Polymerised Water

In my opinion, probably the least distinguished moment in science in the last sixty years occurred in the late 1960s, and not for the seemingly obvious reason. It all started when Nikolai Fedyakin condensed steam in quartz capillaries and found it had unusual properties, including a viscosity approaching that of a syrup. Boris Deryagin improved production techniques (although he never produced more than very small amounts) and determined a freezing point of – 40 oC, a boiling point of » 150 oC, and a density of 1.1-1.2. Deryagin decided there were only two possible reasons for this anomalous behaviour:

(a) the water had dissolve quartz,

(b) the water had polymerised.

Since recently fused quartz is insoluble in water at atmospheric pressures, he concluded that the water must have polymerised. There was no other option. An infrared spectrum of the material was produced by a leading spectroscopist from which force constants were obtained, and a significant number of papers were published on the chemical theory of polywater. It was even predicted that an escape of polywater into the environment could catalytically convert the Earth’s oceans into polywater, thus extinguishing life. Then there was the inevitable wake-up call: the IR spectrum of the alleged material bore a remarkable resemblance to that of sweat. Oops. (Given what we know now, whatever they were measuring could not have been what everyone called polywater, and probably was sweat, and how that happened from a very respected scientist remains unknown.)

This material brought out some of the worst in logic. A large number of people wanted to work with it, because theory validated it existence. I gather the US navy even conducted or supported research into it. The mind boggles here: did they want to encase enemy vessels in toffee-like water, or were they concerned someone might do it to them? Or even worse, turn the oceans into toffee, and thus end all life on Earth? The fact that the military got interested, though, shows it was taken very seriously. I recall one paper that argued Venus was like it is because all its water polymerised!

Unfortunately, I think the theory validated the existence because, well, the experimentalists said it did exist, so the theoreticians could not restrain themselves from “proving” why it existed. The key to the existence is that they showed through molecular orbital theory that the electrons in water had to be delocalized. Most readers won’t see the immediate problem because we are getting a little technical here, but to put it in perspective, molecular orbital theory assumes the electrons are delocalized over the whole molecule. If you further assume water molecules come together, the firsr assumption requires the electrons to be delocalised, which in turn forces the system to become one molecule. If you cannot end up with what you assumed in the first place, your theoretical work is not exactly competent, let alone inspired.

Unfortunately, these calculations involve what are called quantum mechanics. Quantum mechanics is one of the most predictive theories ever, and almost all your electronic devices have parts that would not have been developed but for knowledge of quantum mechanics. The problem is that for any meaningful problem there is usually no analytical solution from the formal quantum theory generally used, and any actual answer requires some rather complicated mathematics, and in chemistry, because of the number of particles, some approximations. Not everyone agreed. The same computer code in different hands sometimes produced opposite results with no explanation of why the results differed. If there were no differences in the implied physics between methods that gave opposing results, then the calculation method was not physical. If there were differences in the physics, then these should have been clearly explained. The average computational paper gives very little insight to what is done and these papers were actually somewhat worse than usual. It was, “Trust me, I know what I’m doing.” In general, they did not.

So, what was it? Essentially, ordinary water with a lot of dissolved silica, i.e. option (a) above. Deryagin was unfortunate in suffering in logic from the fallacy of the accident. Water at 100 degrees C does not dissolve quartz. If you don’t believe me, try boiling water it in a pot with a piece of silica. It does dissolve it at supercritical temperatures, but these were not involved. So what happened? Seemingly, water condensing in quartz capillaries does dissolve it. However, now I come to the worst part. Here we had an effect that was totally unexpected, so what happened? After the debacle, nobody was prepared to touch the area. We still do not know why silica in capillaries is so eroded, yet perhaps there is some important information here, after all water flows through capillaries in your body.

One of the last papers written on “anomalous water” was in 1973, and one of the authors was John Pople, who went on to win a Nobel Prize for his work in computational chemistry. I doubt that paper is one that he is most proud of. The good news is the co-author, who I assume was a post-doc and can remain anonymous because she almost certainly had little control on what was published, had a good career following this.

The bad news was for me. My PhD project involved whether electrons were delocalized from cyclopropane rings. My work showed they were not however computations from the same type of computational code said it did. Accordingly, everybody ignored my efforts to show what was really going on. More on this later.