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Chemical Changes in Liquid Benzene Multiply Shock Compressed to 25 GPa.

S Root¹, Y M Gupta

¹Institute for Shock Physics and Department of Physics, Washington State University, Pullman, Washington 99164, USA. sroot@sandia.gov

The Journal of Physical Chemistry. A

|January 28, 2009

Summary

Under high pressure shock waves, liquid benzene undergoes rapid polymerization at 24.5 GPa. This chemical change, driven by pi-orbital overlap in the liquid state, occurs on sub-microsecond timescales.

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Area of Science:

High-pressure physics and chemistry
Materials science under extreme conditions
Molecular dynamics and spectroscopy

Background:

Understanding the behavior of organic molecules under extreme pressures is crucial for various scientific fields.
Previous studies often lacked the temporal resolution to capture rapid chemical transformations.
Liquid benzene's response to dynamic compression remained largely unexplored at high pressures.

Purpose of the Study:

To investigate the dynamic high-pressure response of liquid benzene using stepwise shock compression.
To monitor molecular and chemical changes on sub-microsecond timescales.
To elucidate the mechanisms and conditions leading to chemical transformations in benzene.

Main Methods:

Utilizing stepwise-loading shock wave experiments with peak stresses from 4 to 25 GPa.
Employing time-resolved Raman spectroscopy to observe real-time molecular changes.
Developing a thermodynamically consistent equation of state (EOS) for shocked benzene.

Main Results:

No chemical changes were observed in Raman spectra up to 20 GPa.
At 24.5 GPa, Raman modes became indistinguishable within 40 ns, indicating rapid chemical transformation.
Calculations revealed sufficient pi-orbital overlap for intermolecular bonding at 24.5 GPa.

Conclusions:

Liquid benzene undergoes polymerization via cycloaddition reactions at 24.5 GPa.
The liquid state and sub-microsecond timescales are critical for this rapid polymerization.
Dynamic compression studies highlight the interplay of pressure, temperature, time, and phase in molecular chemical changes.