Effect of pH on Ether, Ester, and Carbonate Hydrolysis in High-Temperature Water

We examined the hydrolysis of dibenzyl ether, benzyl t-butyl ether, methyl t-butyl ether, methylbenzoate, and diphenylcarbonate in high-temperature liquid water, both with and without added acid or base. The apparent reaction order for H+ did not exceed 0.2 for any of the compounds investigated. Thi...

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Bibliographic Details
Published in:Industrial & engineering chemistry research 2008-02, Vol.47 (3), p.577-584
Main Authors: Comisar, Craig M, Hunter, Shawn E, Walton, Ashley, Savage, Phillip E
Format: Article
Language:English
Subjects:
Applied sciences
Chemical engineering
Exact sciences and technology
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Summary:We examined the hydrolysis of dibenzyl ether, benzyl t-butyl ether, methyl t-butyl ether, methylbenzoate, and diphenylcarbonate in high-temperature liquid water, both with and without added acid or base. The apparent reaction order for H+ did not exceed 0.2 for any of the compounds investigated. This result indicates that hydrolysis of these compounds in high-temperature water (HTW) does not follow the kinetics expected for specific acid catalysis (H+ reaction order = 1.0), as does the hydrolysis at ambient temperatures. Rather, the greater thermal energy in the HTW system allows protonation by water molecules to become faster than protonation by H+ at near-neutral conditions. Because the water-catalyzed path is faster, the occurrence of these acid-catalyzed reactions in HTW with no added acid is not due to the elevated value of K w, the ion product. This finding contradicts the conventional wisdom in this field.
ISSN:0888-5885
1520-5045
DOI:10.1021/ie0702882