Hydrolysis pseudoequilibrium: Challenges and opportunities to sol-gel silicate kinetics

Stephen E. Rankin, Alon V. McCormick

Research output: Contribution to journalArticlepeer-review

23 Scopus citations


We quantitatively model the kinetics of acid-catalyzed hydrolytic condensation of trimethylethoxysilane, a representative monomer for 'sol-gel' inorganic polymerization chemistry. Sol-gel processing is of interest as a flexible route to new ceramic gels, silicone resins, inorganic/organic hybrids, and micro- or meso- porous catalysts such as zeolites. Using principal component analysis of the sensitivity matrix for this model, we quantitatively demonstrate that hydrolysis pseudoequilibrium is not only appropriate but also demanded if unique rate coefficients are to be determined. While this provides a challenge in the sense that hydrolysis kinetics may be difficult to measure, it also provides the opportunity to model alkoxysilane polymerization using only condensation kinetics. Parametric sensitivities are not directly observable however, so we also present an experimentally observable phase portrait signature of hydrolysis pseudoequilibrium. Finally, we discuss why, under hydrolysis pseudoequilibrium, the condensation route (water producing or alcohol producing) is virtually impossible to distinguish from a single batch experiment. (C) 2000 Elsevier Science Ltd. All rights reserved.

Original languageEnglish
Pages (from-to)1955-1967
Number of pages13
JournalChemical Engineering Science
Issue number11
StatePublished - Jun 2000

Bibliographical note

Funding Information:
The authors thank the National Science Foundation and the University of Minnesota Graduate School (for graduate fellowships to SER), the NSF Center for Interfacial Engineering at the University of Minnesota, the Minnesota Supercomputer Institute, and Dow Corning Corporation for research funding and resources contributing to this work.


  • Kinetics
  • Materials processing
  • Model reduction
  • Numerical analysis
  • Polymerization
  • Sol-gel

ASJC Scopus subject areas

  • General Chemistry
  • General Chemical Engineering
  • Industrial and Manufacturing Engineering


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