Review the reference materials (Physical Chemistry (4th Edition) edited by the Physical Chemistry Teaching and Research Section of Tianjin University, Volume I and Volume II).
Postgraduate Entrance Examination for Graduate School of China Academy of Sciences
Physical Chemistry Examination Syllabus (B)
This "Physical Chemistry" (B) examination outline is applicable to the entrance examination for graduate students majoring in chemical engineering in the Graduate School of China Academy of Sciences. Physical chemistry is an important branch of chemistry and the theoretical basis of the whole chemistry and chemical engineering. It explores the basic laws of chemical changes from the relationship between physical phenomena and chemical phenomena of substances. The main contents of physical chemistry course include chemical thermodynamics (statistical thermodynamics), chemical kinetics, electrochemistry, interface chemistry and colloid chemistry. Candidates are required to master the basic concepts, principles and calculation methods of physical chemistry, and have the ability to comprehensively apply the knowledge they have learned to analyze and solve practical problems.
First, the content of the exam
(A) the PVT relationship of gas
1, ideal gas state equation
2. Ideal gas mixture
3. Liquefaction and critical parameters of gas
4. Equation of State of Real Gas
5. Correspondence state principle and generalized compressibility factor graph.
(2) The first law of thermodynamics
1, the basic concept of thermodynamics
2, the first law of thermodynamics
3. Constant volume heat, constant pressure heat and enthalpy
4, heat capacity, constant volume temperature change process, constant pressure temperature change process
5. Joule experiment, thermodynamic energy and enthalpy of ideal gas.
6, gas reversible expansion and compression process
7. Phase change process
8. Enthalpy of solution and enthalpy of mixing
9. Stoichiometric number, reaction progress and standard molar reaction enthalpy
10, and calculate the standard molar reaction enthalpy from the standard molar formation enthalpy and the standard molar combustion enthalpy.
1 1, throttling expansion and Joule-Thomson effect
12, the first law of thermodynamics in steady flow process and its application
(3) the second law of thermodynamics
1, Carnot cycle
2, the second law of thermodynamics
3. Entropy and entropy increasing principle
4. Calculation of entropy change of simple pVT change
5. Calculation of entropy change during phase transition.
6. The third law of thermodynamics and the calculation of entropy change in the process of chemical change
7. Helmholtz function and Gibbs function
8. Basic equations of thermodynamics
9. Clapeyron equation
10, Gibbs-Helmholtz equation and Maxwell relation
(4) Thermodynamics of multicomponent systems
1, partial molar quantity
2. Chemical site
3. Chemical potential of gas components
4. Raoul Law and Henry Law
5. Ideal liquid mixture
6. Ideal dilute solution
7. Dependence of dilute solution
8, fugacity and fugacity factor
9. Activity and active factors
(5) chemical equilibrium
1, isothermal equation of chemical reaction
2. Standard equilibrium constant of ideal gas chemical reaction
3. Influence of temperature on standard equilibrium constant
4. The influence of other factors on the chemical equilibrium of ideal gas.
Influence of pressure on equilibrium conversion rate; Effect of inert components on equilibrium conversion; Friction of reactants
5. Chemical equilibrium of real gas reaction
6. Chemical leveling in mixtures and solutions
(6) phase equilibrium
1, phase law
2. Lever rule
3. Phase diagram of one-component system
4. Vapor-liquid equilibrium phase diagram of binary ideal liquid mixture
5. Gas-liquid equilibrium phase diagram of two-component real liquid mixture
6. Gas-liquid equilibrium phase diagrams of two-component liquid partially miscible system and completely miscible system.
7. Liquid-solid street phase diagram of two-component solid immiscible system
8. Liquid-solid equilibrium phase diagram of two-component solid-state miscible system
9. Phase diagram of binary condensation system of generated compound
10, liquid-liquid equilibrium phase diagram of three-component system.
(7) electrochemistry
1, conductive mechanism of electrolyte solution and Faraday's law
2. Ion migration number
3. Conductivity, Conductivity and Molar Conductivity
4. Average ionic activity factor of electrolyte
5. Determination of reversible battery and electromotive force.
6. Thermodynamics of galvanic cells
7. Electrode potential and liquid junction potential
8. Electrode type
9. Design example of primary battery
10, decomposition voltage
1 1, polarization
12, electrode reaction during electrolysis
(viii) Preliminary statistical thermodynamics
1, the energy levels of various motion forms of particles and the degeneracy of energy levels.
2. The number of microstates of the energy level distribution and the total microstates of the system.
3. Most probable distribution and balanced distribution
4. Maxwell Boltzmann distribution
5. Calculation of particle partition function
6. The relationship between thermodynamic energy and system partition function.
7. Relationship between molar constant volume heat capacity and partition function of the system.
8. The relationship between entropy and system partition function.
9. Relationship between other thermodynamic functions and partition functions
10, the standard equilibrium constant of ideal gas reaction
(9) Interface phenomenon
1, interfacial tension
2. Additional pressure of curved liquid surface and its consequences
3. Solid surface
4. Liquid-solid interface
5, solution surface
chemical kinetics
1, reaction rate and rate equation of chemical reaction
2. The integral form of the rate equation
3. Determination of rate equation
4. Effect of temperature on reaction rate
5. Typical compound reactions
6. Approximate treatment method of compound reaction rate
7. Chain reaction
8. Collision theory of gas reaction
9. Potential energy surface and transition state theory
10, reaction in solution
1 1, heterogeneous reaction
12, photochemistry
13, universality of catalysis
14, single-phase catalytic reaction
15, heterogeneous catalytic reaction
(1 1) colloid chemistry
1, Preparation of Colloidal System
2. Optical properties of colloidal system
3. Dynamic characteristics of limb system
4. Electrical properties of sol system
5. Sol stability and aggregation
Step 6 pause
7. Emulsion
8. Foam
9.aerosol
10, osmotic pressure and viscosity of polymer compound solution
Second, the examination requirements
(A) the PVT relationship of gas
Master the equation of state of ideal gas and the properties of mixed gas (Dalton's law of partial pressure and Ahmad's law of extra volume). Understand the equation of state of real gas (Van der Waals equation). Understand the liquefaction and critical properties of actual gases. Understand the corresponding state principle and compression factor diagram.
(2) The first law of thermodynamics
Explain some basic concepts of thermodynamics, such as system, environment, state, work, heat, change process, etc. Master the first law of thermodynamics and the concept of internal energy. Familiar with work and thermal signs and signs convention. The significance and characteristics of quasi-static process and reversible process are expounded. It is clear that both u and h are state functions and are characteristics of state functions. Skillfully apply the first law of thermodynamics to calculate δ U, δ H, Q and W of ideal gas in isothermal, isobaric and adiabatic processes. Can skillfully use the heat of formation and combustion to calculate the heat of reaction. Gus's law and Kirchhoff's law will be applied to a series of calculations. Understand the meaning of Carnot cycle.
(3) the second law of thermodynamics
Explain the significance of the second law of thermodynamics and its relationship with Carnot's theorem. The importance of understanding clausius inequality. Pay attention to the logical reasoning of formula derivation in the process of entropy function derivation. Memorize the definitions of thermodynamic functions U, H, S, F and G, make clear their physical meanings under special conditions, and how to use them to judge the direction of process change and equilibrium conditions. Using Gibbs-Helmholtz formula and Clausius-krabbe Dragon equation skillfully. Grasp the statistical significance of entropy. Understand the third law of thermodynamics, and make clear the meaning, calculation and application of prescribed entropy.
(4) Thermodynamics of multicomponent systems
Familiar with various expressions of solution concentration and their relationships. Master the definition, essence and universality of ideal solution. Master Raul's Law and Henry's Law. Understand the concepts of fugacity and activity, and how to calculate fugacity coefficient of gas with Newton diagram. Make clear the meaning of partial molar quantity and chemical potential. Master the expression method of chemical potential of each component in solution. Understand the derivation of exponential formula and distribution formula of dilute solution and the general method of thermodynamic treatment of solution problems.
(5) chemical equilibrium
Master the application of reaction isothermal formula. Master the expressions of equilibrium constants of homogeneous and heterogeneous reactions. Understand the meaning of δ RGM0 and estimate the possibility of reaction from δ RGM0. Familiar with the meaning, unit and relationship of KP0, KP, KX and KC. Understand the relationship between equilibrium constant and temperature and pressure, and the influence of inert gas on equilibrium composition, and master its calculation method. The equilibrium constant can be calculated according to the data of standard thermodynamic function. Understand simultaneous equilibrium, reaction coupling, approximate calculation and other processing methods.
(6) phase equilibrium
Master the definitions of phase, group fraction and degree of freedom. Understand the derivation process of phase law and its application in phase diagram. Master the application of lever rule in phase diagram. Focus on mastering the P-X diagram and T-X diagram of the two-liquid system which is completely soluble in each other. In the two-component liquid-solid system, the phase diagram of simple melt is mainly explained, and the drawing and application of the phase diagram are mastered. For three-component system, understand the application of phase diagram of water-salt system and the application of phase diagram in extraction process.
(7) electrochemistry
Grasp the significance of conductivity and molar conductivity and their relationship with solution concentration. Understand the law of independent movement of ions and some applications of conductivity measurement. Familiar with the relationship between mobility number and molar conductivity and ion mobility. Grasp the significance and calculation method of the average ionic activity coefficient of electrolyte. Understand the theory of electrolyte solution (mainly the concept of ionic atmosphere) and use Debye-Hooker limit formula. Master the relationship between electromotive force and Δ Δ RGM, and be familiar with the symbol convention of electrode potential. Familiar with standard electrode potential and its application (including estimation of oxidation capacity and calculation of equilibrium constant, etc.). ). For a given battery, you can skillfully and correctly write out the electrode reaction and battery reaction, and calculate the electromotive force. Clarify the influence of temperature on electromotive force and the calculation of δδrHm and δδrSm. Understand the meaning of decomposition voltage. Understand the causes of polarization.
(viii) Preliminary statistical thermodynamics
Understand the reason why the micro-state number of the whole system is replaced by the micro-state number of the most probable distribution. Clear the definition of partition function and its physical significance. Understand the difference of thermodynamic function between positioning system and non-positioning system. Understand the partition functions of translation, rotation and vibration and their contributions to thermodynamic functions.
(9) Interface phenomenon
Master the concepts of surface Gibbs function and surface tension and understand the relationship between surface tension and temperature. In order to master the cause of additional pressure on curved surface and its relationship with radius of curvature, a simple calculation will be made by using Yang-Laplace formula. Understand the vapor pressure on the surface and learn to use Kelvin formula. Understand the Gibbs adsorption isotherm and the physical significance of each term, and can make simple calculations. Understand the structural characteristics, classification and application of surfactants. Understand the spreading and wetting phenomenon of liquid-solid interface. Understand the adsorption nature of gas-solid surface, the main types of adsorption isotherms and adsorption thermodynamics.
chemical kinetics
Master the basic concepts such as the expression of equal volume reaction rate, elementary reaction, reaction order and reaction molecule number. Mastering the rate equation and characteristics of simple series reaction can determine the series of simple reaction from experimental data. For three typical complex reactions (antagonistic reaction, parallel reaction and series reaction), we can master their own characteristics, and for simpler reactions, we can write the differential formula of the relationship between reaction rate and concentration. Make clear the influence of temperature and activation energy on the reaction rate, understand the meaning of each item in Arrhenius empirical formula, calculate physical quantities such as Ea, A and K, and master the characteristics of chain reaction. Master the approximate processing methods such as steady-state approximation method, balance method and fast control step method. Understand collision theory and transition state theory. Understand the characteristics of the reaction in solution and the effects of solvents and electrolytes on the reaction rate. Understand the characteristics of catalytic reactions and the types of common catalytic reactions. Understand the characteristics of photochemical reactions.
(1 1) colloid chemistry
By mastering the characteristics of dynamic, optical and electrical properties of colloidal dispersion system, we can use these characteristics to analyze the size and charging of colloidal particles and apply them to practice. Understanding the characteristics of sol stability and the influence of electrolyte on sol stability can judge the aggregation ability of electrolyte. Understand the types of emulsion, the function of emulsifier and its application in industry and daily life. Understand the similarities and differences between macromolecular solution and sol. Nan Pingheng knows Tang.
Third, the main reference books
Physical Chemistry (4th Edition) Volumes 1 and 2, edited by Physical Chemistry Department of Tianjin University, Higher Education Press, 200 1.
Four. explain
The main types of questions may include: true or false questions, multiple-choice questions, fill-in-the-blank questions, short-answer questions, calculation questions, comprehensive questions, etc.