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Published byPatience Armstrong Modified over 9 years ago
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Thermodynamics of surfaces and interfaces Atkins (ed. 10): §16C.2 Atkins (ed. 9): §17.8 + 17.10 Atkins (ed. 8): §18.7 + 18.8 Atkins (ed. 7): §6.8 - 6.10
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Na 2 ClO 3 crystals in solution solution
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Large crystals grow; small crystals dissolve T = 0T = 1 day
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Wilhelm Ostwald Large crystals grow; small crystals dissolve T = 0T = 1 day Ostwald ripening (1896)
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Equilibrium: one single crystal T = 0T = 1 dayT = 10 daysT = 30 days
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Equilibrium: one single crystal T = 0T = 1 dayT = 10 daysT = 30 days
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Gibbs-Thomson effect -Interfacial (free) energy between two phases
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Gibbs-Thomson effect -Interfacial (free) energy between two phases -Relevant for P >1 P =2,3 P =1
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Laplace equation γ r γ r+dr equilibrium Laplace equation
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Surface tension γ
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Surface tension and capillary action Pressure of liquid column of height h Laplace equation equilibrium capillary action
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Surface tension and capillary action
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Surface tension and wetting
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partial wetting partial dewetting Work (J/m 2 ) Force (N/m) }
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Kelvin equation (nucleation barrier for condensation) γ l g P in P out Laplace equation Kelvin equation equilibrium constant T
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nucleation barrier reason: interface energy between new phase and old classical nucleation theory –assume spherical nucleus, radius r –driving force: Δμ –surface free energy: γ –volume per growth unit: V 0 γ
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nucleation barrier nucleation barrier and critical radius nucleation barrier depends on supersaturation (Δμ = σ) -low σ: no nucleation -high σ: easy nucleation
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Polymorphism polymorphism: same chemical compound, different crystal structure (possible) differences in -melting point -solubility (bioavailability) -colour -morphology -etc. important for many industries, e.g. pharmaceuticals pseudo-polymorphism crystal structure containing the chemical compound, but including solvent (e.g. hydrate)
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Polymorphism in Venlavaxine
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Stability of polymorphic forms MonotropicEnantiotropic
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Stable Polymorph Computer simulation Cluster Growth
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Metastable Polymorph Computer simulation Cluster Growth
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Stable polymorph Metastable polymorph
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Computer simulation Cluster Growth
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