I admire your naive belief that CJ has a clue about the significance
(or even the meaning) of the "Boltzmann energy."

-----
Richard Schultz                              schultr@mail.biu.ac.il
Department of Chemistry, Bar-Ilan University, Ramat-Gan, Israel
Opinions expressed are mine alone, and not those of Bar-Ilan University
-----
"an optimist is a guy/ that has never had/ much experience"

Finally someone who knows what they're talking
about and is willing to discuss it!

All quotes below are from:
The Structure Of Liquid Water; Novel Insights From Materials
Research; Potential Relevance To Homeopathy
Rustum Roy1, W.A. Tiller2, Iris Bell3, M. R. Hoover4
Received: 2 August 2004     Revised: 6 September 2004 Accepted: 14
September 2005
Materials Research Innovations 9-4: 1433-075X
which can be read at this link:
http://www.rustumroy.com/Roy_Structure%20of%20Water.pdf

I direct your attention to fig 1.7
page 3 of Dr. Roy's paper in the caption
of which he says:

"The classical picture of the
"Random Network Structure" as presented
by Zachariasen in 1932, which has become
"established" as the structure of glass
on the basis of model fitting on x-ray
scattering data. The key assumption (unrecognized
by others for 7 or 8 decades) of this model is that
the structure of all glasses is
"homogeneous" in the same ways as crystals are."

He goes on to say:

"This now outdated image, based on no
direct data from other methods, has dominated the
thinking of the physics and chemistry community
ever since, and it became their "working model"

Roy mentions another theory which has been
mentioned in opposition to the "homogeneity"
one and states that by the 1980's this matter
had been experimentally decided.

"The existence
and high probability of nanoheterogeneity in most strongly bonded
glass and liquid structures
are now established as the "standard model".

"In sharp contrast with the hypothetical calculations based on
Zachariasen's random network theory, is
the direct TEM evidence. Shown are some examples of binary and ternary
glasses, some quenched, some heat-
treated which clearly show actual phase-separation. One can
confidently assume that in many if not most glasses
and in many liquids, structural (-composition) fluctuations must exist
as precursors to such phase separation
(after Mazurin and Porai-koshits) [11])."

Now let's cut to the chase.
I had thought that because of the high rate of
hydrogen bond making and breaking in water,
it would have been impossible to have
temporally persisting structures
(required to hold patterns for diluted
substances of Homeopathy) in ordinary
room temperature water. Other posters,
not worth naming, have offered reasons
about this.

But these "structures" that Roy is talking
about, whose existence he seems to regard as a necessary
and sufficient condition for phase changes,
are apparently large enough and numerous enough
such that their spatial deployment
throughout the water is unaffected by
the bond activity mentioned.

Here, read this noting the last
sentence in particular:
"Turning from the possible nanoheterogeneity of structure, to
kinetics , we examine the
argument that the "rapid breaking and remaking of bonds" excludes the
possibility of different
structures co-existing in liquid water. One can safely assume that
these kinetics do not change
just because phase separation may be involved at essentially a single
temperature. Obviously
these very fast kinetics of breaking and re-formation of bonds are
irrelevant since they take
place within each structural arrangement of units, without
statistically affecting the structure
of the units themselves." (from page 6 of the paper).

Well this is a surprise though I wish
he would have gone into more detail
on the monomer or oligomer composition
of these "structures" - in particular
I don't quite see what physical
forces are causing them to coalesce
and therefore exist though he
does make an argument later
regarding the necessity
of their physical existence
as an explanation of phase
anomalies.

What Roy does do is offer an argument
apparently based on analogy with
other materials and then uses
an argument based on Thermodynamics.
That loses me as I never had a course
on Thermodynamics, but here is the
relevant passage:

"The significance of these data on the thermodynamics of liquid water,
following the earlier
studies of S, Se, Te, etc., can now be summarized, although they may
not be obvious to those
unfamiliar with this branch of thermodynamics. It has been an
established part of
conventional thermodynamics (as see in any textbook on phase diagrams)
that the gas and one
liquid stable regions of a fixed composition can only have one phase,
in contrast to solids
where one can, and often does, find even a dozen phases. There are no
phase transitions of
liquid A ↔ liquid B at a fixed composition. Hence these data--the
extensive earlier work
and now the paper on water--require a major re-thinking on the
structure(s) of water.
These data also provide some important indications on the kinetics of
change of such
structures. The conventional wisdom typically uses the argument that
if new clusters (or nano-"structures") form they must be very
transient because "the lifetime of a bond can be
estimated by the two relations:"

Here Roy gives an equation which estimates the average hydrogen bond
lifespan at about 10-6 seconds (a microsecond)
and of a strong covalent bond at about a million years (!).

He later concludes:
"The point being made here is that the obviously
relevant kinetics are those of the persistence of structural elements
(crystalline form determined clusters, non-heterogeneous regions,
etc.) under near ambient conditions. It is
absolutely certain that at least some of these are reasonably long
lived, since they give us the
distinctive properties."

Now that has me surprised but it gets better.

After referencing Martin Chaplin's website
and his beginnings of a taxonomy of water
molecule structures, Roy gives pictures
of what some of these structures might
look like based on tetrahedron bonding
in figs 8 and 9 on page 12 of the paper.

Now, if this is correct and there are
even just hundreds of such structures,
then their spatial arrangement and number
would be more than enough to encode
patterns.

Roy makes the overall conclusion that:

"On the basis of these well-established materials science principles,
one can conclude that the
structure of liquid water at say 25° C and 1 atm is a highly mobile
assemblage of interactive
clusters (dominantly perhaps of half a dozen different oligomers),
with minor amounts of
dozens of others, and possibly a few larger "polymers" in the 200-H20
range. What is very
significant about this model is that this arrangement of a "zoo" of
mixed sizes of molecules is
also highly likely to be highly anisodesmic. First there will be a
cluster of bond strength
values around the typical hydrogen bond within the cluster, or in
small molecules. But these
intra-cluster bonds are likely to be much stronger than the inter-
cluster van der Waals type
bonds. Most interrogatory experimental tools may be inappropriate for
making this
distinction especially among its weakest bonds. Hence water is ideal
for responses to small
and large changes in all the intensive thermodynamic variables. Water
is therefore probably
the most easily changed phase of condensed matter known. It is this
unique anisodesmicity, or
structural and bonding heterogeneity, that helps explain its amazingly
labile nature and hence
the various extraordinary data, e.g. the clustering of water and
solute in very dilute solutions."

In several places he mentions that confusion
may exist between the chemists idea of
"structure of water" (focus of attention
on bonds and individual molecules, the "bricks")
and the materials scientists' view of same
with focus on the 3d spatial arrangement of
the molecules (the "walls", "buildings" and structures).

Well that's the gist of it.

What do you think?

Does the research he cite in fact support these
very interesting conclusions.  He has apparently
answered in the affirmative both regards
for the possibility of identifying evidence
that they exist AND their temporal persistence.

Intriguing, absolutely intriguing.

Citizen Jimserac

The beginning of wisdom.

+-------- D. C. Sessions <dcs@lumbercartel.com> ---------+

This may be the first intelligent thing that I've seen you post.

-----
Richard Schultz                              schultr@mail.biu.ac.il
Department of Chemistry, Bar-Ilan University, Ramat-Gan, Israel
Opinions expressed are mine alone, and not those of Bar-Ilan University
-----
"You don't even have a clue about which clue you're missing."