Effect of pH on ether, ester, and carbonate hydrolysis in high-temperature water

Craig M. Comisar, Shawn E. Hunter, Ashley Walton, Phillip E. Savage

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49 Scopus citations


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 Kw, the ion product. This finding contradicts the conventional wisdom in this field.

Original languageEnglish (US)
Pages (from-to)577-584
Number of pages8
JournalIndustrial and Engineering Chemistry Research
Issue number3
StatePublished - Feb 6 2008

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Chemical Engineering(all)
  • Industrial and Manufacturing Engineering


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