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Title: Gas-phase pyrolysis of trans 3-pentenenitrile: competition between direct and isomerization-mediated dissociation

Abstract

The flash pyrolysis of trans 3-pentenenitrile (3-PN, CH3–$CH=CH$–CH2–CN) was studied by combining the results of VUV photoionization mass spectra with broadband microwave spectra recorded as a function of the temperature of the pyrolysis tube. The two separated functional groups (vinyl and nitrile) open up isomerization as an initial step in competition with unimolecular dissociation. Primary products were detected by keeping the 3-PN concentration low and limiting reaction times to the traversal time of the gas in the pyrolysis tube (~100 μs). The reaction is quenched and products are cooled by expansion into vacuum before interrogation over the 8–18 GHz region using chirped-pulse broadband methods. 118 nm VUV photoionization of the same reaction mixture provides a means of detecting all products with ionization potentials below 10.5 eV with minimal fragmentation. These results are combined with a detailed computational investigation of the C5H7N and related potential energy surfaces, leading to a consistent picture of the unimolecular decomposition of 3-PN. Loss of two H-atoms to form a 79 amu product is proven from its microwave transitions to contain trans-Z-2,4-pentadienenitrile, while no pyridine is observed. Methyl loss, HCN loss, and breaking the central C(2)–C(3) bond all occur following isomerization of the position of themore » double bond, thereby opening up low-energy pathways to these decomposition channels.« less

Authors:
ORCiD logo [1];  [1];  [1]; ORCiD logo [2]; ORCiD logo [3]
+ Show Author Affiliations
  1. Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry
  2. Florida International Univ., Miami, FL (United States). Dept. of Chemistry
  3. Purdue Univ., West Lafayette, IN (United States). Dept. of Chemistry; Sandia National Lab. (SNL-CA), Livermore, CA (United States). Combustion Research Facility
Publication Date:
Research Org.:
Sandia National Lab. (SNL-CA), Livermore, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1778897
Alternate Identifier(s):
OSTI ID: 1771243
Report Number(s):
SAND-2021-4618J
Journal ID: ISSN 1463-9076; 695592
Grant/Contract Number:  
AC04-94AL85000; FG02-96ER14656; NA0003525
Resource Type:
Accepted Manuscript
Journal Name:
Physical Chemistry Chemical Physics. PCCP
Additional Journal Information:
Journal Volume: 23; Journal Issue: 11; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Mishra, Piyush, Fritz, Sean M., Herbers, Sven, Mebel, Alexander M., and Zwier, Timothy S. Gas-phase pyrolysis of trans 3-pentenenitrile: competition between direct and isomerization-mediated dissociation. United States: N. p., 2021. Web. doi:10.1039/d1cp00104c.
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Mishra, Piyush, Fritz, Sean M., Herbers, Sven, Mebel, Alexander M., & Zwier, Timothy S. Gas-phase pyrolysis of trans 3-pentenenitrile: competition between direct and isomerization-mediated dissociation. United States. https://doi.org/10.1039/d1cp00104c
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Mishra, Piyush, Fritz, Sean M., Herbers, Sven, Mebel, Alexander M., and Zwier, Timothy S. Wed . "Gas-phase pyrolysis of trans 3-pentenenitrile: competition between direct and isomerization-mediated dissociation". United States. https://doi.org/10.1039/d1cp00104c. https://www.osti.gov/servlets/purl/1778897.
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@article{osti_1778897,
title = {Gas-phase pyrolysis of trans 3-pentenenitrile: competition between direct and isomerization-mediated dissociation},
author = {Mishra, Piyush and Fritz, Sean M. and Herbers, Sven and Mebel, Alexander M. and Zwier, Timothy S.},
abstractNote = {The flash pyrolysis of trans 3-pentenenitrile (3-PN, CH3–$CH=CH$–CH2–CN) was studied by combining the results of VUV photoionization mass spectra with broadband microwave spectra recorded as a function of the temperature of the pyrolysis tube. The two separated functional groups (vinyl and nitrile) open up isomerization as an initial step in competition with unimolecular dissociation. Primary products were detected by keeping the 3-PN concentration low and limiting reaction times to the traversal time of the gas in the pyrolysis tube (~100 μs). The reaction is quenched and products are cooled by expansion into vacuum before interrogation over the 8–18 GHz region using chirped-pulse broadband methods. 118 nm VUV photoionization of the same reaction mixture provides a means of detecting all products with ionization potentials below 10.5 eV with minimal fragmentation. These results are combined with a detailed computational investigation of the C5H7N and related potential energy surfaces, leading to a consistent picture of the unimolecular decomposition of 3-PN. Loss of two H-atoms to form a 79 amu product is proven from its microwave transitions to contain trans-Z-2,4-pentadienenitrile, while no pyridine is observed. Methyl loss, HCN loss, and breaking the central C(2)–C(3) bond all occur following isomerization of the position of the double bond, thereby opening up low-energy pathways to these decomposition channels.},
doi = {10.1039/d1cp00104c},
journal = {Physical Chemistry Chemical Physics. PCCP},
number = 11,
volume = 23,
place = {United States},
year = {Wed Mar 10 00:00:00 EST 2021},
month = {Wed Mar 10 00:00:00 EST 2021}
}
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