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Title: n-Heptane cool flame chemistry: Unraveling intermediate species measured in a stirred reactor and motored engine

Abstract

This paper identifies classes of cool flame intermediates from n-heptane low-temperature oxidation in a jet-stirred reactor (JSR) and a motored cooperative fuel research (CFR) engine. The sampled species from the JSR oxidation of a mixture of n-heptane/O 2/Ar (0.01/0.11/0.88) were analyzed using a synchrotron vacuum ultraviolet radiation photoionization (SVUV-PI) time-of-flight molecular-beam mass spectrometer (MBMS) and an atmospheric pressure chemical ionization (APCI) Orbitrap mass spectrometer (OTMS). The OTMS was also used to analyze the sampled species from a CFR engine exhaust. Approximately 70 intermediates were detected by the SVUV-PI-MBMS, and their assigned molecular formulae are in good agreement with those detected by the APCI-OTMS, which has ultra-high mass resolving power and provides an accurate elemental C/H/O composition of the intermediate species. Furthermore, the results show that the species formed during the partial oxidation of n-heptane in the CFR engine are very similar to those produced in an ideal reactor, i.e., a JSR. The products can be classified by species with molecular formulae of C 7H 14O x (x = 0–5), C 7H 12O x (x = 0–4), C 7H 10O x (x = 0–4), C nH 2n (n = 2–6), C nH 2n-2 (n = 4–6), C nH 2n+2O (n =more » 1–4), C nH 2nO (n = 1–6), C nH 2n-2O (n = 2–6), C nH 2n-4O (n = 4–6), C nH 2n+2O 2 (n = 0–4, 7), C nH 2nO 2 (n = 1–6), C nH 2n-2O 2 (n = 2–6), C nH 2n-4O 2 (n = 4–6), and C nH 2nO 3 (n = 3–6). The identified intermediate species include alkenes, dienes, aldehyde/keto compounds, olefinic aldehyde/keto compounds, diones, cyclic ethers, peroxides, acids, and alcohols/ethers. Reaction pathways forming these intermediates are proposed and discussed herein. Finally, these experimental results are important in the development of more accurate kinetic models for n-heptane and longer-chain alkanes.« less

Authors:
ORCiD logo [1];  [1];  [2];  [3];  [4];  [1];  [5];  [6];  [7];  [7];  [5];  [8];  [7];  [4];  [1]
  1. King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Saudi Arabia). Clean Combustion Research Center (CCRC)
  2. Sandia National Lab. (SNL-CA), Livermore, CA (United States). Combustion Research Facility; Physikalisch-Technische Bundesanstalt, Braunschweig (Germany)
  3. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry; Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  4. King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Saudi Arabia). Analytical Core Lab.
  5. Sandia National Lab. (SNL-CA), Livermore, CA (United States). Combustion Research Facility
  6. Sandia National Lab. (SNL-CA), Livermore, CA (United States). Combustion Research Facility; Tsinghua Univ., Beijing (China). Center for Combustion Energy. Dept. of Thermal Engineering
  7. Bielefeld Univ. (Germany). Dept. of Chemistry
  8. Inst. of Engineering Sciences and Systems (CNRS-INSIS), Orléans (France)
Publication Date:
Research Org.:
Sandia National Lab. (SNL-CA), Livermore, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); King Abdullah Univ. of Science and Technology (KAUST), Thuwal (Saudi Arabia); Bielefeld Univ. (Germany); Inst. of Engineering Sciences and Systems (CNRS-INSIS), Orléans (France); Tsinghua Univ., Beijing (China)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); USDOE National Nuclear Security Administration (NNSA); King Abdullah Univ. of Science and Technology (KAUST) (Saudi Arabia); Saudi Aramco (Saudi Arabia); German Research Foundation (DFG); European Research Council (ERC); China Scholarship Council
OSTI Identifier:
1474083
Alternate Identifier(s):
OSTI ID: 1549270
Report Number(s):
[SAND-2018-10258J]
[Journal ID: ISSN 0010-2180; 667992]
Grant/Contract Number:  
[AC04-94AL85000; AC02-05CH11231; 767 OSR-2016-CRG5-3022; KO1363/31-1; 291049-2G-CSafe; 201506210349; AC04-94-AL85000]
Resource Type:
Accepted Manuscript
Journal Name:
Combustion and Flame
Additional Journal Information:
[ Journal Volume: 187]; Journal ID: ISSN 0010-2180
Publisher:
Elsevier
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; n-heptane; auto-oxidation; peroxides; synchrotron VUV photoionization mass spectrometry; APCI Orbitrap mass spectrometry

Citation Formats

Wang, Zhandong, Chen, Bingjie, Moshammer, Kai, Popolan-Vaida, Denisia M., Sioud, Salim, Shankar, Vijai Shankar Bhavani, Vuilleumier, David, Tao, Tao, Ruwe, Lena, Bräuer, Eike, Hansen, Nils, Dagaut, Philippe, Kohse-Höinghaus, Katharina, Raji, Misjudeen A., and Sarathy, S. Mani. n-Heptane cool flame chemistry: Unraveling intermediate species measured in a stirred reactor and motored engine. United States: N. p., 2017. Web. doi:10.1016/j.combustflame.2017.09.003.
Wang, Zhandong, Chen, Bingjie, Moshammer, Kai, Popolan-Vaida, Denisia M., Sioud, Salim, Shankar, Vijai Shankar Bhavani, Vuilleumier, David, Tao, Tao, Ruwe, Lena, Bräuer, Eike, Hansen, Nils, Dagaut, Philippe, Kohse-Höinghaus, Katharina, Raji, Misjudeen A., & Sarathy, S. Mani. n-Heptane cool flame chemistry: Unraveling intermediate species measured in a stirred reactor and motored engine. United States. doi:10.1016/j.combustflame.2017.09.003.
Wang, Zhandong, Chen, Bingjie, Moshammer, Kai, Popolan-Vaida, Denisia M., Sioud, Salim, Shankar, Vijai Shankar Bhavani, Vuilleumier, David, Tao, Tao, Ruwe, Lena, Bräuer, Eike, Hansen, Nils, Dagaut, Philippe, Kohse-Höinghaus, Katharina, Raji, Misjudeen A., and Sarathy, S. Mani. Tue . "n-Heptane cool flame chemistry: Unraveling intermediate species measured in a stirred reactor and motored engine". United States. doi:10.1016/j.combustflame.2017.09.003. https://www.osti.gov/servlets/purl/1474083.
@article{osti_1474083,
title = {n-Heptane cool flame chemistry: Unraveling intermediate species measured in a stirred reactor and motored engine},
author = {Wang, Zhandong and Chen, Bingjie and Moshammer, Kai and Popolan-Vaida, Denisia M. and Sioud, Salim and Shankar, Vijai Shankar Bhavani and Vuilleumier, David and Tao, Tao and Ruwe, Lena and Bräuer, Eike and Hansen, Nils and Dagaut, Philippe and Kohse-Höinghaus, Katharina and Raji, Misjudeen A. and Sarathy, S. Mani},
abstractNote = {This paper identifies classes of cool flame intermediates from n-heptane low-temperature oxidation in a jet-stirred reactor (JSR) and a motored cooperative fuel research (CFR) engine. The sampled species from the JSR oxidation of a mixture of n-heptane/O2/Ar (0.01/0.11/0.88) were analyzed using a synchrotron vacuum ultraviolet radiation photoionization (SVUV-PI) time-of-flight molecular-beam mass spectrometer (MBMS) and an atmospheric pressure chemical ionization (APCI) Orbitrap mass spectrometer (OTMS). The OTMS was also used to analyze the sampled species from a CFR engine exhaust. Approximately 70 intermediates were detected by the SVUV-PI-MBMS, and their assigned molecular formulae are in good agreement with those detected by the APCI-OTMS, which has ultra-high mass resolving power and provides an accurate elemental C/H/O composition of the intermediate species. Furthermore, the results show that the species formed during the partial oxidation of n-heptane in the CFR engine are very similar to those produced in an ideal reactor, i.e., a JSR. The products can be classified by species with molecular formulae of C7H14Ox (x = 0–5), C7H12Ox (x = 0–4), C7H10Ox (x = 0–4), CnH2n (n = 2–6), CnH2n-2 (n = 4–6), CnH2n+2O (n = 1–4), CnH2nO (n = 1–6), CnH2n-2O (n = 2–6), CnH2n-4O (n = 4–6), CnH2n+2O2 (n = 0–4, 7), CnH2nO2 (n = 1–6), CnH2n-2O2 (n = 2–6), CnH2n-4O2 (n = 4–6), and CnH2nO3 (n = 3–6). The identified intermediate species include alkenes, dienes, aldehyde/keto compounds, olefinic aldehyde/keto compounds, diones, cyclic ethers, peroxides, acids, and alcohols/ethers. Reaction pathways forming these intermediates are proposed and discussed herein. Finally, these experimental results are important in the development of more accurate kinetic models for n-heptane and longer-chain alkanes.},
doi = {10.1016/j.combustflame.2017.09.003},
journal = {Combustion and Flame},
number = ,
volume = [187],
place = {United States},
year = {2017},
month = {10}
}

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