Was there an Initial Atmosphere from Accretion?

One of the problems with modern science is that once a paradigm has been selected, a layer of “authorities” is set up, and unless the scientist adopts the paradigm, little notice is taken of him or her. This is where conferences become important, because there is an audience that is more or less required to listen. The problem then for the person who has a different view is to show why that view is important enough to be considered. The barrier is rightly high. A new theory MUST do something the old one did not do, and it must not be contradicted by known facts. As I said, a high barrier.

In the previous post, I argued that the chemicals required for life did not come from carbonaceous chondrites or comets, and that is against standard thought. Part of the reason this view is held is that the gases had to come from somewhere, so from where? There are two obvious possible answers. The first is the gases were accreted with the planet as an atmosphere. In this hypothesis, the Earth formed while the disk gases were still there and simple gravity held them. Once the accretion disk was removed by the star, the hydrogen and helium were lost to space because Earth’s gravity was not strong enough, but other gases were retained. This possibility is usually rejected, and in this case the rejection is sound.

The first part of the proposition was almost certainly correct. Gases would have been accreted from the stellar disk, even on rocky planets, and these gases were largely hydrogen and helium. The next part is also correct. Once the disk gases were removed, that hydrogen and helium would be lost to space because Earth’s gravity was not strong enough to hold it. However, the question then is, how was it lost? As it happens, insufficient gravity was not the primary cause, and the loss was much faster than simply seeping off into space. Early in the life of a new star there are vicious solar winds and extreme UV radiation. It is generally accepted that such radiation would boil off the hydrogen and helium, and these would be lost so quickly that the other gases would be removed by hydrodynamic drag, and only some of the very heavier gases, such as krypton and xenon could remain. There is evidence to support this proposal, in that for krypton and xenon higher levels of heavier isotopes are observed. This would happen if most of these gases were removed from the top of the atmosphere, and since the lighter isotopes would preferentially find their way there, they would be removed preferentially. Since this is not observed for neon or argon isotopes, the argument is that all neon and argon in the atmosphere was lost this way, and if so, all nitrogen and carbon oxides, together with all water in the atmosphere would be lost. Basically, apart from the amount of krypton and xenon currently in the atmosphere, there would be no other gases. The standard theory of planetary formation has it that the Earth was a ball of magma, and if so, all water on the surface would be in the gas phase, so for quite some time Earth would be a dry lump of rock with an atmosphere that had a pressure that would be so low only the best vacuum pumps today could match it.

There could be the objection that maybe the star was not that active and we did retain some gases. After all, we weren’t around to check. Can you see why not? I’ll give the reason shortly. However, if we accept that the gases could not have come from the accretion disk, the other alternative is they came from below the ground, i.e. they were emitted by volacanic activity. How does that stand up?

One possibility might be that gases, including water, were adsorbed on the dust, then subsequently emitted by volcanoes. You might protest that if the Earth was a magma ocean, all that water would be immediately ejected from the silicates as a gas, but it turns out that while water is insoluble in silica at surface pressures, at pressures of 5000 atmospheres, granitic magma can dissolve up to 10% water at 1100 degrees C, at least according to Wikipedia. Irrespective of the accuracy of the figures, high temperature silicates under pressure most certainly dissolve water, and it probably hydrolyses the silicate structure and makes it far less viscous. It has been estimated that the water remaining in the mantle is 100 times greater than the current oceans so there is no problem in expecting that the oceans were initially emitted by volcanic activity. As an aside, deep in the mantle the pressures are far greater than 5000 atmospheres. This water is also likely to be very important for another reason, namely reducing the viscosity and lowering the magma density. This assists pull subduction, where the dry, or drier, basalt from the surface is denser than the other material around it and hence descends into the mantle. If the water were not there, we would not have plate tectonics, and if there were no plate tectonics, there would be no recycling of carbon dioxide, so eventually all the carbon dioxide on the surface would be converted to lime and there would be nothing for plants to use. End of life!

However, we know that our atmospheric gases were not primarily adsorbed as dust. How do we know that? In the accretion disk the number of nitrogen atoms is roughly the same as the number of neon atoms, and their heats of adsorption on dust are roughly the same. The only plausible physical means of separating them in the accretion disk is selective sublimation from ice, but ice simply could not survive where Earth formed. So, if our nitrogen came from the disk by simple physical means, then we would have roughly the same amount of neon in our atmosphere as nitrogen. We don’t, and the amount of neon we have is a measure of the amount of gas we have from such adsorption. Neon is present at 0.0018%, which is not very much.

So, in answer to the initial question, for a period there was effectively no atmosphere. To go any further we have to consider how the planets formed, and as some may suspect, I do not accept the standard theory for reasons that will become apparent in the next post.

Meanwhile, may I remind readers that my ebooks on Smashwords are on discount through July. Links to novels:

Puppeteer: http://www.smashwords.com/books/view/69696

‘Bot War: https://www.smashwords.com/books/view/677836

Troubles: https://www.smashwords.com/books/view/174203

Meanwhile, if you want to know scientifically about biofuels:

Biofuels: https://www.smashwords.com/books/view/454344

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A Response to Climate Change, But Will it Work?

By now, if you have not heard that climate change is regarded as a problem, you must have been living under a flat rock. At least some of the politicians have recognized that this is a serious problem and they do what politicians do best: ban something. The current craze is to ban the manufacture of vehicles powered by liquid fuels in favour of electric vehicles, the electricity to be made from renewable resources. That sounds virtuous, but have they thought out the consequences?

The world consumption of petroleum for motor vehicles is in the order of 23,000 bbl/day. By my calculation, given some various conversion factors from the web, that requires approximately 1.6 GW of continuous extra electric consumption. In fact much more would be needed because the assumptions include 100% efficiency throughout. Note if you are relying on solar power, as many environmentalists want, you would need more than three times that amount because the sun does not shine at night, and worse, since this is to charge electric vehicles, which tend to be running in daytime, such electric energy would have to be stored for use at night. How do you store it?

The next problem is whether the grid could take that additional power. This is hardly an insurmountable problem, but I most definitely needs serious attention, and it would be more comforting if we thought the politicians had thought of this and were going to do something about it. Another argument is, since most cars would be charged at night, the normal grid could be used because there is significantly less consumption then. I think the peaks would still be a problem, and then we are back to where the power is coming from. Of course nuclear power, or even better, fusion power, would make production targets easily. But suppose, like New Zealand, you use hydro power? That is great for generating on demand, but each kWhr still requires the same amount of water availability. If the water is fully used now, and if you use this to charge at night, then you need some other source during the day.

The next problem for the politicians are the batteries, and this problem doubles if you use batteries to store electricity from solar to use at night. Currently, electric vehicles have ranges that are ideal for going to and from work each day, but not so ideal for long distance travel. The answer here is said to be “fast-charging” stops. The problem here is how do you get fast charging? The batteries have a fixed internal resistance, and you cannot do much about that. From Ohm’s law, given the resistance, the current flow, which is effectively the charge, can only be increased by increasing the voltage. At first sight you may think that is hardly a problem, but in fact there are two problems, both of which affect battery life. The first is, in general an overvoltage permits fresh electrochemistry to happen. Thus for the lithium ion battery you run the risk of what is called lithium plating. The lithium ions are supposed to go between what are called intercalation layers on the carbon anode, but if the current is too high, the ions cannot get in there quickly enough and they deposit outside, and cause irreversible damage. The second problem is too fast of charging causes heat to be generated, and that partially destroys the structural integrity of the electrodes.

The next problem is that batteries can be up to half the cost of the purely electric vehicle. Everybody claims battery prices are coming down, and they are. The lithium ion battery is about seven times cheaper than it was, but it will not necessarily get much cheaper because at present ingredients make up 70% of the cost. Ingredient prices are more likely to increase. Lithium is not particularly common, and a massive increase in production may be difficult. There are large deposits in Bolivia but as might be expected, there are other salts present in addition to the lithium salts. There is probably enough lithium but it has to be concentrated from brines and there are the salts you do not want that have to be disposed of, which reduces the “green-ness” of the exercise. Lithium prices can be assumed to go up significantly.

But the real elephant in the room is cobalt. Cobalt is not part of the chemistry of the battery, but it is necessary for the cathode. The battery works by shuttling lithium ions backwards and forwards between the cathode and anode. The cathode material needs to have the right structure to accommodate the ions, be stable so the ions can move in and out, have valence orbitals to accommodate the electron transfer, and the capacity to store as many lithium ions as possible. There are other materials that could replace cobalt, but cobalt is the only one where, when the lithium moves out, something does not move in to fill the spaces. Cobalt is essential for top performance. There are alternatives to use in current technology, but the cost is in poorer lifetimes, and there are alternative technologies, but nobody is sure they work. At present, a car needs somewhere between 7 – 20 kg of cobalt in its batteries, and as you reduce the cobalt content, you appear to reduce the life of the battery.

Cobalt is a problem because the current usage of cobalt in batteries is 48,000 t/a, while world production is about 100,000 t/a. The price is increasing rapidly as electric vehicles become more popular. At the beginning of 2017, a tonne of cobalt would cost $US 32,500; now it is at least $US 80,000. Over half the world’s production comes from the Democratic Republic of Congo, which may not be the most stable country, and worse, most of that 100,000 t/a comes as a byproduct from copper or nickel production. If there were to be a recession and the demand for stainless steel fell, then the production of cobalt would drop. The lithium ion batteries that would not be affected are the laptops and phones; they only need about 10 – 20 g of cobalt. Even worse, there are a lot of these batteries that currently are not being recycled.

In a previous post I noted there was not a single magic bullet to solve this problem. I stick to that opinion. We need a much broader approach than most of the politicians are considering. By broader, I do not mean the approach of denying we even have a problem.

This post is later than my usual, thanks to time demands approaching Easter, and I hope all my readers have a relaxing and pleasant Easter.

Neanderthal Culture

We like to think that culture separates humans from animals, but what is the sign of culture? The reason this is of interest is that recently cave art has been discovered in some Spanish caves that is at least 60,000 years old, which means that it was drawn by Neanderthals as Homo sapiens did not arrive in Europe for another 20,000 years. It is not as distinctive as some of the cave art found in French caves, but that may not be surprising, since it has had to last an additional 30,000 years or so, and some has been dated to over 100,000 years.

Neanderthals are often considered as unsophisticated brutes, incapable of art, and far less technically capable than us. That has often been argued because Homo sapiens made quite sharp arrowheads and Neanderthals did not. It is true that Homo sapiens also made sharper spear tips, but this may be because the two races/species hunted differently. The Neanderthals were ambush hunters in the ice age forests whereas Homo sapiens arrived as grass-lands were appearing, and had to hunt in the open. This may be why the Neanderthals gave way: they simply could not get enough food. That we shall never know. There is also an argument that we have a few per cent of Neanderthal genes, which means the two interbred, which to me suggests they were simply different races and not different species.

As for being clumsy brutes, I saw in a museum near the palace at Versailles some artifacts, and yes, by and large the weapons used by the Neanderthals for hunting were far more clumsy looking, and would need a lot more power to use. But they were far more powerful. They had strength, but not stamina. They had not mastered flint knapping, and I am not sure whether they even knew about flint. We have to be careful in making such statements because although we have a number of artefacts, they tend to have been collected from a few very selected places, and during an ice age, the supply or resources may have been considerably less. However, at this museum there was also a bone flute that was attributed to them. If so, that means they made music. The caves also contained shells with holes pierced in them, strongly suggestive that the shells were made into necklaces.

Now the paintings. The way we know how old they are is interesting. The cave artists used inorganic pigments, by and large, although the black may have been carbon. However, the dating was done by a particularly crafty means. The paintings have a thin layer of calcite over them, deposited by groundwater seeping down over them. The water contains tiny levels of uranium, and when lodged in the calcite, it decays to thorium. (Thorium oxide is effectively insoluble in water, so it would not have been in the original water.) The uranium/thorium ratio allows us to date the calcite, and interestingly, although this layer is relatively thin, they have been able to shave it and find that the deeper calcite is indeed older.

So they drew, they made music, they adorned themselves. Not that much different from us.

A Ball on Mars

In New Zealand we are approaching what the journalists say is “The Silly Season”, the reason being that what with Christmas and New Year, and with it being in the middle of summer, a lot of journalists take holidays, and the media, with a skeleton staff, have to find almost anything to fill in the spaces that the media makes available. So, in the spirit of getting off to an early start, I noticed an image from Mars that looks as if someone left a cannon ball lying around. (The image is easily found on the web, but details are not, so I am not sure where it was found.) So what is it?

Mars_Ball

Needless to say there were some loopy suggestions from “the fringe”, but while it is easy to scoff, it is not so easy to try to guess what it is. The idea of a cannon ball and nothing else borders on the totally bizarre. So what can we see from the image? The remarkable point about this object is it seems to be lying on the surface, which suggest it did not strike it, as otherwise there would be indentations, or, if it were a meteorite, there would be a crater. There clearly isn’t. Equally, however, it looks smooth, which suggests it has been fused, which means it did not arise there. Some have suggested it is a haematite spherule, but that, to me is not that likely, in part because it is so large (the so-called “blueberries” were quite small) and also because there seems to be only one of it, while what created the “blueberries” created a lot of them. In my opinion, it is probably an iron meteorite, and the reason there is no impact crater is that it landed somewhere else, and rolled to this spot.

So maybe time to get a little more serious, and think about iron meteorites. What can we say about them? The Curiosity rover has also found “Egg rock”, which is an iron meteorite about the size of a golf ball. The Rover found iron, nickel and phosphorus as significant constituents, and the phosphorus is present as iron phosphide. There are two important issues here: how did the iron/nickel ball form separately from everything else, and equally important, how did iron phosphide form? That last question may need explanation, because phosphorus does not normally occur as a phosphide, and phosphides only form under highly reducing conditions. (Reducing conditions are usually in the presence of hydrogen and or an active metal at higher temperatures. The opposite, oxidising conditions, occurs when there is oxygen or water present, but not enough hydrogen or metal to scavenge the oxygen.)

Iron phosphide is known to occur in certain iron meteorites, but such meteorites can always be attributed to having formed at a little more than 1 A.U. from, or closer to the star. Chondrites that formed further out, such as in the asteroid belt, always have their phosphorus in the form of phosphate, which is a very stable, oxidised, phosphorus compound. The point about 1 A.U. (the distance of Earth from the sun) is that was where the temperatures were hot enough to melt iron, and the phosphide would form by the molten iron reacting with phosphate to form the phosphide and iron oxide.

Now for the reason for going on about this. One of the JPL team explained that iron meteorites originated from the cores of asteroids. The premise here is that during initial accretion, the dust assembled into an asteroid-sized object, the object got sufficiently hot and the iron and nickel melted and sunk to the core. Later, there was a massive collision and the asteroid’s core shattered, and the meteorites we see are the fragments from the shattering. (Note, the same people argue planets formed by asteroid sized bodies, and bigger, colliding and everything stick together. Here is having your cake and eating it in action.) The first question is, why did the rock melt? One possibility is radioactive isotopes, so it is possible, nevertheless for the explanation to work the asteroid had to melt hot enough to melt iron, and to hold those temperatures for long enough for the iron to work its way to the centre through the very viscous silicates in a very weak gravitational field. A further problem is that the phosphate would dissolve in the silicates, in which case it would not form iron phosphide because the iron would not get there. Calcium phosphate has a density of about 3, very similar to many of the silicates, so it might be difficult for iron phosphide to form in such an asteroid. Only a very few asteroids, and Vesta is one, have iron cores, and there are some reasons to believe Vesta formed somewhere else and moved.

The reason for my interest is that in my ebook, “Planetary Formation and Biogenesis” I argue that the first way accretion started was for the dust in the accretion disk to get hot enough to get sticky, or to form something that could later act like a cement. When the temperatures got up to about 1550 degrees Centigrade, iron melts and in the disk would form globules that would grow to a certain degree. Many of these would also find molten silicates to coat them, so the separation occurred through the temperature generated by the accreting star. Provided these could separate themselves from the gas flow (and there is at least a plausible mechanism) then these would become the raw materials for rocky planets to form. That is why (at least in my opinion) Earth, Venus and Mercury have large iron cores, but Mars does not.

That, of course, has got a little away from the “Martian cannonball” but part of forming a scientific theory is to let the mind wander, to check that a number of other aspects of the problem are consistent with the propositions. In my view, the presence of iron phosphide in an iron meteorite is most unlikely to have come from the core of an asteroid that got smashed up. I still like my theory, but then again, I suppose I am biased.

Ross 128b a Habitable Planet?

Recently the news has been full of excitement that there may be a habitable planet around the red dwarf Ross 128. What we know about the star is that it has a mass of about 0.168 that of the sun, it has a surface temperature of about 3200 degrees K, it is about 9.4 billion years old (about twice as old as the sun) and consequently it is very short of heavy elements, because there had not been enough supernovae that long ago. The planet is about 1.38 the mass of Earth, and it is about 0.05 times as far from its star as Earth is. It also orbits its star every 9.9 days, so Christmas and birthdays would be a continual problem. Because it is so close to the star it gets almost 40% more irradiation than Earth does, so it is classified as being in the inner part of the so-called habitable zone. However, the “light” is mainly at the red end of the spectrum, and in the infrared. Even more bizarrely, in May this year the radio telescope at Arecibo appeared to pick up a radio signal from the star. Aliens? Er, not so fast. Everybody now seems to believe that the signal came from a geostationary satellite. Apparently here is yet another source of electromagnetic pollution. So could it have life?

The first question is, what sort of a planet is it? A lot of commentators have said that since it is about the size of Earth it will be a rocky planet. I don’t think so. In my ebook “Planetary Formation and Biogenesis” I argued that the composition of a planet depends on the temperature at which the object formed, because various things only stick together in a narrow temperature range, but there are many such zones, each giving planets of different composition. I gave a formula that very roughly argues at what distance from the star a given type of body starts forming, and if that is applied here, the planet would be a Saturn core. However, the formula was very approximate and made a number of assumptions, such as the gas all started at a uniform low temperature, and the loss of temperature as it migrated inwards was the same for every star. That is known to be wrong, but equally, we don’t know what causes the known variations, and once the star is formed, there is no way of knowing what happened so that was something that had to be ignored. What I did was to take the average of observed temperature distributions.

Another problem was that I modelled the centre of the accretion as a point. The size of the star is probably not that important for a G type star like the sun, but it will be very important for a red dwarf where everything happens so close to it. The forming star gives off radiation well before the thermonuclear reactions start through the heat of matter falling into it, and that radiation may move the snow point out. I discounted that largely because at the key time there would be a lot of dust between the planet and the star that would screen out most of the central heat, hence any effect from the star would be small. That is more questionable for a red dwarf. On the other hand, in the recently discovered TRAPPIST system, we have an estimate of the masses of the bodies, and a measurement of their size, and they have to have either a good water/ice content or they are very porous. So the planet could be a Jupiter core.

However, I think it is most unlikely to be a rocky planet because even apart from my mechanism, the rocky planets need silicates and iron to form (and other heavier elements) and Ross 128 is a very heavy metal deficient star, and it formed from a small gas cloud. It is hard to see how there would be enough material to form such a large planet from rocks. However, carbon, oxygen and nitrogen are the easiest elements to form, and are by far the most common elements other than hydrogen and helium. So in my theory, the most likely nature of Ross 128b is a very much larger and warmer version of Titan. It would be a water world because the ice would have melted. However, the planet is probably tidally locked, which means one side would be a large ocean and the other an ice world. What then should happen is that the water should evaporate, form clouds, go around the other side and snow out. That should lead to the planet eventually becoming metastable, and there might be climate crises there as the planet flips around.

So, could there be life? If it were a planet with a Saturn core composition, it should have many of the necessary chemicals from which life could start, although because of the water/ice live would be limited to aquatic life. Also, because of the age of the planet, it may well have been and gone. However, leaving that aside, the question is, could life form there? There is one restriction (Ranjan, Wordsworth and Sasselov, 2017. arXiv:1705.02350v2) and that is if life requires photochemistry to get started, then the intensity of the high energy photons required to get many photochemical processes started can be two to four orders of magnitude less than what occurred on Earth. At that point, it depends on how fast everything that follows happens, and how fast the reactions that degrade them happen. The authors of that paper suggest that the UV intensity is just too low to get life started. Since we do not know exactly how life started yet, that assessment might be premature, nevertheless it is a cautionary point.

A personal scientific low point.

When I started my PhD research, I was fairly enthusiastic about the future, but I soon got disillusioned. Before my supervisor went on summer holidays, he gave me a choice of two projects. Neither were any good, and when the Head of Department saw me, he suggested (probably to keep me quiet) that I find my own project. Accordingly, I elected to enter a major controversy, namely were the wave functions of a cyclopropane ring localized (i.e., each chemical bond could be described by wave interference between a given pair of atoms, but there was no further wave interference) or were they delocalized, (i.e. the wave function representing a pair of electrons spread over more than one pair of atoms) and in particular, did they delocalize into substituents? Now, without getting too technical, I knew my supervisor had done quite a bit of work on something called the Hammett equation, which measures the effect or substituents on reactive sites, and in which, certain substituents that had different values when such delocalization was involved. If I could make the right sort of compounds, this equation would actually solve a problem.

This was not to be a fortunate project. First, my reserve synthetic method took 13 steps to get to the desired product, and while no organic synthesis gives a yield much better than 95%, one of these struggled to get over 35%, and another was not as good as desirable, which meant that I had to start with a lot of material. I did explore some shorter routes. One involved a reaction that was published in a Letter by someone who would go on to win a Nobel prize. The very key requirement to get the reaction to work was omitted in the Letter. I got a second reaction to work, but I had to order special chemicals. They turned up after I had submitted my thesis. They travelled via Hong Kong, where they got put aside and forgotten. After discovering that my supervisor was not going to provide any useful advice on chemical synthesis, he went on sabbatical, and I was on my own. After a lot of travail, I did what I had set out to do, but an unexpected problem arose. The standard compounds worked well and I got the required straight line set with minimum deviation, but for the key compound at one extreme of the line, the substituent at one end reacted quickly with the other end in the amine form. No clear result.

My supervisor made a cameo appearance before heading back to North America, where he was looking for a better paying job, and he made a suggestion, which involved reacting carboxylic acids that I already had in toluene. These had already been reported in water and aqueous alcohol, but the slope of the line was too shallow to be conclusive. What the toluene did was to greatly amplify the effect. The results were clear: there was no delocalization.

The next problem was the controversy was settling down, and the general consensus that there was such delocalization. This was based on one main observational fact, namely adjacent positive charge was stabilized, and there were many papers stating that it must on theoretical grounds. The theory used was exactly the same type of programs that “proved” the existence of polywater. Now the interesting thing was that soon everybody admitted there was no polywater, but the theory was “obviously” right in this case. Of course I still had to explain the stabilization of positive charge, and I found a way, namely strain involved mechanical polarization.

So, where did this get me? Largely, nowhere. My supervisor did not want to stick his head above the parapet, so he never published the work on the acids that was my key finding. I published a sequence of papers based on the polarization hypothesis, but in my first one I made an error: I left out what I thought was too obvious to waste the time of the scientific community, and in any case, I badly needed the space to keep within page limits. Being brief is NOT always a virtue.

The big gain was that while both explanations explained why positive charge was stabilized, (and my theory got the energy of stabilization of the gas phase carbenium ion right, at least as measured by another PhD student in America) the two theories differed on adjacent negative charge. The theory involving quantum delocalization required it to be stabilized too, while mine required it to be destabilized. As it happens, negative charge adjacent to a cyclopropane ring is so unstable it is almost impossible to make it, but that may not be convincing. However, there is one UV transition where the excited state has more negative charge adjacent to the cyclopropane ring, and my calculations gave the exact spectral shift, to within 1 nm. The delocalization theory cannot even get the direction of the shift right. That was published.

So, what did I learn from this? First, my supervisor did not have the nerve to go against the flow. (Neither, seemingly, did the supervisor of the student who measured the energy of the carbenium ion, and all I could do was to rely on the published thesis.) My spectral shifts were dismissed by one reviewer as “not important” and they were subsequently ignored. Something that falsifies the standard theory is unimportant? I later met a chemist who rose to the top of the academic tree, and he had started with a paper that falsified the standard theory, but when it too was ignored, he moved on. I asked him about this, and he seemed a little embarrassed as he said it was far better to ignore that and get a reputation doing something more in accord with a standard paradigm.

Much later (I had a living to earn) I had the time to make a review. I found over 60 different types of experiment that falsified the standard theory that was now in textbooks. That could not get published. There are few review journals that deal with chemistry, and one rejected the proposal on the grounds the matter was settled. (No interest in finding out why that might be wrong.) For another, it exceeded their page limit. For another, not enough diagrams and too many equations. For others, they did not publish logic analyses. So there is what I have discovered about modern science: in practice it may not live up to its ideals.

Scientific low points: (2)

The second major low point from recent times is polywater. The history of polywater is brief and not particularly distinguished. Nikolai Fedyakin condensed water in, or repeatedly forced water through, quartz capillaries, and found that tiny traces of such water could be obtained that had an elevated boiling point, a depressed freezing point, and 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 dissolved quartz, (b) the water had polymerized. Everybody “knew” water did not dissolve quartz, therefore it must have polymerized. From the vibrational spectrum of polywater, two new bands were observed at 1600 and 1400 cm-1. From force constant considerations this was explained in terms of each OH bond being of approximately 2/3 bond order. The spectrum was consistent with the water occurring in hexagonal planar units, and if so, the stabilization per water molecule was calculated to be in the order of 250-420 kJ/mol. For the benefit of the non-chemist, this is a massive change in energy, and it meant the water molecules were joined together with a strength comparable to the carbon – carbon bonds in diamonds. The fact that it had a reported boiling point of » 150 oC should have warned them that this had to be wrong, but when a bandwagon starts rolling, everyone wants to jump aboard without stopping to think. An NMR spectrum of polywater gave a broad, low intensity signal approximately 300 Hz from the main proton signal, which meant that either a new species had formed, or there was a significant impurity present. (This would have been a good time to check for impurities.) The first calculation employing “reliable” methodology involved ab initio SCF LCAO methodology, and water polymers were found to be stabilized by polymer size. The cyclic tetramer was stabilized by 177 kJ/mol, the cyclic pentamer by 244 kJ/mol, and the hexamer by 301.5 kJ/mol. One of the authors of this paper was John Pople, who went on to get a Nobel prize, although not for this little effort.

All of this drew incredible attention. It was even predicted that an escape of polywater into the environment could catalytically convert the Earth’s oceans into polywater, thus extinguishing life, and that this had happened on Venus. We had to be careful! Much funding was devoted to polywater, even from the US navy, who apparently saw significant defence applications. (One can only imagine the trapping of enemy submarines in a polymeric syrup, prior to extinguishing all life on Earth!)

It took a while for this to fall over. Pity one poor PhD candidate who had to prepare polywater, and all he could prepare was solutions of silica. His supervisor told him to try harder. Then, suddenly, polywater died. Someone notice the infrared spectrum quoted above bore a striking resemblance to that of sweat. Oops.

However if the experimentalists did not shine, theory was extraordinarily dim. First, the same methods in different hands produced a very wide range of results with no explanation of why the results differed, although of course none of them concluded there was no polywater. If there were no differences in the implied physics between methods that gave such differing results, then the calculation method was not physical. If there were differences in the physics, then these should have been clearly explained. One problem was, as with only too many calculations in chemical theory, the inherent physical relationships are never defined in the papers. It was almost amusing to see, when it was clear there was no polywater, a paper was published in which ab initio LCAO SCF calculations with Slater-type orbitals provide evidence against previous calculations supporting polywater. The planar symmetrical structure was found to be not stable. A tetrahedral structure made by four water molecules results in instability because of excessive deformation of bond angles. What does that mean, apart from face-covering for the methodology? If you cannot have roing structures when the bond angles are tetrahedral, sugar is therefore an impossible molecule. While there are health issues with sugar, impossibility of its existence is not in debate.

One problem with the theory was that molecular orbital theory was used to verify large delocalization of electron motion over the polymers. The problem is, MO theory assumes it in the first place. Verifying what you assume is one of the big naughties pointed out by Aristotle, and you would thing that after 2,400 years, something might have stuck. Part of the problem was that nobody could question any of these computations because nobody had any idea of what the assumed inputs and code were. We might also note that the more extreme of these claims tended to end up in what many would claim to be the most reputable of journals.

There were two major fall-outs from this. Anything that could be vaguely related to polywater was avoided. This has almost certainly done much to retard examination of close ordering on surfaces, or on very thin sections, which, of course, are of extreme importance to biochemistry. There is no doubt whatsoever that reproducible effects were produced in small capillaries. Water at normal temperatures and pressures does not dissolve quartz (try boiling a lump of quartz in water for however long) so why did it do so in small capillaries? The second was that suddenly journals became far more conservative. The referees now felt it was their God-given duty to ensure that another polywater did not see the light of day. This is not to say that the referee does not have a role, but it should not be to decide arbitrarily what is true and what is false, particularly on no better grounds than, “I don’t think this is right”. A new theory may not be true, but it may still add something.

Perhaps the most unfortunate fallout was to the career of Deryagin. Here was a scientist who was more capable than many of his detractors, but who made an unfortunate mistake. The price he paid in the eyes of his detractors seems out of all proportion to the failing. His detractors may well point out that they never made such a mistake. That might be true, but what did they make? Meanwhile, Pople, whose mistake was far worse, went on to win a Nobel Prize for developing molecular orbital theory and developing a cult following about it. Then there is the question, why avoid studying water in monolayers or bilayers? If it can dissolve quartz, it has some very weird properties, and understanding these monolayers and bilayers is surely critical if we want to understand enzymes and many biochemical and medical problems. In my opinion, the real failures here come from the crowd, who merely want to be comfortable. Understanding takes effort, and effort is often uncomfortable.