Discrimination between Molecular and Free-Radical Models of 1-Phenyldodecane Pyrolysis

Phillip E. Savage, Michael T. Klein

Research output: Contribution to journalArticle

32 Citations (Scopus)

Abstract

Liquid-phase thermolyses of 1-phenyldodecane (PDD) with added tetralin-d 12 allowed discrimination between molecular mechanisms and stepwise free-radical mechanisms. The incorporation of a deuterium label into the major pyrolysis product, toluene, proved that free-radical steps were kinetically significant since an intramolecular mechanism would proceed independently of the added tetralin and yield only protonated products. Quantitation of the fraction (DI) of toluene that was singly deuteriated as a function of the ratio (R) tetralin-d 12 /PDD allowed convincing estimation of DI = 1.0 as R → ∞. This demonstrated that at infinite dilution of PDD in tetralin-d 12 , all toluene formed with a deuterium label, suggesting that PDD thermolysis was entirely free-radical.

Original languageEnglish (US)
Pages (from-to)374-376
Number of pages3
JournalIndustrial and Engineering Chemistry Research
Volume26
Issue number2
DOIs
StatePublished - Feb 1 1987

Fingerprint

Free radicals
Free Radicals
Toluene
Thermolysis
Pyrolysis
Deuterium
Labels
Dilution
Liquids
tetralin

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Industrial and Manufacturing Engineering

Cite this

@article{ebaa912cbf4f41b693d1525a53cc257b,
title = "Discrimination between Molecular and Free-Radical Models of 1-Phenyldodecane Pyrolysis",
abstract = "Liquid-phase thermolyses of 1-phenyldodecane (PDD) with added tetralin-d 12 allowed discrimination between molecular mechanisms and stepwise free-radical mechanisms. The incorporation of a deuterium label into the major pyrolysis product, toluene, proved that free-radical steps were kinetically significant since an intramolecular mechanism would proceed independently of the added tetralin and yield only protonated products. Quantitation of the fraction (DI) of toluene that was singly deuteriated as a function of the ratio (R) tetralin-d 12 /PDD allowed convincing estimation of DI = 1.0 as R → ∞. This demonstrated that at infinite dilution of PDD in tetralin-d 12 , all toluene formed with a deuterium label, suggesting that PDD thermolysis was entirely free-radical.",
author = "Savage, {Phillip E.} and Klein, {Michael T.}",
year = "1987",
month = "2",
day = "1",
doi = "10.1021/ie00062a034",
language = "English (US)",
volume = "26",
pages = "374--376",
journal = "Industrial and Engineering Chemistry Research",
issn = "0888-5885",
publisher = "American Chemical Society",
number = "2",

}

Discrimination between Molecular and Free-Radical Models of 1-Phenyldodecane Pyrolysis. / Savage, Phillip E.; Klein, Michael T.

In: Industrial and Engineering Chemistry Research, Vol. 26, No. 2, 01.02.1987, p. 374-376.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Discrimination between Molecular and Free-Radical Models of 1-Phenyldodecane Pyrolysis

AU - Savage, Phillip E.

AU - Klein, Michael T.

PY - 1987/2/1

Y1 - 1987/2/1

N2 - Liquid-phase thermolyses of 1-phenyldodecane (PDD) with added tetralin-d 12 allowed discrimination between molecular mechanisms and stepwise free-radical mechanisms. The incorporation of a deuterium label into the major pyrolysis product, toluene, proved that free-radical steps were kinetically significant since an intramolecular mechanism would proceed independently of the added tetralin and yield only protonated products. Quantitation of the fraction (DI) of toluene that was singly deuteriated as a function of the ratio (R) tetralin-d 12 /PDD allowed convincing estimation of DI = 1.0 as R → ∞. This demonstrated that at infinite dilution of PDD in tetralin-d 12 , all toluene formed with a deuterium label, suggesting that PDD thermolysis was entirely free-radical.

AB - Liquid-phase thermolyses of 1-phenyldodecane (PDD) with added tetralin-d 12 allowed discrimination between molecular mechanisms and stepwise free-radical mechanisms. The incorporation of a deuterium label into the major pyrolysis product, toluene, proved that free-radical steps were kinetically significant since an intramolecular mechanism would proceed independently of the added tetralin and yield only protonated products. Quantitation of the fraction (DI) of toluene that was singly deuteriated as a function of the ratio (R) tetralin-d 12 /PDD allowed convincing estimation of DI = 1.0 as R → ∞. This demonstrated that at infinite dilution of PDD in tetralin-d 12 , all toluene formed with a deuterium label, suggesting that PDD thermolysis was entirely free-radical.

UR - http://www.scopus.com/inward/record.url?scp=0023292738&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0023292738&partnerID=8YFLogxK

U2 - 10.1021/ie00062a034

DO - 10.1021/ie00062a034

M3 - Article

VL - 26

SP - 374

EP - 376

JO - Industrial and Engineering Chemistry Research

JF - Industrial and Engineering Chemistry Research

SN - 0888-5885

IS - 2

ER -