Handbook of the Thermodynamics of Organic Compounds

Stephenson, Richard M.; Malanowski, Stanisław K.

doi:10.1007/978-94-009-3173-2

Cited by 488 publications

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“…21 Since no data for toluene-d 8 were available, the vapor pressures of toluene and toluene-d 8 were measured with capacitance manometers (Baratron, MKS) in a thermostated vacuum cell at about 279 K. The vapor pressure of toluene-d 8 was found to be higher by a factor of (1.04 ( 0.01) while the absolute value for toluene was within 5% of the literature data. 21 The ratio of 1.04 was then used to calculate toluene-d 8 concentrations at the actual temperature of the saturator. H 2 O 2 was introduced by purging a preconcentrated solution at 298 K, 22 concentrations ranged between 3 × 10 14 cm -3 and 1.1 × 10 15 cm -3 .…”

Section: Methodsmentioning

confidence: 84%

Formation of Peroxy Radicals from OH−Toluene Adducts and O₂

Bohn

2001

J. Phys. Chem. A

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The gas-phase reaction of OH radicals with toluene and toluene-d 8 and reactions of the resulting OH adducts with O 2 were studied in N 2 /O 2 mixtures at atmospheric pressure and room temperature. OH production was performed by pulsed 248 nm photolysis of H 2 O 2 . Cw UV-laser long-path absorption at 308 nm was used for time-resolved detection of OH and OH-toluene adducts. The reaction OH + toluene was studied in N 2 and O 2 and similar rate constants of (5.70 ( 0.19) × 10 -12 cm 3 s -1 (N 2 ) and (5.60 ( 0.14) × 10 -12 cm 3 s -1 (O 2 ) were obtained at 100 kPa. For toluene-d 8 the corresponding rate constants are (5.34 ( 0.34) × 10 -12 cm 3 s -1 (N 2 ) and (5.47 ( 0.14) × 10 -12 cm 3 s -1 (O 2 ). Absorption cross-sections of (1.1 ( 0.2) × 10 -17 cm 2 were determined for both the OH-toluene and OH-toluene-d 8 adduct at 308 nm. Rate constants of (4.7 ( 1.4) × 10 -11 cm 3 s -1 and (1.8 ( 0.5) × 10 -10 cm 3 s -1 were determined for the OH-toluene adduct self-reaction and the OH-toluene adduct + HO 2 reaction, respectively. Upper limits e8 × 10 -15 cm 3 s -1 were estimated for any reactions of the OH-toluene adduct with H 2 O 2 or toluene. Adduct kinetics in the presence of O 2 is consistent with reversible formation of peroxy radicals with an estimated rate constant of (3 ( 2) × 10 -15 cm 3 s -1 and an equilibrium constant of (3.25 ( 0.33) × 10 -19 cm 3 (toluene-d 8 : (3.1 ( 1.2) × 10 -19 cm 3 ). The effective adduct loss from the equilibrium can be explained by (i) an additional, irreversible reaction of the adduct with O 2 with a rate constant of (6.0 ( 0.5) × 10 -16 cm 3 s -1 (toluene-d 8 : (4.7 ( 1.2) × 10 -16 cm 3 s -1 ), or (ii) a unimolecular reaction of the peroxy radical, with a rate constant of (1.85 ( 0.15) × 10 3 s -1 (toluene-d 8 : (1.5 ( 0.4) × 10 3 s -1 ). Consequences for the atmospheric degradation of toluene will be discussed.

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Section: Methodsmentioning

confidence: 84%

Formation of Peroxy Radicals from OH−Toluene Adducts and O₂

Bohn

2001

J. Phys. Chem. A

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“…Concentrations of the aromatics were calculated from the Antoine constants collected by Stephenson and Malanowski (1987) and chosen, depending on their k OH , for τ −1 1 to be between 100 and 200 s −1 . Note that the evaluation of the title reactions (as slope of d vs.…”

Section: Chemicalsmentioning

confidence: 99%

Consecutive reactions of aromatic-OH adducts with NO, NO<sub>2</sub> and O<sub>2</sub>: benzene, naphthalene, toluene, m- and p-xylene, hexamethylbenzene, phenol, m-cresol and aniline

et al. 2007

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Abstract. Consecutive reactions of adducts, resulting from OH radicals and aromatics, with the tropospheric scavenger molecules O 2 , NO and NO 2 have been studied for benzene, naphthalene, toluene, m-and p-xylene, hexamethylbenzene, phenol, m-cresol and aniline by observing decays of OH at temperatures where the thermal back-decomposition to OH is faster than 3 s −1 , typically between 300 and 340 K. The experimental technique was resonance fluorescence with flash photolysis of water as source of OH. Biexponential decays were observed in the presence of either O 2 or NO, and triexponential decays were obtained in the presence of NO 2 . The kinetic analysis was performed by fitting the relevant rate constants of the reaction mechanism to whole sets of decays obtained at various concentrations of aromatic and scavenger. In the case of hexamethylbenzene, the biexponential decays suggest the existence of the ipso-adduct, and the slightly higher necessary temperatures show that it is even more stable.In addition, smog chamber experiments at O 2 concentrations from atmospheric composition down to well below 100 ppm have been carried out for benzene, toluene and pxylene. The drop of the effective rate constant of removal by OH occurs at reasonable O 2 levels, given the FP/RF results.Comparison of the adduct reactivities shows for all aromatics of this study that the reaction with O 2 predominates over that with NO 2 under all tropospheric conditions, and that a reaction with NO may only occur after the reaction with O 2 .

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“…Ultimately, this information can be captured in a new parameter on the QSAR solvation equation for ocular and nasal chemesthesis , further expanding its applicability and predictive ability. (Riddick and Bunger, 1970;Boublík et al, 1984;Stephenson and Malanowski, 1987), and of measured or predicted EIT for homologous acetates (top) and n-alcohols (bottom) plotted as a function of variable carbon chain length. EIT for dodecyl acetate and for 1-decanol, 1-undecanol, and 1-dodecanol are predicted from equation (2); the rest are measured values (ComettoMuñiz andCain, 1990, 1991).…”

Section: Insert Figures 9 and 10 About Herementioning

confidence: 99%

Molecular restrictions for human eye irritation by chemical vapors

Cometto‐Muñiz

Cain

Abraham

2005

Toxicology and Applied Pharmacology

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Previous research showed a cut-off along homologous volatile organic compounds (VOCs) in their ability to produce acute human mucosal irritation. The present study sought to specify the particular cut-off homolog for sensory eye irritation in an acetate and n-alcohol series. A 1,900 ml glass vessel system and a three-alternative forced-choice procedure served to test nonyl, decyl, and dodecyl acetate, and 1-nonanol, 1-decanol, and 1-undecanol. Flowrate to the eye ranged from 2 to 8 L/min and time of exposure from 3 to 24 sec. Decyl acetate and 1-undecanol were the shortest homologs that failed to produce eye irritation under all conditions, producing a cut-off effect.Increasing the vapor concentration of decyl acetate and 1-undecanol by 3 and 8 times, respectively, via heating them to 37 °C made either or both VOCs detectable to only half of the 12 subjects tested, even though the higher vapor concentration was well above a predicted eye irritation threshold. When eye irritation thresholds for homologous acetates and n-alcohols were plotted as a function of the longest unfolded length of the molecule, the values for decyl acetate and 1-undecanol fell within a restricted range of 18 to 19 Å.The outcome suggests that the basis for the cut-off is biological, i.e., the molecule lacks a key size or structure to trigger transduction, rather than physical, i.e., the vapor concentration is too low to precipitate detection.

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Handbook of the Thermodynamics of Organic Compounds

Cited by 488 publications

References 0 publications

Formation of Peroxy Radicals from OH−Toluene Adducts and O₂

Formation of Peroxy Radicals from OH−Toluene Adducts and O₂

Consecutive reactions of aromatic-OH adducts with NO, NO<sub>2</sub> and O<sub>2</sub>: benzene, naphthalene, toluene, m- and p-xylene, hexamethylbenzene, phenol, m-cresol and aniline

Molecular restrictions for human eye irritation by chemical vapors

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Handbook of the Thermodynamics of Organic Compounds

Cited by 488 publications

References 0 publications

Formation of Peroxy Radicals from OH−Toluene Adducts and O2

Formation of Peroxy Radicals from OH−Toluene Adducts and O2

Consecutive reactions of aromatic-OH adducts with NO, NO&lt;sub&gt;2&lt;/sub&gt; and O&lt;sub&gt;2&lt;/sub&gt;: benzene, naphthalene, toluene, m- and p-xylene, hexamethylbenzene, phenol, m-cresol and aniline

Molecular restrictions for human eye irritation by chemical vapors

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Formation of Peroxy Radicals from OH−Toluene Adducts and O₂

Formation of Peroxy Radicals from OH−Toluene Adducts and O₂

Consecutive reactions of aromatic-OH adducts with NO, NO<sub>2</sub> and O<sub>2</sub>: benzene, naphthalene, toluene, m- and p-xylene, hexamethylbenzene, phenol, m-cresol and aniline