论文信息 - Kinetics of the Decomposition of Diethyl Peroxide

Kinetics of the Decomposition of Diethyl Peroxide

The kinetics of the gas‐phase decomposition of diethyl peroxide have been studied in a flow system, using excess of toluene. The main reaction products were found to be ethane and formaldehyde, and there were smaller amounts of methane and dibenzyl. The frequency factor of the reaction is 2.1×1013, and the activation energy is 31.7 kcal per mole. The mechanism of the reaction is discussed, and it is shown that the measured rate must refer to the initial dissociation C2H5OOC2H5→2C2H5O. With a new value of 47.8 kcal for the heat of formation of gaseous diethyl peroxide, the heat of formation of the C2H5O radical is calculated to be 8.1 kcal, which agrees satisfactorily with estimates from other kinetic data. Thermochemical values for other reactions involving this radical are calculated.

K. Laidler | R. Rebbert

[1] J. S. Roberts,et al. Kinetics of the Thermal Decomposition of Di‐t‐Butyl Peroxide , 1951 .

[2] A. Trotman‐Dickenson,et al. The Reactions of Methyl Radicals. IV. The Abstraction of Hydrogen Atoms from Cyclic Hydrocarbons, Butynes, Amines, Alcohols, Ethers, and Ammonia , 1951 .

[3] M SZWARC,et al. The determination of bond dissociation energies by pyrolytic methods. , 1950, Chemical reviews.

[4] M. Szwarc. The C–C Bond Energy in Ethylbenzene , 1949 .

[5] A. Egerton,et al. The Decomposition and Ignition of Peroxides. I. Diethylperoxide , 1938 .

[6] E. Steacie,et al. The Homogeneous Unimolecular Decomposition of Gaseous Alkyl Nitrites VIII. The Decomposition of Ethyl and n‐Propyl Nitrites at Low Pressures Together with a General Discussion of the Results for the Entire Series , 1937 .

[7] K. Herzfeld,et al. The Thermal Decomposition of Organic Compounds from the Standpoint of Free Radicals. VI. The Mechanism of Some Chain Reactions , 1934 .

[8] A. Baeyer,et al. Ueber Diäthyl‐peroxyd , 1900 .

[9] G. K. Adams,et al. The homogeneous decomposition of ethyl nitrate , 1949 .

[10] F. F. Rust,et al. Decompositions of Di-t-Alkyl Peroxides. II. Reactions of the Resultant Free Radicals , 1948 .

[11] A. Egerton,et al. Note on heats of formation of ethyl and propyl peroxides , 1940 .