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Equilibrium and non-equilibrium concentration fluctuations in a critical binary mixture.

Fabio Giavazzi1, Alessandro Fornasieri1, Alberto Vailati2

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This study investigates non-equilibrium and equilibrium concentration fluctuations in a near-critical mixture. Researchers observed critical scaling behavior and determined critical exponents, finding agreement with theoretical models.

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Area of Science:

  • Physical Chemistry
  • Soft Matter Physics
  • Thermodynamics

Background:

  • Macroscopic concentration gradients induce non-equilibrium concentration fluctuations (NCF) through coupling with velocity fluctuations.
  • Near critical points, long-ranged equilibrium concentration fluctuations (ECF) can also be present.

Purpose of the Study:

  • To investigate the interplay between NCF and critical ECF in a near-critical aniline/cyclohexane mixture under a vertical concentration gradient.
  • To characterize critical phenomena and dynamic processes in binary mixtures.

Main Methods:

  • Utilized a commercial optical microscope and a custom-made temperature-controlled cell.
  • Acquired simultaneous static and dynamic light scattering data.
  • Studied systems both above and below the critical solution temperature.

Main Results:

  • Observed critical scaling behavior for scattering intensity and diffusion coefficient above the critical temperature, with critical exponents matching 3D Ising values.
  • Characterized the transient interplay between ECF and NCF in the two-phase region.
  • Found that equilibrium scattering intensity, crossover wave vector, and diffusion coefficient exhibit exponential relaxation tied to diffusive kinetics.

Conclusions:

  • The study successfully characterized the coexistence and interplay of equilibrium and non-equilibrium fluctuations in a near-critical binary mixture.
  • Experimental results for critical exponents align with established theoretical models (3D Ising).
  • Demonstrated that dynamic processes, including NCF, are governed by diffusive kinetics in the transient regime.