Lecture 1: Introduction to aquatic chemistry:
Topics covered: - Goals of the course, review of units and concentrations scales, ideal and non-ideal systems, activity and activity coefficients. What is chemical equilibrium analysis and how is it useful?, How do equilibrium models differ from kinetic models? What are the strengths and weaknesses of each approach? Examples of the application of equilibrium analysis to ecosystems biogeochemistry and environmental problems. Readings: Pankow Chapter 1
Lecture 2: Basic Thermodynamic Principles.
Topics covered: Free energy and chemical change, chemical potential, Using free energy change to understand reactions, free energy data sets - standard states and conventions, effects of temperature and pressure on equilibrium constants, combining equilibrium constants. Readings: Pankow Chapter 2.1 through 2.6
Lecture 3: More on concentrations scales and activity, The proton.
Topics covered: Ways to calculate activity - Davies, extended Debeye Huckel, and Guntleberg equations. The proton, what is the proton in solution? the importance of understanding what we measure when we measure pH. Readings: Pankow Chapter 2.7, 2.8, 3. Supplemental Readings (optional) - Measuring pH under different conditions
Lecture 4: Acid Base Chemistry I.
Topics covered: Solutions to equilibrium reactions using fundamental properties - proton balance, mass balance and electrical neutrality. General equations for predicting the behavior of a simple monoprotic acid (HA) and a simple base (NaA). Readings: Pankow Chapter 4, 5.1-5.3 inclusive.
Lecture 5: Acid-Base chemistry II.
Topics Covered: More acids and bases, including activity corrections, pH as a master variable, use of log concentration vs. pH plots. Readings: Pankow 5.4, 5.5, 6
Lecture 6: The dissolved CO2 system in natural waters, alkalinity, total carbon.
Topics covered: Gases in water - review of Henry’s law, definitions of alkalinity and total carbon, calculation of total carbon in systems open and closed to the atmosphere, inorganic carbon and the global C budget. Readings: Pankow 7, 9 (skip 9.83), hand out.
Lecture 7: Buffering, Alkalinity and Titrations.
Topics covered: How solution chemistry changes with the addition of strong acids or bases, equivalence points, practical methods - Gran titrations. Readings: Pankow 7, 10.1.10.2-10.24
Lecture 8: Precipitation and dissolution.
Topics covered: definition of saturation, undersaturation, supersaturation, calculating the solubility of simple salts, conventions used for solubility constants, metal oxides and hydroxides and carbonates. Reading: Pankow Chapter 11, 12.0-12.3 inclusive
Lecture 9: More on Mineral solubility.
Topics Covered: metal carbonates in systems open to the atmosphere - CaCO3 as an example, concentration vs. pH plots. Reading: Pankow Chapter 13.1-13.3, hand out.
Lecture 10: Mineral solubility and The Gibbs Phase rule.
Topics covered: solubility control, multiple solid phases, log concentration vs pH diagrams for multiple solid phases in closed systems, - iron minerals as an example, using the Gibbs Phase rule to constrain equilibrium calculations. Reading: Pankow Chapter 14, 17.1, 17.2 (look over examples in 17.7).
Lecture 11: Complexation.
Topics covered: Definitions of ligands and complexes , formation and dissociation constants of complexes, hydrolysis of metal ions, the importance of pH on hydrolysis, multiple ligands, the stepwise attachment of several ligands, chelates. Reading: Pankow Chapter 18 through 18.6.
Lecture 12: Oxidation Reduction - redox reactions, pe and Eh.
Topics covered: Half cell reactions, the concept of pe and pH, Eh and its relationship to pe, similarities and differences between pe and pH, similarity between redox and acid/base equilibria, the redox chemistry of water. Readings: Pankow 19.1 through 19.4. Supplemental Readings: Hand out on how to make Eh measurements
Lecture 13: Oxidation reduction continued - pe-pH diagrams.
Topics covered: Constructing pe-pH diagrams - a simple example where there are no solid phases hydrogen, oxygen and aqueous chlorine, including solids. Readings: Pankow Chapter 20, and 21
Lecture 14: Oxidation Reduction in natural waters I
Topics covered: Chemistry of C, and N in natural waters, controls on pe in natural systems, chemical vs. biological control. Readings: Pankow Chapter 23-18.104.22.168 inclusive
Lecture 15: Oxidation Reduction in natural waters II
Topics covered: Chemistry of S and Fe, in natural systems. Readings: Morse et al. 1987 "The chemistry of the hydrogen sulfide and iron sulfide systems in natural waters", Earth-Sci. Rev. 24:1-42 and Pankow Chapter 23.3.-23.4
Lecture 16: Oxidation - Reduction III
Topics covered: The evolution of oxygen in the atmosphere, a planetary scale redox titration. Readings: Holland "Atmospheric Oxygen and the biosphere" pp127-136 in Jones and Lawton (eds) Linking Species and Ecosystems, Chapman and Hall, NY. Supplemental Readings Pankow Chapter 24. Note: Holland is a possible guest lecturer
Lecture 17: Adsorption
Topics covered: Theory of the electrical double layer in aqueous systems, inner sphere surface complexes, the role of ligands in promoting or retarding dissolution. Readings: Pankow 26.1, 26.2, 26.3, Stumm 1995 "The inner sphere surface complex: A key to understanding surface reactivity".In: Huang et al. (eds) Aquatic Chemistry: Interfacial and Interspecies Processes.
Lecture 17: Ion Exchange
Topics covered: What is ion exchange, treating ion exchange as an equilibrium problem, electrostatic sorption in ion exchange. Readings: Dzombak and Hudson, 1995 Ion Exchange: The contributions of diffuse layer sorption and surface complexation" In: Huang et al. (eds) Aquatic Chemistry: Interfacial and Interspecies Processes.
Lecture 18: Practical approaches to modeling adsorption and ion exchange
Topics covered: Langmuir, Freundlich and linear models, what to do with messy systems, using empirical data to determine adsorption coefficients, examples of successful models using adsorption. Reading: Weber et al. 1995, " Distributed reactivity in the sorption of hydrophobic organic contaminates in natural aquatic systems" In Huang et al. (eds),
Lecture 19: More examples of equilibrium models and how equilibrium models can be combined with kinetic models.
Readings: Mattigod, S. 1995 Chemical Equilibrium and Reaction Models: Applications and future trends. pp1-5 In: Chemical Equilibrium and Reaction models, SSSA Special publication 42., Crosby et al. 1985, Modeling the effects of acid deposition: Assessment of a lumped parameter model of soil water and stream water chemistry Water Resources Research 21: 51-63.
Lecture 20: Review, discussion of projects
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