Study-Unit Description

Study-Unit Description


CODE CHE2370

 
TITLE Chemical Thermodynamics and Kinetics

 
UM LEVEL 02 - Years 2, 3 in Modular Undergraduate Course

 
MQF LEVEL 5

 
ECTS CREDITS 4

 
DEPARTMENT Chemistry

 
DESCRIPTION Pre-requisite study-unit

- CHE1330 - Principles of Physical Chemistry
- CHE1200 - Mathematics for Chemists

Content

  1. Internal energy: open, closed and isolated systems; heat and work - the sign conventions; internal energy and
      internal energy changes, U and ΔU; state functions; the first law of thermodynamics

  2.  Enthalpy: definition of enthalpy and enthalpy changes, H and ΔH; thermochemical equations, standard
       conditions and conventions of standard conditions; relationship between U and ΔH; Hess's law; ΔH for various
       processes; heats of formation; combustion; bond dissociation; phase change; solution; calculation of
        ΔH(reaction) from enthalpy changes of formation, bond energies, Hess cycles; variation of ΔH with
       temperature; heat capacities: constant volume heat capacity, Cv , and constant pressure heat capacity, Cp;
       Kirchoff's equation; applications; measurement of ΔH.

  3.  Entropy: The second law of thermodynamics, Clausius inequality; quantitative measures of ΔS: 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; variation of ΔS 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;ΔS in chemical reactions; the use
       of ΔS of the universe to predict chemical reactivity.

  4.  Free energy functions: prediction of chemical reactivity by concentrating on the system - the free energy
       functions; Helmholtz free energy; Gibbs free energy; properties of the Gibbs free energy, pressure dependence
       of the Gibbs free energy, temperature dependence of the Gibbs free energy (The Gibbs-Helmholtz equation.)

  5.  Chemical potential, simple mixtures, chemical reactions and equilibria: definition of chemical potential, 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;
       mixtures, Gibbs-Duhem equation; gaseous mixtures, the chemical potential of gaseous solutions, Gibbs energy,
       entropy and enthalpy of mixing, liquid mixtures, chemical potential of ideal liquid solutions, ideal-dilute liquid
       solutions, real liquid solutions - activities, Gibbs energy, entropy and enthalpy of mixing for liquids, colligative
       properties, bhemical reactions and equilibria, reaction Gibbs energy and equilibria, response of equilibria to
       external disturbances: 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, experimental techniques, temperature dependence of reaction rates
       (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, molecularity of a reaction, molecularity vs. order,
      rate laws of elementary reactions , consecutive elementary reactions, variations of concentrations with time, the
      rate-determining step, the steady state approximation, pre-equilibria.

  9. A theoretical approach to chemical kinetics: collision theory, 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.

10. Chemical kinetics for various processes: enzyme reactions - The Michaelis-Menten mechanism (an example of
      consecutive elementary reactions); Lindemann-Hinshelwood Mechanism - First-order gas phase kinetics -
      Unimolecular Reactions, relationship between the overall rate constant of a composite reaction (Exemplified
      through the Lindemann-Hinshelwood mechanism), Chain Reactions: the rate laws of chain reactions, example of
      a chain reaction having a simple rate law - The Rice-Herzfeld mechanism for the pyrolysis of ethanal in the
      absence of air, example of a chain reaction having a complicated rate law - The formation of HBr from
      hydrogen and bromine, special case: explosions, catalysis and oscillation: catalysis, autocatalysis ,
      oscillating reactions.

Web-site: http://staff.um.edu.mt/jgri1/teaching/che2372


Recommended Texts:

- Atkins P.W., Physical Chemistry, 6th Ed., by Oxford University Press.
- Thermodynamics of Chemical Processes, Oxford University Press. ISBN: 0-19-855963-1
- Physical Chemistry, 3rd Ed., by J.W. Noggle, Harper Collins. ISBN: 0-673-52341-1.


Supplementary Reading:

- Atkins P.W., The Elements of Physical Chemistry, 2nd Ed., Oxford University Press.
- Smith E.B., Basic Chemical Thermodynamics, 3rd Ed., by Oxford University Press. ISBN: 0-19-855564-4
- Atkins P.W., Trapp C.A., Cady M.P. and Giunta C., Student's Solution Manual for Physical Chemistry, 6th Ed., Oxford University Press. ISBN: 0-19-850319-9

 
STUDY-UNIT TYPE Lecture and Tutorial

 
METHOD OF ASSESSMENT
Assessment Component/s Sept. Asst Session Weighting
Examination (2 Hours) Yes 100%

 
LECTURER/S Joseph Noel Grima (Co-ord.)

 

 
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