Marian Paluch Co-workers: Ż. Wojnarowska K. Grzybowska A. Grzybowski K. Kamiński K. Adrjanowicz P. Włodarczyk J. Pionteck (Christian-Albrechts University.

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Presentation transcript:

Marian Paluch Co-workers: Ż. Wojnarowska K. Grzybowska A. Grzybowski K. Kamiński K. Adrjanowicz P. Włodarczyk J. Pionteck (Christian-Albrechts University of Kiel, Germany) Univerity of Silesia, Poland

Entropic models Thermodynamic scaling

VH is a popular pharmaceutical material correcting irregular heart beat and reducing blood pressure problems T g = 325 K Protic ionic liquid

the structural (α-) relaxation the structural (α-) relaxation Dielectric measurements

T g (P) PVT measurementsDSC measurements T τ = T(τ=5s) ΔC g (T g ) =0.52 J/gK

The Kohlraush-Williams-Watts function Time –Temperature – Pressure principle is not valid in case of VH The α-loss peak becomes narrower with compression !

Effect of pressure on fragility VFT equation: Isobaric fragility:

Activation volume: Activation equation:

Volume Temperature 0  E V /E P  1 activation energy at constant volume: activation energy at constant pressure:

>>1 ~ 1 comparable 0 P T dominate V dominate            Thermal effects become more importent with increasing pressure

Isothermal fragility decreases with the increase in temperature

I method II method The exponent γ is slightly dependent on pressure

m=3γ γ es = γ = 2.45 A. Grzybowski, M. Paluch, and K. Gryzbowski J. Phys. Chem. (2009)

Bulk modulus γ = 10.7 A.N. Papathanassiou, Phys. Rev. E (2009)

The Avramov model is an entropic model

logτ 0 = -9.9 ± 0.1 F 0 = 6.9 ± 0.1 Π = 207 ± 6 C/c P = ± 0.1 β = 0.91 ± 0.22 The fitting parameters:

Calculated: From experiment:

γ G = 2.47 ± 0.1 D = 4.65 ± 0.2 γ G = 1.3 The fitting function: where: (a) (b) The fitting parameters: Calculated from eq. (a) R. Casalini, et. al. J. Chem. Phys (2006)

1.Taking into account the behavior of some properties like: the shape of relaxation function of the α-relaxation, isothermal fragility or pressure dependence of γ, VH (and probably other glass-forming liquids which belong to the same class of materials as VH) cannot be counted among strongly correlating systems. 2.The relationship between dynamic and thermodynamic properties established within entropy Avramov model is not supported by experimental data of VH