南开大学有机化学课件 有机化学反应基本问题.ppt

有机化学反应的基本问题 Understanding Organic Reaction;本章的主要内容;Reaction Coordinate Diagrams反应坐标图或反应势能变化图;The field of chemistry that describes the properties of a system at equilibrium is called thermodynamics (热力学) 热力学第一定律：能量守衡与转化定律 ——能量可以从一种形式转化成另一种形式，在转化过程中，能量总值不变 热力学第二定律：自发过程的不可逆性 ——不可能从单一热源吸热，使之全部转化为功，而不引起其他变化 热力学第三定律：熵变的计算;热力学状态函数 ——内能 U，体系各种能量的总和，绝对值不可知 ——熵 S，体系无序程度，有规定熵 ——吉布斯自由能 G ——亥姆霍兹自由能 A ——焓 H 分析研究这些状态函数的变化值;Thermodynamics——几个基本概念和重要的关系式;Thermodynamics;When △G0 is negative, the reaction is exergonic（放能的）, has a favorable equilibrium constant, and can occur spontaneously. When △G0 is positive, the reaction is endergonic（吸能的）, has an unfavorable equilibrium constant, and cannot occur spontaneously.;Thermodynamics;Thermodynamics;Thermodynamics;Thermodynamics;Thermodynamics;Thermodynamics;Thermodynamics;Kinetics（动力学）is the field of chemistry that describes the rates of chemical reactions and the factors that affect those rates. —— reaction rate and affecting facters, reaction progress (反应速率及影响因素，反应进程等);Kinetics;Kinetics;Kinetics;Kinetics;Ea (activation energy) —— 活化能 —— indicate the energy barrier, the greater the energy barrier (Ea), the slower the reaction rate;4、Transition state (过渡态）theory — represents the highest-energy state involved in the reaction. — bonds in the transition state are partially broken and formed. — is unstable and cannot be isolated, but we can imagine it.;4、Transition state (过渡态）theory;热力学控制与动力学控制;三、Reaction Mechanisms;Reaction Mechanisms反应的具体步骤：键的断裂顺序和连接顺序每步反应中的能量变化以及反应速率反应立体化学;Reaction Mechanisms烷烃自由基卤代反应;Reaction Mechanisms烷烃自由基卤代反应;Reaction Mechanisms烷烃自由基卤代反应; ;Active Intermediates;Carbocations and Radicals —— For both carbocations and radicals, the observed order of stability is： 30 20 10 +CH3 ( or .CH3 ) —— Hyperconjugation（超共轭作用）;Active Intermediates Structures and Stability（结构与稳定性）;Carbocations and Radicals 碳正离子的稳定性 30苄基型30烯丙型 20苄基型20烯丙型 30 20 ~ 10苄基型~10烯