Decomposition of 4,4-Dimethylpent-1-ene in the Presence of Oxygen between 400 and 500 deg C: Oxidation Chemistry of Allyl Radicals

DOI: 10.1039/ft9918700681

Source and publish data:

Journal of the Chemical Society - Faraday Transactions p. 681 - 689 (1991)

Update date:2022-08-17

Topics:

Authors:

Lodhi, Zulfiqar H.

Walker, Raymond W.

Read Full Text PDF DownLoad Join now for total 90,000,000 free articles

Article abstract of DOI:10.1039/ft9918700681

The decomposition of 4,4-dimethylpent-1-ene (DMP) in the presence of O2 has been used as a source of allyl radicals over the temperature range 400-500 deg C.The reaction has been studied in both KCl-coated (peroxy species destroyed at the surface) and aged boric-acid-coated vessels (peroxy species preserved), and the basic mechanism shown to be: (1) (2).Previous studies have shown that 99percent of the t-butyl radicals undergo reaction (2), so that the system is an excellent source of allyl and HO2 radicals.A full product analysis has carried out over a wide range of mixture composition and associated mechanistic aspects discussed.It is shown that allyl radicals are unreactive towards both DMP and O2 and that they react mainly in radical-radical processes. (3) (8) (18).Values of k₈/k₁₈ = 0.37, 0.38 and 0.42 are obtained at 400, 440 and 480 deg C, respectively.From a reasonably reliable estimate of and , values of k₈ = (3.3 +/- 0.9) * 1E9 and k₁₈ = (7.4 +/- 2.4) * 1E9 dm³ mol^-1 s^-1 are obtained at 480 deg C.No previous estimates of these rate constants are available in the literature.Values of k₄ have been determined and when combined with independent data at higher temperatures give log(A₄/s^-1) = 14.19 +/- 0.25 and E₄ = 255.5 +/- 5.3 kJ mol^-1 over the range 400-1025 deg C.DMP -> (CH3)2C=CH2 + CH3CH=CH2 (4).A value of K₁₁ = (2.5 +/- 1) * 1E2 dm³ mol^-1 s^-1 has been obtained at 480 deg C and shown to be consistent with the reaction's high endothermicity. (11)

Full text of DOI:10.1039/ft9918700681

View Article Online / Journal Homepage / Table of Contents for this issue

View Article Online

Products guided by the article

Product name:1,3-Butadiene

Cas No:106-99-0

R&D Labs maybe for 106-99-0

Suzhou Kangrun Pharmaceutical, Inc

Contact:86-512-63912376，63913329

Address:Building 2, No. 2358 ,Chang'an Rd, Wujiang Economic Development Zone Pioneering park, china
Zhejiang Kangfeng Chemical Co.,LTD.

Contact:+86-579-86709687

Address:Xueshizhai Industrial Zone, Weishan Town,Dongyang City, Zhejiang Province ,China
Hangzhou Yingshanhua Pigment Chemicals Co.,Ltd.

Contact:+86-0150-58101658

Address:Nanyang Economic DevelopmentZong,Xiaoshan,Hangzhou,China
Zhenjiang Huayu I/E Co.,LTD

Contact:86-511-85210668 0511-85210668, 85210818, 85210898

Address:Yihai Garden E-902,NO.99 Daxi RD., Zhenjiang Jiiangsu ,China
Shouguang Nuomeng Chemical Co., Ltd.

Contact:+86-536-5119508/18363669993

Address:Hou Zhen Industrial Park, Shouguang, Shandong, China

Relevant to this article

Synthesis and antimicrobial activity of tetradentate ligands bearing hydrazone and/or thiosemicarbazone motifs and their diorganotin(IV) complexes

Doi:10.1016/j.jinorgbio.2016.07.002
(2016)
Design, synthesis, cytotoxicity, HuTopoIIα inhibitory activity and molecular docking studies of pyrazole derivatives as potential anticancer agents

Doi:10.1016/j.bioorg.2016.10.001
(2016)
TiO₂ photocatalytic reduction of bis(2-dipyridyl)disulfide to 2-mercaptopyridine by H₂O: Incorporation effect of nanometer-sized Ag particles

Doi:10.1039/a805820b
(1998)
Transglycosylation reactions with a crude culture filtrate from Thermoascus aurantiacus

Doi:10.1016/S0008-6215(00)00061-6
(2000)
In Situ Phase Separation into Coupled Interfaces for Promoting CO₂ Electroreduction to Formate over a Wide Potential Window

Doi:10.1002/anie.202110000
(2021)
Revisiting the stability of endo/exo diels-alder adducts between cyclopentadiene and 1,4-benzoquinone

Doi:10.1590/S0103-50532010000100017
(2010)

Article Doi