Research on Chemical Intermediates

, Volume 41, Issue 8, pp 5565–5586 | Cite as

Micellar catalysis of quinquivalent vanadium oxidation of methanol to formaldehyde in aqueous medium

  • Pintu Sar
  • Aniruddha Ghosh
  • Debranjan Ghosh
  • Bidyut Saha


The kinetics of oxidation of methanol by quinquivalent vanadium in aqueous sulfuric acid medium has been studied at 313 K under pseudo-first-order condition by UV–vis spectrophotometry. Nonfunctional sodium dodecyl sulfate (SDS) surfactant solution was used as a microheterogeneous micellar catalyst. The reaction rate and selectivity strongly depend on the chosen surfactant, and in some cases also on the surfactant concentration. The critical micelle concentration (CMC) values of the SDS surfactant in aqueous medium as well as in the presence of the substrate methanol were determined by the conductivity method, matching well with the kinetically determined CMC value. SDS was found to be an excellent catalyst for oxidation of methanol by vanadium(V) in aqueous sulfuric acid medium, leading to the corresponding oxidized product (formaldehyde), which was detected by 1H nuclear magnetic resonance (NMR). The micellar catalysis by SDS is due to strong binding of the cationic oxidant with the anionic surfactant. Formation of aggregates by the catalytic surfactant was studied using optical microscopy, and the change in shape and size of the aggregates in the reaction condition was studied by using scanning electron microscopy and the dynamic light scattering method. Mechanisms for this oxidation reaction in aqueous medium as well as with micellar catalyst are proposed, being completely supported by our experimental results.


Methanol Quinquivalent vanadium Sodium dodecyl sulfate (SDS) Critical micelle concentration (CMC) Micellar catalysis Formaldehyde 



z-Averaged hydrodynamic mean diameter


Specific conductivity


Total surfactant concentration


Absorption wavelength


Critical micelle concentration


Critical aggregation concentration


Pseudo-first-order rate constant


Standard reduction potential


Sodium dodecyl sulfate


Calcium dodecyl sulfate




Half-life of oxidation




Interaction parameter



The authors would like to thank UGC, New Delhi and CSIR, New Delhi for providing financial help in the form of research grant and fellowship, The University of Burdwan, Burdwan, India for providing infrastructural facilities, and Mr. Atanu Basak of the Department of Chemistry, Visva-Bharati, Santiniketan, India for his kind help.

Supplementary material

11164_2014_1682_MOESM1_ESM.doc (162 kb)
Supplementary material 1 (DOC 162 kb)


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Copyright information

© Springer Science+Business Media Dordrecht 2014

Authors and Affiliations

  • Pintu Sar
    • 1
  • Aniruddha Ghosh
    • 1
  • Debranjan Ghosh
    • 2
  • Bidyut Saha
    • 1
  1. 1.Homogeneous Catalysis Laboratory, Department of ChemistryThe University of BurdwanBurdwanIndia
  2. 2.Department of ChemistryKrishna Chandra CollegeBirbhumIndia

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