Calorimetric study of peroxycarboxylic ester synthesis

Area of Science:

• Chemical Engineering
• Process Safety
• Organic Chemistry

Background:

• Organic peroxides pose significant hazards due to their exothermic reactions.
• Assessing thermal process safety is critical for safe handling.
• Key safety characteristics include overall heat production and adiabatic temperature rise.

Purpose of the Study:

• To present calorimetric investigation results for the synthesis of four peroxycarboxylic esters.
• To assess the exothermic potential and thermal safety of these compounds.
• To discuss the influence of process parameters on heat generation.

Main Methods:

• Calorimetric investigation of peroxycarboxylic ester synthesis.
• Measurement of overall heat production and adiabatic temperature rise.
• Analysis of synthesis criticality based on temperature levels and Stoessel's criticality classes.

Main Results:

• The second step in the two-step synthesis exhibited higher exothermic potential.
• Overall heat production ranged from 126-135 kJ/mol, largely independent of the carboxylic acid residue in tert-Butyl peroxycarboxylic esters.
• Calculated adiabatic temperature rise was 70-80K.
• The synthesis was graded as highly critical based on temperature levels.

Conclusions:

• The synthesis of tert-Butyl and tert-Amyl peroxycarboxylic esters involves significant exothermic potential.
• Accurate assessment of thermal characteristics is vital for safe industrial-scale production.
• Understanding heat generation dynamics is key to mitigating risks associated with organic peroxide synthesis.