01-化学热力学.ppt

;1. 系统与环境 系统（system）:被研究的对象。 环境 （surroundings）:与系统密切相关的部分。 ;系统的分类; 所谓均匀是指其分散度达到分子或离子大小的数量 级。 相与相之间有明确的界面，超过此相界面，一定有 某些宏观性质（如密度、组成等）要发生突变。 ; 说 明;3. 状态与状态函数 状态 (state)：描述系统各种宏观性质的的综合表现。 状态函数 (state function) :描述系统状态的物理量。;; 2.0 7.0 2.0 1;二、热力学第一定律（first law of thermodynamics）;2. 功 (work) 定义：以W表示。 功（W）与途径有关，不是状态函数。 规定：环境对系统做功：W 0 系统对环境做功：W 0;体积功的推导;膨胀功： W = - P·ΔV;3. 热力学能（内能）(thermodynamic energy) 定义： 指系统内一切能量的总和，以U表示。 U是状态函数，热力学能变化只与始态、终态有关，与变化途径无关。 至今尚无法直接测量，只能测量 ?U。 ?U = U2 – U1;ΔU = U2 – U1 = Q + W;1.化学反应的热效应（heat effect）（反应热） 定义：是指当生成物与反应物的温度相同时，只做体积功的条件下，化学反应过程中吸收或放出的热量。 分类：等容反应热（QV）和等压反应热（ Q P ）两种。;在封闭系统、恒压、不做非体积功的条件下： W = - pΔV = - p (V2 – V1)，Q = Q P ， ΔU = U2 – U1 = Q P - p (V2 – V1)， Q P = (U2 + pV2) - (U1 + pV1)， 令 H = U + pV，H是状态函数 则：ΔH = H2 – H1 = Q p（恒压反应热）;? H是状态函数。 ? 焓和内能一样，具有能量的量纲。 焓的绝对值无法确定。 ? 焓变ΔH ： 吸热反应（endothermic），ΔH 0 放热反应（exothermic）， ΔH 0 ;3. 盖斯定律（Hess’s law）;; Born in Geneva, Switzerland, his father was an artist and in 1805 moved the family to Russia to find work. Beginning in 1822, Hess studied medicine at the University of Tartu. He qualified as a physician in 1825.Hess turned to chemistry after a meeting with J?ns Jakob Berzelius, the famous Swedish chemist, and went to Stockholm University to study under him. On his return to Russia, Hess joined an expedition to study the geology of the Urals before setting up a medical practice in Irkutsk. In 1830, Hess took up chemistry full time, researching and teaching, and later became a professor at the Saint Petersburg Technological Institute. His most famous paper, outlining his law on thermochemistry, was published there in 1840. His principle came to be called Hesss Law, which holds that in a series of chemical reactions, the total energy gained or lost depends only on the initial and final states, regardless of the number of steps. This is also known as