Lecture-Chapter-03-2nd Law.pptx

Physical Chemistry Chapter 3 热力学第二定律 The Second Law of Thermodynamics 第三章 热力学第二定律 自发过程与热力学第二定律 (3.1-3.2) Carnot 循环与Carnot定理 (3.3) 熵 (3.4-3.5) 熵变计算 – PVT过程与相变过程 (3.7) 熵的统计意义 (3.8-3.9) 熵变 – 第三定律与化学反应过程 (3.14) 第二定律与Helmholtz 和 Gibbs 函数 (3.10-3.12) 热力学函数关系 (3.6, 3.13) 自发过程的不可逆性 自然界中任一孤立系统总是自发趋向热力学平衡， 而不需要环境作功 自发过程的逆过程不会自动发生，回复到起始状态需 要环境作功：环境的状态会变化 ? 不可逆 尽管过程中能量守恒 热传导：热不会自发从低温到高温 摩擦生热：热不会自动转化为功 膨胀过程：自由膨胀不可逆 相变过程：超冷水可变为冰，反之不行 混合过程：扩散 化学反应：H2 + O2 的燃烧 。。。 存在一个量或性质，来描述过程的不可逆性。 3 不可逆过程 - 例 摩擦的存在使自然界中凡涉及到热现象的过程都是 不可逆的。 不可逆的过程： 物体的下落，恒温： 下落中功变为热； Kelvin: 不能从恒温大气吸热做功以举起物体而不引起其他变化。 恒温理想气体膨胀： 无摩擦准静态：Yes 真空自由膨胀：No 恒外压膨胀：No 4 Spontaneity 自发性 5 This variable is called entropy 熵 The concept of entropy arose as 19th-century scientists attempted to maximize the work output of engines. Can we convert heat to work completely in a process? Can we convert work to heat completely in a process? Can we have a repeating machine to do these ? Examples … Certain variable determines the spontaneous direction “There is a natural asymmetry in the efficiency of converting work to heat and converting heat to work.” Heat Engines 热机 6 Heat Engine converts heat flow into mechanical work. Cyclic 循环 Absorbs heat from high-T body (qH 0), performs work (-w 0) (We get work from the engine) Emits heat (-qC 0) to low-T body. Heat Engines 7 For each cycle, 0 = dU = q + w = qH – (– qC) + w = qH + qC + w Efficiency of the heat engine 热机效率: Heat Engines 8 A Steam Engine 蒸汽机 A Carnot Engine Carnot热机 P-V Work 9 Expansion: By removing mass from the piston one by one Does work to the surrounding the most Or We can obtain the most amount of work from the system P-V Work 10 Compression: By adding mass to the piston one by one Require the least amount of work from outside for the compression Heat Engines 11 System does maximum work in reversible expansion System receives minimum work in reversible compression ? Efficiency of a reversible engine is the upper limit to the efficiency of a real engine. ?