Description of various systems. Concepts of states, accessible states and distribution. Probability concepts. Maxwell - Boltzmann’s statistics for the systems of independent particles. Partition functions. The relationship of partition function to the various thermodynamic functions. Transitional, vibrational and rotational partitional functions and equilibrium constant. Statistical thermodynamics. Applications to equilibrium and chemical kinetics. Bose-Einstein’s and Fermi-Dirac’s statistics.
Electrical Double Layer: Interface. A look into the interface; OHP and IHP. Contact adsorption Gibbs Surface Excess. Potential differences across metal solution interfaces(open circuit potential,equilibrium potential,etc). Outer and surface potential differences. Galvani potential difference. Electrochemical potential difference. Interfacial tension. Lippmann’s equation. Helmholtz-perrin model, Gouy-Chapmann model. Stern model, and BDM (Bockris-Devanathan-Muller) model. Charge density. Differential capacitance. Shape of capacitance-charge curve. The Capacitance hump
• Explanation (quantitative) of the properties of macroscopic systems (e.g. thermodynamic functions) using the knowledge of the properties of individual molecules (obtained from molecular spectroscopy or quantum chemistry)
• Providing rigorous definitions of thermodynamic quantities and derivations of the laws of thermodynamics from the laws of quantum mechanics.
• Obtaining information on the properties of single molecules and their interaction from the knowledge of macroscopic (bulk) properties of matter
• Describe how a galvanic (voltaic) cell operates, with the concepts of electrodes, salt bridges, half-cell equations, net cell reaction, and cell diagram.
• Write an accurate cell diagram for a given cell, or describe a cell from a cell diagram. Understand and explain the role of inert electrodes.
• Describe the standard hydrogen electrode and explain how other standard electrode potentials are related to it.
• Use tabulated standard potentials, Eoredox. Eoox, to compare the reducing/oxidizing strength of species involved in redox reactions.
Course Learning Outcomes
On completion of the course, students will be able to:
• Understand the laws of thermodynamics and a systematic definition of thermodynamic potentials as general formalism of thermodynamics.
• Learn to recognize, define, and solve problems in equilibrium and statistical thermodynamics.
• Student recognizes the difference between temperature and heat.
• Account for the physical interpretation of partition functions and be able to calculate thermodynamic properties of model systems.
• Account for the physical interpretation of distribution functions and discuss and show how these can be used in calculations of basic thermodynamic properties.
• Account for the fundamental ideas in the Debye-Huckel theory and use the theory for calculations of properties of electrolytes.
• Identify the relationship and correct usage of infinitesinal work, work, energy, heat capacity, specific heat, latent heat, and enthalpy.
completion of the course, students will be able to:
• Recognize oxidation reduction (redox) reactions and be able to:
assign oxidation numbers to atoms in molecules and ions
write the oxidation and reduction half reactions
identify the compounds being oxidized and reduced
identify the oxidizing agent and reducing agent
balance a redox reaction by the half-reaction method
• Describe the functions of the various components of simple voltaic and electrolytic cells.
• Diagram electrochemical cells, labeling the anode, cathode, and directions of ion and electron movement.
• Given appropriate reduction potentials,
calculate the cell voltage (standard cell potential) generated by a voltaic cell
determine the relative strengths of oxidizing or reducing agents
use standard reduction potentials to predict whether a given reaction will be spontaneous when all of the reactants and products are present in their standard states (under standard conditions)
• Understand the relationship between Eo cell, ∆G°, and K for oxidation-reduction reactions and be able to:
calculate ∆G° from Eo cell and perform the reverse operation
calculate K from Eo cell and perform the reverse operation
• Use the Nernst equation to calculate the cell potential or the concentration of a substance under nonstandard conditions.
• Discuss how a spontaneous redox reaction can be used to create a battery and
recognize the connection between the components of the cell and the properties of the battery
recognize the chemical reaction used in a lead-acid storage battery and lithium ion battery
Discuss the difference between galvanic and electrolytic cells and: calculate the time, current, and the amount of substance produced/consumed in an electrolysis reaction.
Statistical thermodynamics • Description of various systems Pg.# 1 and 2
integration and summation
Concepts of states Pg.# 9-11
Probability concepts Pg. # 252-255
Maxwell Boltzmann’s statistics for the systems of independent particles Pg. # 339-343
The thermodynamic information in the partition function, pg#45
Relation of partition function with thermodynamic functions
translational, rotational and vibrational partition functions
partition function and equilibrium constant
Book Title : Basic Chemical Thermodynamics
Author : Smith E.B.
Edition : 4th
Publisher : Oxford University Press 1990
Book Title : Thermodynamics and Statistical Mechanics
Author : 5. Seddon J.M. and Gale J.D
Edition : 2002
Publisher : Royal Soc Chem, UK
Book Title : Thermodynamics, Statistical Thermodynamics”, and Kinetics
Author : 7. Engel, Thomas and Philip Reid
Edition : 1st 2006
Publisher : Benjamin Cummings
Book Title : Electrochemical Methods
Author : Bard A.J. and Faulkner L.R
Publisher : John Wiley and Sons (2001).