物理化学双语教学2（厦门大学）chapter07.pptVIP

* Solid-solid Phase Transitions Fig. 7.9 (a) Phase diagram of S (part) E t/℃ 80 120 160 P / 10 5 Pa 102 100 10-2 10-4 10-6 104 gas B C liquid monoclinic orthorhombic solid 95 119 151 Three triple points: B: 95 oC C: 119 oC E: 151 oC Physical Chemistry Chapter 7 * Solid-solid Phase Transitions There are many different types of Phase Transition. Fusion, vaporization…… Ehrenfest Classification: Changes of enthalpy and volume (7.15) Physical Chemistry Chapter 7 * Solid-solid Phase Transitions Because ?trsV and ?trsS are non-zero for melting and vaporization for such transitions, the slopes of the chemical potential plotted against either pressure or temperature are different on either side of the transition. The first derivatives of the chemical potentials with respect to pressure and temperature are discontinuous at the transition. First-order phase transition ? Tt H Tt V Tt S Tt CP Tt T Physical Chemistry Chapter 7 * Solid-solid Phase Transitions CP is the slope of H-T. at Tt, the slope of H and Cp are infinite. First-order phase transition A first-order phase transition is also characterized by an infinite heat capacity at the transition temperature. ? Tt H Tt V Tt S Tt CP Tt T Physical Chemistry Chapter 7 * Solid-solid Phase Transitions The first derivative of the chemical potential with respect to temperature is continuous but its second derivative with respect to temperature is discontinuous at the transition. Second-order phase transition A continuous slope of ? (a graph with the same slope on either side of the transition) implies that the volume and entropy (and hence the enthalpy) do not change at the transition. The heat capacity is discontinuous at the transition but does not become infinite. Physical Chemistry Chapter 7 * Solid-solid Phase Transitions First-order phase transition Second-order phase transition ? Tt H Tt V Tt S Tt CP Tt T ? Tt H Tt V Tt S Tt CP Tt T Physical Chemistry Chapter 7 * Solid-solid Phase Transitions First-order Second-order CP Tt T