Martian Fluvial Flows, Placid and Catastrophic

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Despite the fact that, apart localized dust surfaces in summer, the surface of Mars has had average temperatures that never exceeded about minus 50 degrees C over its lifetime, it also has had some quite unexpected fluid systems. One of the longest river systems starts in several places at approximately 60 degrees south in the highlands, nominally one of the coldest spots on Mars, and drains into Argyre, thence to the Holden and Ladon Valles, then stops and apparently dropped massive amounts of ice in the Margaritifer Valles, which are at considerably lower altitude and just north of the equator. Why does a river start at one of the coldest places on Mars, and freeze out at one of the warmest? There is evidence of ice having been in the fluid, which means the fluid must have been water. (Water is extremely unusual in that the solid, ice, floats in the liquid.) These fluid systems flowed, although not necessarily continuously, for a period of about 300 million years, then stopped entirely, although there are other regions where fluid flows probably occurred later. To the northeast of Hellas (the deepest impact crater on Mars) the Dao and Harmakhis Valles change from prominent and sharp channels to diminished and muted flows at –5.8 k altitude that resemble terrestrial marine channels beyond river mouths.

So, how did the water melt? For the Dao and Harmakhis, the Hadriaca Patera (volcano) was active at the time, so some volcanic heat was probably available, but that would not apply to the systems starting in the southern highlands.

After a prolonged period in which nothing much happened, there were catastrophic flows that continued for up to 2000 km forming channels up to 200 km wide, which would require flows of approximately 100,000,000 cubic meters/sec. For most of those flows, there is no obvious source of heat. Only ice could provide the volume, but how could so much ice melt with no significant heat source, be held without re-freezing, then be released suddenly and explosively? There is no sign of significant volcanic activity, although minor activity would not be seen. Where would the water come from? Many of the catastrophic flows start from the Margaritifer Chaos, so the source of the water could reasonably be the earlier river flows.

There was plenty of volcanic activity about four billion years ago. Water and gases would be thrown into the atmosphere, and the water would ice/snow out predominantly in the coldest regions. That gets water to the southern highlands, and to the highlands east of Hellas. There may also be geologic deposits of water. The key now is the atmosphere. What was it? Most people say it was carbon dioxide and water, because that is what modern volcanoes on Earth give off, but the mechanism I suggested in my “Planetary Formation and Biogenesis” was the gases originally would be reduced, that is mainly methane and ammonia. The methane would provide some sort of greenhouse effect, but ammonia on contact with ice at minus 80 degrees C or above, dissolves in the ice and makes an ammonia/water solution. This, I propose, was the fluid. As the fluid goes north, winds and warmer temperatures would drive off some of the ammonia so oddly enough, as the fluid gets warmer, ice starts to freeze. Ammonia in the air will go and melt more snow. (This is not all that happens, but it should happen.)  Eventually, the ammonia has gone, and the water sinks into the ground where it freezes out into a massive buried ice sheet.

If so, we can now see where the catastrophic flows come from. We have the ice deposits where required. We now require at least fumaroles to be generated underneath the ice. The Margaritifer Chaos is within plausible distance of major volcanism, and of tectonic activity (near the mouth of the Valles Marineris system). Now, let us suppose the gases emerge. Methane immediately forms clathrates with the ice (enters the ice structure and sits there), because of the pressure. The ammonia dissolves ice and forms a small puddle below. This keeps going over time, but as it does, the amount of water increases and the amount of ice decreases. Eventually, there comes a point where there is insufficient ice to hold the methane, and pressure builds up until the whole system ruptures and the mass of fluid pours out. With the pressure gone, the remaining ice clathrates start breaking up explosively. Erosion is caused not only by the fluid, but by exploding ice.

The point then is, is there any evidence for this? The answer is, so far, no. However, if this mechanism is correct, there is more to the story. The methane will be oxidised in the atmosphere to carbon dioxide by solar radiation and water. Ammonia and carbon dioxide will combine and form ammonium carbonate, then urea. So if this is true, we expect to find buried where there had been water, deposits of urea, or whatever it converted to over three billion years. (Very slow chemical reactions are essentially unknown – chemists do not have the patience to do experiments over millions of years, let alone billions!) There is one further possibility. Certain metal ions complex with ammonia to form ammines, which dissolve in water or ammonia fluid. These would sink underground, and if the metal ions were there, so might be the remains of the ammines now. So we have to go to Mars and dig.

 

 

 

 

 

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Anzac Day

April 25 is a public holiday in New Zealand and Australia, in remembrance of the Australian and New Zealand Army Corps landing at Anzac Cove, in Gallipoli during World War 1, hence our major remembrance day remembers a disaster. In my opinion, the campaign illustrated just about most of what was wrong with the way World War 1 was fought by the allies. The Ottomans had entered the war on the German side, and the objective of the campaign was to take Constantinople and remove them from the war. That was a noble goal, but it left open the question, was it achievable with the resources available and did the Allies go about it in a sensible fashion? There were several strategic mistakes straight away (in my opinion, anyway).

The first mistake was to underestimate the enemy. It was generally felt that the Ottomans would have no heart for fighting. The British started with a naval blockade in the Dardanelles, using a number of obsolete battleships that were not doing anything else. This was pointless and had no worthwhile objective. You cannot defeat an enemy without at least the option of occupying his ground. The Ottomans mined the Dardanelles, and the British and French lost some obsolete battleships. With that, they managed to raise the morale of the enemy, and that was a critical mistake. The Ottomans had had a recent history of failure, and if troops feel they will fail, they usually do. If, on the other hand, they feel they are up to the job, they probably are. Another critical mistake was that the move gave away the element of surprise and flagged that a military operation was imminent. The Ottomans prepared.

Undeterred, the allies made landings on various parts of the northern side of the Gallipoli peninsula, with the main force of British and French at Cape Helles at the Western end, and the Anzacs at Anzac Cove. Things started badly for the Anzacs when the Royal Navy made a navigational error and landed them at the wrong place, which had a narrow beach and steep hills rising from close to the beaches. Now you might think that the commander of the invasion, seeing they were in the wrong place and not only that, a most unsuitable place, might order the navy to take them to somewhere better, but no. Incompetence has to be matched with stupidity! The landing was faced by only two companies but they had good defensive positions on the hills. There were serious casualties since there was no cover, and lot of time was wasted, which gave the Ottomans time to bring up reinforcements. On finally advancing, the troops found the terrain to be badly broken, with ravines and spurs; ideal for defence, terrible for rapid progress. Worse, the Anzacs had almost useless maps.

So with the attack bogged down in two places, you might think things couldn’t get any worse? Then you would be wrong. A third invasion was launched with an extra 70,000 British troops. The key to note here is that the British High Command regarded the Gallipoli attack as a bit of a side show, possibly put on to keep Churchill happy because this was his pet project. That meant the commanders sent to this campaign were the ones who were lesser lights. Now, with two lesser lights already bogged down, the third had to be a really dim light. Sir John Monash was later to describe the commanders as, “the most abject collection of Generals ever collected in one spot.”

The overall commander for the landing at Suvla Bay was Sir Frederick Stopford, chosen largely because he was the only one left with adequate seniority.

Stopford had been brought out of retirement, and although only 61, he was in very poor health, and before leaving for Gallipoli, had to get someone else to lift his dispatch case onto a train. He had never commanded troops in battle. The Divisional commanders were not much better. One, Major General Hammersley, had just got over a nervous breakdown, and collapsed on the first day of the landing. The first formal objective of Suvla Bay was to advance and take two important hills, as this would relieve the pressure on the Anzacs, but Stopford and his Divisional commanders seemed to believe they could not do this. No surprise here; if you think you can’t, generally you won’t. Stopford felt that success depended on surprise and it was important to keep all information from the Ottomans. Accordingly, his Brigadiers were not told of the plan until the last minute, they were only given a brief glimpse of the landing site, and many landed without maps. To make matters worse, they were given “targets” to occupy, but the Navy landed them in the opposite order. Had there been a slightly more dynamic commander, and had the Brigadiers been supplied with proper maps, the objectives could have been swapped, but no, the landing boats had to criss-cross, then unload on reefs. Thanks to the lack of maps, the men given the task of taking Suvla point simply got lost. Those tasked with taking Hill 10 had no idea which hill it was.

Even stranger, Brigadier General Hill, commanding 6,000 men on transport vessels, awoke unexpectedly to find himself under fire at Suvla Bay. He had no idea he was to take part in a landing, and had no orders as to where to land. Stopford felt he was up to this task: they would land and support the 11th Division attack on Hill 10. These orders assumed the 11th was attacking Hill 10. As it happened, they were still on the beach, which meant chaos on the beach.

Rather interestingly, there was no attempt at reconnaissance, which meant one of his commanders decided to create a five-mile diversionary attack on his target hill. This diversion went straight at the only real system of opposition trenches, while the primary target, as it happened, was essentially undefended. Later, three other Brigade commanders were happily resting on Hill 10, and while some troops had captured two other objectives, they needed reinforcements, but all communications seemed to have broken down. So had logistic support. Stopford had even overlooked in a Turkish summer the necessity of supplying the troops with water, and presumably everything else.

You may think this would sum up all the incompetence and stupidity of Suvla Bay. Unfortunately, it merely scratches the surface. The overall result was that it achieved nothing, there was no reprieve for the Anzacs, and the whole Gallipoli campaign was soon to collapse. Only the withdrawal was done competently. The ordinary soldiers at Gallipoli fought with great courage and determination. Their commanders fought with unparalleled stupidity and incompetence. So the Anzacs and others were lucky to get out of Gallipoli? Not really. Their next destination was the Somme where the losses were even greater than at Gallipoli, and the stupidity was still there in good order. The Anzac ceremonies end with, “Lest we forget.” Yes, we must remember the brave fallen, but also we should ensure a level of competence in commanders if we ever have to fight again.

Science, Lies, War Gases and Similar Agents

Most people will have noticed the news of the recent attack on Syria regarding an alleged chemical attack by Assad on Douma. Forty people were alleged to have been killed. If true, that is terrible, but is it true? In war, truth is seldom clear. The evidence so far has been allegations by the “white helmets”, a group that is essentially a medical recovery team for ISIS and other Wahabbi groups, and hence hardly unbiased, and there have also been images of people standing around and then being hosed down with water. The chemicals started out as “maybe sarin”, but this melded into on report of a mix of hydrogen cyanide and chlorine, and finally, just chlorine. Neither sarin victims nor chlorine victoims would be just standing around, while had it been hydrogen cyanide and chlorine, these two would react together and cancel each other out. If you are going to spread rumours, a little knowledge of chemistry helps.

There was then a rush to judgment before the OPCW inspectors could get there. I have seen claims the inspectors are irrelevant because Assad would have “cleaned up”. Assad, of course, had won Douma and offered the Wahabbis a free bus ride to Idlib, so while he controlled the area, why would he make such an attack? Most of the Wahabbis has left before the attack was alleged to have occurred, so why then? That makes no sense. Daesh, etc, had a motive: get the US to bomb Assad. So, if there were such an attack, it is still unclear who attacked.

So, what would I expect the inspectors to find? First, if forty people died, there will be relatives to say how. Second, if it were sarin, that sticks around long enough that nobody would be too keen on cleaning up, and evidence of the cleaning would be obvious. The nature of the bodies would be obvious too. If it were chlorine, it would leave characteristic damage to bodies, and also to survivors. If you check the records of WW 1, survivors had characteristic symptoms for months, if not forever. So there will be evidence. There will also be the means of delivery. Yes, in principle that could be removed, but there will be evidence of that.

Finally, if it were chlorine, it could even have been an accident. If Daesh were destroying things rather than giving it to Assad before they left, a small explosion near a gas cylinder might have ruptured it. Also, just because there is chlorine somewhere does not mean it is there as a war gas. Chlorine is an excellent agent for removing pathogens from water. Denying Syria chlorine would effectively condemn them to outbreaks of things like cholera.

So, what about the strike? At the time of writing this, truth is in very short supply. The US says no missiles were intercepted, Syria say about 2/3 were. However, the target seemed to be three fairly large buildings, two of which are supposed to be places where chemical weapons are stored, and one was allegedly a centre for chemical weapons research. That raises the question, if the US was so certain they contained chemical weapons, why blow them up? The threat was the chemicals would be released onto the local population, which seems to me to be irresponsible. If they knew there were chemical weapons there, why not insist on inspectors going in long before this sequence started? Note that these places had been inspected five months previously, and no sign of chemical weapons had been found.

The New York Times somehow obtained a video of what was left of the research centre within hours of the strike. Obviously the claim it was struck and effectively destroyed is true. There is rubble everywhere. But standing on the rubble was someone waving something in the air. To me, that does not seem as if there were a lot of chemical weapons there because if sarin, say, was broken open near him, he would be dead.

One of the things that really puzzled me was this. I am a professional chemist, and have spent a certain amount of my time doing organic synthesis, so I know what such a laboratory should look like. None of what I would expect was able to be seen in these pictures. Thus a laboratory to make chemicals for such weapons would need fairly substantial objects to do the syntheses on (minimum – benches), very substantial objects to enclose such sites so as to protect the workers, very large fans etc to remove fumes, large equipment to capture such fumes and neutralize them, various bits of equipment, lots of pipes to move air and water, and as far as water goes, a laboratory that big would need at a minimum a two inch water supply pipe, and when bombs wrecked the building, I would expect the pipes to rupture, so I would expect water flooding out. I would also expect the remains of fires, from the chemicals used. None of that is in the pictures. Now the rubble will bury some of the equipment (but not hide leaky pipes) and assuming the water supply comes from the road, the rubble would bury the only means to turn of that water. The only “contents” of the building I could see was a lot of what looked like office waste. Finally, another surprise: there were no casualties. That, of course, is good and I am not bloodthirsty, but if these buildings were storing chemical weapons, wouldn’t you expect some security guards? Surely Assad would not leave barrels of sarin lying around waiting for someone to steal them? So if there were no casualties, presumably nobody was in the building, and that makes storing chemical weapons more unlikely.

Accordingly, I think it is important to find out what that building really did. I get rather suspicious of claims they “know” that chemical weapons are being made in a building. I recall one such building in Iraq that turned out not to be making chemical weapons, but rather it was reconstituting baby formula. Everybody who makes these mistakes just shrugs their shoulders and moves on. The victims of the attack cannot do that.

A final comment. Assad once had and used chemical weapons, but before the West howls at what an animal he is, recall he was supplied with these chemicals from the West. If you sell him this sort of thing, what do you expect him to do with them? Put them in a museum? The supplier of the weaponry is effectively an accessory to the subsequent crime, in my opinion.

Colonizing Mars

Recently, Elon Musk threw a Tesla car at Mars and somewhat carelessly, missed. How can you miss a planet? The answer is, not unsurprisingly, quite easily. Mars might be a planet, and planets might seem large, but they are staggeringly small compared with the solar system. But whatever else this achieved, it did draw attention back to thoughts of humans on Mars, and as an exercise, it is not simple to bring the two together. Stephen Hawking was keen on establishing a colony there, mainly as some sort of reserve for humanity in case we did something stupid with out own planet. Would we do that? Unfortunately, the answer is depressingly quite possibly.

So what is required to get to Mars? First, not missing. NASA has shown that it can do this, so in principle this problem is solved. The second requirement is to arrive at the surface at essentially zero vertical velocity, and NASA has not been quite so successful at that, nevertheless, we can assume that landing will be with a piloted shuttle, so this should be able to be done. So far, so good? Well, not quite, because when you get there you have to have enough “stuff” to ensure you can survive. If it is a scientific exploration, the people will be away for over two years, so at a minimum, they will need groceries for two years, unless they grow their own food. They will need their own oxygen and water unless they can recycle it. They will need some means of getting around or there is no point in going, and they will need some sort of habitat. If they are settlers they will need a lot more because they are not coming back.

The obvious first thing to for settlers to do is to have somewhere to live. We can assume that the ship that brought them will provide a temporary place, although if the ship is to be recycled back to earth and they came down in a shuttle, this is a priority. At the same time they must build facilities to grow their own food and make oxygen. This raises the question, how many people could actually grow food and guarantee to do it well enough not to starve in a totally different environment to here? I am not sure you can train for that, but even if you can, there will still need to be a lot of food taken as well as oxygen. However, let’s assume these settlers are really competent and they are raring to get on with it.

The first requirement would be enough area to do it, so they would need a giant glass house (or houses). That means glass, and metal to hold it, but there is worse. You have to pressurize it, because the Martian atmospheric pressure on average is only about ½% of Earth’s. That means you need a strong pump, but because of the aggressive nature of dust in the atmosphere much of the time, you need some form of filter. The air is about 95.3% carbon dioxide, about 2.7% nitrogen and 1.6% argon. If you want to recover the oxygen to breathe, you want to boost the nitrogen so that what is produced is breathable as air, and that requires a major gas separator. The best way is probably to seriously overpressurise it, so the carbon dioxide comes out as a liquid, and keep the rest. However, there is another problem: you need water, so that equipment will probably have to be made even more complicated so the water in the atmosphere can be recovered. The next problem is that if the glasshouse is to be pressurized, it has to be leak-proof. All the joints have to be sealed with something that will not decay under UV radiation, and worse than that, a deep footer is needed around the glasshouse. That means digging a deep trench, pouring concrete, and sealing the walls. Finally, the whole regolith inside the glasshouse has to be treated to decompose its strong oxidizing nature (but this does produce a small amount of oxygen) otherwise the soil will sterilize anything you plant, then you have to add some actual soil. Many of these operations would be best done mechanically, but they each need their own machine.

You may notice that all of these things costs weight, and that is not what is wanted on a space ship. So the question is, how much can be brought there? There is a second requirement. Every time you use a machine, you need fuel. That has to be electric, which means either batteries, which so far would require huge numbers to keep going all day, or fuel cells, but if fuel cells are selected, what will be the fuel? Note that two fuels are required; one to “burn” and the other to burn it in, as there is no oxygen in the atmosphere worth having. Either way, a serious energy producer is required because not only do you have to power things, but you have to keep your glasshouse warm. The night-time temperatures can drop below minus 100 degrees Centigrade. The most obvious source is nuclear, either fission or fusion, but that requires shielding and even more weight.

The above is just some of the issues. I wrote a novel (Red Gold) that involved Martian settlement. The weight of the two ships was twenty million tonne each, and each had a thermonuclear propulsion system that detached and could be used as power plants and mineral separation units later. The idea was that construction materials would be made there, but even if that is done, a huge amount of stuff has to be taken. Think of the cost of lifting forty million tonne of stuff from Earth into orbit alone. Why two ships? Because everything should be done in duplicate, in case something goes wrong. Why that much stuff? Because you want this not to be some horrible exercise in survival.

At this stage I shall insert a small commercial. Red Gold is a story of such colonization, and of fraud, and it includes a lot more about what it might take to colonize Mars. It is available on Kindle Countdown discounts from 13 – 19 April. (http://www.amazon.com/dp/B009U0458Y)

How Earth Cools

As you may have seen at the end of my last post, I received an objection to the existence of a greenhouse effect on the grounds that it violated the thermodynamics of heat transfer, and if you read what it says it is essentially focused on heat conduction. The reason I am bothering with this post is that it is an opportunity to consider how theories and explanations should be formed. We start by noting that mathematics does not determine what happens; it calculates what happens provided the background premises are correct.

The objection mentioned convection as a complicating feature. Actually, the transfer of heat in the lower atmosphere is largely dependent on the evaporation and condensation of water, and wind transferring the heat from one place to another, and it is these, and ocean currents, that are the problems for the ice caps. Further, as I shall show, heat conduction cannot be relevant to the major cooling of the upper atmosphere. But first, let me show you how complicated heat conduction is. The correct equation for one-dimensional heat conduction is represented by a partial differential equation of the Laplace type, (which I would quote if I knew how to get such an equation into this limited htm formatting) and the simplest form only works as written when the medium is homogenous. Since the atmosphere thins out with height, this clearly needs modification, and for those who know anything about partial differential equations, they become a nightmare once the system becomes anything but absolutely simple. Such equations also apply to convection and evaporative transfer, once corrected for the nightmare of non-homogeneity and motion in three dimensions. Good luck with that!

This form of heat transfer is irrelevant to the so-called greenhouse effect. To show why, I start by considering what heat is, and that is random kinetic energy. The molecules are bouncing around, colliding with each other, and the collisions are elastic, which means energy is conserved, as is momentum. Most of the collisions are glancing, and that means from momentum conservation that we get a range of velocities distributed about an “average”. Heat is transferred because fast moving molecules collide with slower ones, and speed them up. The objection noted heat does not flow from cold to hot spontaneously. That is true because momentum is conserved in collisions. A molecule does not speed up when hit by a slower molecule. That is why that equation has heat going only in one way.

Now, suppose with this mechanism, we get to the top of the atmosphere. What happens then? No more heat can be transferred because there are no molecules to collide with in space. If heat pours in, and nothing goes out, eventually we become infinitely hot. Obviously that does not happen, and the reason becomes obvious when we ask how the heat gets in in the first place. The heat from the sun comes from the effects of solar radiation. Something like 1.36 kW/m^2 comes in on a surface in space at right angles to the line from the sun, but the average is much less on the surface of earth as the angle is at best normal only at noon, and if the sun is overhead. About a quarter of that is directly reflected to space, and that may increase if the cloud cover increases. The important point here is that light is not heat. When it is absorbed, it will direct an electronic transition, but that energy will eventually decay into heat. Initially, however, the material goes to an excited state, but its temperature remains constant, because the energy has not been randomised. Now we see that if energy comes in as radiation, it follows to get an equilibrium, equivalent energy must go out, and as radiation, not heat, because that is the only way it can get out in a vacuum.

The ground continuously sends radiation (mainly infrared) upwards and the intensity is proportional to the fourth power of the temperature. The average temperature is thus determined through radiant energy in equals radiant out. The radiance for a given material, which is described as a grey body radiator, is also dependent on its nature. The radiation occurs because any change of dipole moment leads to electromagnetic radiation, but the dipoles must change between quantised energy states. What that means is they come from motion that can be described in one way or another as a wave, and the waves change to longer wavelengths when they radiate. The reason the waves representing ground states switch to shorter wavelengths is that the heat energy from collisions can excite them, similar in a way to when you pluck a guitar string. Thus the body cools by heat exciting some vibratory states, which collapse by radiation leaving them. (This is similar to the guitar string losing energy by emitting sound, except that the guitar string emits continuous decaying sound; the quantised state lets it go all at once as one photon.)

Such changes are reversible; if the wave has collapsed to a longer wavelength when energy is radiated away, then if a photon of the same frequency is returned, that excites the state. That slows cooling because the next photon emitted from the ground did not need heat to excite it, and hence that same heat remains. The reason there is back radiation is that certain frequencies of infrared radiation leaving the ground get absorbed by molecules in the atmosphere when their molecular vibrational or rotational excited states have a different electric moment from the ground state. Carbon dioxide has two such vibrational states that absorb mildly, and one that does not. Water is a much stronger absorber, and methane has more states available to it. Agriculture offers N2O, which is bad because it is harder to remove than carbon dioxide, and the worst are chlorocarbons and fluorocarbons, because the vibrations have stronger dipole moment changes. Each of these different materials has vibrations at different frequencies, which make them even more problematical as radiation at more frequencies are slowed in their escape to space. The excited states decay and emit photons in random directions, hence only about half of that continues on it way to space, the rest returning to the ground. Of that that goes upwards, it will be absorbed by more molecules, and the same will happen, and of course some coming back from up there with be absorbed at a lower level and half of that will go back up. In detail, there is some rather difficult calculus, but the effect could be described as a field of oscillators.

So the take-away message is the physics are well understood, the effect of the greenhouse gases is it slows the cooling process, so the ground stays warmer than it would if they were not there. Now the good thing about a theory is that it should predict things. Here we can make a prediction. In winter, in the absence of wind, the night should be warmer if there is cloud cover, because water is a strong greenhouse material. Go outside one evening and see.

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.

Misleading Accusations

Fake news is becoming more common, and most of it is either political in nature or it is an attempt to be humorous. Last week I posted on the attempted murder of the two Skripals. Since then there have been a raft of accusations, some of which border on the pathetic, and some of which are definitely misleading.

The first example comes from the Russians. A Russian ambassador stated that for the British to be able to identify this agent as a Novichok, they must have a sample, therefore they are making it. There was then the implication that this could have been the source, although he never actually said he believed it. This last implication is just plain stupid. I am quite convinced the British would not do this. If they wanted to get rid of the Skripals, which I do not believe they would, at the very least they would do it in a way that would not harm anyone else. It is almost as if the Russian government sees itself as some sort of gangster organization and thinks everyone else is too. That is why I think it was a stupid comment; it is the sort of thing that immediately backfires.

But what about the point that Porton Down must have samples? That is just plain wrong. They must have some sort of expertise, but since it is the UK national defence laboratory, that expertise should be taken for granted. If so, it is a rather straightforward task to identify something like that. We know what the structures involve, and such structures do not occur in nature. You have to have some idea what it could be before you start if your sample is really small, but given the circumstances, that would be a given. One approach would be to run a mass spectrum of the sample (having done some sort of chromatographic purification), and do it under a few different conditions. One such determination would be low energy ionization to determine the overall molecular weight, which tells you how many atoms are there, and if the instrument is good enough, the molecular formula. That is because although all elements comprise protons and neutrons, which have a constant mass, the binding energy varies from atom to atom, and from relativity there are clear but very small mass differences between the various possibilities from the general molecular weight. The next attempt would be hit it with higher energy, which would break it into fragments, and again the molecular weights of the fragments will tell you how the various groups are assembled. Finally, some small groups will give you more information, and the exercise then is to interpret how to put this back together again. Of course had they ever had access to a sample, they would have records of the fragmentation patterns of all the Novichoks they knew about. So there is little doubt the British authorities would have been able to find out what this was without having to go around making or having samples.

However, then the British politicians made a further statement: we can tell where it came from through the structure. Sorry, but you can’t. That statement violates the first law of thermodynamics, from which you can show the nature of a chemical is independent of how it was made, or from where. Had there been tonnes of the stuff, yes, then you might, not directly from the structure but rather once you knew what it was, you would know who made it because chemical plant, by and large, gets dedicated to making one substance and there would probably be only one making some of these components. But at the gram level, there is no way of knowing from its structure where it came from.

The problem with these sort of comments is they sound convincing to those who do not know much about the general subject However, eventually someone points out the errors and conspiracy theories start up. When it becomes known that the authorities made politically desirable statements, all sorts of rubbish comes out of the woodwork. Another problem with such announcements is that they may look to be politically desirable at the time, but what about the downstream consequences? In this case, the desire to blame Russia has set off some tit for tat diplomatic expulsions, and some sanctions. Now what? Why could that not have waited until the evidence came in? If it can be shown that Russian agents did it, then surely the various actions would be stronger and even the Russians might seem embarrassed. But suppose some individual or small rogue organization did it? Now Russia has been made angry for no good purpose. Nothing has been done that could not have waited, so why not wait and make sure the conclusions are right?

Sergei Skripal, Novichoks, and Accusations

One of the more depressing pieces of news this week was the attempted assassination of Sergei Skripal and his daughter Yulia by what appears to be a Novichok agent. There is a large family of these, which were developed in the old Soviet Union as chemical weapons. Their structure involves a phosphoramidate or a phosphonate, either of which is often fluorinated. These can be made simply by mixing two chemicals: a substituted phosphoryl compound with at least one halogen on it, and if there happen to be two fluoride substituents, displacing one of these leaves the other fluoride as part of what is desired. The other compound appears to usually involve an amine or an oxime, and phosgene oxime (a chemical weapon in its own right called CX) appears to form particularly active Novichoks. A major advantage of these as war chemicals is that they can be made by mixing the chemicals at the point of use, which makes them safer to handle up to use, especially if they can be mixed remotely. The Novichoks are extremely dangerous, as can be seen in that when the Skripals collapsed after being poisoned elsewhere, a policeman who came to help was himself struck down by residue seemingly adhering to the Skripals.

As might be expected, everyone has jumped up and down blaming the Russians, and of course, they may well be to blame. The Russian case for innocence is not helped by the poisoning of Alexander Litvinenko some time ago with 210-polonium, which in some ways was quite clever in that after administering, it takes several days before any symptoms appear, so the villain would have left the country before a crime was even recognized. While we do not know who did that, the actual use of such an isotope meant that the perpetrator had to have access to extremely dangerous isotopes, and that strongly suggests a nation such as Russia. You can’t make such isotopes in a shed, even with an unlimited budget.

However, Novichoks are not particularly difficult to make for a skilled chemist. The synthesis would involve some sophisticated equipment and quite a bit of patience to make them from chemicals you could often purchase if you were in the chemical business, but they are not impossible for someone with the necessary skill. It would be very difficult to make them on a large scale, but a gram of each precursor would not be that difficult. There are other sources. They were developed in the old Soviet Union, and not just in Russia. Uzbekistan was one of the places, and I would suspect other parts also had some of the necessary chemicals. Of course Russia would be a good source.

Teresa May delivered some sort of ultimatum to the Russian government: either account for all your Novichok agents within about 36 hours, or “face the consequences”. With the best will in the world, I doubt a country as large as Russia could account for its entire chemical stock in that short a time. Probably much less than a gram of each precursor would have been used, and I doubt any country could account for that degree of accuracy in a chemical stock in that time, if ever. However, Sergei Lavrov, the Russian Foreign Minister, did make a response: he asked for a sample of the Novichok. Given there were could be many of them, and the different ones could well have originated from different places, wanting to know the structure is a reasonable request. Maybe a sample of the agent is too much to ask, but at the least a mass spectrum would be helpful because that should define which Novichok was used, assuming it was one.

As it happens, Russia did not respond to May’s demands. Now what? The problem with delivering an ultimatum is that if the other side declines to give in, you have to deliver, and Britain’s position is too weak to worry Russia.

So, who else could be responsible? What we have to realize is that Skripal, as a double agent, managed to hand over a GRU list of agents in the West, most of whom were promptly arrested. Now suppose, many years later, some were released? Or one of their associates who managed to avoid detection found out where the Skripals were? Anyone want to bet they would not have a motive? The man they trusted, a senior officer in their own organization, handed them over to the West, and they, whose lives had been ruined, don’t want payback? And why a Novichok? The real problem with them is there is a good chance the damage is permanent. The victim may recover, but only partially, and some nerve damage will be permanent. That would be revenge.

So how do we find out? My guess is good old police work. It is known when it happened, where it happened, it was a public place so someone must know something. Britain has a large number of surveillance sites, and with any luck, images of the perpetrators will be available. Let us wait and see what the investigations produce before jumping on the bandwagon. Evidence is what we need. Facts. Not wild accusations. Maybe it was the Russian government, but not necessarily. If the perpetrator can be identified, at least an arrest warrant can be issued. In the meantime, being a KGB defector does not look like being a good position to have.