CY6127: Chemical Processes at Surfaces and Interfaces

Course objectives: To introduce the basic concepts of surface and interfacial chemistry. The subject is very diverse and interdisciplinary in nature. The topics cover the chemical processes that occur at solid-liquid, solid-gas and liquid-gas interfaces. The spectroscopy and microscopy methods to study the interfacial phenomena are also included in the syllabus for the benefit of chemistry, physics, engineering, and biology students.

Course Outcomes:
(i) Understand concepts of solid-liquid, solid-gas, liquid-gas interfaces
(ii) Apply fundamental principles of chemistry to chemical processes occurring at interfaces
(iii) Apply spectroscopic methods to study interfaces and interfacial phenomena

Course Contents:

Solids and solid surfaces : Crystalline surfaces, single crystal surface structures, surface relaxation, clean and adsorbate induced surface reconstructions, bimetallic and semiconductor surfaces, adsorbate overlayer structures and notations, thermodynamics of solid surfaces, surface energy and defects, surface diffusion, band structure of solids, Fermi energy and work function, density of states, quantum wires, nanostructures, and semiconductor quantum dots.

Energetics and kinetics of chemisorption, adsorption isotherms, measurement of heats of adsorption and isosteres, adsorption on porous materials, capillary condensation phenomenon and hysteresis. Kinetics of catalytic reactions on surfaces, structure sensitivity, chemisorbed molecular species on surfaces and Blyholder model of chemisorption bond, surface reaction mechanisms, oscillatory reactions. Friction and lubrication forces, polymer coated surfaces.

Spectroscopy methods to study solid surfaces, x-ray and UV photoemission spectroscopies, Inverse photoemission, Auger spectroscopy, LEED structure determination and RHEED, scanning probe microscopies (STM & AFM), Thermal methods, vibrational spectroscopy (RAIRS & HREELS, SERS).

Liquids and liquid surfaces: microscopic picture of liquid surface, surface and interfacial tension, Young-Laplace equation and its application, measurement of surface tension, Kelvin equation and capillary forces, nucleation and growth of aggregates, Ostwald ripening, surface excess and Gibbs adsorption isotherm. Organized molecular assemblies, surfactants and detergency, films of insoluble surfactants, Langmuir films and LB films, Langmuir trough, surface pressure-area relationships, self-assembling structures, soluble and insoluble monolayers, contact angle and wetting, capillary rise, dispersion, colloids, micelles (CMC), oil-water- surfactant phase diagram, vesicles, microemulsions, aerosols, surfactant and lipid membranes, liquid crystals, ionic liquids.

Electrode/electrolyte interface, electrochemical methods, cyclic voltammetry, electrochemistry on single crystal surfaces, shape-dependent electrocatalysis, semiconductor/electrolyte interface, spectroelectrochemistry.

Text Books:

1. Peter Atkins, J. De Paula, Atkins’ Physical Chemistry 9th edition, 2010
2. H. Kuhn, H.-D. Forsterling, D.H. Waldeck, Principles of Physical Chemistry, Wiley 2nd edition, 2009
3. Physical chemistry – A molecular approach, D.A. McQuarrie and J.D. Simon, 1998
4. A.W. Adamson, A.P. Gast, Physical Chemistry of Surfaces, Wiley, 1997
5. G.A. Somorjai, Y. Li , Introduction to Surface Chemistry and Catalysis, 2nd edition, 2010
6. H.-J Butt, K. Graf and M. Kappal, Physics and Chemistry of Interfaces, 3rd
edition, Wiley-VCH, 2013

Reference Books:

1. Catalysis : Principles and applications, Editors : B. Viswanathan, S. Sivasanker, A.V. Ramaswamy, Narosa Publishers, 2002
2. I. Chorkendorff, J.W. Niemantsverdriet, Concepts of Modern Catalysis and Kinetics, 2nd edition, Wiely-VCH, 2007
3. A. Zangwill, Physics at Surfaces, Oxford University Press, 1988
4. Jacob N. Israelachvili, Intermolecular and surface forces, 3rd edition, Elsevier- Academic Press, 2011