Journal of Thermal Analysis and Calorimetry

, Volume 120, Issue 1, pp 633–639 | Cite as

Influence of deteriorated solvent on induction period of Grignard reagent formation

  • Mieko Kumasaki
  • Kuninori Tanaka
  • Teruhito Otsuka


The influence of a degraded solvent on Grignard reagent formation was investigated in terms of heat release behaviour. Since degraded solvent is supposed to contain peroxide by oxidation with air as well as water from atmosphere, peroxide in this study was intentionally produced by the storage of tetrahydrofuran in a pressurized oxygen atmosphere and the induction periods were measured. The induction period which appears prior to the main exothermic reaction increased with increasing amounts of peroxide and water content, respectively. However, there was a difference in heat release behaviour; the reaction including peroxide showed a delay in the heat release and two exothermic peaks, while the solvent that included water simply showed a delay in the start of the reaction. γ-Butyrolactone was found to be a product derived from peroxide, by component analysis of the oxidized solvent. γ-Butyrolactone caused an induction period when it was added to the solvent. This work suggests a deteriorated solvent can lead to inappropriate handling which cause a runaway reaction and gives insight to the chemical industry that manages the risk of potentially hazardous chemical reactions.


Induction period Grignard reagent formation reaction Peroxide Chemical reaction hazards 


  1. 1.
    Bou-Diab L, Fierz H. Autocatalytic decomposition reactions, hazards and detection. J Hazard Mater. 2002;93:137–46.CrossRefGoogle Scholar
  2. 2.
    Gustin JL. Thermal stability screening and reaction calorimetry Application to runaway reaction hazard assessment and process safety management. J Loss Prevent Proc. 1993;6:275–91.CrossRefGoogle Scholar
  3. 3.
    Serra E, Nomen R, Sempere J. Maximum temperature attainable by runaway of synthesis reaction in semi-batch processes. J Loss Prevent Proc. 1997;10:211–5.CrossRefGoogle Scholar
  4. 4.
    Kumasaki M. The solvent effects on Grignard reaction, IChemE Symposium Series No. 53; 2007.Google Scholar
  5. 5.
    Am Ende DJ, Clifford PJ, DeAntonis DM, SantaMaria C, Brenek SJ. Preparation of Grignard reagents: FTIR and calorimetric investigation for safe scale-up. Org Process Res Dev. 1999;3:319–29.CrossRefGoogle Scholar
  6. 6.
    Tanaka K, Kumasaki M, Miyake A. Influence of Mg surface layer for induction period of Grignard reagent formation. J Therm Anal Calorim. 2013;113:1395–401.CrossRefGoogle Scholar
  7. 7.
    Garst JF, Soriaga MP. Grignard reagent formation. Coord Chem Rev. 2004;248:623–52.CrossRefGoogle Scholar
  8. 8.
    Kanoufi F, Combellas C, Hazimeh H, Mattalia J-M, Marchi-Delapierre C, Chanon M. Alkyl halides reactions with cathodes or with magnesium. Grignard reagent studied with radical clocks. What is the step competing with the isomerisation of the intermediate radical? J Phys Org Chem. 2006;19:847–66.CrossRefGoogle Scholar
  9. 9.
    Tilstam U, Weinmann H. Activation of Mg metal for safe formation of grignard reagents on plant scale. Org Process Res Dev. 2003;6:906–10.CrossRefGoogle Scholar
  10. 10.
    Reichardt C, Welton T. Solvents and solvent effects in organic chemistry. Weinheim: Wiley-VCH; 2011.Google Scholar
  11. 11.
    Dasler W, Bauer CD. Removal of peroxides from organic solvents. Ind Eng Chem. 1946;18:52–4.Google Scholar
  12. 12.
    Hamstead AC. Destroying peroxides of isopropyl ether. Ind Eng Chem. 1964;56:37–42.CrossRefGoogle Scholar
  13. 13.
    Armarego WLF, Chai C. Purification of laboratory chemicals. USA: Butterworth-Heinemann; 2013.Google Scholar
  14. 14.
    Kito H, Fujiwara S, Kumasaki M, Miyake A. Assessment of autoxidative resistance for organic solvent by pressure monitoring test. Int J Saf. 2010;9:43–6.Google Scholar
  15. 15.
    Mitchell J. Organic analysis, vol. 4. New York: Interscience; 1960. p. 1–64.Google Scholar
  16. 16.
    Hawkins EGE. Organic peroxides. London: E.&FF. Spon; 1961. p. 332.Google Scholar
  17. 17.
    Johnson RM, Siddiqi IW. The determination of organic peroxides. New York: Pergamon Press; 1970.Google Scholar
  18. 18.
    Swern D. Organic peroxides, vol. 1. NewYork: Wiley-Interscience; 1969. p. 497.Google Scholar
  19. 19.
    Kumasaki M, Fujimoto Y, Ando T. Calorimetric behaviors of hydroxylamine and its salts caused by Fe(III). J Loss Prevent Proc. 2003;16:507–12.CrossRefGoogle Scholar
  20. 20.
    Kumasaki M. An explosion of a tank car carrying waste hydrogen peroxide. J Loss Prevent Proc. 2006;19:307–11.CrossRefGoogle Scholar
  21. 21.
    Kumasaki M. Calorimetric study on the decomposition of hydroxylamine in the presence of transition metals. J Hazard Mater. 2004;115:57–62.CrossRefGoogle Scholar
  22. 22.
    Kowhakul W, Kumasaki M, Arai M, Tamura M. Calorimetric behaviors of N2H4 by DSC and superCRC. J Loss Prevent Proc. 2006;19:452–8.CrossRefGoogle Scholar
  23. 23.
    Kryk H, Hessel G, Schmitt W, Tefera N. Safety aspects of the process control of Grignard reactions. Chem Eng Sci. 2007;62:5198–200.CrossRefGoogle Scholar
  24. 24.
    Shurvell HF, Southby MC. Infrared and Raman spectra of tetrahydrofuran hydroperoxide. Vib Spectrosc. 1997;15:137–46.CrossRefGoogle Scholar
  25. 25.
    McDermott DP. Vibrational assignments and normal-coordinate analyses of γ-butyrolactone and 2-pyrrolidinones. J Phys Chem. 1986;90:2569–74.CrossRefGoogle Scholar
  26. 26.
    Rein H, Criegee R. Ueber das Tetrahydrofuran-peroxyd. Angew Chem. 1950;62:120.CrossRefGoogle Scholar
  27. 27.
    Vozza JF. Products of the reaction between gamma-butyrolactone and phenylmagnesium bromide. J Org Chem. 1959;24:720–4.CrossRefGoogle Scholar

Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2015

Authors and Affiliations

  • Mieko Kumasaki
    • 1
  • Kuninori Tanaka
    • 1
  • Teruhito Otsuka
    • 2
  1. 1.Graduate School of Environment and Information ScienceYokohama National UniversityYokohamaJapan
  2. 2.National Institute of Occupational Safety and Health, JapanKiyoseJapan

Personalised recommendations