Physical Chemistry 2 (SA)

Overview

STAFF

NAME CONTRIBUTION
Prof. A. Mills
andrew.mills@qub.ac.uk Introduction to Practicals (1 Lecture); Basic Reaction Kinetics (8 Lectures, and 1 tutorial.); Thermodynamics (8 Lectures, 1 tutorial and 1 class test); Photochemical Kinetics and Techniques (5 Lectures, and 1 tutorial).
Dr. A. Doherty
a.p.doherty@qub.ac.uk Surfaces and Interfaces (6 Lectures, and 1 tutorials); Dynamic Electrochemistry (3 lectures)

Introduction to Practicals:
• Introduction to the basic material necessary for the performing of the practicals as well as a focus on the context of these practicals with respect to the courses taught in the module.

Basic Reaction Kinetics:
• rate law and reaction order, reaction stoichiometry, molecularity, elementary and non-elementary reactions, single and multiple reactions, parallel and series reactions, multi-step processes, Arrhenius equation, manipulation and use of rate equations, diffusion-controlled and activation- controlled kinetics;
• interpretation of experimental kinetic data;
• integrated rate equations, equilibria kinetics.

Thermodynamics:
• Review of H, S and G functions, the laws of thermodynamics and Hess’s law.
• Kirchhoff’s equation, Trouton’s Rule. Calculation of DH, DS and DG at temperatures other than 298 K.
• The reaction Gibbs Energy, Chemical equilibrium and mixing and the Van’t Hoff Reaction Isotherm.
• The Van’t Hoff Reaction Isochore, the Classius-Clapeyron equation and vapourisation.
• The Clapeyron equation and melting.
• Concept of activities and chemical potentials.
• Ideal and real mixtures (Raoult’s and Henry’s laws).
• Fractional distillation.
• Phase equilibria.
• Colligative properties.
• Derivations of equations for elevation of boiling point, depression of freezing point and osmotic pressure.
• Mean activity coefficient.
• Activity vs. concentration; activity coefficient and its calculation from the Debye-Hückel equations (limited and extended).
• Thermodynamic and concentration equilibrium constants.
• Solubility and solubility products.
• The 'Thermodynamics' section of the course will only be examined in the open book class test, i.e. no 'Thermodynamics' based question will appear on the exam paper.

Surfaces and Interfaces:
• Solid-Solid, Gas-Liquid, Liquid-Liquid, Liquid-Solid and Gas-Solid
• Review of important applications
• Surface thermodynamics
• Surface energy, surface tension, interfacial tension, surface phenomena and surface characteristics
• Absorption, adsorption and reactions on surfaces
• Physisorption,
• Chemisorption,
• Empirical and derived adsorption isotherms;
• Linear
• Freundlich
• Langmuir
• BET
• Adsorption thermodynamics
• Adsorption kinetics and mechanisms
• Adsorption’s role in heterogeneous catalysis
• Adsorption and surface chemistry in chromatography
• Thermodynamics of mass distribution between phases

Dynamic electrochemistry
• Revision of the Nernst equation, electrodes, electrochemical cells, cell thermodynamics.
• Galvanic cells vs. electrolytic cells.
• Electrochemical Kinetics
• Tafel equation
• Butler-Volmer equation
• Transfer coefficient / symmetry factor
• Over-potential, kinetic and mass transfer
• Exchange current density
• Charge transfer resistance
• Heterogeneous electron transfer rate constant
• Corrosion mechanisms and corrosion rates measurement
• Electrical capacitance, structure of the electrode/electrolyte interface, electrochemical double layer capacitance, energy stored in a capacitator.

Photochemical Kinetics and Techniques
• The course will examine the Stern-Volmer equation and deviations from it. The techniques to be studied will be: (i) single photon counting, (ii) phase modulation and (iii) flash photolysis.

Learning Objectives

On successful completion of this module a learner should be able to:
• apply basic principles of thermodynamics and kinetics, physical chemical separation and their applications to selected chemical systems and dynamic electrochemistry. In particular students will be familiar with the basic terminology used in thermodynamics and kinetic and physical chemical separation and be confident to apply these principles to physical processes and chemical transformations.

Skills

On successful completion of this module a learner should be able to:
• apply basic principles of thermodynamics and kinetics, physical chemical separation and their applications to selected chemical systems and dynamic electrochemistry. In particular students will be familiar with the basic terminology used in thermodynamics and kinetic and physical chemical separation and be confident to apply these principles to physical processes and chemical transformations.

Assessment

ASSESSMENT

Exam session Semester 1

Assessment Profile
Element type Element weight (%)
1. Examination 60
2. Open book class Test 10
3. Practical 20
4. Tutorial 10

Course Requirements:
• Practical attendance at 80%,
• Practical report submission 80%,
• Both Coursework and Examination must be passed at 40%
• Examination note: You are asked to answer 2 out of 2 questions in 1.5hrs. The 'Thermodynamics' section of the course will only be examined in the open book class test, i.e. no 'Thermodynamics' based question will appear on the exam paper. Equation sheets provided for the kinetics parts of this course will be available in the exam.