In Situ Raman Spectroscopy of the Decomposition of Tertiary Butyl Peroxy Pivalate under High Pressure and High Temperature

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Abstract:

The decomposition of tertiary butyl peroxy pivalate (TBPPI), in n-hexane, under a pressure of 1900 bar and at a temperature of 100 °C, was studied in situ with the use of a transportable high-throughput fiber-optic Raman spectrometer. The Raman probe was conveniently coupled to an optical high-pressure cell containing the TBPPI. Time-resolved experiments with a 10 wt % solution of TBPPI in n-hexane were carried out, and information on the mechanism of decomposition and the (first-order) kinetics was obtained. It is shown that the main decomposition products of TBPPI are CO2 and t-butanol. From first-order kinetic fits, of the Raman profiles of intensity vs. time of reactants and products, the rate constant for the decomposition of TBPPI and the formation of CO2 is found to be 1.65·10-3s-1 (half-life time for TBPPI of approximately 420 s). t-Butanol formation occurs at a slower rate of approximately 1.22·10-3s-1 (characteristic time of 566 s).

Keywords: DECOMPOSITION; HIGH; PEROXIDE; PRESSURE; RAMAN

Document Type: Research Article

DOI: http://dx.doi.org/10.1366/0003702011951669

Affiliations: 1: Department of Chemical Technology, Darmstadt University of Technology, Petersenstraße 20, D-64287 Darmstadt, Germany 2: DSM Research, P.O. Box 18, 6160 MD Geleen, The Netherlands

Publication date: February 1, 2001

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