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Avoiding the Kauzmann Paradox via Interface-Driven Divergence in States.
Andrew Martin1,2, Jason R Green3,4, Martin Thuo1,2
1Department of Materials Science and Engineering, North Carolina State University, Raleigh, NC, 27695, USA.
Angewandte Chemie (International Ed. in English)
|March 19, 2025
Summary
The Kauzmann paradox (KP) is challenged by surface chemical speciation in core-shell particles (CSPs). This phenomenon prevents equilibrium phase transitions, offering new insights into deep undercooling and glass formation.
Area of Science:
- Materials Science
- Physical Chemistry
- Non-equilibrium Thermodynamics
Background:
- The Kauzmann paradox (KP) posits that deeply supercooled liquids may possess lower entropy than crystalline solids.
- While equilibrium thermodynamics extensively studies this entropy catastrophe, solidification is a far-from-equilibrium process.
Purpose of the Study:
- To investigate how far-from-equilibrium processes, specifically surface chemical speciation in core-shell particles (CSPs), impact the Kauzmann paradox.
- To explore the possibility of avoiding the entropy catastrophe during deep undercooling.
Main Methods:
- Experimental and theoretical analysis of solidification in CSPs.
- Modeling of nonequilibrium processes, including surface tensor asymmetry and thermodynamic speed limits.
- Analysis of entropy production and configurational entropy in glass formation.
Main Results:
- Surface chemical speciation in CSPs perturbs entropy production, hindering continuum equilibrium phase transitions.
- Speciation-induced surface stress divergence generates nonequilibrium fluxes, frustrating homogeneous nucleation and enabling deep undercooling.
- A modified form of the Kauzmann paradox emerges under thermodynamic speed limits, which can be averted by incorporating an interfacial state.
Conclusions:
- Surface chemical speciation in CSPs offers a novel mechanism to avoid the Kauzmann paradox's entropy catastrophe.
- Deep undercooling and glass formation can be achieved without violating fundamental thermodynamic principles by considering interfacial states.
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