Mechanisms and kinetics of noncatalytic ether reaction in supercritical water. 2. Proton-transferred fragmentation of dimethyl ether to formaldehyde in competition with hydrolysis

Journal of Physical Chemistry A

Volumn 109, Issue 16, 2005, Pages 3558-3564

  Nagai, Yasuharu ^a   Matubayasi, Nobuyuki ^a   Nakahara, Masaru ^a  

^a KYOTO UNIVERSITY   (Japan)

Author keywords

[No Author keywords available]

Indexed keywords

ACETIC ACID; ALDEHYDES; CHARGE TRANSFER; CHEMICAL BONDS; FORMALDEHYDE; HYDROLYSIS; OXIDATION; PROTONS; REACTION KINETICS;

CARBONIC ACIDS; DIMETHYL ETHERS; HYDROTHERMAL ETHER REACTION; SUPERCRITICAL WATER;

ETHERS;

EID: 18444379946     PISSN: 10895639     EISSN: None     Source Type: Journal    
DOI: 10.1021/jp0505328     Document Type: Article

References (22)

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18. 1 the longest reaction time examined was 20 h, whereas that for DME is 200 h. This is because the reactions of DME with and without water are much slower than those of diethyl ether.
19. Morooka, S.; et al. Manuscript in preparation.
20. 15 Thus, these reactions are characteristic of high temperatures.
21. March, J. Advanced Organic Chemistry: Reactions, Mechanisms, and Structure, 4th ed.; John Wiley & Sons: New York 1992; Chapter 16, p 937; Chapter 19, p 1233.
22. 10 times according to the rule of thumb for the rate: a 2-fold rate constant increase with a temperature elevation of 10 K. This indicates that the time scale for the DME reactions is reduced from 200 h (673 K) to on the order of 10 μs (1000 K) within the same reaction mechanism.