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From Molecules to Materials: Engineering New Ionic Liquid Crystals Through Halogen Bonding

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Interfacial chemical reactivity enhancement.

Dor Ben-Amotz¹

¹Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA.

The Journal of Chemical Physics

|February 23, 2024

Summary

Chemical reactions in liquid droplets are enhanced by product adsorption at interfaces. Reactivity increases with product size and decreases with polarity, aromaticity, and charge, especially for cations.

Area of Science:

Physical Chemistry
Chemical Thermodynamics
Surface Chemistry

Background:

Chemical reactions can be influenced by interfaces.
Liquid droplets present unique interfacial environments for chemical processes.

Purpose of the Study:

To predict and understand interfacial enhancements of chemical reaction equilibria and rates in liquid droplets.
To identify key molecular properties driving interfacial reactivity.

Main Methods:

Combined theoretical and experimental analysis.
Self-consistent solutions of reaction and adsorption equilibria.
Experimental determination of interfacial adsorption free energies and critical micelle concentration correlations.

Main Results:

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Interfacial reactivity enhancement is primarily driven by the product's adsorption free energy.
Reactant surface activity has a smaller, indirect influence.
Interfacial reactivity increases with product size and decreases with polarity, aromaticity, and charge.

Conclusions:

Product adsorption free energy is the dominant factor in interfacial reactivity enhancement.
Reactions with small, neutral, or charged products show limited enhancement unless specific surface-active interactions occur.
Molecular structure significantly impacts surface activity and thus interfacial reactivity.