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1、Kinetics动力学,Thermodynamics determines whether and in which direction a reaction will happen, and what the concentrations of constituents are involved in the reaction 热力学决定了反应是否发生、反应的方向以及参与到反应之中的物质浓度问题。 Kinetics say how fast a reaction happens, sequence of steps in the reaction, and some of the facto
2、rs that control the rates of reactions 动力学则说明反应发生的速率有多快、反应步骤的顺序以及控制反应速率的一些因素 Further Reading (Chapter 3 in Hobbs),Rate of reaction is typically measured as the change in concentration (moles/L) with time 反应速率通常通过浓度(mol/L)随时间的变化来测量 This change may be a decrease or an increase 改变可能是增加的也可能是减小的 Likewise
3、 the concentration change may be of reactants or products 同样，改变浓度的物质可能是反应物也可能是生成物,反应速率=浓度/时间,Rate has units of moles per liter per unit time - M s-1, M h-1 速率的单位是摩尔每升每单位时间，如M s-1、M h-1 Consider the hypothetical reaction 对于这个假设的反应 aA + bB cC + dD We can write,Note the use of the negative sign 注意负号的使用
4、 - rate is defined as a positive quantity 反应速率被定义为正量 - rate of disappearance of a reactant is negative 那么，反应物的消耗速率就是负的 2N2O5(g) 4NO2(g) + O2(g),Rate may be expressed in three main ways: 反应速率主要有以下三个表达方式： Average reaction rate: a measure of the change in concentration with time 1、平均反应速率：浓度随时间变化的度量 2.
5、Instantaneous rate: rate of change of concentration at any particular instant during the Reaction 2、瞬时速率：反应过程中某一特定瞬间的浓度变化速率 3. Initial rate: instantaneous rate at t = 0 - that is, when the reactants are first mixed 3、初始速率：t=0时即反应物最初混合时的瞬时速率，,Rate Laws 速率定律,Rate law = a mathematical function describi
6、ng the turnover rate of the compound of interest as a function of the concentrations of the various species participating in the reaction 速率定律：用来描述相关的化合物的转化速率的数学函数，即各种参与反应的物质的浓度的函数 May or may NOT have a theoretical basis可能有或没有理论基础 “Many reactions occur at a decreasing rate with increasing time becau
7、se the reaction rate diminishes as the concentrations of the reactants diminish” “很多反应随着时间的增加反应速率逐渐减小？，因为反应物浓度减小会降低反应速率”,Hobbs (2000),Rate Laws,“m” indicates the order of the reaction with respect to species “A”. Determined experimentally. “m”指关于物质A的反应级数，由实验确定。 “k” = rate coefficient (or specific re
8、action rate coeff.); determined for a specific reaction at a specific temp “K”=速率常数（或特定的速率系数），由特定温度下的具体反应确定,A = products,Reaction rate,Rate Laws,“m, n, o” indicate the order of the reaction with respect to each species; determine experimentally overall reaction order = m+n+o “m, n, o”分别是关于每种物质的反应级数，
9、实验确定的总反应级数=m+n+o Reaction orders can be: first, second, third 反应级数可以是一级、二级、三级,A + B + C = products,First order reactions一级动力反应,Take integral of equation above, and get equation below: 将以上等式积分，得到下面的等式：,t = 0.693 / k,Plot of first order reaction 一级动力反应的图片,半衰期的长度固定,Example of 1st order reaction1级动力反应范例
10、,If a reaction has a single reactant and the value of the exponent is one, then it is said to be a first-order reaction. 如果反应物只有一种，而且指数为1，那么称这种反应为一级动力反应 Write rate law for above equation:,H2O2 (l) H2O(l) + 1/2O2(g),Wikipedia,Second Order Reaction二级动力反应,If integrated如果积分: 得到1/At = k”t + 1/Ao Inverse
11、concentration linear in time 浓度的倒数和时间程线性关系,t = 1 / k Ao,Plot of second order reaction 2级动力反应图,A,time,Half lives are not constant with time for second order reactions 二级反应动力学反应物质的半衰期随时间推移变化,Example of 2nd order reaction二级动力反应范例,A second-order reaction depends on the concentrations of one second-order
12、 reactant, or two first-order reactants. 二级动力反应取决是否有一个二级反应物或者两个一级反应物？ Write rate law for above equations:,2NO2 (g) 2NO(g) + O2(g),Wikipedia,CO2 + H2O H2CO3,Pseudo first order reactions伪一级反应,pseudo-first order: concentration of one reactant remains essentially constant over time (often because it is
13、in large excess compared to the other reactant) 伪一级动力反应：一种反应物剩余的浓度基本不变（经常由于它与其他物质相比，浓度过量）,B浓度不变,Reaction Mechanism反应机理,Often we write a chemical reaction 我们经常写化学反应式 How we write it is often not how it happens 但是我们所写的通常不是它如何发生的 Many kinds of reaction mechanisms 有很多反应的机理,Single Step (Elementary) React
14、ion Process单步（基本）反应过程,Unimolecular 单分子反应 CaCO3 Ca2+ + CO32- Bimolecular 双分子反应 CO2 + H2O H2CO3 Termolecular 三分子反应 2 FeS2 + 3 O2 + 2 H2O 2 Fe3+ + 4H2SO4 No four or more molecule processes have been identified because chances of 4 molecules colliding is very, very small (making reaction rate super smal
15、l) 没有4或者4以上的分子反应被检测到，因为4分子同时碰撞的机会非常非常小（使得反应速率非常小）,Rate Laws For Elementary基本反应速率定律,Simple to write 书写简单 Unimolecular H2CO3 H+ + HCO3- dH2CO3/dt = kH2CO3 Bimolecular CO2 + H2O H2CO3 dCO2/dt = kCO2H2O,Reaction order is not necessarily related to the stoichiometry of the reaction, unless the reaction i
16、s elementary. 反应级数不一定和反应的化学计量数有关，除非反应是基本反应 In single step process, reaction order = coefficient of reactant in chemical equation 在单步反应过程中，反应级数=化学式中反应物的系数 Complex reactions may or may not have reaction orders equal to their stoichiometric coefficients 复杂反应的反应级数可能和化学计量系数相等 Not all first order reactions, are single step, monomolecular reactions 不是所有的一级反应都是单步反应、单分子反应,Important Note重要提示,Hobbs (2000),Overview of Elementary Reactions基本反应回顾,Note: for Zero-Order reactions rate is independent of the
