物理化学是高等院校药学类、医学类各专业的基础课，是继无机化学、有机化学、分析化学 课程后开设的重要理论化学课程，是培养药学类、医学类各专业人才知识结构与能力素质的重要 组成部分。通过本课程的教学，使学生能比较系统地掌握物理化学的基本原理、基本概念、基本 定律，熟悉或了解其在药学、医学等专业方面的应用，为后续相关专业课程的学习打好基础，并 使学生得到一般科学方法的训练以及逻辑思维能力、知识应用能力和实验技能的提高，能够运用 物理化学的原理、方法指导医药研究、生产。目前国内物理化学双语教材很少，主要适用于化工 专业，内容与医药学类院校适用的教学大纲不太相符。因此，基于高等院校双语教学的趋势，以 及中外合作办学专业的发展，迫切需要出版一本适合医药学类专业的双语教材。
    本教材根据药学类、医学类专业本科生的培养目标及特点，本着系统和重点相结合的原则， 以教材大纲为基本框架，对大纲所要求的基本理论作简明清晰的阐述，各章节联系逻辑紧密，与 医药的应用有机结合，是一本带有“药味”的教材。本教材的编写以英文为主，在必要的专业 词汇处标注中文。教材各章编写模块包括：学习目标、正文、重点小结、目标检测、参考答案。 本教材英文专业术语的表达，主要参考了《中华人民共和国药典》2015 年版英文版，同时也参 考了其他英文版教材及论文要求。双语形式有助于学生掌握英语专业词汇和提升英语阅读能力， 为以后论文撰写奠定基础，另一方面也有利于提升参与对外交流与合作的能力。
    本教材主要分为 8 章，内容包括热力学第一定律与热化学、热力学第二定律与化学平衡、相 平衡、电化学、化学动力学、表面现象、溶胶、大分子溶液。本教材力求简单明了，全面准确地 阐述了物理化学的基本概念、基本原理、重要定律及其应用，以满足药学、医学类各专业学生对 物理化学课程教学的要求。本教材可供中药学类、药学类及相关专业学生使用。
    本教材的编写工作分工：绪论及第一章，邵江娟、姚薇薇、林舒；第二章，李晓飞、钱坤； 第三章，冯玉、曹姣仙；第四章，赵晓娟、刘强；第五章，申蕊、黄宏妙；第六章，张明波、韩 宁；第七章，张彩云、何玉珍；第八章，张洪江、刘靖丽；附录，邵江娟。
    在编写修订过程中得到参编院校领导和各位同行的大力支持，在此表示衷心的感谢！由于编 者知识水平所限，不足之处在所难免，敬请各校师生在使用过程中，予以指正。

本书是全国高等医药院校中药学专业双语规划教材，根据本学科教学大纲的基本要求和课程特点编写而成。体现高等院校中药学专业培养的特点，着力提高药学类专业学生的实践操作能力。坚持理论知识“必需、够用”为度。强调教材的针对性、实用性、条理性和先进性，既注重对学生基本技能的培养，又适当拓展知识面，实现职业教育与终身学习的对接，为学生后续发展奠定必要的基础。本书供中药学类专业师生使用。

目录￤ Contents \t


Introduction …………………………………………………………………………………1 Section 1\tResearch Objects, Methods and Contents of Physical Chemistry ………………… 1 Section 2\tLearning Methods of Physical Chemistry\t………………………………………… 2 Section 3\tApplications of Physical Chemistry to Medicine…………………………………… 3

Chapter 1\tThe First Law of Thermodynamics and Thermochemistry …………………5 Section 1\tThe Basic Concepts\t………………………………………………………………… 6 1.1\tSystem and surroundings …………………………………………………………………………6
  1.2\tExtensive and intensive properties ………………………………………………………………6 1.3\tEquilibrium ………………………………………………………………………………………6 1.4\tState and state function……………………………………………………………………………7 1.5\tProcess and path …………………………………………………………………………………8 1.6\tHeat and work ……………………………………………………………………………………8 Section 2\tWork and Process …………………………………………………………………… 9
2.1\tThe general expression for work …………………………………………………………………9 2.2\tFree expansion ………………………………………………………………………………… 10
  2.3\tExpansion against constant pressure ………………………………………………………… 10 Section 3\tReversible Process …………………………………………………………………… 10 3.1\tReversible expansion…………………………………………………………………………… 10
3.2Isothermal reversible expansion ……………………………………………………………… 11
3.3Features of reversible processes ……………………………………………………………… 11
Section 4\tThe First Law of Thermodynamics and Thermodynamic Energy ………………… 12
4.1\tEmpirical expression of the first law of thermodynamics …………………………………… 12 4.2\tThermodynamic energy ……………………………………………………………………… 12
4.3\tMathematical equation of the first law of thermodynamics ………………………………… 13
Section 5\tEnthalpy ……………………………………………………………………………… 14
  5.1Special significance of heat in constant volume and constant pressure process……………… 14
  5.2Definition and properties of enthalpy ………………………………………………………… 15 Section 6\tHeat Capacity ………………………………………………………………………… 15 6.1\tDefinition of heat capacity …………………………………………………………………… 15
  6.2Constant volume heat capacity and constant pressure heat capacity ………………………… 16
  6.3Empirical equation of heat capacity …………………………………………………………… 18 Section 7\tApplication of the First law of Thermodynamics to Ideal Gas …………………… 18 7.1\tIdeal gas………………………………………………………………………………………… 18
7.2\tThe relationship between Cp and CV of ideal gas ……………………………………………… 21 7.3\tJoule experiment ……………………………………………………………………………… 22

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物理化学￤ Physical Chemistry

7.4\tIsothermal process of ideal gas………………………………………………………………… 23
7.5\tAdiabatic process of ideal gas ………………………………………………………………… 24
Section 8\tThermal Effects of Chemical Reaction ……………………………………………… 26
8.1\tRelationship between reaction heat at constant volume and reaction heat at
    constant pressure ……………………………………………………………………………… 27 8.2\tThermochemical equation …………………………………………………………………… 29
  8.3\tHess’s Law……………………………………………………………………………………… 30 Section 9\tSeveral Thermal Effects ……………………………………………………………… 31 9.1\tStandard Heat of Formation …………………………………………………………………… 31 9.2\tStandard Heat of Combustion ………………………………………………………………… 33 Section 10\tThe Relationship between Heat of Reaction and Temperature—— Kirchhoff’s Law …… 34

Chapter 2\tThe Second Law of Thermodynamics and Chemical Equilibrium ……… 39
Section 1\tThe 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\tCarnot Cycle and Carnot Theorem……………………………………………………… 41 2.1\tCarnot Engine ………………………………………………………………………………… 41 2.2\tCarnot’s theorem ……………………………………………………………………………… 44 Section 3\tConcept 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\tEntropy criterion ……………………………………………………………………………… 49 Section 4\tEssence 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\tCalculation of Entropy Change……………………………………………………… 52
5.1Entropy change in the process of simple state change………………………………………… 52
5.2Entropy change of phase change ……………………………………………………………… 55 5.3\tCalculation of molar entropy ………………………………………………………………… 56
5.4\tThe third law of thermodynamics …………………………………………………………… 57
Section 6\tHelmholtz Function and Gibbs Function…………………………………………… 59
6.1\tHelmholtz function (work function) ………………………………………………………… 59 6.2\tGibbs function (free energy) ………………………………………………………………… 60
6.3\tCalculation of Gibbs function ………………………………………………………………… 61
Section 7\tthe Relationship between Thermodynamic State Functions …………………………… 64
  7.1\tFundamental relations of thermodynamics…………………………………………………… 65 7.2\tMaxwell relations ……………………………………………………………………………… 65 Section 8\tPartial Molar Quantity and Chemical Potential …………………………………… 66
2\t8.1\tPartial molar quantity ………………………………………………………………………… 67




Contents ￤目录


8.2\tChemical potential …………………………………………………………………………… 68 8.3\tChemical potential of gas ……………………………………………………………………… 71
8.4\tChemical potential of solution components ………………………………………………… 72
Section 9\tApplication Examples of Chemical Potential ……………………………………… 75
9.1Colligative properties of dilute solution ……………………………………………………… 75
9.2Distribution law and its application …………………………………………………………… 78
Section 10\tChemical 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\tPhase Equilibrium ………………………………………………………… 93
Section 1\tBasic Concepts ……………………………………………………………………… 94
1.1\tPhase …………………………………………………………………………………………… 94
  1.2\tNumber of Independent Components………………………………………………………… 94 1.3\tDegree of Freedom …………………………………………………………………………… 96 1.4\tPhase Rule ……………………………………………………………………………………… 96 Section 2\tOne-Component System …………………………………………………………… 97 2.1\tThe p-T phase diagram for water ……………………………………………………………… 98 2.2\tClapeyron - Clausius equation …………………………………………………………………100 Section 3\tTwo-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\tThe principle of rectification……………………………………………………………………107
3.4\tPerfectly immiscible liquid system —— steam distillation ……………………………………109
Section 4\tTwo-Component Liquid-Liquid System with the Highest Critical Dissolution Temperature ……………………………………………………………………… 110
Section 5\tTwo-Component Solid-Liquid System for Forming a Simple Eutectic Mixture …… 111
  5.1\tDrawing the phase diagram by thermal analysis method ……………………………………111 5.2\tAnalysis of the phase diagram …………………………………………………………………112 5.3\tApplication of phase diagrams …………………………………………………………………113 Section 6\tThree-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\tElectrochemistry ……………………………………………………………123
Section 1\tConductivity of Electrolyte Solution\t…………………………………………… 124
  1.1\tConducting mechanism of electrolyte solution ………………………………………………124 1.2\tFaraday’s laws …………………………………………………………………………………125 Section 2\tThe Conductance of the Electrolyte Solution …………………………………… 126
2.1\tConductance of electrolytes ……………………………………………………………………126\t3




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\tElectromotive Force of Battery …………………………………………………… 131 3.1\tGalvanic cell ……………………………………………………………………………………131 3.2\tReversible battery ………………………………………………………………………………132
  3.3\tThermodynamics of reversible battery…………………………………………………………133 Section 4\tApplication of Conductivity Measurement ……………………………………… 134 4.1\tTesting 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\tChemical Kinetics……………………………………………………………142
Section 1\tBasic Concepts …………………………………………………………………… 143
1.1\tRepresentation of chemical reaction rate………………………………………………………143
  1.2\tMeaning of reaction mechanism ………………………………………………………………144 1.3\tLaw of mass action ……………………………………………………………………………145 Section 2\tEffect 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\tDetermination of Reaction Order………………………………………………… 153 3.1\tIntegral method…………………………………………………………………………………153 3.2\tDifferential method ……………………………………………………………………………155 Section 4\tComplex Reactions\t……………………………………………………………… 156 4.1\tReversible reaction ……………………………………………………………………………156 4.2\tParallel reaction…………………………………………………………………………………158 4.3\tConsecutive reaction……………………………………………………………………………159 Section 5\tEffect of Temperature on Reaction Rate ………………………………………… 161 5.1\tVan’t Hoff’s rule of thumb ……………………………………………………………………161 5.2\tThe Arrhenius formula …………………………………………………………………………161 5.3\tConcept of activation energy …………………………………………………………………164
5.4\tMethod to predict the storage time of drug……………………………………………………165
Section 6\tEffect 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\tEffect of ionic strength …………………………………………………………………………170 Section 7\tCatalysis …………………………………………………………………………… 171
7.1\tBasic characteristics of catalysis ………………………………………………………………171
7.2\tSingle-phase catalytic reaction …………………………………………………………………174
Section 8\tPhotochemical Reaction ………………………………………………………… 179
4\t8.1\tMechanism of photochemical reaction ………………………………………………………179




Contents ￤目录


    8.2\tThe law of photochemical equivalent …………………………………………………………180 8.3\tQuantum efficiency ……………………………………………………………………………181

Chapter 6\tSurface Phenomena …………………………………………………………186 Section 1\tSpecific Surface Area and Specific Surface Energy ……………………………… 187 1.1\tSpecific surface area ……………………………………………………………………………187
1.2\tSpecific surface Gibbs function ………………………………………………………………188 1.3\tSurface tension …………………………………………………………………………………189
  1.4\tThermodynamic criteria for studying surface phenomena……………………………………190 Section 2\tWetting and Spreading …………………………………………………………… 191 2.1\tWetting …………………………………………………………………………………………191 2.2\tSpreading ………………………………………………………………………………………192 Section 3\tEffect 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\tMetastable state…………………………………………………………………………………197 Section 4\tAdsorption 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\tSurfactants ………………………………………………………………………… 201 5.1\tClassification of surfactants ……………………………………………………………………201
5.2The hydrophile-lipophile balance (HLB) value of surfactants ………………………………206
5.3Diverse applications of surfactants ……………………………………………………………208
Section 6\tAbsorption 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\tAbsorption at the Solid-Liquid Interface ………………………………………… 221 7.1\tAbsorption of molecules ………………………………………………………………………221 7.2\tAbsorption of ions ……………………………………………………………………………222 7.3\tSolid absorbents ………………………………………………………………………………223

Chapter 7\tSol ……………………………………………………………………………228 Section 1\tIntroduction of Colloidal Chemistry …………………………………………… 228 Section 2\tDispersion System ………………………………………………………………… 229 2.1\tConcept of dispersion system …………………………………………………………………229
  2.2\tClassification of dispersion system ……………………………………………………………229 2.3\tColloidal dispersion ……………………………………………………………………………230
Section 3\tTypes of Colloidal System and Characteristics of Sol …………………………… 230
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物理化学￤ Physical Chemistry

3.1\tTypes of colloidal system ………………………………………………………………………230
  3.2\tCharacteristics of lyophilic and lyophobic sols ………………………………………………231 Section 4\tPreparation and Purification of Sol ……………………………………………… 232 4.1\tPreparation of sol ………………………………………………………………………………232 4.2\tPurification of sol ………………………………………………………………………………234 Section 5\tOptical Properties of Sol ………………………………………………………… 235 5.1\tTyndall effect……………………………………………………………………………………235
  5.2\tUltramicroscope shows up the presence of individual particles………………………………236 5.3\tRayleigh Scattering Formula …………………………………………………………………237 5.4\tColor of sol ……………………………………………………………………………………238 Section 6\tDynamic Properties of Sol………………………………………………………… 238 6.1\tBrownian movement……………………………………………………………………………238 6.2\tDiffusion ………………………………………………………………………………………239
  6.3\tSedimentation and sedimentation equilibrium ………………………………………………240 Section 7\tElectrical Properties of Sol\t……………………………………………………… 241 7.1\tElectric phenomenon …………………………………………………………………………241 7.2\tSource of sol particle charge ……………………………………………………………………243
7.3\tElectrical double layer theory …………………………………………………………………245
  7.4\tStructure of colloidal micelle …………………………………………………………………246 Section 8\tStability and Condensation of Sol………………………………………………… 247 8.1\tStability of sol …………………………………………………………………………………247
8.2\tCoagulation or precipitation of sol ……………………………………………………………248

Chapter 8\tMacromolecular Solution\t……………………………………………… 253
Section 1\tStructure 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\tMacromolecular 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\tOsmotic 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\tDonnan membrane balance ……………………………………………………………………261 Section 4\tViscosity of Macromolecular Solution ………………………………………… 263
4.1Meaning and determination method of viscosity ……………………………………………263
4.2Viscosity of macromolecular solution …………………………………………………………264
6\t4.3\tViscosity of macromolecular electrolyte solution ……………………………………………265




Contents ￤目录


Section 5\tGel ………………………………………………………………………………… 266
5.1\tFormation of gel ………………………………………………………………………………266
5.2\tStructure of gel …………………………………………………………………………………266
    5.3Gelation and influencing factors ………………………………………………………………267
    5.4Swelling and influencing factors of dry glue …………………………………………………267 5.5\tSyneresis and thixotropy ………………………………………………………………………267
Appendix ( 附录 ) ……………………………………………………………………… 270 参考文献………………………………………………………………………………… 274