Thermal reactions of decalin. II. A mass spectrometric study

Ondruschka, Bernd; Zimmermann, G.; Ziegler, U.

doi:10.1016/0165-2370(90)85003-6

Cited by 12 publications

(5 citation statements)

References 13 publications

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“…Experimental results previously reported on decalin pyrolysis at high temperature [34][35][36] have shown that the most probable initiation steps of thermal cracking are the carbon-carbon (C 9 -C 10 ) bond cleavage (Figure 2a) and hydrogen abstraction (from C 1 , C 2 , C 9 ) reactions (Figure 2b). In addition, experimental data on thermal decomposition of decalin carried out under near critical and supercritical conditions indicated the interconversion between cis-and trans-decalin and identified toluene, 1-butylcyclohexene, and 1-methylcyclohexene as products.…”

Section: Resultsmentioning

confidence: 91%

Thermal Decomposition of Decalin: An Ab Initio Study

Chae

Violi

2007

J. Org. Chem.

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Density functional theory calculations (B3LYP and BH&HLYP functionals) of the potential energy surface have been performed to investigate the mechanisms of decalin breakdown, and the Rice-Ramsperger-Kassel-Marcus and transition state theory methods have been used to compute the high-pressure limit thermal rate constants for the new reaction pathways. The new pathways connect decalin to five primary monoaromatic species: benzene, toluene, styrene, ethylbenzene, and xylene. The reactions used for the new routes are carbon-carbon bond cleavage reaction, dissociation reaction, and hydrogen abstraction and addition reactions. A kinetic analysis was performed for pyrolytic conditions, and benzene, toluene, and xylene were identified as major products.

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Section: Resultsmentioning

confidence: 91%

Thermal Decomposition of Decalin: An Ab Initio Study

Chae

Violi

2007

J. Org. Chem.

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“…2x10 13 s -1 for each identical alkylic bond which can be broken and 3.3x10 13 s -1 for an allylic bond.…”

Section: Figure 13 Tablementioning

confidence: 99%

“…O'Neal and Benson studied the diradical mechanism of pyrolysis of some three- and four-membered ring compounds and of some polycyclic molecules. , For most species, Arrhenius parameters estimated by these authors were consistent with available experimental data. Recently, Tsang 8,9 proposed reaction channels to account for the fate of diradicals in the case of cyclohexane and cyclopentane and Billaud et al and Ondruschka et al in the case of decalin, but no previous publication gives any clues about the fate of diradicals obtained from tricyclic species. Concerning propagation reactions, the rate constants of the decomposition by β-scission involving the opening of a ring or of the isomerization involving polycyclic transition states are still very uncertain.…”

Section: Introductionmentioning

confidence: 99%

Primary Mechanism of the Thermal Decomposition of Tricyclodecane

et al. 2006

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To better understand the thermal decomposition of polycyclanes, the pyrolysis of tricyclodecane has been studied in a jet-stirred reactor at temperatures from 848 to 933 K, for residence times between 0.5 and 6 s and at atmospheric pressure, corresponding to a conversion between 0.01% and 25%. The main products of the reaction are hydrogen, methane, ethylene, ethane, propene, 1,3-cyclopentadiene, cyclopentene, benzene, 1,5-hexadiene, toluene, and 3-cyclopentylcyclopentene. A primary mechanism containing all the possible initiation steps, including those involving diradicals, as well as propagation reactions has been developed and allows experimental results to be satisfactorily modeled. The main reaction pathways of consumption of tricyclodecane and of formation of the main products have been derived from flow rate and sensitivity analyses.

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“…The role of diradical species created from breaking C–C bonds in ring-opening processes for cyclic and polycyclic compounds has been previously studied. ,,− Williams and co-workers suggested a mechanism where breaking the central C–C bond shared by two five-membered rings or a C–H bond of a CH 2 group would likely be the initiation step in the unimolecular decomposition of TCD. The significant study by Herbinet et al presented some thermochemistry and a comprehensive detailed kinetic model including diradical species created from initial unimolecular cleavage of the C–C bonds in TCD.…”

Section: Introductionmentioning

confidence: 99%

Bond Energies and Thermochemical Properties of Ring-Opened Diradicals and Carbenes of exo-Tricyclo[5.2.1.0^2,6]decane

2015

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Exo-tricyclo[5.2.1.0(2,6)]decane (TCD) or exo-tetrahydrodicyclopentadiene is an interesting strained ring compound and the single-component high-energy density hydrocarbon fuel known as JP-10. Important initial reactions of TCD at high temperatures could cleave a strained carbon-carbon (C-C) bond in the ring system creating diradicals also constrained by the remaining ring system. This study determines the thermochemical properties of these diradicals (TCD-H2 mJ-nJ where m and n correspond to the cleaved carbons sites) including the carbon-carbon bond dissociation energy (C-C BDE) corresponding to the cleaved TCD site. Thermochemical properties including enthalpies (ΔH°f298), entropies (S(T)), heat capacities (Cp(T)), and C-H and C-C BDEs for the parent (TCD-H2 m-n), radical (TCD-H2 mJ-n and m-nJ), diradical (TCD-H2 mJ-nJ), and carbene (TCD-H2 mJJ-n and m-nJJ) species are determined. Structures, vibrational frequencies, moments of inertia, and internal rotor potentials are calculated at the B3LYP/6-31G(d,p) level of theory. Standard enthalpies of formation in the gas phase for the TCD-H2 m-n parent and radical species are determined using the B3LYP density functional theory and the higher level G3MP2B3 and CBS-QB3 composite methods. For singlet and triplet TCD diradicals and carbenes, M06-2X, ωB97X-D, and CCSD(T) methods are included in the analysis to determine ΔH°f298 values. The C-C BDEs are further calculated using CASMP2(2,2)/aug-cc-pvtz//CASSCF(2,2)/cc-pvtz and with the CASMP2 energies extrapolated to the complete basis set limit. The bond energies calculated with these methods are shown to be comparable to the other calculation methods. Isodesmic work reactions are used for enthalpy analysis of these compounds for effective cancelation of systematic errors arising from ring strain. C-C BDEs range from 77.4 to 84.6 kcal mol(-1) for TCD diradical singlet species. C-H BDEs for the parent TCD-H2 m-n carbon sites range from 93 to 101 kcal mol(-1) with a similar range seen for loss of the second hydrogen to generate the diradical singlet species. A wider range for C-C BDEs is seen for the carbenes from about 77 to 100 kcal mol(-1) as compared to the diradicals. Results from the DFT methods for the parents, radicals, diradicals, and carbenes are in good agreement with results from the composite methods using our sets of work reactions.

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Thermal reactions of decalin. II. A mass spectrometric study

Cited by 12 publications

References 13 publications

Thermal Decomposition of Decalin: An Ab Initio Study

Thermal Decomposition of Decalin: An Ab Initio Study

Primary Mechanism of the Thermal Decomposition of Tricyclodecane

Bond Energies and Thermochemical Properties of Ring-Opened Diradicals and Carbenes of exo-Tricyclo[5.2.1.0^2,6]decane

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Thermal reactions of decalin. II. A mass spectrometric study

Cited by 12 publications

References 13 publications

Thermal Decomposition of Decalin: An Ab Initio Study

Thermal Decomposition of Decalin: An Ab Initio Study

Primary Mechanism of the Thermal Decomposition of Tricyclodecane

Bond Energies and Thermochemical Properties of Ring-Opened Diradicals and Carbenes of exo-Tricyclo[5.2.1.02,6]decane

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Bond Energies and Thermochemical Properties of Ring-Opened Diradicals and Carbenes of exo-Tricyclo[5.2.1.0^2,6]decane