目录￤ Contents
Introduction …………………………………………………………………………………1 Section 1 Research Objects, Methods and Contents of Physical Chemistry ………………… 1 Section 2 Learning Methods of Physical Chemistry ………………………………………… 2 Section 3 Applications of Physical Chemistry to Medicine…………………………………… 3
Chapter 1 The First Law of Thermodynamics and Thermochemistry …………………5 Section 1 The Basic Concepts ………………………………………………………………… 6 1.1 System and surroundings …………………………………………………………………………6
1.2 Extensive and intensive properties ………………………………………………………………6 1.3 Equilibrium ………………………………………………………………………………………6 1.4 State and state function……………………………………………………………………………7 1.5 Process and path …………………………………………………………………………………8 1.6 Heat and work ……………………………………………………………………………………8 Section 2 Work and Process …………………………………………………………………… 9
2.1 The general expression for work …………………………………………………………………9 2.2 Free expansion ………………………………………………………………………………… 10
2.3 Expansion against constant pressure ………………………………………………………… 10 Section 3 Reversible Process …………………………………………………………………… 10 3.1 Reversible expansion…………………………………………………………………………… 10
3.2Isothermal reversible expansion ……………………………………………………………… 11
3.3Features of reversible processes ……………………………………………………………… 11
Section 4 The First Law of Thermodynamics and Thermodynamic Energy ………………… 12
4.1 Empirical expression of the first law of thermodynamics …………………………………… 12 4.2 Thermodynamic energy ……………………………………………………………………… 12
4.3 Mathematical equation of the first law of thermodynamics ………………………………… 13
Section 5 Enthalpy ……………………………………………………………………………… 14
5.1Special significance of heat in constant volume and constant pressure process……………… 14
5.2Definition and properties of enthalpy ………………………………………………………… 15 Section 6 Heat Capacity ………………………………………………………………………… 15 6.1 Definition of heat capacity …………………………………………………………………… 15
6.2Constant volume heat capacity and constant pressure heat capacity ………………………… 16
6.3Empirical equation of heat capacity …………………………………………………………… 18 Section 7 Application of the First law of Thermodynamics to Ideal Gas …………………… 18 7.1 Ideal gas………………………………………………………………………………………… 18
7.2 The relationship between Cp and CV of ideal gas ……………………………………………… 21 7.3 Joule experiment ……………………………………………………………………………… 22
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物理化学￤ Physical Chemistry
7.4 Isothermal process of ideal gas………………………………………………………………… 23
7.5 Adiabatic process of ideal gas ………………………………………………………………… 24
Section 8 Thermal Effects of Chemical Reaction ……………………………………………… 26
8.1 Relationship between reaction heat at constant volume and reaction heat at
constant pressure ……………………………………………………………………………… 27 8.2 Thermochemical equation …………………………………………………………………… 29
8.3 Hess’s Law……………………………………………………………………………………… 30 Section 9 Several Thermal Effects ……………………………………………………………… 31 9.1 Standard Heat of Formation …………………………………………………………………… 31 9.2 Standard Heat of Combustion ………………………………………………………………… 33 Section 10 The Relationship between Heat of Reaction and Temperature—— Kirchhoff’s Law …… 34
Chapter 2 The Second Law of Thermodynamics and Chemical Equilibrium ……… 39
Section 1 The Second Law of Thermodynamics ……………………………………………… 40
1.1Common characteristics of the spontaneous process——irreversibility …………………… 40
1.2Empirical description of the second law of thermodynamics………………………………… 41 Section 2 Carnot Cycle and Carnot Theorem……………………………………………………… 41 2.1 Carnot Engine ………………………………………………………………………………… 41 2.2 Carnot’s theorem ……………………………………………………………………………… 44 Section 3 Concept of Entropy——Entropy and Entropy Increase Principle ………………… 46
3.1Heat-temperature quotient of reversible cyclic processes and reversible processes——
entropy function ……………………………………………………………………………… 46
3.2Heat-temperature quotient of irreversible cyclic processes and irreversible processes ………… 47
3.3The principle of entropy increase ……………………………………………………………… 49 3.4 Entropy criterion ……………………………………………………………………………… 49 Section 4 Essence of the Second Law: Statistical Significance of Entropy …………………… 50
4.1Entropy and thermodynamic probability——Boltzmann formula…………………………… 50
4.2Essence of the second law of thermodynamics ……………………………………………… 51
Section 5 Calculation of Entropy Change……………………………………………………… 52
5.1Entropy change in the process of simple state change………………………………………… 52
5.2Entropy change of phase change ……………………………………………………………… 55 5.3 Calculation of molar entropy ………………………………………………………………… 56
5.4 The third law of thermodynamics …………………………………………………………… 57
Section 6 Helmholtz Function and Gibbs Function…………………………………………… 59
6.1 Helmholtz function (work function) ………………………………………………………… 59 6.2 Gibbs function (free energy) ………………………………………………………………… 60
6.3 Calculation of Gibbs function ………………………………………………………………… 61
Section 7 the Relationship between Thermodynamic State Functions …………………………… 64
7.1 Fundamental relations of thermodynamics…………………………………………………… 65 7.2 Maxwell relations ……………………………………………………………………………… 65 Section 8 Partial Molar Quantity and Chemical Potential …………………………………… 66
2 8.1 Partial molar quantity ………………………………………………………………………… 67
Contents ￤目录
8.2 Chemical potential …………………………………………………………………………… 68 8.3 Chemical potential of gas ……………………………………………………………………… 71
8.4 Chemical potential of solution components ………………………………………………… 72
Section 9 Application Examples of Chemical Potential ……………………………………… 75
9.1Colligative properties of dilute solution ……………………………………………………… 75
9.2Distribution law and its application …………………………………………………………… 78
Section 10 Chemical Equilibrium ……………………………………………………………… 80
10.1Direction and equilibrium conditions of chemical reaction ………………………………… 81
10.2Isothermal equation of chemical reaction …………………………………………………… 83
10.3Calculations of standard molar Gibbs function and equilibrium constant of reaction …… 84
10.4Effect of temperature on the chemical equilibrium constant ……………………………… 87
Chapter 3 Phase Equilibrium ………………………………………………………… 93
Section 1 Basic Concepts ……………………………………………………………………… 94
1.1 Phase …………………………………………………………………………………………… 94
1.2 Number of Independent Components………………………………………………………… 94 1.3 Degree of Freedom …………………………………………………………………………… 96 1.4 Phase Rule ……………………………………………………………………………………… 96 Section 2 One-Component System …………………………………………………………… 97 2.1 The p-T phase diagram for water ……………………………………………………………… 98 2.2 Clapeyron - Clausius equation …………………………………………………………………100 Section 3 Two-Component Gas-Liquid System …………………………………………… 101
3.1Two-component gas-liquid phase diagram of perfectly miscible ideal liquid mixture ………102
3.2Two-component gas-liquid phase diagram of perfectly miscible non-ideal liquid mixture ……105 3.3 The principle of rectification……………………………………………………………………107
3.4 Perfectly immiscible liquid system —— steam distillation ……………………………………109
Section 4 Two-Component Liquid-Liquid System with the Highest Critical Dissolution Temperature ……………………………………………………………………… 110
Section 5 Two-Component Solid-Liquid System for Forming a Simple Eutectic Mixture …… 111
5.1 Drawing the phase diagram by thermal analysis method ……………………………………111 5.2 Analysis of the phase diagram …………………………………………………………………112 5.3 Application of phase diagrams …………………………………………………………………113 Section 6 Three-Component System ………………………………………………………… 114
6.1Composition representation and characteristics of three-component system ………………114
6.2The phase diagram of partially miscible three-component system……………………………115
Chapter 4 Electrochemistry ……………………………………………………………123
Section 1 Conductivity of Electrolyte Solution …………………………………………… 124
1.1 Conducting mechanism of electrolyte solution ………………………………………………124 1.2 Faraday’s laws …………………………………………………………………………………125 Section 2 The Conductance of the Electrolyte Solution …………………………………… 126
2.1 Conductance of electrolytes ……………………………………………………………………126 3
物理化学￤ Physical Chemistry
2.2Conductivity measurement of electrolyte solution ……………………………………………127
2.3The relationship between κ and c or Λm and c …………………………………………… 128
2.4Law of the independent migration of ions——Kohlrausch’s Law ……………………………129 Section 3 Electromotive Force of Battery …………………………………………………… 131 3.1 Galvanic cell ……………………………………………………………………………………131 3.2 Reversible battery ………………………………………………………………………………132
3.3 Thermodynamics of reversible battery…………………………………………………………133 Section 4 Application of Conductivity Measurement ……………………………………… 134 4.1 Testing water purity ……………………………………………………………………………134
4.2Determination of ionization and ionization equilibrium constant of weak electrolyte ………134
4.3Determination of solubility of insoluble salts …………………………………………………135
Chapter 5 Chemical Kinetics……………………………………………………………142
Section 1 Basic Concepts …………………………………………………………………… 143
1.1 Representation of chemical reaction rate………………………………………………………143
1.2 Meaning of reaction mechanism ………………………………………………………………144 1.3 Law of mass action ……………………………………………………………………………145 Section 2 Effect of Concentration on Reaction Rate ……………………………………… 147
2.1Kinetic equation of first-order reaction and its characteristics ………………………………147
2.2Kinetic equation of second-order reaction and its characteristics……………………………… 151
2.3Kinetic equation of zero-order reaction and its characteristics ………………………………152 Section 3 Determination of Reaction Order………………………………………………… 153 3.1 Integral method…………………………………………………………………………………153 3.2 Differential method ……………………………………………………………………………155 Section 4 Complex Reactions ……………………………………………………………… 156 4.1 Reversible reaction ……………………………………………………………………………156 4.2 Parallel reaction…………………………………………………………………………………158 4.3 Consecutive reaction……………………………………………………………………………159 Section 5 Effect of Temperature on Reaction Rate ………………………………………… 161 5.1 Van’t Hoff’s rule of thumb ……………………………………………………………………161 5.2 The Arrhenius formula …………………………………………………………………………161 5.3 Concept of activation energy …………………………………………………………………164
5.4 Method to predict the storage time of drug……………………………………………………165
Section 6 Effect of Solvent on Reaction Rate ……………………………………………… 171
6.1Effect of solvent’s polarity and solvation ………………………………………………………168
6.2Effect of solvent’s dielectric constant …………………………………………………………169 6.3 Effect of ionic strength …………………………………………………………………………170 Section 7 Catalysis …………………………………………………………………………… 171
7.1 Basic characteristics of catalysis ………………………………………………………………171
7.2 Single-phase catalytic reaction …………………………………………………………………174
Section 8 Photochemical Reaction ………………………………………………………… 179
4 8.1 Mechanism of photochemical reaction ………………………………………………………179
Contents ￤目录
8.2 The law of photochemical equivalent …………………………………………………………180 8.3 Quantum efficiency ……………………………………………………………………………181
Chapter 6 Surface Phenomena …………………………………………………………186 Section 1 Specific Surface Area and Specific Surface Energy ……………………………… 187 1.1 Specific surface area ……………………………………………………………………………187
1.2 Specific surface Gibbs function ………………………………………………………………188 1.3 Surface tension …………………………………………………………………………………189
1.4 Thermodynamic criteria for studying surface phenomena……………………………………190 Section 2 Wetting and Spreading …………………………………………………………… 191 2.1 Wetting …………………………………………………………………………………………191 2.2 Spreading ………………………………………………………………………………………192 Section 3 Effect of High Dispersion on Physical Properties ……………………………… 193
3.1Additional pressure on curved liquid surface——Laplace Equation …………………………193
3.2Effect of high dispersion on vapor pressure……………………………………………………195
3.3Effect of high dispersion on solubility …………………………………………………………197 3.4 Metastable state…………………………………………………………………………………197 Section 4 Adsorption on the Surface of Solution …………………………………………… 199
4.1Adsorption phenomena on the surface of solution ……………………………………………199
4.2Gibbs adsorption isotherm formula and its application ………………………………………200 Section 5 Surfactants ………………………………………………………………………… 201 5.1 Classification of surfactants ……………………………………………………………………201
5.2The hydrophile-lipophile balance (HLB) value of surfactants ………………………………206
5.3Diverse applications of surfactants ……………………………………………………………208
Section 6 Absorption at the Solid-Gas Interface …………………………………………… 216
6.1Physisorption and chemisorption ……………………………………………………………216
6.2Soild-Gas surface absorption isotherms ………………………………………………………217
6.3Freundlich adsorption isotherm ………………………………………………………………218
6.4The monolayer absorption theory——the Langmuir adsorption isotherm …………………218
6.5Multilayer absorption theory——BET absorption isotherms …………………………………220 Section 7 Absorption at the Solid-Liquid Interface ………………………………………… 221 7.1 Absorption of molecules ………………………………………………………………………221 7.2 Absorption of ions ……………………………………………………………………………222 7.3 Solid absorbents ………………………………………………………………………………223
Chapter 7 Sol ……………………………………………………………………………228 Section 1 Introduction of Colloidal Chemistry …………………………………………… 228 Section 2 Dispersion System ………………………………………………………………… 229 2.1 Concept of dispersion system …………………………………………………………………229
2.2 Classification of dispersion system ……………………………………………………………229 2.3 Colloidal dispersion ……………………………………………………………………………230
Section 3 Types of Colloidal System and Characteristics of Sol …………………………… 230
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物理化学￤ Physical Chemistry
3.1 Types of colloidal system ………………………………………………………………………230
3.2 Characteristics of lyophilic and lyophobic sols ………………………………………………231 Section 4 Preparation and Purification of Sol ……………………………………………… 232 4.1 Preparation of sol ………………………………………………………………………………232 4.2 Purification of sol ………………………………………………………………………………234 Section 5 Optical Properties of Sol ………………………………………………………… 235 5.1 Tyndall effect……………………………………………………………………………………235
5.2 Ultramicroscope shows up the presence of individual particles………………………………236 5.3 Rayleigh Scattering Formula …………………………………………………………………237 5.4 Color of sol ……………………………………………………………………………………238 Section 6 Dynamic Properties of Sol………………………………………………………… 238 6.1 Brownian movement……………………………………………………………………………238 6.2 Diffusion ………………………………………………………………………………………239
6.3 Sedimentation and sedimentation equilibrium ………………………………………………240 Section 7 Electrical Properties of Sol ……………………………………………………… 241 7.1 Electric phenomenon …………………………………………………………………………241 7.2 Source of sol particle charge ……………………………………………………………………243
7.3 Electrical double layer theory …………………………………………………………………245
7.4 Structure of colloidal micelle …………………………………………………………………246 Section 8 Stability and Condensation of Sol………………………………………………… 247 8.1 Stability of sol …………………………………………………………………………………247
8.2 Coagulation or precipitation of sol ……………………………………………………………248
Chapter 8 Macromolecular Solution ……………………………………………… 253
Section 1 Structure of Macromolecular Compound ……………………………………… 254
1.1Structural characteristics of macromolecular compound ……………………………………254
1.2Average relative molecular mass of macromolecular compound ……………………………255
1.3Basic properties of macromolecular solution …………………………………………………256
Section 2 Macromolecular Electrolyte Solution …………………………………………… 257
2.1Significance of macromolecular electrolyte ……………………………………………………257
2.2Electrical properties of macromolecular electrolyte solution …………………………………257
2.3Stability of macromolecular electrolyte solution ………………………………………………258
2.4Buffering properties of protein…………………………………………………………………258
2.5Interaction of macromolecular electrolytes ……………………………………………………259
Section 3 Osmotic Pressure of Macromolecular Solution ………………………………… 259
3.1Abnormal osmotic pressure of macromolecular solution ……………………………………259
3.2Determination of average relative molecular mass of macromolecules by osmotic pressure ……261 3.3 Donnan membrane balance ……………………………………………………………………261 Section 4 Viscosity of Macromolecular Solution ………………………………………… 263
4.1Meaning and determination method of viscosity ……………………………………………263
4.2Viscosity of macromolecular solution …………………………………………………………264
6 4.3 Viscosity of macromolecular electrolyte solution ……………………………………………265
Contents ￤目录
Section 5 Gel ………………………………………………………………………………… 266
5.1 Formation of gel ………………………………………………………………………………266
5.2 Structure of gel …………………………………………………………………………………266
5.3Gelation and influencing factors ………………………………………………………………267
5.4Swelling and influencing factors of dry glue …………………………………………………267 5.5 Syneresis and thixotropy ………………………………………………………………………267
Appendix ( 附录 ) ……………………………………………………………………… 270 参考文献………………………………………………………………………………… 274
