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The stability-limit conjecture revisited
Pheerawich Chitnelawong1, Francesco Sciortino2, Peter H Poole1
1Department of Physics, St. Francis Xavier University, Antigonish, Nova Scotia B2G 2W5, Canada.
The Journal of Chemical Physics
|June 24, 2019
Summary
The stability-limit conjecture (SLC) is thermodynamically permissible, even with liquid-liquid transitions. This resolves thermodynamic inconsistencies and explains water
Area of Science:
- Thermodynamics
- Physical Chemistry
- Materials Science
Background:
- The stability-limit conjecture (SLC) posits a re-entrant spinodal in supercooled water, explaining diverging thermodynamic responses.
- Previous arguments questioned the SLC's thermodynamic consistency with general principles.
- The SLC's relation to the proposed liquid-liquid phase transition in water remains a key area of investigation.
Purpose of the Study:
- To re-evaluate the thermodynamic viability of the stability-limit conjecture (SLC).
- To clarify the SLC's compatibility with liquid-liquid phase transitions.
- To explore unusual thermodynamic behaviors in systems with multiple phase transitions.
Main Methods:
- Analysis of a model equation of state for water.
- Thermodynamic modeling to demonstrate binodal-spinodal termination points.
- Investigation of critical-point-free scenarios for liquid-liquid transitions.
Main Results:
- Demonstrated that a binodal can terminate on a spinodal without a critical point.
- Established the thermodynamic permissibility of the SLC in systems with both liquid-gas and liquid-liquid transitions.
- Clarified unusual thermodynamic behaviors, including critical-point-free liquid-liquid transitions.
Conclusions:
- The stability-limit conjecture is thermodynamically permissible.
- The SLC can coexist with liquid-liquid phase transitions, resolving prior inconsistencies.
- Findings have implications for understanding supercooled water and liquid silicon behavior.
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