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Title: A vacuum ultraviolet photoionization study on high-temperature decomposition of JP-10 (exo-tetrahydrodicyclopentadiene)

Abstract

Here, two sets of experiments were performed to unravel the high-temperature pyrolysis of tricyclo[5.2.1.02,6] decane (JP-10) exploiting high-temperature reactors over a temperature range of 1100 K to 1600 K, Advanced Light Source (ALS), and 927 K to 1083 K, National Synchrotron Radiation Laboratory (NSRL), with residence times of a few tens of microseconds (ALS) to typically 144 ms (NSRL). The products were identified in situ in supersonic molecular beams via single photon vacuum ultraviolet (VUV) photoionization coupled with mass spectroscopic detection in a reflectron time-of-flight mass spectrometer (ReTOF). These studies were designed to probe the initial (ALS) and also higher order reaction products (NSRL) formed in the decomposition of JP-10 – including radicals and thermally labile closed-shell species. Altogether 43 products were detected and quantified including C1–C4 alkenes, dienes, C3–C4 cumulenes, alkynes, eneynes, diynes, cycloalkenes, cyclo-dienes, aromatic molecules, and most importantly, radicals such as ethyl, allyl, and methyl produced at shorter residence times. At longer residence times, the predominant fragments were molecular hydrogen (H 2), ethylene (C 2H 4), propene (C 3H 6), cyclopentadiene (C 5H 6), cyclopentene (C 5H 8), fulvene (C 6H 6), and benzene (C 6H 6). Accompanied by electronic structure calculations, the initial JP-10 decomposition viamore » C–H bond cleavages resulting in the formation of the initial six C 10H 15 radicals was found to explain the formation of all products detected in both sets of experiments. These radicals are not stable under the experimental conditions and further decompose via C–C bond β-scission processes. These pathways result in ring opening in the initial tricyclic carbon skeletons of JP-10. Intermediates accessed after the first β-scission can further isomerize or dissociate. Complex PAH products in the NRLS experiment (naphthalene, acenaphthylene, biphenyl) are likely formed via molecular growth reactions at elevated residence times.« less

Authors:
 [1];  [1]; ORCiD logo [1];  [2];  [2]; ORCiD logo [2];  [3];  [3]; ORCiD logo [3];  [4];  [4];  [5]
  1. Univ. of Hawaii at Manoa, Honolulu, HI (United States). Dept. of Chemistry
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  3. Florida Intl Univ., Miami, FL (United States). Dept. of Chemistry and Biochemistry
  4. Univ. of Science and Technology of China, Hefei (China). National Synchrotron Radiation Lab. (NSRL)
  5. Shanghai Jiao Tong Univ. (China). MOE Key Lab. for Power Machinery and Engineering (KLPME)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; US Air Force Office of Scientific Research (AFOSR)
OSTI Identifier:
1459380
Grant/Contract Number:  
AC02-05CH11231; FA9550-15-1-0011
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print); Journal Volume: 19; Journal Issue: 24; Related Information: © the Owner Societies 2017.; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
10 SYNTHETIC FUELS; 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Zhao, Long, Yang, Tao, Kaiser, Ralf I., Troy, Tyler P., Xu, Bo, Ahmed, Musahid, Alarcon, Juan, Belisario-Lara, Daniel, Mebel, Alexander M., Zhang, Yan, Cao, Chuangchuang, and Zou, Jiabiao. A vacuum ultraviolet photoionization study on high-temperature decomposition of JP-10 (exo-tetrahydrodicyclopentadiene). United States: N. p., 2017. Web. doi:10.1039/c7cp01571b.
Zhao, Long, Yang, Tao, Kaiser, Ralf I., Troy, Tyler P., Xu, Bo, Ahmed, Musahid, Alarcon, Juan, Belisario-Lara, Daniel, Mebel, Alexander M., Zhang, Yan, Cao, Chuangchuang, & Zou, Jiabiao. A vacuum ultraviolet photoionization study on high-temperature decomposition of JP-10 (exo-tetrahydrodicyclopentadiene). United States. doi:10.1039/c7cp01571b.
Zhao, Long, Yang, Tao, Kaiser, Ralf I., Troy, Tyler P., Xu, Bo, Ahmed, Musahid, Alarcon, Juan, Belisario-Lara, Daniel, Mebel, Alexander M., Zhang, Yan, Cao, Chuangchuang, and Zou, Jiabiao. Fri . "A vacuum ultraviolet photoionization study on high-temperature decomposition of JP-10 (exo-tetrahydrodicyclopentadiene)". United States. doi:10.1039/c7cp01571b. https://www.osti.gov/servlets/purl/1459380.
@article{osti_1459380,
title = {A vacuum ultraviolet photoionization study on high-temperature decomposition of JP-10 (exo-tetrahydrodicyclopentadiene)},
author = {Zhao, Long and Yang, Tao and Kaiser, Ralf I. and Troy, Tyler P. and Xu, Bo and Ahmed, Musahid and Alarcon, Juan and Belisario-Lara, Daniel and Mebel, Alexander M. and Zhang, Yan and Cao, Chuangchuang and Zou, Jiabiao},
abstractNote = {Here, two sets of experiments were performed to unravel the high-temperature pyrolysis of tricyclo[5.2.1.02,6] decane (JP-10) exploiting high-temperature reactors over a temperature range of 1100 K to 1600 K, Advanced Light Source (ALS), and 927 K to 1083 K, National Synchrotron Radiation Laboratory (NSRL), with residence times of a few tens of microseconds (ALS) to typically 144 ms (NSRL). The products were identified in situ in supersonic molecular beams via single photon vacuum ultraviolet (VUV) photoionization coupled with mass spectroscopic detection in a reflectron time-of-flight mass spectrometer (ReTOF). These studies were designed to probe the initial (ALS) and also higher order reaction products (NSRL) formed in the decomposition of JP-10 – including radicals and thermally labile closed-shell species. Altogether 43 products were detected and quantified including C1–C4 alkenes, dienes, C3–C4 cumulenes, alkynes, eneynes, diynes, cycloalkenes, cyclo-dienes, aromatic molecules, and most importantly, radicals such as ethyl, allyl, and methyl produced at shorter residence times. At longer residence times, the predominant fragments were molecular hydrogen (H2), ethylene (C2H4), propene (C3H6), cyclopentadiene (C5H6), cyclopentene (C5H8), fulvene (C6H6), and benzene (C6H6). Accompanied by electronic structure calculations, the initial JP-10 decomposition via C–H bond cleavages resulting in the formation of the initial six C10H15 radicals was found to explain the formation of all products detected in both sets of experiments. These radicals are not stable under the experimental conditions and further decompose via C–C bond β-scission processes. These pathways result in ring opening in the initial tricyclic carbon skeletons of JP-10. Intermediates accessed after the first β-scission can further isomerize or dissociate. Complex PAH products in the NRLS experiment (naphthalene, acenaphthylene, biphenyl) are likely formed via molecular growth reactions at elevated residence times.},
doi = {10.1039/c7cp01571b},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 24,
volume = 19,
place = {United States},
year = {Fri May 05 00:00:00 EDT 2017},
month = {Fri May 05 00:00:00 EDT 2017}
}

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Works referenced in this record:

Density‐functional thermochemistry. III. The role of exact exchange
journal, April 1993

  • Becke, Axel D.
  • The Journal of Chemical Physics, Vol. 98, Issue 7, p. 5648-5652
  • DOI: 10.1063/1.464913