物化上双语课件final review12

1、 ：华东理工大学物理化学教研室Physical ChemistryYing Hu(Fifth edition)Bilingual ProgramFramework of the Chapter7.1 IntroductionI. Fundamental Principles of Chemical Kinetics 7.2 Rates of Chemical Reactions7.3 Reaction-Rate Equations7.4 Integrated Reaction-Rate Equations 7.5 Opposite Reactions7.6 Consecutive Reacti

2、ons7.7 Parallel Reactions7.8 Effect of Temperature on Reaction RatesII. Characteristic Parameters in Chemical Kinetics7.9 Experimental Methods in Chemical Kinetics7.10 Data Processing in Chemical Kinetics7.11 Experimental Methods for Rapid Reactions7.12 Semi-Empirical MethodsIII. Reaction Mechanisms

3、7.13 Reaction Mechanisms and Rate Equations7.14 Mono-Molecular Reactions7.15 Principles of Microscopic Reversibility and Detailed Equilibrium 7. Chemical KineticsIn which, k is Rate Coefficient, For a reaction The rate equation is, , , are Partial Orders, the extents of influence of the substances o

4、n the reaction rate. They could be positive and negative, integers or non-integers. The reaction rate is defined as:OrderRate equationCharacteristics Differential Integrated Linear plottingkA Dimension Half life t1/2012aAbB PFor the first order opposite reactionswhen cB = xe, cA=cA0 xe, the integrat

5、ed rate equation isk1, k-1 Plots lgxex against t showing a straight line, from the slope of the line, we can calculate k1+k1. Equilibrium Constant Kck1, k-1 Plots lgxex against t showing a straight line, from the slope of the line, we can calculate k1+k1. For the first order consecutive reactions Ra

6、te Equations Integrated Rate Equations For a parallel reaction with the same reaction orders, The ratio of the product concentrations is the same as the ratio of the reaction constantsArrhenius Equation The temperature dependence for the reaction rate.Activation energy Ea is a constantThe assumption

7、 of a Pre-Equilibrium ApproximationThe reaction rate is determined by the controlling step of the intermediate to the product. Meanwhile, the elementary reaction of the reactant to the intermediate almost reaches equilibrium. The assumption of a Steady State ApproximationThe intermediate concentrati

8、ons can be considered as unchanged with time, and very low 12.1 IntroductionI. Principles of Statistical Mechanics12.2 Description of Microscopic States12.3 Fundamental Postulates of Statistical Mechanics 12.4 The Most Probable DistributionII. Statistical Distributions of Independent-Particle System

9、s12.5 Maxwell-Boltzmann Distribution12.6 Molecular Partition FunctionIII. Thermodynamic Properties of Independent-Particle Systems12.7 Thermodynamic Functions of Independent-Particle Systems12.8 Standard Molar Heat Capacity of Gases12.9 Heat Capacity of Crystals12.10 Standard Molar Entropy of Gases1

10、2.11 Standard Equilibrium Constant of Gaseous Reactions Framework of the Chapter12.1 Introduction Dependent-Particle SystemIndependent-Particle SystemNon-Localized-Particle SystemLocalized-Particle SystemMacroscopic systems composed of a large number of microscopic particles. Classification of Molec

11、ular MovementsTranslational motions tRotation motions r , Vibration motions, v Electrons motions, eNuclear motions. n Degenerate energy level, quantum states have the same energy, Degeneracy, the number of these quantum states. Energy-Level SpacingFor a macroscopic state, it is possible to have vari

12、ous distributions (configurations). Each distribution contains a certain number of microscopic states. A macroscopic state covers a fixed number of microscopic states. Thermodynamic Probability Maximum-Term Method Fundamental Postulates of Statistical Mechanics Classification of Molecular MovementsT

13、ranslational motions tRotational motions r Vibrational motions, v k, Boltzmann constant, 13.806581024JK1 Degenerate energy level, quantum states have the same energy, Degeneracy, the number of these quantum states. Energy-Level Spacing (mV1.5) -1 I -1 Diatomic moleculesMulti-atom moleculesLinear Mul

14、ti-atom moleculesTranslational (x, y, z) of the center of mass333Rotational (three axes)232Vibrational13n-63n-5 Degree of Freedom of Motion 3n degrees of freedom of motionConservation of particle Constraints Conservation of energy For a macroscopic state, it is possible to have various distributions

15、 (configurations). Each distribution contains a certain number of microscopic states. A macroscopic state covers a fixed number of microscopic states. Thermodynamic Probability The Most Probable Distribution Boltzmann Relation Maxwell-Boltzmann Distribution The lower the energy lever and the larger

16、Boltzmann factor, the larger the degeneracy, the higher probability of finding particles in that energy level will be. molecular partition function 2. Factorial Characteristics of the Molecular Partition Functions qt qr qv Translation Rotation VibrationEnergy levelPartition functionCharacteristics12

17、.6 Molecular Partition FunctionRotational temperature Symmetry number Vibrational temperature Energy Equipartition Theorem If the temperature is high enough15.1 Introduction15.2 Interfacial Tension and Interfacial ExcessI. Thermodynamics of Interfaces15.3 Fundamental Equations and Equilibrium Condit

18、ions15.4 Laplace Equation15.5 Kelvin Equation15.6 Gibbs Isotherm15.7 WettingII. Characteristic Properties of Interfacial Equilibria15.8 Vapor-Liquid Interface and Liquid-Liquid Interface15.9 Surfactants and Surface Films15.10 Adsorptions on Solid Surface15.11 Semi-Empirical and Theoretical Methods f

19、or Gas-Solid AdsorptionsIII. Rate Processes in Interfaces15.12Dynamic Interfacial Tension15.13Chemical Reactions in Surface Membranes15.14Heterogeneous Catalysis15.15Heterogeneous Catalytic KineticsFramework of the Chaptergeneralized displacement.As, the interfacial area, the interfacial tensiongene

20、ralized forceThe interfacial tension decreases with temperature. Unit Interfacial Excesssolute i is enriched in the interfacial layersolute i is repelled in the interfacial layer Positive adsorption Negative adsorptionKelvin equationLaplace equation Capillary Rise or Depression Gibbs IsothermFor a b

21、inary system For dilute solutions, c2ACBWetting Spreading CoefficientWhen Wa Wc, is positive, G is correspondingly negative, spreading can then happen. When is negative, G is positive, spreading could not happen, Youngs Equationadhesive wettingnon-wettingContact angle is the angle between vectors g,

22、l and l,s. Surface Coverage def is the saturated amount of adsorption when covered with a monomolecular layer. Physical Adsorption and Chemical Adsorption Physisorption Van der Waals interaction Non-selectivityMonolayer or multilayerReversibleChemisorption Chemical bondSelectivityMonolayer Irreversi

23、bleLangmuir Adsorption Isotherm For a monomolecular layer adsorption Framework of the Chapter16.1 IntroductionI. Equilibrium Properties of Electrolyte. 16.2 Activities of Electrolyte Solutions16.3 Theories and Semi-Empirical Methods 16.4 Applications II. Transport Properties of Electrolyte Solutions

24、 16.5 Mechanism of Electric Conductance of Electrolyte Solutions 16.6 Mobility and Transference Number of Ions 16.7 Electric Conductivity 16.8 Other Applications of Electric Conductance 16.9 Diffusion in Electrolyte Solutions16.10 Theoretical and Semi-Empirical Methods III. Reaction-Rate Properties

25、of Electrolyte Solutions16.11 Ionic Reaction in Solution16. Electrolyte Solutions Activity aB of Electrolyte as a Whole Mean Ionic Activity For First-Kind Electrolyte SolutionsFor very dilute solution Debye-Hckel Equation of Activity Factor Ionic Strength 16.5 Mechanism of Electric Conductance of El

26、ectrolyte SolutionsFaradays Law MobilityTransference numberConductivity 16.7 Electric Conductivity Electric ConductivityMolar Electric Conductivity the molar electric conductivity at infinite dilution, is m when the concentration approaches zero. Kohlrausch Relation For the dilute solution of strong

27、 electrolytes Relation between Molar Electric Conductivity and MobilityDissociation Constant of weak electrolytes For very dilute solutions, the ionic molar conductivity is determined by the solvent, the temperature and the nature of the ion, irrelevant to other ions in solution.3. Ionic Molar (Elec

28、tric) Conductivity Definition Independent Migration Law of Ions Degree of Dissociation and Dissociation Constant of Weak Electrolytes 16.8 Other Applications of Electric Conductance(2) Solubility and Solubility Product of Sparingly Soluble Salts c is very smallSolubilitySolubility ProductFor the 1-1

29、 type sparingly soluble salt 17.1 IntroductionI. Electrochemical Equilibria 17.2 Electromotive Force of Galvanic Cell and Interfacial Potential Difference17.3 Thermodynamics of Electrochemical Systems 17.4 Potential and Standard Potential of Cell Reaction 17.5 Potential and Standard Potential of Ele

30、ctrode Reaction 17.6 Various Types of Electrodes and Standard Cell 17.7 Electrochemical-Equilibrium Calculations 17.8 Concentration Cell and Liquid-Junction Potential II. Theories of Electrode-Solution Interface 17.9 Outer Potential, Surface Potential and Inner Potential17.10 Surface Excess Charge a

31、nd Double-Layer Capacitance17.11 Electric Double-Layer Models and Outer Potential17.12 Absolute Potential of Electrode Reaction III. Electrochemical Kinetics17.13Relations among Reaction Rate, Current and Potential17.14Polarization Phenomena and Over-Potential17.15Examples of Application17.16Transit

32、ion-State Theory of Electrode Reactions17. Electrochemistry galvanic cellelectrolytic cellspontaneous reactionNonspontaneous reactionRedox reactionOxidationReductionAnodeCathodeHalf reaction: Ox + e- Red C+A-C-A+17.1 Introduction17.1 IntroductionThe difference between electrochemical reactions and ordinary reactions (1) Electrochemical reactions are carried out in cells panied by a charge flow (2) Thermodynamic Characteristics of Electrochemical Reactions (3) Kinetic Characteristics of Electrochemical ReactionsReaction rates are strongly affected by the i