Das Propin/Propadien‐Gleichgewicht

Cordes, J. F.; Günzler, Helmut

doi:10.1002/cber.19590920508

Cited by 27 publications

(5 citation statements)

References 3 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…d From ref . f Computed using (expt, propyne) and the enthalpy of isomerization that was reported in ref and reanalyzed in ref . g From ref .…”

Section: Resultsmentioning

confidence: 99%

“…Where possible, we report , which are based on experimental data. We derived by combining the determined from the heat of combusion of propyne, with the experimentally determined heat of isomerization. , Many species have insufficient data for derivation of . For such species, we have used ab initio calculations to estimate .…”

Section: Computational Resultsmentioning

confidence: 99%

See 1 more Smart Citation

Chlorination Chemistry. 2. Rate Coefficients, Reaction Mechanism, and Spectrum of the Chlorine Adduct of Allene

Atkinson

Hudgens

2000

J. Phys. Chem. A

View full text Add to dashboard Cite

Cavity ring-down (CRD) spectroscopy and ab initio calculations have determined the reaction rate coefficients, mechanism, and thermochemistry relevant to the addition of a chlorine atom to allene. Chlorine atoms were produced by laser photolysis at 351 nm and the addition reaction products were probed at a variable delay by CRD spectroscopy using a second laser pulse. Ab initio results indicate that the only persistent addition product is the 2-chloroallyl (C 3 H 4 Cl) radical. We measured the continuum spectrum of the 2-chloroallyl radical between 238 and 252 nm and determined the absorption cross section, σ 240 (C 3 H 4 Cl) ) (2.5 ( 0.5) × 10 -17 cm 2 . By fitting the C 3 H 4 Cl absorption data to complex kinetic mechanisms, rate coefficients at 298 K were found to be k(Cl+C 3 H 4 ; 656 Pa, N 2 ) ) (1.61 ( 0.27) × 10 -10 cm 3 molecule -1 s -1 , k(Cl+C 3 H 4 ; 670 Pa, He) ) (1.34 ( 0.24) × 10 -10 cm 3 molecule -1 s -1 , and k(Cl+C 3 H 4 ; 1330 Pa, He) ) (1.75 ( 0. 25) × 10 -10 cm 3 molecule -1 s -1 . The rate coefficient of the self-reaction displayed no pressure dependence between 434 and 1347 Pa in N 2 buffer giving k(C 3 H 4 Cl+C 3 H 4 Cl) ) (3.7 ( 1.0) × 10 -11 cm 3 molecule -1 s -1 . A study of the addition reaction of 2-chloroallyl radical and oxygen molecule determined σ 240 (C 3 H 4 ClO 2 ) ) (3.6 ( 0.7) × 10 -18 cm 2 and k(O 2 +C 3 H 4 Cl, 705 Pa N 2 ) ) (3.6 ( 0.4) × 10 -13 cm 3 molecule -1 s -1 . The listed uncertainties denote two standard deviations, and those for rate coefficients include the uncertainty of the appropriate absorption cross section.

show abstract

“…d From ref . f Computed using (expt, propyne) and the enthalpy of isomerization that was reported in ref and reanalyzed in ref . g From ref .…”

Section: Resultsmentioning

confidence: 99%

Section: Computational Resultsmentioning

confidence: 99%

Chlorination Chemistry. 2. Rate Coefficients, Reaction Mechanism, and Spectrum of the Chlorine Adduct of Allene

Atkinson

Hudgens

2000

J. Phys. Chem. A

View full text Add to dashboard Cite

show abstract

“…To maintain consistent energy relationships, thermochemical enthalpies involved in reaction 4 were computed using the experimentally known Δ f H ° T (propyne), when possible. Key among these is Δ f H ° T (allene), which we derived by combining Δ f H ° T (propyne) with the experimentally determined heat of isomerization. , …”

Section: Results and Analysesmentioning

confidence: 99%

“…e From ref . f Computed using Δ f H ° 298.15 (expt,propyne) and the enthalpy of isomerization that is reported in ref and reanalyzed in ref . g From ref .…”

Section: Results and Analysesmentioning

confidence: 99%

Chlorination Chemistry. 1. Rate Coefficients, Reaction Mechanisms, and Spectra of the Chlorine and Bromine Adducts of Propargyl Halides

Atkinson

Hudgens

1999

J. Phys. Chem. A

View full text Add to dashboard Cite

Cavity ring-down spectroscopy (CRDS), end-product analysis, and ab initio calculations have determined absorption cross sections, rate coefficients, reaction mechanisms, and thermochemistry relevant to the addition of halogen atoms to propargyl chloride and propargyl bromide. Halogen atoms were produced by laser photolysis, and the addition reaction products were probed at a variable delay by CRDS using a second laser pulse. We report the continuum spectra of C3H3Cl2 (1,2-dichloroallyl), C3H3ClBr (1-chloro-2-bromoallyl), and C3H3Br2 (1,2-dibromoallyl) radicals between 238 and 252 nm and the absorption cross sections, σ240(C3H3Cl2) = (4.20 ± 1.05) × 10-17 cm2 molecule-1 and σ242(C3H3Br2) = (1.04 ± 0.31) × 10-17 cm2 molecule-1. When the observed data are fit to complex reaction schemes, the 298 K rate coefficients for formation of 1,2-dihaloallyl radicals at 665 Pa were found to be k(Cl + C3H3Cl) = (1.2 ± 0.2) × 10-10 cm3 molecule-1 s-1 and k(Br + C3H3Br) = (2 ± 1) × 10-12 cm3 molecule-1 s-1. At 298 K and 665 Pa the self-reaction rate coefficients of these radicals were found to be k(C3H3Cl2 + C3H3Cl2) = (3.4 ± 0.9) × 10-11 cm3 molecule-1 s-1 and k(C3H3Br2 + C3H3Br2) = (1.7 ± 1.1) × 10-11 cm3 molecule-1 s-1. The listed uncertainties are twice the standard deviation of individual determinations, and those for rate coefficients include the uncertainty of the appropriate absorption cross section.

show abstract

“…Although not attractive for laboratory syntheses of aliene hydrocarbons, prototropic or thermal catalytic rearrangement of alkynes are of potential value as industrial processes, since they are adaptable to largescale continuous operation. Catalysts cited for the partial conversion of propyne into propadiene include active carbon (126), Floridin (a siliceous sand) (527), alumina (124,125), and aluminates (143). Calculations based on spectroscopic data and heats of hydrogenation show that the percentage of propadiene at equilibrium with propyne increases with rising temperature (195), but a practical limit of about 350°is imposed by the onset of dimerization and polymerization.…”

Section: Industrial Methodsmentioning

confidence: 99%

The Chemistry of Allenes

Taylor¹

1967

Chem. Rev.

252

View full text Add to dashboard Cite

Das Propin/Propadien‐Gleichgewicht

Abstract: Die Gleichgewichtslage der Isomerisierungsreaktion Propin ⇌ Propadien wurde im Temperaturbereich von 100 bis 370° unter Zuhilfenahme der Infrarotspektroskopie ermittelt.

Cited by 27 publications

References 3 publications

Chlorination Chemistry. 2. Rate Coefficients, Reaction Mechanism, and Spectrum of the Chlorine Adduct of Allene

Chlorination Chemistry. 2. Rate Coefficients, Reaction Mechanism, and Spectrum of the Chlorine Adduct of Allene

Chlorination Chemistry. 1. Rate Coefficients, Reaction Mechanisms, and Spectra of the Chlorine and Bromine Adducts of Propargyl Halides

The Chemistry of Allenes

Contact Info

Product

Resources

About