01 Chapter 0-1 Introduction.pptx

第1页：绪论 目录页

1. A map of physical chemistry
2. About author
3. About text
4. About course

第2页：物理化学的三大理论支柱

Rests on three main conceptual theories: quantum mechanics, statistical mechanics, thermodynamics. 1、A map of physical chemistry

第3页：量子力学的研究对象

量子力学的研究对象

Quantum mechanics describes the motions and energies of microscopic particles, such as electrons, nuclei, atoms, and molecules. Given an expression for the potential energy of interaction of any group of these particles, quantum mechanics allows us, atleast in principle, to compute properties of the particles such as the probabilities that they have certain positions and moment a, and the quantized energy levels 1、A map of physical chemistry

第4页：热力学的宏观视角

热力学的宏观视角

In contrast to quantum mechanics, thermodynamics deals with the interdependence of macroscopic properties, such as the temperature, pressure, and concentrations. This general theory has two facets useful in applications to the lifesciences.

The first, thermodynamics places strict limitations on the inter conversion of different forms of energy. Since the inter conversion of heat, chemical energy, electrical energy, mechanical energy, and light is basic to life, it is clear that thermodynamics must beat the center of any physical description of living matter.

1、A map of physical chemistry

第5页：热力学预测化学平衡

热力学预测化学平衡

The second important facet of thermodynamic theory is that it allows us to predict the position of any chemical equilibrium, knowing only the properties of the substances involved in the reaction. This is of great importance in understanding metabolism.

1、A map of physical chemistry

第6页：热力学与化学动力学

热力学与化学动力学

In addition to these two facets, thermodynamics is such a familiar theory to physical chemists that its concepts are borrowed for use in other less fundamental theories, such as that of chemical kinetics. This is why we take up thermodynamics at the start of the book, and treat it thoroughly enough so that before long you may regard it as an old friend.

1、A map of physical chemistry

第7页：热力学概要与两大定律

热力学概要与两大定律

Thermodynamics: Physical behaviour of solid, liquid, gas and mixed phases Energy inter conversion via physical (e. g., compression, expansion, mixing, heating, cooling, etc.) and chemical (chemical reactions, combustion, ionization, etc.) processes 1 st law: “ book - keeping ”, making sure energy is conserved, and knowing where energy goes or comes from 2 nd law: “ spontaneity ”, knowing why processes actually occur, why beautiful, orderly entities are created from seeming ingly randomness Practical applications: industrial processes, everyday phenomena, safe chemistry, understanding new materials 1、A map of physical chemistry

第8页：统计力学的桥梁作用

统计力学的桥梁作用

Statistical mechanics bridges the microscopic realm of quantum mechanics and the macroscopic realm of thermodynamics. This theory tells us how to use the energies of the individual particles described by quantum mechanics to arrive at the properties of the macroscopic system.

1、A map of physical chemistry

第9页：统计力学算例：液氩压力

统计力学算例：液氩压力

An example of an application of statistical, mechanics is the computation of the pressure (a macroscopic property) of liquid argon as a function of its temperature and volume. Values of the pressure, in good agreement with experiment, can be calculated if one starts with an accurate potential energy function for the interaction of two argon atoms.

Such a potential energy function can be obtained from quantum mechanics. 1、A map of physical chemistry

第10页：数学语言与误差估计

数学语言与误差估计

The newcomer to the study of physical chemistry finds one feature: the language of mathematics. There are three reasons for use math. The first is precise definition. The second benefit is the possibility of math deduction.

The third reason for using m a this more important in science. Scientists can estimate the probable error in a quantity they are calculating or measuring. Few scientific experiments lead to a clear “ yes ” or “ no ” answer;

more often the answer are of the form “ maybe yes ” or “ perhaps no ”. To be sure of the conclusion, one must be able to judge the size of the error in the measurements and to know just how big is the “ perhaps ”. 1、A map of physical chemistry

第11页：物理化学的分支学科

量子化学、结构化学、化学热力学、热化学、统计热力学、化学动力学、溶液理论、电化学、光化学、胶体化学、磁化学、放射化学、原子核化学、结晶化学等1、A map of physical chemistry

第12页：关于作者 Peter Atkins

• 2、About authors — Peter Atkins Peter Atkins is professor of chemistry at Oxford University, a fellow of Lincoln College, and the author of more than thirty books for students and a general audience. A frequent lecturer in the United States and throughout the world on chemistry and chemical education, he has held visiting professorships in Israel, France, Japan, China, and NewZealand.
• Professor Atkins worked in industry for two years before studying at Leicester University, where he received his Ph. D., and at the University of California, LosAngeles. His Physical Chemistry broke new ground by stressing understanding above the memorization of facts and formulas. Nearly 20 years later, it is still the leading text in its field. His other books include Inorganic Chemistry; The Elements of Physical Chemistry; Concepts in Physical Chemistry; Quanta; and, most recently, Molecular Quantum Mechanics (all published by Oxford University Press). Molecules, The Second Law, and Atoms, Electrons, and Change, and The Periodic Kingdom. He serves on the International Union of Pure and Applied Chemistry' s committee on physical chemistry.

第13页：关于作者 Julio de Paula

关于作者 Julio de Paula

Julio dePaul a is professor of chemistry at Haverford College, where he teaches general chemistry, physical chemistry, and biophysical chemistry, and conducts research in photochemistry and photo biology. 2、About authors — Julio de Paul a After obtaining a doctorate in chemistry from Yale University, he was a National Institutes of Health Postdoctoral Fellow at Michigan State University, and then took up his current position at Haverford in 1989.

He was awarded a Henry Dreyfus Teacher - Scholar Award in 1998.

第14页：教材结构：平衡篇

教材结构：平衡篇

3、About textbook … Part 1: Equilibrium 1 The properties of gases 2 The First Law: the concepts 3 The First Law: the machinery 4 The Second Law: the concepts 5 The Second Law: the machinery 6 Physical transformations of pure substances 7 Simple mixtures 8 Phase diagrams 9 Chemical equilibrium 10 Equilibrium electrochemistry

第15页：教材结构：结构篇

教材结构：结构篇

Part 2: Structure 11 Quantum theory: introduction and principles 12 Quantum theory: techniques and applications 13 Atomic structure and atomic spectra 14 Molecular structure 15 Molecular symmetry 16 Spectroscopy 1: rotational and vibrational spectra 17 Spectroscopy 2: electronic transitions 18 Spectroscopy 3: magnetic resonance 19 Statistical thermodynamics: the concepts 20 Statistical thermodynamics: the machinery 21 Molecular interactions 22 Macromolecules and aggregates 23 The solid state 3、About textbook

第16页：教材结构：变化篇

Part 3

Change 24 Molecules in motion 25 The rates of chemical reactions 26 The kinetics of complex reactions 27 Molecular reaction dynamics 28 Processes at solid surfaces 29 Dynamics of electron transfer 3、About textbook

第17页：教材结构（续）

3、About textbook

第18页：物理化学的研究内容

物理化学的主要理论支柱— — 热力学、统计力学和量子力学

• 物质的任一均匀状态— — 相相变、能量转化和化学变化— — 物理化学变化可能性：平衡问题— — 化学热力学速率：到达平衡所需的时间— — 化学动力学
• 分子、原子结构及微观粒子的运动规律— — 统计力学、结构化学及量子化学4、About course

第19页：学习物理化学的方法

理论联系实际— — 化工、材料、冶金、轻工

• 勤于思考、认真推理
• 堂课教学与习题练习结合
• 堂课教学与实验相结合
• 领会解决实际问题的科学方法4、About course … 学习物理化学的要求及方法

第20页：做题的重要性

做题的重要性

Trying to learn physical chemistry solely by reading a textbook without working problems is about as effective as trying to improve your physique by reading a book on body conditioning without doing the recommended physical exercises.

I. N. Levine, Physical Chemistry, 5 th Edition, McGraw Hill, 20024、About course … 学习物理化学的要求及方法

第21页：以问题为中心的学习

Physical Chemistry is not a “ memory - based ”, learn - by - rote discipline, but is centred upon problem - based learning. However, you must practice solving problems, deriving equations, etc. to become proficient. 4、About course … 学习物理化学的要求及方法

第22页：物理化学实验的意义

物理化学实验的意义

I believe that the physical chemistry laboratory is the place for a student to begin to make the transition from student to scientist. We accomplish this by treating each experiment as a small research problem, and by thinking about in terms of choosing a problem, searching the literature, designing the experiment, executing the experiment, reducing the data, analyzing the errors, and writing the report.

- - - - - - - - R. J. S i me Physical Chemistry: Methods, Techniques, and Experiments, 19884、About course … 学习物理化学的要求及方法

第23页：课程安排与考核方式

4、About course

• 三学期，周学时3, EXAM, homework - - - - - in English
• Final grade: 70 % from EXAM, 30 % from homework,
• 2 - 3 人组成学习小组，一起讨论，用英文完成习题解答
• 考试题目全部选自书上习题或例题
• 多看“ Checklist of key ideas ”
• 参考书目： 1、胡英等编，《物理化学》 (第四版) 高等教育出版社， 19992、天津大学编，王正列、周亚平修订，《物理化学》 (第四版) 高等教育出版社， 20013、南京大学编，《物理化学》 (第四版) 高等教育出版社， 1993

第24页：气体的性质 章节封面

… This chapter establishes the properties of gases that will be used throu

第25页：气体的状态

• 1.1 The state of gases Physical properties — — Physical state Same physical properties — — same physical state Equation of state Ex: the state of a pure gas (p, T, V, n): p = f (T, V, n) … The perfect gas

第26页：压力与压力单位

• (a) PressureS I unit of p: 1 P a = 1 N m - 2 = 1 kg m - 1 s - 2 Standard pressure: p : 105 P a (1 bar) A table of pressure units: p 4

第27页：力学平衡

the higher pressure and lower pressure Mechanical equilibrium

第28页：气压计测压

• the measurement of pressure barometer … H g

第29页：压力计测压

• the measurement of pressure … manometer

第30页：热平衡

• (b) temperature Thermal equilibrium

第31页：热力学第零定律

• (b) temperature Zero Law of thermodynamics

第32页：温标与温度测量

• the measurement of temperature The 0 thLaw leads to the use of a thermometer  Celsius scale θ / º C  Perfect - gas temperature scale  Thermodynamic temperature scale Thermodynamic (Kelvin) and Celsius temp. T / K = θ / º C + 273.15 … T / K

第33页：气体定律

1.2 The gas laws

• Boyle’ s (波义尔) Law at constant T and n:
• Gay - Lussac’ s (盖－吕萨克) Law at constant p and n:
• Charles’ s Law at constant V and n:
• Avogadro’ s (阿伏加德罗) Principle at constant T and p:
• The Perfect Gas Law: perfect gas equation R: gas constant

第34页：气体定律

第35页：混合气体与道尔顿分压定律

…

• Mixture of gases
• Dalton’ s law (道尔顿定律)
• Mole fraction, partial pres

第36页：混合气体的组成表示

• Mixture of gases

第37页：实际气体与理想气体偏差

Real Gases 理想气体分子无体积，分子间无相互作用，低压、高温气体可近似用理想气体定律处理。实际气体并不严格服从理想气体定律，尤其在高压、低温或在将要凝聚成液体时偏离更为明显。

第38页：实际气体的研究内容

Real Gases Molecular Interactions Compression factor Virial coefficients Condensation Critical Constants Van der Waals Equation Corresponding States

第39页：分子间相互作用

1.3 Molecular interactions … 实际气体偏离理想气体定律的主要原因是分子间的相互作用。分子间的排斥力有助于膨胀。分子间的吸引力有助于压缩。

第40页：分子间相互作用

第41页：分子间排斥力与吸引力

1.3 Molecular interactions … 分子间的排斥力是一种短程相互作用力，它只有在分子互相靠近几乎接触时才起作用，约在分子直径尺度范围。高压气体的状况与其类似。分子间的吸引力是一种较长程力，它在分子比较靠近但又不接触时起作用，约在几个分子直径尺度范围。

第42页：分子间作用力与压力区间

1.3 Molecular interactions 低压下，分子相互远离，不发生相互作用，可用理想气体定律描述在高压下，分子间的排斥力起主要作用，气体表现为不可压缩。在中等压力条件下，分子间距离为几个分子大小，气体可压缩。

第43页：压缩因子 Z

(a) The compression factor, Z … The compression factor of a gas can be defined as where Vmis the molar volume, V / n Ideal gas: Z = 1 And then

第44页：压缩因子偏离 1 的含义

压缩因子偏离 1 的含义

(a) The compression factor, Z Departure from Z = 1 means that a gas is not behaving as an ideal gas. Intermediate Pressure: Z < 1 Compression is favoured, due to dominance of attractive forces High Pressure: Z > 1 Expansion is favoured, as repulsive forces come into play

第45页：维里方程与维里系数

(b) Virial coefficients … 若将压缩因子Z 用级数展开： Z = 1 + B’ P + C’ P 2 + … 或则有实际气体的Virial equation of state: PVm = RT (1 + B’ P + C’ P 2 + …) 或 … 其中B, C, … 分别为第一、第二… 维里系数，通常取二项即可。当P → 0，或V m → ，则维里方程还原为理想气体方程。

第46页：维里系数与理想气体差异

(b) Virial coefficients … 虽然当P → 0 或V m →  时，维里方程还原为理想气体方程，但是压缩因子Z 对压力的一阶导数并不还原为理想气体： = B’ + 2 C’ P + … → B’ as P → 0 but B’  0 或BasVm →  but B  0 而对理想气体， Z = 1，它关于P 的导数必为零

第47页：波义耳温度

(b) Virial coefficients … 由于维里系数与温度有关，在低压或大的摩尔体积时，在Z ~ P 曲线上总可以找到一点温度，使Z → 1，而斜率为零，这点的温度称之为： Boyle

第48页：CO2 实验等温线与冷凝

(c) Condensation CO 2 实验等温线 … Liquid Critical point Supercritical fluid 气液二相区高温大摩尔体积(与理想气体相似) A  B 

第49页：临界点与临界常数

• Critical point of the gas (marked with a star) At which: (∂ P / ∂ V m) T = 0 and (∂ P 2 / ∂ V m 2) T = 0
• Critical temperature, T c
• Critical pressure, Pc
• Critical molar volume, V c
• Critical constants: T c, Pc, V c
• Supercritical fluid: T > T c, Single phase, much denser than typical gases (d) Critical constants … p 18: Table 1.4

第50页：范德华方程的提出

范德华方程的提出

Johannes Did erik vanderWaal s (1837 - 1923), a Dutch physicist, won the 1910 Nobel Prize in Physics for his work on the equation of state for gases and liquids. This is an semi empirical theory, which means it is based upon experimental observations, combined with arigourous thermodynamic treatment.

1.4 The van der Waals equation …

第51页：范德华方程的体积与压力修正

• Molecules: repulsive interaction small and impenetrable sphere, nonzero volume Free moving in volume V - n b, not in volume V V  V - n b
• Pressure: attractive force The frequency of collision with the walls The force of each collision P  P + a (n / V) 21.4 The van der Waals equation … … Depends on

第52页：范德华系数 a 与 b

1. 4 The van der Waals equation … … a and b: van der Waals coefficients P 19: Table
2. 5 or or：

第53页：范德华方程估算摩尔体积

1.4 The van der Waals equation … … Example: Using ven der Waals equation to estimate a molar volume carbon

第54页：范德华方程算例与压缩因子

1. 4 The van der Waals equation … a =
2. 610 L 2 at m mol - 2 and b =
3. 29  10 - 2 L mol - 1 RT / P =
4. 41

第55页：习题 1.19 氮气定容加热

习题 1.19 氮气定容加热

Exercise (p 27) 1.19 (a) In an industrial process, nitrogen is heated to 500 K at a constant volume of 1.000 m 3. The gasinters the container at 300 K and 100 at m. The mass of the gas is 92.4 kg. Use the vanderWaal s equation to determine the approximate pressure of the gas at its working temperature of 500 K.

For nitrogen, a = 1.352 L 2 atmmol - 2, b = 0.0387 Lmol - 1.

第56页：习题 1.19 解题思路

习题 1.19 解题思路

Exercise (p 27) 1.19 (a) The amount of gas is first determined from its mass; then the vanderWaal s equation is used to determine its pressure at the working temperature. The initial conditions of 300 K and 100 at m are in a sense of superfluous information.

V = 1.000 m 3 = 1.000  103 L

第57页：范德华方程的适用范围

(a) The reliability of the equation … … Using ven der Waals equation to predict the behavior of real gas at mode

第58页：范德华等温线对比

(a) The reliability of the equation … … Apart from the oscillations below the critical temp., some calculated is

第59页：麦克斯韦构造

(a) The reliability of the equation … The oscillations, the vanderWaal sloops, are unrealistic and should be r

第60页：临界常数与范德华系数关系

(b) The relationship between critical constants and van der Waals coefficients … At critical point of the gas:

第61页：其他状态方程：R-K 方程

(c) Some other equations of state … (Table 1.6) …

• R - K (Redlich - Kwong) equation Constants a and bare different from t

第62页：其他状态方程：B-W-R 方程

(c) Some other equations of state … …

• B - W - R (Benedict - Webb - Rubin) equation A 0, B 0, C 0, α, γ, a, b

第63页：贝塞罗方程

(c) Some other equations of state …

• Berthelot (贝塞罗) equation 此方程考虑了温度对分子间相互吸引力的影响。

第64页：对应状态原理

1.5 The principle of corresponding states … (对应状态原理) … 理想气体状态方程是一个不涉及各种具体气体特性的普遍化方程，而真实气体状态方程中往往含有与气体种类有关的各种常数，如范德华常数、维里系数等。能否导

第65页：对比变量的定义

1.5 The principle of corresponding states … (对应状态原理) … First we introduce the reduced variables of a gas by dividing the actual

第66页：范德华对应状态原理

1.5 The principle of corresponding states … (对应状态原理) … VanderWaal s first proposed the principle of corresponding states: Real

第67页：范德华方程的对比形式

1.5 The principle of corresponding states … (对应状态原理) … VanderWaal s expressed the VanderWaal s equation in terms of the reduced

第68页：临界参数与范德华系数换算

1.5 The principle of corresponding states (对应状态原理) … Expressed the critical constants in terms of van derWaals constants a an

第69页：对应状态原理图

… T / T c = T / T c = T / T c = 1.0

第70页：对应状态原理小结

1.5 The principle of corresponding states … (对应状态原理) … 因此，所谓对应状态原理，就是当不同物质处于相同的对比温度和对比压力时，即处于对应状态，此时不但压缩因子，而且其它的一些物理性质如导热系数、比热容

第71页：习题 1.24 硫化氢估算

Exercise (p 27) 1.24 (b) Use the vanderWaal s parameters for hydrogen sulfide to calculate approximate values of (a) the Boyle temperature of the gas and (b) the radius of a H 2 S molecule regarded as a sphere.

第72页：习题：波义耳温度计算

Exercise (p 27) (a) The Boyle temperature is the temperature at which vanishes. According to the vanderWaal s equation:

第73页：习题：大摩尔体积极限

Exercise (p 27) In the limit of large molar volume, V m > > b, we have

第74页：习题：排除体积与分子直径

习题：排除体积与分子直径

Exercise (p 27) By interpreting b as the excluded volume of a mole of spherical molecules, we can obtain an estimate of molecular size. The centres of spherical particles are excluded from a sphere whose radius is the diameter of those spherical particles (i.

e. twice their radius); The Avogadro constant times the volume is the molar excluded volume b:

第75页：课后作业与习题清单

Homework (p 27) Exercises (a): 1.5, 1.8, 1.13, 1.18, 1.20, 1.25 Problems: 1.5, 1.20