Title: This is not your fathers or my mothers physical chemistry course.
1- This is not your fathers (or my mothers)
physical chemistry course. - Michelle Francl
- Bryn Mawr College
-
Bryn Mawr College was founded in 1885 with a
mission to provide graduate education to women.
2Course Goals
Oure termes so lerned and queynte Whan we be
ther where we shul exercise Oure elvish craft, we
seme wondrous wyse, Oure termes be so lerned and
so queynte. Yet wil I telle them, as they come
to mynde, Though I can not them set right in
their kind As sal armoniak, verdegres,
boras Geoffrey Chaucer Traditionally, the
earliest known production of what Chaucer calls
sal armoniak, or ammonium chloride, was from
the burning of camel dung in the temple of
Jupiter Ammon in what is now Libya hence sal
ammoniac or salt of Ammon. This term is the
root for amine and eventually amino acid.
- Use quantitative, mathematical approach to the
description and analysis of the structure and
behavior of matter - Apply these methods to other fields
- Appreciate the strength and limitations of the
methods - Take and succeed in a next course in physical
chemistry or subfield - Read the literature as a novice
- Retain student interest in the field
3Calculus of Hours
The Curta is a precision calculating machine
for all arithmetical operations. Curta adds,
subtracts, multiplies, divides, square and cube
roots... and every other computation arising in
science and commerce... Available on a trial
basis. Price 125 From an advertisement in the
back pages of Scientific American in the 1960s.
This is about 700 in 2002 dollars about the
same price as Mathematica.
- There is not as much time as you think
- Less than 40 hours/semester in the classroom
- Read 180,000 words
- Do 150-200 problems
- 150 to 200 hours total/semester
4Authority vs. Activity
Life is good for only two things, discovering
mathematics and teaching mathematics. Siméon
Poisson
5Strategies should be
Josiah Willard Gibbs was not paid a salary for
the first 9 years of his job at Yale. Once he
had a job offer from Johns Hopkins University in
Maryland, Yale began to pay him. He gained little
recognition for his work during his lifetime
mainly because of his inability to communicate
his ideas so that others could understand the
concepts he was discussing.
6Active
Let us learn to dream, gentlemen then perhaps
we will find the truth. But let us beware of
publishing our dreams until they have been tested
by the waking understanding. August Kekule von
Stradonitz (taken from The Scientific Attitude,
2nd Edn by Frederic Grinnell)
- Talk less, they learn more
- Using the pause procedure to enhance lecture
recall. Ruhl, K. L., Hughes, C. A., Schloss,
P. J. (1987, Winter). Teacher Education and
Special Education, 10, 14-18 - The importance of lecture in general-chemistry
course performance Birk, J.P., Foster, J. (1993)
J Chem Ed 70 179 - Departing from Lectures An Evaluation of a
Peer-Led Guided Inquiry Alternative Lewis,
S.E., Lewis, J.E. (2005) J Chem Ed 82 135 - Do less, they learn more
- Effects of lecture information density on medical
student achievement Russell. I.J., Hendricson,
W.D., Herbert, R.J. (November, 1984).. Journal
of Medical Education, 59, 881-889
7Active Materials
- Materials they can talk about
- Physical Chemistry A Guided Inquiry Atoms,
Molecules and Spectroscopy. R. S. Moog, J. N.
Spencer, J. J. Farrell Houghton Mifflin Boston,
2004. )POGIL/NSF - Physical Chemistry Online (PCOL)
http//pcol.ch.iup.edu/ NSF - Culture of Chemistry Physical Chemistry in
Context NSF - Materials they can use
- SymMath collection at JCE http//jchemed.chem.wis
c.edu/JCEDLib/SymMath/index.html
Science (n.) The attempt by subroutines in an
operating system to deduce the source code, and
write the instruction manual. Dave Logan
8Connected
Katharine Blodgett was the first woman to earn a
Ph.D. in physics from Cambridge under Ernest
Rutherford after Irving Langmuir intervened on
her behalf. She earned her A.B. from Bryn Mawr
College early in the last century. She is best
known for her work on Langmuir-Blodgett films.
- Context rich materials
- Who, what, where, when, why?
- As such, physical chemistry underlies much
of modern science and is a motor driving advances
in a very wide range of fields. Building on
information and concepts from chemistry, physics,
mathematics, physical chemistry contributes to
and is stimulated by areas as diverse as
medicine, molecular biology, biochemistry,
molecular engineering, chemical engineering,
materials science and earth sciences. - Advantages
- Engagement
- Performance
- Retention
9Context Rich Problems
The famous Boltzmann equation, Sk ln ?, is
inscribed on Boltzmanns tombstone in Vienna,
Austria. Boltzmann did not write it in this
form, however, Planck did. Boltzmann also has
two other equations named for him, the first is a
diffusion equation used in neutron transport
theory and the second describes particles in a
gravitational field.
- Context Free
- Find an expression for the half-life of the
third-order reaction 3A ? B. - Contextualized
- The gas-phase formation of phosgene, CO Cl2 ?
COCl2 is 3/2 order with respect to CO. Derive
the integrated rate equation for a 3/2 order
reaction. Derive the expression for the
half-life. - Context rich
- In a paper by Bada, Protsch and Schroeder Nature
241, 394 (1973), the rate of isomerization of
isoleucine in fossilized bone is used as an
indication of the average temperature of the
sample since it was deposited. The reaction - L-isoleucine ? D-alloisoleucine
- iso allo
- produces a nonbiological amino acid,
D-alloisoleucine, that can be measured using an
automatic amino acid analyzer. At 200C, this
first order reaction has a half-life of 125,000
years and its activation energy is 139.7 kJ
mol-1. After a very long time, the ratio allo/iso
reaches an equilibrium value of 1.38. You may
assume that this equilibrium constant is
temperature independent. - For a hippopotamus mandible found near a warm
spring in South Africa, the allo/iso ration was
found to be 0.42. Assuming that no allo was
present initially, calculate the ratio of the
concentration of allo now present to the
concentration of allo after a very long time
(Note the correct answer is between 0.40
and0.60). - Radiocarbon dating, which is temperature
independent, indicated an age of 38,600 years for
the hippo tooth.
10Connected Materials
- Develop materials keyed to primary scientific
literature - Proof of concept NSF CCLI-EMD grant
- Early adopter cadre
- Development of materials
- Assessment
Nano comes from the Greek for dwarf nanos.
11What they are not
- Not to teach library or literature skills
- Not to replace texts
- Not to add new topics
Does anyone actually use nanowires? Well, Dr. Ock
in Spiderman 2 claimed to use nanowires to
connect his neural circuitry to a machine
circuit. In fact, silicon nanowires have
recently been used to build sensors for DNA. The
sensors are designed to detect the presence of
mutations in a cystic fibrosis gene. Nano
Letters 2004, 4, 51 -54
12What they are
- Flexible
- Stand alone
- Extendable
- Context-rich
Engineers think that equations approximate the
real world. Scientists think that the real world
approximates equations. Mathematicians are
unable to make the connection.
13Design of Materials
- Papers
- Short
- Current
- Readable
- Cross disciplinary
- Problems
- Critical reading
- Basic concepts
- Variety
- Extendable
- Marginalia
- Hook
- Faces of chemistry
- History
A Case of Mistaken Identity Fischer of Fischer
projections is not the Fischer of Fischer
carbenes, and yet another Fischer lends his name
to the Fischer-Tropsch reaction All, however,
were German.
14First order kinetics and ostrich eggs
- Kinetics
- Archeology
- Biochemistry
Chaos is a name for any order that produces
confusion in our minds. George Santayana
15Background
Prof. Francisco received his Ph.D. in 1983 from
MIT, then spent time as a post-doctoral fellow at
Cambridge. Prof. Franciscos group blends high
resolution laser spectroscopy and sophisticated
electronic structure theory to tease out the
connections between reaction rates and chemical
structure in free radical chemistries. His
research has been key to showing that some
refrigerants, such as HFCs may not pose the same
hazards to the ozone layer as CFCs.
- How many millions of years ago were these
sediments deposited? Were the colors in this
folio applied when it was printed, or sometime
later? Is this a modern hippo bone, or a fossil
of some similar, earlier species? Just how old
is it? The determination of the age of an
artifact or sample is a crucial question in many
fields, including geology, paleontology,
archaeology, anthropology and history. Context
often provides a clue to the age of an object.
For example, the style of decoration of a vase or
the types of pigments applied to a fresco can be
used to narrow the time period in which a
particular artifact was produced. How deeply
something is buried is yet another source of
information about an items age. Provenance, or
the written record of an objects history, is
another source from which the age of an object
can be determined. These approaches obviously
cannot be applied to find an age for every object
or specimen. Chronometric methods, such as the
familiar 14C dating, can be brought to bear when
the relative dates derived from contextual
information are inadequate, or when forgery is
suspected. - Amino acids are nearly always found in the L-form
in natural products, such as proteins.
Uncatalyzed epimerization at the chiral carbon
is, not surprisingly, an exceedingly slow.
16Problems
Alan Turing is perhaps best known for his work on
codes in World War II, particularly with the
Enigma machines. He is also often called the
father of computer science. Turing also had a
long standing interest in chemistry, and was a
long distance running of near Olympic caliber.
- In an early paper describing this method
Science, 1970, 170, 730-732, there is a note
that at equilibrium a small excess of
D-alloisoleucine is present (at 140oC they report
the ratio of alloisoleucine to isoleucine is
1.25), but that for most amino acids the
equilibrium constant between the L and D forms is
1. Why should that be? Why do you suppose it is
different for isoleucine? - Using the expression in question 5 and the
parameters given in the paper, compute the
forward rate constant at 144oC. What is the
value of the rate constant for the reverse
reaction at this temperature?
17Marginalia
Winning the Prize wasnt half as exciting as
doing the work. Maria Goeppert Mayer Nobel Prize
winner in physics (1963)
- How old is a whale?
- Humans are among the longest-living mammals, with
a life-span on the order of 100 years. Human
ages can be verified by consulting birth and
census records. Whales are also apparently very
long-lived, but discovering the age of a whale is
a somewhat more daunting task and the life-spans
of most whale species have not been established.
The ages of some whales, such as blue whales and
fin whales can be determined by counting the
layers of ear wax in their inner ears. .. The
degree of racemization of aspartic acid in the
lens of the eye has been used to find the ages in
20 different species, including humans. Ages
were obtained for 48 different whales, one which
had an apparent age of 211 years Can. J. Zool.
1999, 77, 571580, making the bowheads the
longest living mammals known!
- What can you do with an M.D./Ph.D.?
(Bio)chemical kinetics, of course. - Maude Menten (1879-1960) was an early M.D./Ph.D.,
and one of the first women to become a physician
in Canada. . - Unnatural Amino Acids
- Thirty years ago, it was assumed that all amino
acid residues in naturally occurring polypeptides
were in the L-form. We now know there are a few
exceptions. For example, some polypeptide
antibiotics found in fungi incorporate D-amino
acids. It is thought that in most cases the
peptide is synthesized with all L-amino acids,
subsequently individual amino acids undergo
enzymatically catalyzed epimerization. Only one
such epimerase has been identified to date. The
serine epimerase found in the venom of the funnel
spider, Agelenopsis aperta
18Further Reading
There was a time when the newspapers said that
only twelve men understood the theory of
relativity. I do not believe that there ever was
such a time. There might have been a time when
only one man did, because he was the only guy who
caught on, before he wrote his paper. But after
people read the paper a lot of people understood
the theory of relativity in some way or other,
certainly more than twelve. On the other hand, I
think I can safely say that nobody understands
quantum mechanics. R. Feynman in The Character
of Physical Law. 1965
- Reliability of Amino Acid Racemization Dating
and Paleotemperature Analysis on Bones, M. L.
Bender, Nature, 1974, 252, 378-379. Dr. Bada
Replies, J.L. Bada, ibid. 1974, 252, 379-381.
An early controversy over the accuracy of the
dates obtained from amino acid racemization. - See the whole Chaucerian litany in either Middle
English or Modern English at http//classiclit.abo
ut.com/library/bl-etexts/gchaucer/bl-gchau-can-can
-m.htm. Want the full medieval experience?
Images of the full text of two 15th century
versions can be found at http//www.bl.uk/treasure
s/caxton/homepage.html. You can read the Canons
Yeomans Tale in (almost) its original form
thanks to the British Library.
19Further information
- See http//www.brynmawr.edu/Acads/Chem/NSFpchem/
- E-mail mfrancl_at_brynmawr.edu
20Blogging
- Marginalia
- Topics
- Solicit and post student contributions
- CultureOfChemistry.blogspot.com
Physics is very muddled again at the moment it
is much too hard for me anyway, and I wish I were
a movie comedian or something like that and had
never heard anything about physics! Wolfgang
Pauli (1900-1958) From a letter to R. Kronig, 25
May 1925.
21Acknowledgements
- Anne McCoy
- Michael Moore
- Lynn Melton
- Maria Pacheco
- Carol Parish
- Virginia Pett
- Ray Rataiczak
- Tracy Schoolcraft
- Marcy Towns
- Matt Tuchler
- Jane Van Doren
- John Wheeler
- Stephanie Schaertel
- Kathleen Howard
- Joseph Alia
- Swarna Basu
- Joseph Brom
- Jeanne Bundens
- Franklin Chen
- Lisa Chirlian
- Paul Davis
- Raymond Esquerra
- Brian Gilbert
- Rainer Glaser
- Sam Glazier
- Alan Goren
- Steve Gravelle
- Barry Hicks
- David Horner
- Jerry Jasinski
- Kristin Krantzman
- Patti Lang
- NSF DUE
- Bryn Mawr College
Activation Energy The useful quantity of energy
available in one cup of coffee.
22Assessment
Which picture is of Gibbs?