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Homogeneous Equilibria for Gaseous Reactions
For gas-phase reactions, the equilibrium constant may be expressed in terms of either the molar concentrations (Kc) or partial pressures (Kp) of the reactants and products. A relation between these two K values may be simply derived from the ideal gas equation and the definition of molarity. According to the ideal gas equation:
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The free energy change associated with dissolving a solute in a liter of solvent is called the free energy of a solution, ΔGsolution. The overall ΔGsolution is expressed as the balance of ΔGinteraction against the always-favorable free-energy of mixing, ΔGmixing. Solution formation is favorable if  ΔGsolution is less than zero, whereas it is unfavorable if ΔGsolution is greater than zero. In short, for a solution to form and complete dissolution to take place,...
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Heterogeneous Nucleation in Solutions on Rough Solid Surfaces: Generalized Gibbs Approach.

Alexander S Abyzov1, Leonid N Davydov1, Jürn W P Schmelzer2

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This study investigates heterogeneous nucleation on rough surfaces, finding that surface defects like cones significantly alter critical cluster formation and can shift the spinodal curve, especially with good wettability.

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Area of Science:

  • Physical Chemistry
  • Materials Science
  • Thermodynamics

Background:

  • Heterogeneous nucleation is crucial for phase transitions in solutions.
  • Previous models often assume critical clusters match macroscopic phase parameters.
  • Surface roughness significantly impacts nucleation kinetics and thermodynamics.

Purpose of the Study:

  • To investigate heterogeneous nucleation of new phases on rough solid surfaces.
  • To account for differences between critical cluster and macroscopic phase parameters using generalized Gibbs approach.
  • To analyze the influence of surface imperfections (cones) on nucleation.

Main Methods:

  • Utilized the generalized Gibbs approach for thermodynamic analysis.
  • Modeled surface imperfections as cones to simplify analysis.
  • Investigated the dependence of catalytic activity on cone angle and supersaturation.

Main Results:

  • The catalytic activity of conical defects depends on cone angle and solution supersaturation.
  • Surface imperfections significantly affect the work of critical cluster formation.
  • Good wettability with surface defects shifts the spinodal towards lower supersaturation compared to planar surfaces.

Conclusions:

  • Surface imperfections critically influence heterogeneous nucleation.
  • The cone angle and supersaturation determine the extent of metastability range alteration.
  • This work provides insights into controlling phase transitions via surface engineering.