Journal of Physical Chemistry p. 4099 - 4106 (1990)
Update date:2022-08-10
Topics:
Mackie, John C.
Colket III, Meredith B.
Nelson, Peter F.
The kinetics of pyridine dilute in argon have been studied in a single-pulse shock tube, using cappilary column GC together with GC/MS and FTIR spectroscopy for product determination, over the temperature range of 1300-1800 K and total pressures of 7-11 atm.At the lower end of the studied temperatures, cyanoacetylene was found to be the principal nitrogen-containing product.At elevated temperature hydrogen cyanide predominated.Other major products were acetylene and hydrogen.Thermochemical estimates of the isomeric cyclic pyridyls produced in the pyrolysis indicate that the ortho isomer is unique in being able to undergo facile cleavage to an open-chain cyano radical from which cyanoacetylene is produced.Several sources of HCN were identified in the system.The m- and p-pyridyls may eliminate HCN in a molecular process.An important source of HCN at high temperatures is the addition of H-atoms to cyano compounds, especially cyanoacetylene, but also acetonitrile and acrylonitrile which are produced in the pyrolysis.The pyrolysis is a chain process initiated principally by C-H bond fission to form o-pyridyl.A 58-step reaction model is presented and shown to substantially fit the observed profiles of the major product species.From this model we derive a value for the rate constant of the principal initiation reaction, C5H5N --> o-C5H4N + H (1), of k1=1015.9+/-0.4exp(-98 +/- 3 kcal mol-1/RT)s-1 between 1300 and 1800 K and at a total pressure of about 10 atm.
View MoreMelone Pharmaceutical Co., ltd
Contact:+86-411 82593920, 82593631
Address:No 232, JInma Roda, Development Zone, Dalian, China
Contact:+86-158-05817090
Address:ROOM 9F, FLAT 2, GUODU DEVELOPING BLDG, No.182, ZHAOHUI ROAD
Shenzhen ZheYi Chemicals Co.,LTD(Shanghai Branch)
Contact:+86-21-54159691
Address:Room1002,Building No.2, Lane 98 Bixiu Road,Minhang District, Shanghai,China 201100
Hangzhou Dawn Ray Pharmaceutical Co.,Ltd
website:http://www.dawnraypharma.com/
Contact:+86-571-85335020
Address:1018 Guangyin Building,No.42 E.Fengqi Road,Hangzhou,310012 China
website:http://www.uvchemkleys.com
Contact:+86 21 3868 0172
Address:RM-1203, Ziguang Building, #341 Shangcheng Road, Pudong Dist, Shanghai
Doi:10.1021/ja01532a055
(1959)Doi:10.1016/j.catcom.2013.03.020
(2013)Doi:10.4314/bcse.v32i3.12
(2018)Doi:10.1021/acs.joc.9b02462
(2019)Doi:10.1016/j.jcat.2019.04.041
(2019)Doi:10.1016/0040-6031(81)80034-2
(1981)