Journal of Solution Chemistry

, Volume 41, Issue 3, pp 525–535 | Cite as

Anomalies in the Change of Volumetric Parameters of the Diels–Alder Reaction in Solution

  • Vladimir D. KiselevEmail author
  • Alexander V. Bolotov
  • Ilzida I. Shakirova
  • Helen A. Kashaeva
  • Lubov N. Potapova
  • Alexander I. Konovalov


In this article negative values of the activation volume in retro-Diels–Alder reactions are interpreted in terms of the different possibilities of penetration of the solvent molecules into the sterically branched structures of the adduct and activated complex. Empty spaces, inaccessible to penetration of solvent molecules, lead to increases of the molar volume of the screened adducts in solution and, consequently, to a less negative value of the Diels–Alder reaction volume. The values of partial molar volumes of anthracene, maleic anhydride and the adducts cyclopentadiene–maleic anhydride, anthracene–maleic anhydride and anthracene–tetracyanoethylene, in several solvents, were calculated from the solution density data.


Diels–Alder reaction Solvent effect Reaction volume Partial molar volume Intramolecular holes 



This work was supported by the Russian Federal Agency of Education (No P-2345, GK No 14.740.11.0377, GK No OK-1/2010). We also appreciate fruitful comments from the reviewers, which helped for us in finalizing this manuscript.


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Copyright information

© Springer Science+Business Media, LLC 2012

Authors and Affiliations

  • Vladimir D. Kiselev
    • 1
    Email author
  • Alexander V. Bolotov
    • 1
  • Ilzida I. Shakirova
    • 1
  • Helen A. Kashaeva
    • 1
  • Lubov N. Potapova
    • 1
  • Alexander I. Konovalov
    • 1
  1. 1.Department of Physical Chemistry, Butlerov Institute of ChemistryKazan Federal UniversityKazanRussian Federation

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