexes 1 , 4 and 6 as catalysts for the derivatization of 1,1,3,3,3-pentafluoropropene provided products, which were generated by hydrodefluorination, hydrometallation and germylation reactions.     

Dissociation and IVR pathways for the CF3H(H2O)3 cluster

Classical trajectory simulations are used to study the intramolecular dynamics of isolated CF₃H and the CF₃H(H₂O)₃ cluster, by either exciting the CH stretch local mode to then=6 level or by adding an equivalent amount of energy to an OH stretch normal mode. Energy transfer from the CH local mode is statistically the same for CF₃H(H₂O)₃ as for isolated CF₃H, and agrees with previous experimental studies. Clusters excited with 6 quanta in the CH local mode are remarkably stable. Though the CF₃H-(H₂O)₃ intermolecular potential is only 1.5 kcal/mol, only 1 of 26 clusters excited with 6 quanta in the CH local mode dissociate within 10 ps. The absorption linewidth for the CH local mode in CF₃H(H₂O)₃ is related to IVR within CF₃H and not to the unimolecular lifetime of the cluster. When an OH stretch normal mode of the cluster is excited, energy transfer to CF₃H is negligible and nearly one half of the clusters dissociate within 10 ps.     

The DFT and ab initio investigations on the mechanism of CF3O2 + H reaction

The mechanisms for the reaction of CF₃O₂ with atomic hydrogen were studied with ab initio and DFT methods. The results reveal that the reaction could take place on the singlet and triplet potential energy surfaces (PES). For the singlet PES, addition/elimination and substitution mechanisms are determined, and the former one is dominant. The most favorable channel involves the association of CF₃O₂ with H atom to form CF₃O₂H (IM1) via a barrierless process, and then the O–O bond dissociates to give out CF₃O + OH. The secondary product might be CF₃OH + O, formed from the O–O bond cleavage in the initial adduct CF₃O(H)O (IM2). Other products such as CF₃ + O₂H, HF + CF₂O₂ and O₂ + CHF₃ are of no importances because of higher barriers. On the triplet PES, only substitution mechanism is located. With higher barriers involving, the channels on the triplet PES could be negligible compared with the channels on the singlet PES.     

Long path-FTIR studies of some atmospheric reactions involving CF3OO and CF3O radicals

In attempts to obtain kinetic and mechanistic data required for an assessment of atmospheric fate of alternative halocarbons containing a CF₃ group, reactions of the key free radical intermediates CF₃OO and CF₃O with several atmospheric compounds (i.e., NO, NO₂, alkanes and alkenes) have been studied at 297 ± 2 K in 700 torr of air. Experiments employed the long path-FTIR spectroscopic method for product analysis and the visible (400 nm) photolysis of CF₃NO → CF₃ + NO as a source for the precursor radical CF₃. Numerous labile and stable F-containing molecular products have been characterized based on kinetic and spectroscopic data obtained at sufficiently short photolysis time (≤1 min) to minimize heterogeneous decay on the reactor walls. Major new findings have been made for the reactions involving CF₃O radicals. The behavior of CF₃O radicals has been shown to be markedly different from that of CH₃O radicals, i.e., (1) O₂-reaction: no evidence for the F-atom transfer reaction CF₃O + O₂ → CF₂ O + FOO; (2) NO-reaction: addition reaction CH₃O + NO (+M) → CH₃ONO (+M), but F-transfer reaction CF₃O + NO → CF₂O + FNO; (3) NO₂-reaction: addition reaction for both radicals, but F-transfer reaction CF₃ + NO₂ → CF₂O + FNO₂ to a minor extent; (4) alkane-reaction: much faster H-abstraction by CF₃O, comparable to HO; (5) alkene-reaction: much faster addition reaction of CF₃O, comparable to HO. These results are summarized in this paper.     

Atmospheric degradation mechanisms of a simulant organophosphorus pesticide isopropyl methyl methylphosphonate: A theoretical consideration

Calculations using density functional theory were performed to explore the mechanisms for atmospheric degradation of isopropyl methyl methylphosphonate (IMMP). The potential energy surface profiles for OH‐initiated reaction of IMMP were constructed, and all possible degradation channels were considered. Rate constants were further calculated using transition state theory. It was established from these calculations that H‐abstractions from alkyl groups have much lower energy barriers than substitutions of alkoxyl groups, and four possible H‐abstraction channels are competitive. Investigations into the secondary reactions under the presence of O₂/NO were also performed. It is shown that O₂ addition, reaction of peroxide radicals with NO to form RO radicals, and removal of ·RO are the major degradation pathways for alkyl radicals. Four selected products, CH₃OP(O)(CH₃)OC(O)CH₃, CH₃OP(O)(O)CH₃, (CH₃)₂CHOP(O)(CH₃)OH, and (CH₃)₂CHOP(O)(CH₃)OCH?O, are predicted to be the major products in this study. © 2013 Wiley Periodicals, Inc.     

Atmospheric pressure chemical vapour deposition of WO3 thin films from a volatile fluorinated tungsten oxo‐alkoxide precursor,W(O)(OCH2CF3)4

The monomeric tungsten oxo‐fluoroalkoxide W(O)(CH₂CF₃)₄ ( 1 ) was synthesized from W(O)Cl₄ and CF₃CH₂OH in the presence of ammonia. It was used in atmospheric pressure chemical vapour deposition experiments to deposit non‐stoichiometric WO_2.9 when used as a single‐source precursor or stoichiometric WO₃ when O₂ was used as co‐reagent. Copyright © 2008 John Wiley & Sons, Ltd.     

Kinetics and mechanism of the thermal gas‐phase oxidation of perfluorobutene‐2 in presence of trifluoromethyl hypofluorite

The oxidation of perfluorobutene‐2 (C₄F₈) initiated by trifluoromethyl hypofluorite (CF₃OF) in presence of O₂ has been studied at 323.1, 332.6, 342.5, and 352.0 K, using a conventional static system. The initial pressure of CF₃OF was varied between 4.8 and 23.6 Torr, that of C₄F₈ between 48.7 and 302.4 Torr, and that of O₂ between 51.5 and 270.4 Torr. Several runs were made in presence of 325.5–451.2 Torr of N₂. The main products were COF₂, CF₃C(O)F, and CF₃OC(O)F. Small amounts of compound containing ? CF(CF₃)? O? C(O)CF₃ group were also formed, as detected by ¹³C NMR spectroscopy. The oxidation is a homogeneous short‐chain reaction, attaining, at the pressure of O₂ used, the pseudo‐zero‐order condition with respect to O₂ as reactant. The reaction is independent of the total pressure. Its basic steps are as follows: the thermal generation of CF₃O^? radicals by the abstraction of fluorine atom of CF₃OF by C₄F₈, the addition of CF₃O^? to the alkene, the formation of perfluoroalkoxy radicals RO^? in presence of O₂, and the decomposition of these radicals via the C? C bond scission, giving products containing ? C(O)F end group and reforming RO^? and CF₃O^? radicals. The mechanism consistent with experimental results is postulated. © 2003 Wiley Periodicals, Inc. Int J Chem Kinet 35: 532–541, 2003     

UV laser photolysis of silacyclopent‐3‐ene: effect of admixtures on nature of chemically vapour‐deposited organosilicon films

Examination of ArF laser‐induced gas‐phase photolysis of silacyclopent‐3‐ene, occuring as extrusion of silylene, in the presence of admixtures reveals that photolysis is not interfered with in the presence of N₂, CO and CO₂, but it is in the presence of O₂, 2‐C₄F₈, CH₃OH, CD₃OH, CF₃CH₂OH and CH₃CO₂H. Formation of volatile products and solid deposited films incorporating fluorine or oxygen atoms is interpreted in terms of reactions of silylene with the admixtures. Copyright © 2002 John Wiley & Sons, Ltd.     

4‐Ethoxycarbonyl‐3‐hydroxy‐3‐phenylcyclohexanone

The title compound, ethyl 2‐hydroxy‐4‐oxo‐2‐phenyl­cyclo­hexane­carboxyl­ate, C₁₅H₁₈O₄, was obtained by a Michael–Aldol condensation and has the cyclo­hexanone in a chair conformation. The attached hydroxy, ethoxy­carbonyl and phenyl groups are disposed in β‐axial, β‐equatorial and α‐­equatorial configurations, respectively. An intermolecular hydrogen bond, with an O?O distance of 2.874 (2) Å, links the OH group and the ring carbonyl. Weak intermolecular C—H?O=C (ester and ketone), O—H?O=C (ketone) and C—H?OH hydrogen bonds exist.     

Synthesis and Properties of CF3(OCF3)CH‐Substituted Arenes and Alkenes†

A silver‐mediated oxidative trifluoromethylation of easily accessible α‐trifluoromethyl alcohols with TMSCF₃ was developed to access novel CF₃(OCF₃)CH‐containing compounds. Deprotonation of CF₃(OCF₃)CH‐substituted arenes afforded synthetically useful CF₃O‐substituted gem‐difluoroalkenes. Furthermore, evaluation of the lipophilicities (log P) indicated that CH(OCF₃)CF₃ is more lipophilic than the common fluorinated motifs such as CF₃, OCF₃, and SCF₃, thus rendering the CH(OCF₃)CF₃ motif appealing in drug discovery.     

Gas‐phase chemistry of dihydromyrcenol with ozone and OH radical: Rate constants and products

A bimolecular rate constant, k_{OH + dihydromyrcenol}, of (38 ± 9) × 10^?12 cm³ molecule^?1 s^?1 was measured using the relative rate technique for the reaction of the hydroxyl radical (OH) with 2,6‐dimethyl‐7‐octen‐2‐ol (dihydromyrcenol,) at 297 ± 3 K and 1 atm total pressure. Additionally, an upper limit of the bimolecular rate constant, k, of approximately 2 × 10^?18 cm³ molecule^?1 s^?1 was determined by monitoring the decrease in ozone (O₃) concentration in an excess of dihydromyrcenol. To more clearly define part of dihydromyrcenol's indoor environment degradation mechanism, the products of the dihydromyrcenol + OH and dihydromyrcenol + O₃ reactions were also investigated. The positively identified dihydromyrcenol/OH and dihydromyrcenol/O₃ reaction products were acetone, 2‐methylpropanal (O?CHCH(CH₃)₂), 2‐methylbutanal (O?CHCH(CH₃)CH₂CH₃), ethanedial (glyoxal, HC(?O)C(?O)H), 2‐oxopropanal (methylglyoxal, CH₃C(?O)C(?O)H). The use of derivatizing agents O‐(2,3,4,5,6‐pentafluorobenzyl)hydroxylamine (PFBHA) and N,O‐bis(trimethylsilyl)trifluoroacetamide (BSTFA) clearly indicated that several other reaction products were formed. The elucidation of these other reaction products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible dihydromyrcenol/OH and dihydromyrcenol/O₃ reaction mechanisms based on previously published volatile organic compound/OH and volatile organic compound/O₃ gas‐phase reaction mechanisms. © 2006 Wiley Periodicals, Inc. *

1 This article is a US Government work and, as such, is in the public domain of the United States of America

Int J Chem Kinet 38: 451–463, 2006     

Reactions of trifluoromethyl-substituted arylacetylenes with arenes in superacids

Protonation of the C≡C bond in trifluoromethyl-substituted arylacetylenes ArC≡CCF₃ by the action of superacids (CF₃SO₃H or HSO₃F) generates vinyl cations ArC⁺=CHCF₃ which react with arenes Ar′H to give alkenes Ar(Ar′)C=CHCF₃. Protonation of the latter at the C=C bond in the reaction medium yields stable cations Ar(Ar′)C⁺-CH₂CF₃ which are converted into E/Z-isomeric alkenes Ar(Ar′)C=CHCF₃ and/or alcohols Ar(Ar′)C(OH)CH₂CF₃ as a result of quenching of superacid reaction solution.     

Synthesis of ϵ‐Caprolactam from Cyclohexanone Oxime Using Zeolites Hβ, HZSM‐5, and Alumina Pillared Montmorillonite

The Beckmann rearrangement of cyclohexanone oxime (CHO) to ?‐caprolactam (?‐C) was studied in a plug flow reactor at 300–400°C under atmospheric pressure by using Hβ, ZSM‐5, and alumina pillared montmorillonite. With Hβ(X) Y zeolites, raising the SiO₂/Al₂O₃ molar ratio (X) results in the enhancement of catalyst acid strength with concomitant decrease of the total acid amount. In creasing the calcination temperature (Y) causes remarkable diminution of catalyst surface area, acid strength, and acid amount. A similar trend was found for AlPMY catalysts. In there action of CHO, the initial catalytic activity correlates well with the total acid amount of various catalysts except for Hβ(10) Y (Y > 600°C). The reaction proceeds on both Brönsted and Lewis acid sites and the catalyst deactivation most likely occurs at the strong Brönsted acid sites. The effect of solvents in the feed on the catalytic results was also investigated; it was found that polar solvents such as ethanol or n‐butanol give high ?‐C yield and longer catalyst life time. In the reaction of CHO/C₂H₅OH over Hβ(10)800 at 400°C and W/F 74.6 gh/mol, the CHO conversion and ?‐C yield remain 100% and 92%, respectively, for at least 20 h time‐on‐stream. The reaction paths and the mechanism for ?‐C formation are proposed.     

Chlorine initiated photooxidation studies of hydrochlorofluorocarbons (HCFCs) and hydrofluorocarbons (HFCs): Results for HCFC-22 (CHClF2); HFC-41 (CH3F); HCFC-124 (CClFHCF3); HFC-125 (CF3CHF2); HFC-134a (CF3CH2F); HCFC-142b (CClF2CH3); and HFC-152a (CHF2CH3)

Data on the tropospheric degradation of proposed substitutes for ozone depleting CFCs were obtained by conducting photochemical oxidation studies of HCFCs and HFCs using long path Fourier transform infrared spectroscopy. The hydrogen abstraction reactions were initiated using Cl radicals rather than OH radicals because of the rather unreactive nature of the compounds. The experimental product yields at T = 25 ± 3°C and 700 Torr of dry air were: CHClF₂ (1.11 ± 0.06 C(O)F₂); CClFHCF₃ (1.00 ± 0.04 CF₃C(O)F); CF₃CHF₂ (1.09 ± 0.05 C(O)F₂); CClF₂CH₃ (0.98 ± 0.03 C(O)F₂); CHF₂CH₃ (1.00 ± 0.05 C(O)F₂); CF₃CH₂F (0.16 ± 0.03 CF₃CF(O), and 0.83 ± 0.22 HFC(O)), where all standard deviations are 2σ. For each compound, the critical step in determining the oxidation products was the decomposition of a halogenated alkoxy radical. For HCFC-22 and HCFC-124, the major alkoxy radical decomposition route was Cl elimination. The HFC-125 product data were consistent with C? C cleavage of a two carbon alkoxy radical as the major decomposition route whereas both C? C cleavage and H abstraction by O₂ were significant contributors to the decomposition of the HFC-134a alkoxy radical. Secondary Cl reactions in the HCFC-142b and HFC-152a experiments prevented an unambiguous determination of the decomposition modes; the data are consistent with both C? C bond scission and Cl reactions with halogenated aldehydes producing the oxidation product C(O)F₂. With the exception of the HFC-134a and HFC-125 data, the proposed mechanisms can account for the major oxidation products. For HFC-134a and HFC-125, a number of product bands could not be identified. The bands are likely due to products from reactions involving the CF₃O₂ radical. © John Wiley & Sons, Inc.     

Atmospheric chemistry of CF3CH2CH2OH: kinetics, mechanisms and products of Cl atom and OH radical initiated oxidation in the presence and absence of NOX

Relative rate techniques were used to study the kinetics of the reactions of Cl atoms and OH radicals with CF(3)CH(2)C(O)H and CF(3)CH(2)CH(2)OH in 700 Torr of N(2) or air diluent at 296 +/- 2 K. The rate constants determined were k(Cl+CF(3)CH(2)C(O)H) = (1.81 +/- 0.27) x 10(-11), k(OH+CF(3)CH(2)C(O)H) = (2.57 +/- 0.44) x 10(-12), k(Cl+CF(3)CH(2)CH(2)OH) = (1.59 +/- 0.20) x 10(-11), and k(OH+CF(3)CH(2)CH(2)OH) = (6.91 +/- 0.91) x 10(-13) cm(3) molecule(-1) s(-1). Product studies of the chlorine initiated oxidation of CF(3)CH(2)CH(2)OH in the absence of NO show the sole primary product to be CF(3)CH(2)C(O)H. Product studies of the chlorine initiated oxidation of CF(3)CH(2)CH(2)OH in the presence of NO show the primary products to be CF(3)CH(2)C(O)H (81%), HC(O)OH (10%), and CF(3)C(O)H. Product studies of the chlorine initiated oxidation of CF(3)CH(2)C(O)H in the absence of NO show the primary products to be CF(3)C(O)H (76%), CF(3)CH(2)C(O)OH (14%), and CF(3)CH(2)C(O)OOH (< or =10%). As part of this work, an upper limit of k(O(3)+CF(3)CH(2)CH(2)OH) < 2 x 10(-21) cm(3) molecule(-1) s(-1) was established. Results are discussed with respect to the atmospheric chemistry of fluorinated alcohols.     

Determination of the isomerization rate constant HOCH2CH2CH2CH(OO·)CH3 →HOC·HCH2CH2CH(OOH)CH3. Importance of intramolecular hydroperoxy isomerization in tropospheric chemistry

The rate constant of the title reaction is determined during thermal decomposition of di-n-pentyl peroxide C₅H₁₁O( )OC₅H₁₁ in oxygen over the temperature range 463–523 K. The pyrolysis of di-n-pentyl peroxide in O₂/N₂ mixtures is studied at atmospheric pressure in passivated quartz vessels. The reaction products are sampled through a micro-probe, collected on a liquid-nitrogen trap and solubilized in liquid acetonitrile. Analysis of the main compound, peroxide C₅H₁₀O₃, was carried out by GC/MS, GC/MS/MS [electron impact EI and NH₃ chemical ionization CI conditions]. After micro-preparative GC separation of this peroxide, the structure of two cyclic isomers (3S*,6S*)3α-hydroxy-6-methyl-1,2-dioxane and (3R*,6S*)3α-hydroxy-6-methyl-1,2-dioxane was determined from ¹H NMR spectra. The hydroperoxy-pentanal OHC( )(CH₂)₂( )CH(OOH)( )CH₃ is formed in the gas phase and is in equilibrium with these two cyclic epimers, which are predominant in the liquid phase at room temperature. This peroxide is produced by successive reactions of the n-pentoxy radical: a first one generates the CH₃C·H(CH₂)₃OH radical which reacts with O₂ to form CH₃CH(OO·)(CH₂)₃OH; this hydroxyperoxy radical isomerizes and forms the hydroperoxy HOC·H(CH₂)₂CH(OOH)CH₃ radical. This last species leads to the pentanal-hydroperoxide (also called oxo-hydroperoxide, or carbonyl-hydroperoxide, or hydroperoxypentanal), by the reaction HOC·H(CH₂)₂CH(OOH)CH₃+O₂→O()CH(CH₂)₂CH(OOH)CH₃+HO₂. The isomerization rate constant HOCH₂CH₂CH₂CH(OO·)CH₃→HOC·HCH₂CH₂CH(OOH)CH₃ (k₃) has been determined by comparison to the competing well-known reaction RO₂+NO→RO+NO₂ (k₇). By adding small amounts of NO (0–1.6×10¹⁵ molecules cm⁻³) to the di-n-pentyl peroxide/O₂/N₂ mixtures, the pentanal-hydroperoxide concentration was decreased, due to the consumption of RO₂ radicals by reaction (7). The pentanal-hydroperoxide concentration was measured vs. NO concentration at ten temperatures (463–523 K). The isomerization rate constant involving the H atoms of the CH₂( )OH group was deduced: or per H atom: The comparison of this rate constant to thermokinetics estimations leads to the conclusion that the strain energy barrier of a seven-member ring transition state is low and near that of a six-member ring. Intramolecular hydroperoxy isomerization reactions produce carbonyl-hydroperoxides which (through atmospheric decomposition) increase concentration of radicals and consequently increase atmospheric pollution, especially tropospheric ozone, during summer anticyclonic periods. Therefore, hydrocarbons used in summer should contain only short chains (<C₄) hydrocarbons or totally branched hydrocarbons, for which isomerization reactions are unlikely. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet 30: 875–887, 1998     

The Stability of α‐Hydroperoxyalkyl Radicals

High‐level ab initio and Born–Oppenheimer molecular dynamic calculations have been carried out on a series of hydroperoxyalkyl (α‐QOOH) radicals with the aim of investigating the stability and unimolecular decomposition mechanism into QO+OH of these species. Dissociation was shown to take place through rotation of the C?O(OH) bond rather than through elongation of the CO?OH bond. Through the C?O(OH) rotation, the unpaired electron of the radical overlaps with the electron density on the O?OH bond, and from this overlap the C=O π bond forms and the O?OH bond breaks spontaneously. The CH₂OOH, CH(CH₃)OOH, CH(OH)OOH, and α‐hydroperoxycycloheptadienyl radical were found to decompose spontaneously, but the CH(CHO)OOH has a decomposition energy barrier of 5.95 kcal mol^?1 owing to its steric and electronic features. The systems studied in this work provide the first insights into how structural and electronic effects govern the stabilizing influence on elusive α‐QOOH radicals.