in article [email hidden], Jim Menegay at
[email hidden] wrote on 3/31/04 4:07 PM:
Quoted message said:Guy Hoelzer <[email hidden]> wrote in message
news:<[email hidden]>...
Quoted message said:in article [email hidden], Jim Menegay
at [email hidden] wrote on 3/26/04 8:14 PM:
Quoted message said:Guy Hoelzer <[email hidden]> wrote in message
news:<[email hidden]>...
> As I understand it, entropy cannot be concretely
> defined for anything other than a closed system.
I believe this is correct with respect to classical (pre-
Prigogine) thermodynamics.
> The closest thing we know of that satisfies this
> condition [closed system] is the universe as a
> whole ...
I believe this is incorrect. Perhaps you are confusing
"closed" systems with "isolated" systems.
A "closed system" is one that does not exchange matter
with its surroundings. It may exchange heat and work
with its surroundings. (We need to measure these flows,
which may be difficult in practice.)
Right. In your terminology, which I have seen before, I
meant an isolated system. In my terminology, isolation is
a matter of degree, but closure is absolute.
Quoted message said:Examples of closed systems are the universe, the solar
system (approximately closed), or the contents of any
stoppered beaker.
Thanks for being clear on your semantics here. As I meant
a "closed system", neither the solar system nor a
stoppered beaker would qualify;
[snip]
This is not some wild and wooly scientific frontier land
of "complex systems thermo", with unsettled terminology.
We were talking about civilized territory here - classical
thermodynamics. It is one thing for you frontier folk to
use Humpty Dumpty semantics, where words mean whatever you
want them to mean. But in the civilized world, words are
taken to mean what the textbooks say they mean - no more,
no less. And, sooner or later, if you frontiersmen succeed
in your mission of reintegrating with and enriching
civilization, you are going to have to start using the
civilized meanings of words, not your own.
I appreciate your point, but I agree with the point Tim made
in his response. Use of these terms have varied across
disciplines that are brought together under the umbrella of
complex systems science. I don't think I was being sloppy,
and I did not just make up my definitions without
considering traditional semantics. I have been strongly
influenced by the use of language in spatial population
genetics, in which the term "isolation" is conventionally
used as a continuous variable. It would be unusual to use
the term "closed" in this field, although I for one would
take it to mean complete isolation. Whether or not you find
my defense convincing, I think it is increasingly important
to keep an open mind regarding the different conventions
existing in different disciplines as new fields emerge, such
as complex systems science, that link historically disparate
disciplines.
Quoted message said:Quoted message said:Quoted message said:In principle, entropy can be measured for any closed
system by integrating dS = dQrev / T.
I am not comfortable interpreting your equation, and
don't have the time at the moment to investigate it ...
There is no rush, take your time. You only need to
understand this if you wish to discuss classical
thermodynamics without looking like an uneducated fool. It
is not my equation. It is the textbook definition of
entropy. Has been for over a hundred years.
Right. This is the Clausius equation, which is only defined
for systems at or very close to equilibrium. To bring this
thread back from this diversion, the notion of entropy and
how it can be measured has had a bit of a tortured history
since Clausius' time. I won't bring up Shannon's information-
based notion of entropy here, but I would like to turn the
discussion to consider the role of entropy in systems far-from-
equilibrium (Prigogine's goal) because this is the framework
in which it would relate to biological systems like
organisms. I think that all biological systems are
dissipative systems, to use Prigogine's language.
Quoted message said:Quoted message said:Quoted message said:There is nothing particularly mysterious or inaccessible
about classical entropy. But its definition does presume
that you can measure heat flow and temperature. This
means that you have to be close to (or at) thermal
equilibrium. You don't need to be close to chemical
equilibrium, as long as no chemical reactions are
occuring.
These sound like non-existent conditions to me; heat is
flowing, but there is thermal equilibrium, and no
chemical reactions are occurring. How is this
"accessible"?
Perhaps my statement was lacking in clarity here. Heat CAN
flow, but in a state of thermal equilibrium no heat is
actually flowing (between system and surroundings).
(Incidentally, "system" and "surroundings" are also
technical terms, defined in all of the textbooks).
Regarding chemical reactions, perhaps I should have said
that no net reactions are occurring at the macro level.
At the micro level, we of course continue to have, for
example, 2H2O <--> OH- + H3O+, but no net flow in either
direction. As an example of a system far from chemical
equilibrium, but with a well defined entropy, I had in
mind a beaker of nitro-glycerin. Another example would
be one of Tim's supersaturated solutions, in the absence
of a seed.
OK. These are unstable equilibria. This is not a novel
concept for me. However, neither of these examples represent
systems. I took the time to look up "system", and it
confirmed my understanding that a system is constituted as a
functionally integrated whole. An arbitrary volume of liquid
with externally imposed boundaries does not qualify.
Quoted message said:Thermodynamics is not rocket science. It is explained in
any good first year course in chemistry or physics.
My threshold for absorbing condescension is being tested at
this point.
Quoted message said:It is used daily by millions of chemists, engineers, PBS
auto mechanics, and even rocket scientists. Thermodynamics
is not an enigma, though it can be used as a starting
point for those who like to discover, explore, or sell
enigmas.
Are you claiming that what is "known" about thermodynamics
is perfect? It is both absolutely correct and complete?
There are no "enigmas" left in thermodynamics? I guess that
would explain your satisfaction with equilibrial models.
Quoted message said:And finally, thermodynamics is not the same discipline as
statistical thermodynamics, though the two disciplines
illuminate each other and stand in a relationship that E.
O. Wilson would call discipline and anti-discipline.
This is an interesting point that I had not considered.
Guy