EGEE 510

PHYSICAL CHEMISTRY IN ENERGY, GEO-ENVIRONMENTAL AND MINERAL ENGINEERING

 

Here is the Fall 2008 syllabus!

 

 

In 1927 Heitler and London (Z. Physik, Vol. 44, p. 455) applied quantum mechanics to explain the H-H bonding in H2 and gave birth to quantum chemistry. Two years later Dirac (Proc. Royal Soc. London, A123, p. 714) proclaimed that the “underlying physical laws necessary for the mathematical theory of a large part of physics and the whole of chemistry are thus completely known.” In 1998 the Nobel Prize in Chemistry was awarded to Pople and Kohn for the development of computational methods in quantum chemistry and of the density functional theory. So, in principle (and in most cases still ONLY in principle), chemical kinetics can now be predicted from quantum chemistry (which is introduced in Chs. 8 and 9 of Atkins, PChem8) or from (statistical) thermodynamics (which is discussed in Chs. 2-7 and 16-17). But in practice, 'chemistry' has indeed been reduced to 'physics' during the 20th century! (Hopefully, biology will be reduced to chemistry in the 21st century...)

 

That's why physical chemistry is today THE most important scientific 'discipline' that forms the basis of ALL (OK... maybe not all, but certainly MOST) engineering applications.

 

In most practical situations, chemical kinetics (see Chs. 21-24 of Atkins) is still an experimental field, although we can increasingly rely on order-of-magnitude estimations using first principles. In the first part of our course we shall review the highlights of phase and chemical equilibrium which allows us to determine the concentrations of species of interest and the ultimate composition of any reacting mixture. In the second part we shall review the highlights of chemical kinetics -- which allow us to determine more realistic compositions -- and illustrate their relevance and applicability to selected energy, geo-environmental and mineral engineering issues.

 

The objective of this course, apart from reviewing the applications of thermodynamics and kinetics, is to provide an exercise in targeted and stimulated self-study.  In particular, the key to our success will be that you come to 'class' prepared to discuss the topics and issues summarized below (and discussed at length in a physical chemistry textbook).

 

 

--OVERVIEW AND APPLICATIONS OF THERMODYNAMICS--

 

As an introductory exercise, during the first week of class, when we shall have no group meetings (i.e., we shall have no “class”), you are asked to do the following:

(1) Develop a habit of reading and learning with the following tools beside you: (a) Internet (e.g., google.com, Web of Science); (b) Excel, and (c) Mathematica (or any other higher-power math software than Excel, especially for quick visualization of equations).

(2) Retrieve from the electronic library the classical JACS paper by Brunauer, Emmett and Teller where the BET equation has been presented for the first time. (Do you need help to find this paper?)

(3) Which phase (or chemical?!) equilibrium does this equation describe?

(4) If possible, based on the information provided, use Excel to obtain the surface area of any material discussed in the paper. Here is some material for discussion...

(5) Analyze some of the tables and figures as carefully as you can, and try to ‘derive’ (or identify) some of the numbers that appear in some of them, based on the information provided in the text or in (an)other table(s) or figure(s).

(5a) See here a few relevant Mathematica calculations...  And here an update... Be prepared to discuss them (or to ask specific questions about them)!

(6) Use the “LeChatelier principle” to justify the adsorption trends shown in Table IV. (Is adsorption always exothermic? Does it matter whether it’s ‘physical’ or ‘chemical’?)

 

Some of the principal milestones in the development of thermo:

          -1760s: Black, heat capacities, latent heats (“calorimetry”)

          -1840s: Mayer, interconversion of heat and work (1st law)

          -1840s: Joule, interconversion of heat and work (Who’s done it first... A fascinating story!)

          -1850s: Kelvin, absolute temperature and 2nd law

          -1850s: Clausius, entropy and 2nd law

          -1870s: Gibbs, phase rule and chemical potential (“free energy”)

          -1880s: Helmholtz, equilibrium and free and bound energy

          -1880s: van’t Hoff, equilibrium constant

          -1900s: Nernst, 3rd law

Isn’t it remarkable that in only half a century essentially all the key concepts became rather clear (despite the fact that the relevant issues -- e.g., energy, heat, work -- had been studied for centuries)?!

 

Key G/S phase equilibrium concepts:

          -collision frequency (units?)

          -surface coverage (monolayer, multilayer)

          -intermolecular interactions

          -adsorption isotherm (Langmuir, BET, Freundlich, Dubinin, etc.)

          -others?

 

HW1 (accepted until 9/17), Atkins8: D7.1-7.5, E7.1, E7.9, E7.12, P7.2, P7.4, A7.36, D25.3, D25.5-25.7, E25.1, E25.4, E25.8, E25.13, P25.2, P25.6, A25.33. (Note: Parts of these problems will be solved during our class discussions or as ‘hints’, to be posted here in due course.)

 

Criteria for selection of a ‘good’ paper for (exam) analysis:

-Any research paper (or thesis, or report) must contain figures and/or tables that present one or all of the following types of results:

          (a) ‘Raw’ data: e.g., temperature or pressure vs. composition.

          (b) Data analysis: in our case, this is typically the determination of equilibrium parameters (e.g., properties such as equilibrium constant or partition coefficient) for a system, reaction, or process.

          (c) Correlations: establishment (e.g., discovery, confirmation, rediscovery) of relationships between structure and properties (in a ‘scientific’ study) or between properties and behavior (in an ‘engineering’ study).

-A ‘good’ paper for analysis will contain information in each one, or at least two, of these categories.

 

 

 

LRR3@psu.edu (updated 09/03/2008).