Physical chemistry of electrolyte solutions

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Course teacher

Associate teachers

Status of the course

Course objectives

The aim of the course is a systematic review and extension of basic knowledge of structural, thermodynamic and transport properties of electrolyte solutions derived from lectures in physical chemistry.

Course enrolment requirements and entry competences required for the course

Learning outcomes expected at the level of the course (4 to 10 learning outcomes)

Upon successful completion of the program, students will be able to:
1) explain the main characteristic whereby electrolytes are distinguished from other solutions, 2) apply the thermodynamic quantities for the treatment of equilibrium conditions, 3) explain the different conductivity chemical models, 4) understand the theoretical treatment of transport properties based on the interionic attraction theory of Debye and Huckel 5) independently determine the equilibrium constant for the reaction of ionic associations, 6) interpret the experimental and theoretical data.

Course content broken down in detail by weekly class schedule (syllabus)

Lectures
1st week: Introduction. Classification of solvents and electrolytes. Non-electrostatic interactions. Triple-ion formation.
2nd week: Spectroscopic studies of association. Ionizing solvation reactions. Thermodynamic energy functions and their variables. The chemical potential of electrolytes in solutions.
3rd week: Partial molar quantities. Attractive potentials of spatially fixed ions and dipoles. Van der Waals potential. Ions and molecules in homogeneous dielectric media.
4th week: Dipole molecule in a homogeneous dielectric medium. Reaction field. Complete ion-ion interaction potentials in solutions.
5th week: Particle size parameters (solvent molecules, inorganic and organic ions). Ions and molecules in the gas phase, (gas phase equilibria of electrolytes, ion clustering by solvent molecules. Ion solvation in the liquid phase. Extrapolation methods and extrathermodynamic assumptions.
6th week: Examples of solvation studies. Diffusion (measuring methods, self-diffusion, coupled diffusion.
7th week: Charge transport. Single ion conductivities. Empirical investigation on electrolyte conductivity. Viscosity. Dielectric polarization.
8th week: Static permittivity. Measurement of high-frequency permittivity. Phenomenological aspects. Relaxation processes of pure liquids and their mixtures.
9th week: Relaxation spectra of electrolyte solutions (solvent and ion pairs relaxation). Dielectric decrement. Solvent relaxation time. Distribution and correlation functions.
10th week: Chemical model at low electrolyte concentrations - lcCM. The mean force potential, the activity coefficient of the lcCM, the ion pair concept of the lcCM.
11th week: Properties of electrolyte solutions at the lcCM. Measurement of the solvent activity. Activity coefficients and osmotic coefficients.
12th week: Experimental osmotic coefficients. Fitting equations for osmotic and activity coefficient. Pitzer equations, extended lcCM equation. Partial molar enthalpy.
13th week: Chemical kinetics as a test for chemical models on the MM level. Primary kinetic salt effect.
14th week: Solvent effects. Transport equations on the lcCM level. Hydrodynamic ion-ion interactions.
15th week: Electrophoretic term of the conductivity equation. Limiting law of conductivity.
Seminars
Solving numerical problems.
Laboratory exercises
1. Molar conductivity of symmetrical electrolytes. 2. The chemical model of conductivity. 3. Thermodynamic quantities for the association reaction. 4. Determination of stability constants of chlorocadmium complexes in water by direct potentiometry. 5. Thermodynamic study of CdCl2 in water from potential difference measurements. 6. Determination of limiting transference number for sodium ion from aqueous solutions of NaCl using potentiometry method.

Format of instruction:

Student responsibilities

Students are required to attend classes (lectures and seminars 80%, and laboratory exercises 100%) and actively participate in the teaching process. This will be recorded and evaluated in making a final assessment.