Bubblefish said:
Here is a post from a link on Dr. Lo's paper that was addressed by pragmatist. I am posting this as refrence. I am not qualified to discuss it or clarify it.
I simply note that all of you find all of this information about him, but you dont seem to find where he may have addressed some of your concerns.
Dr. Lo responded to the critique on his work, and here is a copy of that below.
Well, thank you for that, I wasn't aware of Prof Engelking's critique. However, Dr Lo's rebuttal doesn't exactly address
my concerns - in fact it only increases them! Let me address the scientific issues, I'll address your other post when I get some more time.
Bubblefish said:
Rebuttal of Professor Engelking's Argument
By Shui-Yin Lo
An E-Mail from Professor Paul Engelking, University of Oregon, was posted on the Internet with a commentary from the bulletin board host ``IE Crystals Debunked!'' Professor Engelking apparently was responding to a query from Mark Dallara and his E-Mail is presumed to be a commentary on the Shui-Lin Lo paper ``Anomalous State of Ice'' published in Modern Physics Letters B, 10(19):909-919, 1996. Professor Engelking
stated he found the theory to be erroneous in several places and cited two problems with one of the basic calculations.
Problem 1, E & M
The crucial point of Prof. Engelking's critique is which is the correct form of Gauss law to use in the problem being addressed:
Equation 1 * D ds = Q ** Or
Equation 2 * E ds = Q **
· * closed surface (I could not find the symbol for this J. Collins)
· ** quantum of charge.
Professor Engelking stated that the correct form to use for a polarizable medium such as water is equation one and that use of the second equation was not correct. He went on to say ``If Lo's statement of Gauss? law would be true, it would be true only in a vacuum; it is incorrect in a polarizable medium such as water.''
Gauss' law as stated in equation 2 is certainly true in a vacuum. However, a water molecule consists of one nucleus of oxygen and two nuclei of hydrogen plus ten electrons surrounding them, all of which are in vacuum. Since all water molecules consist of nuclei, hydrogen and electrons in vacuum, Gauss' law as expressed in equation 2 is fundamentally correct in any situation, contrary to Professor Engelking's assertion.
The quantity of D in equation one is a derived one and has meaning only in a macroscopic medium. The definition of D and derivation of equation 1 from equation 2 are found in published papers (J.D. Jackson, Classical Electrodynamics, Section 4.2,
p. 103: L.D. Landau and E.M. Lifshitz, Electrodynamics of Continuous Media, Chapter 2,
Section 6, p.36).
Considering the published work of Jackson, and Landau and Lifshitz, equation 1 may be used when considering a macroscopic medium of water liquid but not in a small water cluster. Equation 2 is used when counting the layer of water molecules around an ion with only two or three layers. The number of water molecules is small. It is not correct to use equation 1 as it would be likely to yield an incorrect result, as pointed out in the paper ``Anomalous State of Ice''.
What a load of nonsense! Let's get this clear.
Firstly, Lo is absolutely correct that the actual medium between the molecules is vacuum. However, that doesn't justify his assumption. What he says would be true, if and
only if you were dealing with a single isolated water molecule and an ion both in an absolute ideal vacuum free from electromagnetic fields. The electric field of a charged body in vacuum extends to infinity in all directions. When two charged bodies are brought into proximity their respective fields overlap and combine. If the two bodies are isolated, then it is easy to calculate the fields and forces involved between them. We only need to consider the scalar magnitudes of the fields and the distance between the bodies.
However, if there are other charges present, regardless of
where they are located in space, those charges will affect the net fields and forces acting on the two bodies. As soon as one extra body (i.e. 3 total) is introduced the problem becomes vectorial in nature with respect to the effective distribution of charges. For example, in water, we refer to a "dipole" moment - but water isn't actually a dipole, it's a tripole (2 H's and one O) and so the dipole moment is a vector which is an approximation of the major axis of the
effective charge distribution. However, even though we have considered the major axis of charge distribution, the fact remains that the
actual field around the molecule is not spherically symmetrical and there is a uneven distribution of the field which varies with radial position. So the "dipole moment" of water is simply a convenient approximation when we are dealing with the
net effect of a molecule on something which is at a relatively great distance away. The dipole moment is totally meaningless at very short range (i.e. at the magnitude of bond lengths).
Anyway, let's imagine a real water molecule, which is in proximity to other water molecules,
and it is hydrogen bonded to them (as is the case in water). We now introduce a single free ion into this field of pure water. Whilst the actual net charge of the ion is fixed the
effective charge of the entire water molecule considered as a whole will be an approximation derived from the composite fields of the component particles. And not only that, it will also be dependent on the fields of the other water molecules
around it. Note: I really mean
around - not just between. The effective net charge of the water molecule as presented to the ion, will be influenced by other water molecules even if they are not
between the ion and the water molecule under consideration, because the fields of the particles involved cover the
whole of space, not just the space between the ion and the water molecule,
and because the ion will not couple
only to one single water molecule!
The ion will couple to
all particles in the whole of space - i.e. the entire universe. Of course we can discount the effect of particles at great distances away because their effects will be negligible. But we cannot discount the local environment of multiple water molecules in relative proximity to the ion.
There is however a problem if we want to calculate the actual fields and forces. Firstly the actual problem is a quantum problem at this scale, so we are not necessarily dealing with absolutely fixed and rigid positions and geometries. We cannot possibly know the exact geometries because of the Heisenberg Uncertainty Principle. So the best we can do is approximate. But even with that constraint the problem still cannot be solved analytically (even if we knew the wavefunctions) because it's a classic example of what is known as the 3 Body Problem. It is currently believed to be
impossible to analytically solve dynamic systems which involve more than two bodies - and it is impossible to analytically solve the quantum wavefunctions. So no exact calculation is possible. However, in reality we can get round problems of this type using dynamic approximations (for example the Self Consistent Field method) which is a series of recursive approximations which can sometimes give a numerical answer in such cases.
But even approximations like SCF have their limits. In the case of many water molecules you can't even practically get away with things like SCF. So what we do, when there are many bodies involved is we use overall approximations based on the macroscopic environment that we are able to measure. And in that case, we say that the dielectric constant of water is 80. That is a macroscopic approximation, that takes into account the effect of
many water molecules and their combined fields and forces on
any point within the grouping under consideration. It makes no difference that there is a vacuum between the ion and the water molecule - the
effective environment that both objects are in, affects both in such a way that the best approximation is to simply take the permittivity as being 80 at
all points in space within the body of water.
Now, in practice, of course the
actual permittivity will be inhomogeneous within a polar medium. It may well drop to less than 80 at specific points but the exact value cannot be known and also we
do know that it will always be considerably more than that of free space in a polar solvent like water. It's possible to use things like the Lorentz-Debye-Sack theory and the Born approximation to give estimates. And of course, the actual value will also depend on the charge of the ion. But either way it's totally inappropriate to use free space permittivity. Engelking is quite correct in what he says.
So to summarize, there are two ways of approaching such a calculation such as the one Lo tried to do. The first is to take it as a discrete quantum problem, derive the composite wavefunctions and solve them by approximation (because it's impossible to do it analytically in any event, and even the quantum approximation is far too difficult to do in practice if there are a great many bodies involved). The second is to use an overall macroscopic classical approximation that will gve us a crude but approximately accurate model of the overall environment - and we do that by using the displacement field (not the true E field) and by using relative permittivities.
What Lo did however, was to take a group of figures related to macroscopic approximations (such as the dipole moment) and then tried to derive a classical (not quantum) analytical solution for a many body quantum problem (which is impossible) - and then discarded specific elements of the macroscopic model he was using in order to fit his strange idea. Which is a total travesty. He claims to be a quantum physicist yet appears not to be familiar with elementary classical physics, let alone quantum physics!
And if that is not enough, even his arithmetic is suspect! For example he uses a dipole moment of 2.45 Debyes for water. The measured (and internationally recognised) experimental value of the dipole moment for water at room temperature and pressure is roughly 1.85 Debyes. Of course it varies with the degree of hydrogen bonding and the state of the water. A value of 2.45 Debyes is around the value for ice. But the entire calculation is just so far removed from reality as to beggar belief, this is not the work of someone who understands physics.
This is in addition to the points I raised before about the total misapplication of Gauss's Law. Gauss's Law relates to
flux not field - a physicist would know the difference. And in addition Gauss's Law does not assume that all fluxes are spherically symmetrical, all it takes into account is that the total flux crossing the surface of integration is a certain value - it does not mean that there are not local variations in the field,
or that the surface of integration has to be the surface of a sphere. It's usually drawn like that in high school textbooks because it's easier to understand it like that - but that is a simplified version for kiddies, not people purporting to be physics professors.
I didn't mention his idea of equating the "pressure" on the water molecule to the energy density. Of course
dimensionally the energy density is equivalent to a pressure. Energy divided by distance gives force, and force over area is pressure. So energy over volume (energy density) is dimensionally the same as force over area. But that doesn't mean that it can be directly, qualitatively interpreted in the same way. The idea of a "spherically symmetric" pressure on a water molecule arising from a net linear moment of electrostatic force doesn't make any sense at all. As I said before, it's just so absurd I didn't even think it necessary to comment further. It's like saying that shooting someone in the foot is the same as crushing them to death from all directions!
Bubblefish said:
Another point that is crucial in the application of the Second Law of Thermodynamics is that is has to be applied to an isolated system. For a system that interacts with its surroundings, entropy can actually decrease, e.g., A human being is more ordered than his surrounding entropy. In order to maintain such order, entropy inside a human actually has to decrease to enable him to grow. This does not violate the second law of thermodynamics because the entropy of his surroundings increases. Since the crystals occupy only a small percentage of the aqueous solution, they are by no means
isolated. Therefore the second law of thermodynamics cannot be applied to IE crystals unless the surrounding water solution are also taken into account, which was apparently not considered by Professor Engelking when he critiqued the Anomalous State of Ice.
Any individual process or action or reaction has to obey the Second Law. Which means in practice that every reaction has to have a net increase in entropy. If Lo now insists that a localised internal decrease of entropy is offset by an external increase, then it follows that the two actions have to be coupled. In which case his equations are wrong because they don't show the external effect coupled and how it influences the reaction. In effect, the argument that "my calculations are correct because there are more things going on than my calculations show" is absurd in itself! It doesn't need much more comment than that.
And talk about shooting yourself in the foot - Lo ignores the effect of hydrogen bonding on the permittivity and argues that his molecules act in isolation in free space above - then when confronted by an argument against a breach of the second law, he tries to convince us that normal water molecules are rigidly hydrogen bonded and are not free and cannot move in isolation which is the very thing assumed in his calculations! The contradiction is absurd.
I note that Engelking doesn't argue against Lo's proposition on energetic grounds, solely on entropy - but I believe it's not energetically feasible either, for the reasons which I stated last time. Either way, energetically
or entropically it doesn't make any sense.
.