Lecturer:              Dr. Joseph N. Grima (www)
    Teaching Assistant:    Alfred Aquilina, B.Sc.(Hons)(e-mail)

    Website:             http://staff.um.edu.mt/jgri1/teaching/che2370

    Main Textbooks:      Atkins' Physical Chemistry (OUP)
                         Principles of Phys. Chemistry (Prentice Hall)
 

Syllabus: 

1. The internal energy
• Open, closed and isolated systems
• Heat and work - the sign conventions
• Internal energy and internal energy changes, U and DU
• State functions
• The first law of thermodynamics

2. Enthalpy
• Definition of enthalpy and enthalpy changes, H and DH
• Thermochemical equations, standard conditions and conventions of standard conditions
• Relationship between DU and DH
• Hess's law
• DH for various processes:
1. Heats of formation
2. Combustion
3. Bond dissosiation
4. Phase change
5. Solution
• Calculation of DH(reaction) from:
1. enthalpy changes of formation
2. bond energies
3. Hess cycles
• Varaition of DH with temperature
• Aside - Heat capacities: constant volume heat capacity, c_v , and constant pressure heat capacity, c_p.
• Kirchoff's equation
• Applications
• Measurment of DH.

3. Entropy
• Entropy, S - The second law of thermodynamics, Classius inequality 
• A quantitative measures of DS:
• Entropy changes during the phase change - Trouton's rule
• Changes in entropy during isothermal expansions of an ideal gas,
• Changes in entropy during the heating of an ideal gas,
• Varaition of DS with temperature
• Combining the first and second laws of thermodynamics - the fundamental equations of thermodynamics 
• The third law of thermodynamics - absolute entropies
• Entropy and chemical processes
• DS in chemical reactions
• The use of DS of the universe to predict chemical reactivity

4. Free energy functions
• Prediction of chemical reactivity by concentrating on the system - the free energy functions
• The Helmholtz free energy,
• The Gibbs free energy,
• Standard Gibbs energy of a reaction
• Properties of the Gibbs free energy
• The pressure dependence of the Gibbs free energy,
• The temperature dependence of the Gibbs free energy (The Gibbs-Helmholtz equation.)

5. Chemical potential, simple mixtures, chemical reactions and equilibria
   (i) Chemical potential - the definition
• Chemical potential for a pure substances
• pure ideal gases
• pure liquids
• pure real gases.
• Chemical potential for mixtures of ideal gases - partial molar Gibbs free energy, the fundamental equation of chemical thermodynamics
   (ii) Mixtrures
• The Gibbs-Duhem equation
• Gaseous mixtures
• The chemical potential of gaseous solutions 
• The Gibbs energy, entropy and enthalpy of mixing
• Liquid mixtures
• The chemical potential of ideal liquid solutions
• The chemical potential of ideal-dilute liquid solutions
• The chemical potential of real liquid solutions - activities
• The Gibbs energy, entropy and enthalpy of mixing for liquids
• Colligative properties
   (iii) Chemical reactions and equilibria
• Reaction Gibbs energy and equilibria 
• Response of equilibria to external disturbances - The Le Chatelier's principle 
• Response of equilibria to pressure 
• Response of equilibria to temperature (van't Hoff equation)
• Applications to selected systems
• Metal ore reduction (Ellingham diagrams)
• Acids/bases 

 

6. Chemical Kinetics - Introduction
• Introduction
• Experimental techniques
• The temperature dependence of reaction rates (The Arrhenius equation)

7. Empirical Reaction Kinetics
• Identification of the rate law and the calculation of k from experiments.
• The determination of the rate law from:
• The isolation method 
• Method of initial rates 
• The integration method 
• Fractional lifetime method 
• Comparison of these methods
• Reactions approaching equilibrium 
• Relaxation techniques

8. Elementary reaction kinetics
• Definition of Elementary reactions
• The molecularity of a reaction
• Molecularity vs. order
• The rate laws of elementary reactions 
• Consecutive elementary reactions - Variations of concentrations with time
• A full inverstigation of a simple mechanism involving two consecutive recations
• Approximations:
• The steady state approximation (SSA)
• The rate-determining step approximation (RDS)
• More complicated mechanisms - The concept of a pre-equilibrium

9. Chemical kinetics for various processes
• Enzyme Reactions - The Michaelis-Menten mechanism (an example of consecutive elementary reactions)
• The Lindemann-Hinshelwood Mechanism - First-order gas phase kinetics - Unimolecular Reactions
• Aside - The Relationship between the overall rate constant of a composite reaction (Examplified through the Lindemann-Hinshelwood mechanism)
• Chain Reactions
• Introduction
• The rate laws of chain reactions:
1. Example of a chain reaction having a simple rate law - The Rice-Herzfeld mechanism for the pyrolysis of ethanal in the absence of air.
2. Example of a chain reaction having a complicated rate law - The formation of HBr from hydrogen and bromine.(See also this aside.) 
• Special case: Explosions
• Catalysis and oscillation 
• Catalysis 
• Autocatalysis 
• Oscillating reactions

10. A theoretical approach to chemical kinetics
• Collision theory
• The reaction profile in the Collision theory 
• Derivation of the rate law through the Collision theory
• Activated complex theory
• The reaction profile in the ACT
• Derivation of the rate law through the ACT (the thermodynamic derivation)
• The activated complex theory and reactions between ions.