The decomposition of tertiary butyl peroxy pivalate (TBPPI), in <i>n</i>-hexane, under a pressure of 1900 bar and at a temperature of 100 °C, was studied <i>in situ</i> 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 <i>n</i>-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 CO<sub>2</sub> and <i>t</i>-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 CO<sub>2</sub> is found to be 1.65·10<sup>-3</sup>s<sup>-1</sup> (half-life time for TBPPI of approximately 420 s). <i>t</i>-Butanol formation occurs at a slower rate of approximately 1.22·10<sup>-3</sup>s<sup>-1</sup> (characteristic time of 566 s).
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