Notes and Background Information
Why this site was written
Almost all Internet sites that deal with thermodynamics and kinetics are
summaries from standard textbooks, formal lectures, cryptic collections of slides,
or oversimplified paragraphs. Yet, no topic in chemistry is more obscure than
the second law if a reader is plunged into equations before being clearly told
what physical events they refer to. Because there wasn't any site for those
who wanted to get a good qualitative view of the subjects, secondlaw site
was written.
This site begins without equations and introduces only the classic Clausius
definition of q(rev)/T in the main text. It is totally about acquiring a general
sense of how the world works "according to the second law and chemical
kinetics". The approach used to the second law is that of Kelvin -- the
key example being of energy spreading out, flowing from a concentrated/intense
state to one that is dispersed or spread out. Prototypical examples would be
a hot pan cooling down, a tire blowing out -- never the other way around. These
common human experiences seem almost childish, too trivial to think about. However,
their implications can be used to correlate an enormous range of physical events
in everyday life and in complex chemistry.
This is the "macro" or large scale approach to thermodynamics. The
molecular approach of Boltzmann is introduced only in the Appendix. This may not
be best. It was done to encourage the student by keeping the development of
the simplest ideas moving and reach a conclusion, rather than getting bogged
in details that can be better developed in class. (Or in 2ndlaw.com,
that is designed for the more advanced class.)
The touch of philosophy and a brief introduction to a bridge to the humanities
on the "Last page" could be greatly expanded. It is, somewhat, in
shakespeare2ndlaw.com. However,
there are a host of articles, light and serious, that could be written. The
reader is invited to do so. I will not be able to.
Our human goals conflict with the physical world described by the second law. Ancient myths (and, lightly, our modern Murphy's Law) embody this conclusion but exaggerate, personify, and make it sinister. Satan? Fate? Karma? Job's trials? Robert Frost's questions about "something not loving a wall"? Are these really useful concepts in view of the way the physical world works?