Physical chemistry, lecture

chemistry

obligatory courses

The main goal of this lecture is thermodynamic and kinetic description of physical and chemical processes and application of basic physic chemical knowledge for description of materials properties. This knowledge is applied in others brunches of chemistry - inorganic, organic , technology, biochemistry.

Classroom
Remote learning

After finishing this course student will be acquainted with mathematical description of physico-chemical processes by means of thermodynamics, thermochemistry and electrochemistry, as well as phenomenological and molecular interpretation of such processes.

Thematic scope:

Thermodynamics

Subject of chemical thermodynamics, the concept of the physical system and the environment, the basic concepts of classical mechanics. Perfect gas, parameters of state. Quantum model of an ideal gas. Internal energy. Number of microstates (thermodynamic probability), entropy. Boltzmann distribution, internal energy of an ideal gas, entropy of an ideal gas.

Sackur-Tetrode equation. Thermal equilibrium - thermodynamic definition of temperature, mechanical equilibrium - thermodynamic definition of pressure, equilibrium associated with the exchange of molecules - thermodynamic definition of chemical potential. The concept of a total differential, total differential of entropy and internal energy.

The first law of thermodynamics. Heat, work, volume work. Examples of reversible and irreversible processes. The second law of thermodynamics, the production of entropy.

Internal energy and the heat of the process. System in contact with the surroundings at constant pressure - enthalpy. Enthalpy and the heat of the process. Thermodynamic functions of a chemical reaction. The relationship between the internal energy of a reaction and the enthalpy of a reaction.

System in contact with the surroundings at a constant temperature - free energy. System in contact with the surroundings at constant temperature and pressure - free enthalpy. Free energy and spontaneity of processes. Free enthalpy and spontaneity of processes. Legendre transformation. New thermodynamic functions as Legendre transforms of internal energy.

Internal energy and enthalpy versus process heat. Free energy and spontaneity of processes. Free enthalpy and spontaneity of processes.

Partial derivatives of thermodynamic functions, Maxwell relations. Internal energy as a function of temperature and volume. Enthalpy as a function of temperature and pressure. Relationship between Cp and Cv. Entropy as a function of (T, V) and (T, p). Thermodynamic functions of an ideal gas. Calculation of the heat of reaction from thermodynamic data. Calorimetric measurements. Determination of the entropy of substances.

Chemical potential, molar chemical potential. Relationship between the (molar) chemical potential and free enthalpy. Thermodynamic functions of an open system. Extensive and intensive variables. Changes of free enthalpy during a chemical reaction. The equilibrium condition of a chemical reaction. Law of mass action, van't Hoff equation.

Chemical kinetics:

Reaction rate - definition, kinetic equations, reaction rate constant, differential form of kinetic equations. Solutions of differential equations for 0, 1, 2 and nth order, half-life.

Kinetic equations of complex reactions. Competing, consecutive and equilibrium reactions.

Steady state approximation (consecutive reaction, consecutive reaction with pre-equilibrium). Michaelis-Menten model of enzymatic kinetics. The dependence of the rate constant on temperature.

Electrochemistry

Ideal and real solutions. Ion-ion interactions in electrolyte solutions (Debye-Hückel theory). Ion-solvent interactions in electrolyte solutions (Born theory). Ion interactions with an external electric field (Ohm's law, specific and molar conductivity of electrolyte solutions, the concept of ion mobility, dependence of specific and molar conductivity on electrolyte concentration).

Electron transfer processes in solutions, electron transfer in the presence of a conducting phase (metal), the electrode in equilibrium (redox potential of the electrode). Kinetically and diffusion controlled processes. Galvanic cells (cell scheme and principles of notation, electromotive force, the relationship of EMF with thermodynamic functions of the reaction).

1. Atkins, P.W., et al., Physical Chemistry. 2018: Oxford University Press; 11th Edition.

2. Pigoń, K., Ruziewicz, Z., Chemia fizyczna: Podstawy fenomenologiczne. 1. 2007: Wydawnictwo Naukowe PWN.

3. Hołyst, R., A. Poniewierski, Thermodynamics for Chemists, Physicists and Engineers. 2012: Springer Netherlands.

4. 4. Shroeder D.V., An introduction to thermal physics. 2000: Addison Wesley Longman.

5. Jackowska, K., Repetytorium – Elektrochemia, 2017: Wydział Chemii UW, Zakład Dydaktyczny Chemii Fizycznej.

After the course the student:

- knows the basic terms and how to use them in thermodynamics, thermochemistry, chemical kinetics, electrochemistry,

- knows the main relationships in Physical Chemistry and how to use them,

- knows the basis of fundamental physicochemical processes,

- is able a direction of physicochemical processes after the change of various parameters, like temperature, pressure, concentration, potential,

- knows which experimental methods one can use in the studies of physicochemical processes,

is able to determine the fundamental physicochemical parameters from experimental data

- is able to interpret experimental data and infer appropriate conclusions.

Attending classes is compulsory. Two unexcused absences are allowed (in the case of more absences, a sick leave is required).

The lecture is divided into two blocks, which end with written partial tests. Partial tests are assessed as follows: I - 20 points, II - 20 points, so a total of 40 points can be obtained. A student who has obtained at least 38 points in the partial tests will be released from the exam with 5! grade. The rest of the participants take the entire material for the exam, but the maximum number of points that can be obtained for the exam is 60. The score for the entire course is the sum of the points for the partial tests and the exam - a maximum of 40 + 60 = 100 points.

Points are converted into a grade as follows:

0 - 50.00 - N / A

50.01 –60.00 - 3

60.01 –70.00 - 3 +

70.01 –80.00 - 4

80.01 –90.00 - 4 +

90.01 –98.00 - 5

98.01 –100.00 - 5!

In the event of failure to complete the course, the student takes a written exam on the entire material (in the re-sit session). The maximum number of points in the re-sit examination is 100. Points are converted into the grade in the same way as above.

Not applicable