HOMOGENEOUS DECOMPOSITION OF VINYL ETHERS - HEAT OF FORMATION OF ETHANAL-2-YL

被引:46
作者
ROSSI, M
GOLDEN, DM
机构
[1] Thermochemistry and Chemical Kinetics Group, Sri International, Menlo Park, California
关键词
D O I
10.1002/kin.550110705
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
The thermal unimolecular decomposition of three vinylethers has been studied in a VLPP apparatus. The high‐pressure rate constant for the retro‐ene reaction of ethylvinylether was fit by log k (sec−1) = (11.47 + 0.25) ‐ (43.4 ± 1.0)/2.303 RT at <T> = 900 K and that of t ‐ butylvinylether by log k (sec−1) = (12.00 ± 0.27) ‐ (38.4 ± 1.0)/2.303 RT at <T> = 800 K. No evidence for the competition of the higher energy homolytic bond‐fission process could be obtained from the experimental data. The rate constant compatible with the CO bond scission reaction in the case of benzylvinylether was log k (sec−1) = (16.63 ± 0.30) ‐ (53.74 ± 1.0)/2.303 RT at <T> = 750 K. Together with ΔHf,3000(benzyl·) = 47.0 kcal/mol, the activation energy for this reaction results in ΔHf,3000(CH2CHO) = +3.0 ± 2.0 kcal/mol and a corresponding resonance stabilization energy of 3.2 ± 2.0 kcal/mol for 2‐ethanalyl radical. Copyright © 1979 John Wiley & Sons, Inc.
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页码:715 / 730
页数:16
相关论文
共 21 条
[1]   THERMAL DECOMPOSITION OF ALKYL VINYL ETHERS .2. INHIBITED DECOMPOSITIONS OF T-BUTYL ISOPROPYL AND 2-CHLOROETHYL VINYL ETHERS [J].
BAMKOLE, TO ;
EMOVON, EU .
JOURNAL OF THE CHEMICAL SOCIETY B-PHYSICAL ORGANIC, 1968, (03) :332-&
[2]   INFRARED CRYOGENIC STUDIES .12. ALKENES IN ARGON MATRICES [J].
BARNES, AJ ;
HOWELLS, JDR .
JOURNAL OF THE CHEMICAL SOCIETY-FARADAY TRANSACTIONS II, 1973, (04) :532-539
[3]  
Benson S.W., 1976, THERMOCHEMICAL KINET, Vsecond
[4]   NONBONDED ATTRACTION IN METHYL VINYL ETHER [J].
BERNARDI, F ;
EPIOTIS, ND ;
YATES, RL ;
SCHLEGEL, HB .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1976, 98 (09) :2385-2390
[5]   MICROWAVE SPECTRUM CONFORMATION DIPOLE MOMENT AND BARRIER TO INTERNAL ROTATION IN METHYL VINYL ETHER [J].
CAHILL, P ;
GOLD, LP ;
OWEN, NL .
JOURNAL OF CHEMICAL PHYSICS, 1968, 48 (04) :1620-&
[6]  
DURIG JR, 1978, J CHEM PHYS, V69
[7]  
Forst W., 1973, THEORY UNIMOLECULAR
[8]   COMPARISON OF RRK AND RRKM THEORIES FOR THERMAL UNIMOLECULAR PROCESSES [J].
GOLDEN, DM ;
SOLLY, RK ;
BENSON, SW .
JOURNAL OF PHYSICAL CHEMISTRY, 1971, 75 (10) :1333-&
[9]  
GOLDEN DM, 1973, ANGEW CHEM, V84, P602
[10]   MICROWAVE SPECTRUM AND ROTATIONAL ISOMERISM IN BUTENE-1 [J].
KONDO, S ;
HIROTA, E ;
MORINO, Y .
JOURNAL OF MOLECULAR SPECTROSCOPY, 1968, 28 (04) :471-&