### Module Details

 The information contained in this module specification was correct at the time of publication but may be subject to change, either during the session because of unforeseen circumstances, or following review of the module at the end of the session. Queries about the module should be directed to the member of staff with responsibility for the module.
 Title Physical Chemistry IIA Code CHEM261 Coordinator Dr G Sedghi Chemistry G.Sedghi@liverpool.ac.uk Year CATS Level Semester CATS Value Session 2016-17 Level 5 FHEQ First Semester 7.5

CHEM152

### Aims

• To explain the application of the 1st and 2nd laws of thermodynamics to chemical reactions.
• To reinforce the basic ideas on factors affecting the rates of chemical reactions and quantify the kinetics.

• ### Learning Outcomes

Discuss the difference between ideal and real gases.

Discuss the 1st and 2nd laws of thermodynamics in the context of chemica l reactions.

Carry out thermochemical calculations involving enthalpy, entropy and Gibbs free energy.

Calculate equilibrium constants from thermodynamic data
Discuss the concept of the chemical potential and its application under ideal and non-ideal conditions.
Analyse experimental data for the determination of  reaction orders and rate coefficients, using appropriate methods depending on the type of data available
Derive and apply rate equations and integrated rate equations for 0th, 1st and 2nd order reactions.

Show an understanding of activation barriers and apply the Arrhenius equation.

Describe qualitatively and quantitatively the kinetics of simple parallel, consecutive, and equilibration reactions.
Apply the pre-equilibrium and steady state approximations.
Describe different decay processes of photoexcited states and analyse their kinetics  quantitatively.

Use mathematical procedures and graphs for quantitative data analysis and problem solving.

Present and discuss the solution to problems in a small-group environment.

Lecture -

Tutorial -

### Syllabus

Thermodynamics

1. Revision of material in Chem152: Ideal gas equation, standard states, first law of thermodynamics, heat & work, enthalpy, Hess'' law cycles, entropy, Gibbs energy, equilibrium constant. Examples of calculations using tables of thermodynamic data.
2. Heat capacity at constant volume or pressure, temperature dependence of internal energy and enthalpy.
3. Second law of thermodynamics, statistical description of entropy. Dependence of entropy on temperature and pressure, third law of thermodynamics.
4. Gibbs free energy, changes at constant temperature or pressure. Equilibrium constant K, relation to Gibbs free energy, variation with temperature an d pressure, relation to mole fraction.
5. Chemical potential, equilibrium and the extent of reaction. Effect of temperature and pressure on equilibria. Extension from gas phase reactions to all reactions.
6. Real gases, deviations from ideal behaviour, virial and van der Waals equations of state.
7. Ideal liquids and solutions. Raoult''s law. The chemical potential of components in ideal mixtures: standard and reference states. Colligative properties. Deviations from ideality.
8. Phase transition of pure substances and mixtures; enthalpy and entropy change upon phase transition; phase diagrams.

Kinetics

1. Revision of material in Chem152: Chem ical reaction rates, rate equation, reaction orders, integrated rate equations, half life, activation energy barriers and Arrhenius equation.
2. Derivation of zero-, first- and second order integrated rate eqns. Determination of reaction order and rate constant: straight plots. Half-life time of a reaction.
3. Kinetic gas model, collision rates. Simple collision theory (SCT). Potential energy barriers. Reactive Encounters. Comparison of SCT with experimental results. Steric hindrance. Transition state. TransitionState Theory.
4. Consecutive reactions. The rate determining step.
5. Parallel reactions. Reverse reaction and relaxation towards equilibrium.
6. Pre-equilibrium; steady state approximation. Diffusion-controlled reactions.
7. Michaelis-Menten Mechanism. Lindemann-Hinshelwood mechanism. Chain reactions.

### Teaching Schedule

 Lectures Seminars Tutorials Lab Practicals Fieldwork Placement Other TOTAL Study Hours 18 3 21 Timetable (if known) Private Study 54 TOTAL HOURS 75

### Assessment

EXAM Duration Timing
(Semester)
% of
final
mark
Resit/resubmission
opportunity
Penalty for late
submission
Notes
Unseen Written Exam  1.5 hours  First semester  80  Yes    Assessment 2 Notes (applying to all assessments) Tutorials contributing to the assessment of all learning outcomes by short answer, short essay type, and problem-solving questions, some of which are discussed in small group tutorials, where student participation is expected and assessed, while others are part of assignments to be submitted after the tutorial. Students are expected to spend two hours preparing for each tutorial and three hours preparing the assignment after each tutorial This work is not marked anonymously. Written Examination assessing learning outcomes is by short answer, short essay type, and problem-solving questions.
CONTINUOUS Duration Timing
(Semester)
% of
final
mark
Resit/resubmission
opportunity
Penalty for late
submission
Notes
Coursework  3 sets  First semester  20  No reassessment opportunity  Standard UoL penalty applies  Assessment 1 There is no reassessment opportunity,