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Ultrafast Time-resolved Near-IR Stimulated Raman Measurements of Functional π-conjugate Systems
Published on: February 10, 2020
Reaction kinetics of acetone peroxide formation and structure investigations using Raman spectroscopy and X-ray
L Jensen1, P M Mortensen, R Trane
1Department of Chemical and Biochemical Engineering, Technical University of Denmark, DK-2800 Kgs. Lyngby, Denmark.
Applied Spectroscopy
|January 17, 2009
Summary
The reaction rate of triacetone triperoxide (TATP) formation increases with temperature and acidity. Raman spectroscopy and DFT calculations suggest ring closure is the rate-limiting step in TATP synthesis.
Area of Science:
- Chemical kinetics
- Organic chemistry
- Spectroscopy
Background:
- Triacetone triperoxide (TATP) is a significant energetic material.
- Understanding the kinetics of TATP formation is crucial for safety and control.
- Previous studies have explored TATP synthesis, but detailed kinetic analysis under varying conditions is ongoing.
Purpose of the Study:
- To investigate the effect of pH and temperature on the reaction kinetics of TATP formation.
- To identify intermediate products and the rate-determining step in the reaction between acetone and hydrogen peroxide.
- To characterize TATP precipitates using Raman spectroscopy and X-ray diffraction.
Main Methods:
- Raman spectroscopy was used to monitor liquid mixtures of acetone and hydrogen peroxide over time.
- Density Functional Theory (DFT)/Hartree-Fock calculations were performed to model reaction pathways and spectra.
- Single crystal X-ray diffraction was employed to analyze crystallized products.
Main Results:
- TATP formation intermediates were observed within one day at 25°C.
- Reaction rate increases with temperature and sulfuric acid addition.
- The reaction rate is first-order with respect to H+ concentration.
- A crystal formed at 343 K was identified as diacetone diperoxide (DADP) via X-ray diffraction, distinct from typical TATP.
Conclusions:
- Ring closure is the likely rate-determining step in TATP formation.
- Reaction kinetics are significantly influenced by temperature and pH (H+ concentration).
- Under specific conditions (343 K), DADP can be a co-product or alternative product in TATP synthesis mixtures.
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