物理化学(偏摩尔量).pptVIP

* 物理化学(Ⅰ) PHYSICAL CHEMISTRY （9） 过程方向和限度判据： 孤立系统 DS，熵增加原理 封闭系统 DS，熵增加原理 绝热过程 DA，赫姆霍兹函数减小原 理 等温无功（等V, W’=0） DG，吉布斯函数减小原理 等温等压W’＝0 ？（有物质交换发生） 开放系统 DS，考虑环境、构建孤立系 其它过程 第三章 溶液热力学基础 Thermodynamics of Multi-component Systems (Solution Chemistry) 3.1 Partial molar quantities(偏摩尔量) Characteristics of multi-component and heterogeneous systems (1) Composition and the amounts of substances are changeable in systems involving phase transitions and chemical reactions. (对其中的一相而言,可看作开放系统) Volume Change upon Mixing of C2H5OH(A) and H2O(B) wA% VA*/cm3 VB*/cm3 (VA*+VB*)/cm3 V/cm3 DV/cm3 20 25.34 80.32 105.66 103.24 2.42 40 50.68 60.24 110.92 106.93 3.99 60 76.02 40.16 116.18 112.22 3.96 80 101.36 20.08 121.44 118.56 2.88 (2) Nonadditivity of extensive properties, such as volume。 (3) More than 3 independent variables are needed to define the state of a system. 2. Partial molar quantities Taking volume as an example. For a system at thermal and mechanical equilibrium, we have Define: as partial molar volume of substance B Partial molar internal energy Partial molar enthalpy Partial molar entropy Partial molar volumes of H2O and CH3CH2OH at 25oC Discussion: ① Partial molar quantities are intensive properties of a system. （强度性质） ② Perspectives of physical significance V xB nB Changing rate of V against nB at a given state (T, p, and concentration xB). 偏摩尔体积也可看作是在等温等压的条件下，在无限大的系统中加入1 mol B所引起系统体积的变化量。 ③ Conditions: Constant T and p. ④ For a mono-component system, 3. Two important equations of partial molar quantities (1) Additivity of partial molar properties (偏摩尔量的集合公式，或加和公式) 在指定T，p 均不变的条件下 V是nB的一次齐函数。 根据齐函数的Euler定理 即： (2) Gibbs - Duhem equation At constant T and p, From By comparison, we have For