Role of symmetry and energy in structural phase transitions
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Role of symmetry and energy in structural phase transitions
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Re: Role of symmetry and energy in structural phase transitions
Thermodynamic order of the phase transition (Ehrenfest’s classification):
smallest order of the derivatives of the Gibbs free energy G (with respect to the relevant
variable, T or p) which are discontinuous across the transition
First-order transitions:
the first-order derivatives (entropy S and volume V) are discontinuous, leading to enthalpy
(latent heat) ∆H and volume ∆V jumps
dG = -SdT + Vdp (1)
Second-order transitions:
the second-order derivatives (heat capacity Cp and compressibility β) are discontinuous,
whereas the first-order ones are continuous (no heat or volume effects):
∆S = 0, ∆H = 0, ∆V = 0
d2G = - (Cp/T)dT2 -Vβdp2 -VαdTdp (2)
Phase α stable for T < Tc, phase β stable for T > Tc →
∆G = Gβ -Gα > 0 for T < Tc, ∆G = Gβ -Gα < 0 for T > Tc ?
smallest order of the derivatives of the Gibbs free energy G (with respect to the relevant
variable, T or p) which are discontinuous across the transition
First-order transitions:
the first-order derivatives (entropy S and volume V) are discontinuous, leading to enthalpy
(latent heat) ∆H and volume ∆V jumps
dG = -SdT + Vdp (1)
Second-order transitions:
the second-order derivatives (heat capacity Cp and compressibility β) are discontinuous,
whereas the first-order ones are continuous (no heat or volume effects):
∆S = 0, ∆H = 0, ∆V = 0
d2G = - (Cp/T)dT2 -Vβdp2 -VαdTdp (2)
Phase α stable for T < Tc, phase β stable for T > Tc →
∆G = Gβ -Gα > 0 for T < Tc, ∆G = Gβ -Gα < 0 for T > Tc ?
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