Friday, January 9, 2009

Long Chains of Water

Under the right conditions, water itself can polymerize, or form chains of molecules. This little known fact was first discovered in Soviet Defense Department-funded labs in the Polytechnic Institute of the ancient town of Kostroma, in the Golden Circle of Old Russia. There a Russian Chemist named Nikolai Fedyakin discovered that he could make small quantities of a hyperviscous water with an elevated boiling point and a depressed freezing point.

Fedyakin was obviously a low-level guy in the Soviet hierarchy, so the Russians soon put their top surface chemist, B.V. Derjaguin, on the problem.(1) Derjaguin continued to work on the problem with his assistant Churaev until the Russians were sure that there were no military applications to this spectacular new discovery.(2) Then they published those discoveries in the West. (3,4)

From there, Western scientists took up the task of characterizing this new form of what’s probably the most commonly used substance on earth. (5,6,7,8) Human beings had been looking at water for millenia, and looking at it scientifically for centuries, without discovering this amazing property of the substance. In a similar vein, a soccer-ball shaped molecule of carbon was discovered in soot thirty years later, another case of something wonderful being hidden in a substance so common, no one bothered to look at it critically anymore.

Western scientists attempted to explain this amazing form of water with a variety of theories (9,10), the most promising being a form of p-electron delocalization. (11) No one was ever able to completely figure out just what was going on at the molecular level, however, because no one was able to synthesize large quantities of the substance.

Derjaguin himself (12) took a crack at providing an explanation a few years after the excitement in the West had died down. But it was not until recently that there was any hope of explaining the forces that bind this unique and possibly useful form of water together. With the recent advances in both experiment (13) and supercomputing (14,15), we are beginning to explore the forces behind the clustering of water molecules, we are beginning to understand the ways that water molecules can cluster together.

1. Derjaguin, B. V., Churaev, N. V., Fedjakin, N. N., et al., Izv. Akad. Nauk. S.S.S.R., ser. khimich., N10, 2178 (1967).
2. Derjaguin, B. V., and Churaev, N. V., New Properties of Liquids (in Russian) (Nauka, Moscow, 1971).
3. Derjaguin, B. V., and Churaev, N. V., J. Coll. Interface Sci., 36, 415 (1971).
4. Derjaguin, B. V., and Churaev, N. V., Nature Phys. Sci., 232, 131 (1971).
5. C. T. O'Konski “Covalent Polymers of Water.” Science 168, 1089-1091 (1970)
6. C. A. Angell and E. J. Sare “Vitreous Water: Identification and Characterization.” Science 168, 280-281 (1970)
7. S. W. Rabideau and A. E. Florin “Anomalous Water: Characterization by Physical Methods.” Science 169, 48-52 (1970)
8. G. A. Castellion, D. G. Grabar, J. Hession, and H. Burkhard “Polywater: Methods for Identifying Polywater Columns and Evidence for Ordered Growth.” Science 167, 865-868 (1970)
9. L. C. Allen and P. A. Kollman “A Theory of Anomalous Water” Science 167, 1443-1454 (1970)
10. J. W. Linnett “Structure of Polywater” Science 167, 1719-1720 (1970)
11. R. P. Messmer “Polywater: Possibility of p-Electron Delocalization.” Science 168, 479-480 (1970)
12. Derjaguin, B. V., and Churaev, N. V., “Nature of "Anomalous Water” Nature 244, 430 - 431 (1973)
13. C.J. Gruenloh, J.R. Carney, C.A. Arrington, T.S. Zwier, S.Y. Fredericks, K.D. Jordan
“Infrared Spectrum of a Molecular Ice Cube: The S4 and D2d Water Octamers in Benzene-(Water)8” Science 276 1678 – 1681 (1997)
14. C.J. Tsai and K.D. Jordan, "Theoretical Study of the (H20)6 Cluster," Chemical Physics Letters 213, 181-88 (1993).
15. C.J. Tsai and K.D. Jordan, "Theoretical Study of Small Water Clusters: Low-Energy Fused Cubic Structures for (H2O)n, n=8, 12, 16 and 20," Journal of Physical Chemistry 97, 5208-10 (1993)

I hope you enjoyed this nicely documented piece I just put together.

Because it is complete and utter horse shit.

Fedyakin was real. He, as far as I know, was a two bit polytechnic teacher not associated with the Soviet Defense forces in any way expect the way that every Academic was in that highly militarized society. And, by the way, in the Soviet Union it was "Ministry of Defense", not "Defense Department".

Derjaguin and Churaev did run with the discovery, and then tout their results in the West. Western scientists did try to reproduce the results and study the structure of the substance for about four years. However, and I skipped this part, there were plenty of problems reproducing the results. I selectively did not cite these skeptical article from the heyday of polywater research:

W. M. Madigosky “Polywater or Sodium Acetate?” Science 172, 264-265 (1971)

D. L. Rousseau “ ‘Polywater’ and Sweat: Similarities between the Infrared Spectra” Science 171, 170-172 (1971)

S. L. Kurtin, C. A. Mead, W. A. Mueller, B. C. Kurtin, and E. D. Wolf “‘Polywater’: A Hydrosol?” Science 167, 1720-1722 (1970)

By the early seventies, Western scientists had concluded that polywater, which had only ever been made in trace amounts, was actually water with a whole lot of impurities in it, which explained the change in viscosity and colligative properties.

In addition, unless you actually went to look up the last Derjaguin reference, you would not be aware that it was actually the publication where he finally recanted and admitted that the Western scientists were correct about the composition of polywater.

And what about the more recent papers I cited? Well, water can polymerize to a slight degree via various methods of attraction between the molecules. Small polymers, less than a few hundred repeating units long, are often referred to as oligomers, and small amounts of these in a water sample will not cause the viscosity or colligative property changes claimed for polywater. The polywater part of the above essay has NOTHING to do with the water cluster work I cited. I just wanted to make that clear because one of the authors of the legitimate papers is a very old and dear friend of mine.

So the next time someone comes citing papers that actually come to the opposite conclusion of that of the citing “authority” (cough James Blodgett cough*), remember this: Always go back and READ THE ORIGINAL SOURCE when someone is citing papers in a scientific argument. Also, when you see papers that are more than a few years old being cited, go back and check to see if there are retractions, arguments, or alternative explanations proposed in the literature. Just because an argument cites scientific publications, it does not necessarily follow that the argument is scientifically valid.

*Specifically this reference, which predicts black holes - in certain very unlikely scenarios of string theory - and also predicts their rapid decay. You can't have one without the other, the theory predicts both events, but that title "Black Hole Factories" doesn't give you a clue as to that conclusion, you need to go look up the paper for yourself to find it. Bad physicist, bad.


CW said...

Good stuff John... As I was reading I was thinking "oh yeah - polywater - I remember something about that... It was all because Fedyakin's capillary tubes had oils or other impurities in them? I also remember it from Star Trek :) It seems like the history of science is full of stuff like that. "Ectoplasm" would be my personal favourite.

Jim Wright said...

Hey now. I myself have made polywater.

It's simple really and I don't understand how a chemist could miss it. Also my results are 100% reproducible in a variety of delicious flavors.

Take 1qt boiling water, add 1 box Jell-O instant mix...

What? Trust me, it'll change the hell out of the viscosity. Especially after an hour or so in the fridge. Try adding a can of fruit cocktail.

Teach the controversy, that's all I'm saying here.

CW said...

Jimbo you forgot the vodka. Of course vodka solves the polymers, which is why we need scientists like John to help us with the formula for Electric Jello. When I was an undergraduate the chemists always had the best Electric Jello.

Jim Wright said...

Electric Jello.

served by the tray, in little tiny plastic shot glasses by a well endowed girl in a halter top. Ah, I miss those days.

Jim Wright said...

Also, scientifically speaking this is why the Americas weren't able to reproduce the Russian results - not enough vodka.