How do Rocky Planets Form?

A question in my last post raised the question of how do rocky planets form, and why is Venus so different from Earth? This will take two posts; the first covers how the planets form and why, and the second how they evolve immediately after formation and get their atmospheres.

First, a quick picture of accretion. At first, the gas cloud collapses and falls into the star, and in this stage the star the size of the sun accretes something like 2.5 x 10^20 kg per second. Call that stage 1. When the star has gobbled up most of the material, such accretion slows down, and in what I shall call stage 2 it accretes gas at least four orders of magnitude slower. The gas heats due to loss of potential energy as it falls into the star, although it also radiates heat from the dust that gets hot. (Hydrogen and helium do not radiate in the infrared easily.) In stage 1, the gas reached something like 1600 degrees C at 1 A.U. (the distance from Earth to the sun). In stage 2, because far less gas was falling in, the disk had temperatures roughly what bodies have now. Even in stage 2, standard theory has it that boulder-sized objects will fall into the star within about a hundred years due to friction with the gas.

So how did planets form? The standard explanation is that after the star had finished accreting, the dust very rapidly accreted to planetesimals (bodies about 500 km across) and these collided to form oligarchs, and in turn these collided to form planets. I have many objections to this. The reasons include the fact there is no mechanism to form the planetesimals that we assume to begin with. The calculations originally required one hundred million years (100 My) to form Earth, but we know that it had to be essentially formed well before that because the collision that formed the Moon occurred at about 50 My after formation started. Calculations solved the Moon-forming problem by saying it only took 30 My, but without clues why this time changed. Worse, there are reasons to believe Earth had to form within about 1 My of stage 2 because it has xenon and krypton that had to come from the accretion disk. Finally, in the asteroid belt there is evidence of some previous collisions between asteroids. What happens is they make families of much smaller objects. In short, the asteroids shatter into many pieces upon such collisions. There is no reason to believe that similar collisions much earlier would be any different.

The oldest objects in the solar system are either calcium aluminium inclusions or iron meteorites. Their ages can be determined by various isotope decays and both had to be formed in very hot regions. The CAIs are found in chondrites originating from the asteroid belt, but they needed much greater heat to form than was there in stage 2. Similarly, iron meteorites had to form at a temperature sufficient to melt iron. So, how did they get that hot and not fall into the sun? The only time the accretion disk got sufficiently hot at a reasonable distance from the sun was when the star was accreting in stage 1. In my opinion, this shows the calculations were wrong, presumably because they missed something. Worse, to have enough material to make the giants, about a third of the stellar mass has to be in the disk, but observation of other disks in stage 2 shows there is simply not enough mass to make the giants.

The basic argument I make is that whatever was formed in the late stages of stellar accretion stayed more or less where it was. One of the puzzles of the solar system is that most of the mass is in the star, but most of the angular momentum resides in the planets, and since angular momentum has to be conserved and since most of that was with the gas initially, my argument is any growing solids took angular momentum from the gas, which sends then mass further from the star, and it had to be taken before the star stopped accreting. (I suggest a mechanism in my ebook.)

Now to how the rocky planets formed. During primary stellar accretion, temperatures reached about 1300 degrees C where Mars would form and 1550 degrees C a little beyond where Earth would grow. This gives a possible mechanism for accretion of dust. At about 800 degrees C silicates start to get sticky, so dust can accrete into small stones there, and larger ones closer to the star. There are a number of different silicates, all of which have long polymers, but some, especially aluminosilicates are a little more mobile than others. At about 1300 degrees C, calcium silicate starts to phase separate out, and about 1500 degrees C various aluminosilicates phase separate. This happens because the longer the polymer, the more immiscible it is in another polymer melt (a consequence of the first two laws of thermodynamics, and which makes plastics recycling so difficult.) If this were the only mechanism for forming rocky planets, the size of the finished planet would diminish significantly with distance from the star. Earth, Venus and Mercury are in the wrong order. Mercury may have accreted this way, but further out, stones or boulders would be the biggest objects.

Once primary stellar accretion ends, temperatures were similar to what they are now. Stones collide, but with temperatures like now, they initially only make dust. There is no means of binding silicates through heat. However, if stones can come together, dust can fill the spaces. The key to rocky planet formation is that calcium silicate and calcium aluminosilicates could absorb water vapour from the disk gases, and when they do that, they act as cements that bind the stones together to form a concrete. The zone where the aluminosilicates start to get formed is particularly promising for absorbing water and setting cement, and because iron starts to form bodies here, lumps of iron are also accreted. This is why Earth has an iron core and plenty of water. Mars has less water because calcium silicate absorbs much less water, and its iron is mainly accreted as fine dust.

Finally, Mars is smaller because the solids density is less, and the disk is cleared before it has time to fully grow. The evidence for the short-lived disk is from the relatively small size of Jupiter compared with corresponding planets around similar sized stars that our sun cleared out the accretion disk sooner than most. This is why we have rocky planets, and not planets like the Neptune-sized planets in the so-called habitable zone around a number of stars. Venus is smaller than Earth because it was harder to get going, through the difficulty of water setting the cement, which is partly why it has very little water on its surface. However, once started it grows faster since the density of basaltic rocks is greater. Mercury is probably smaller still because it formed a slightly different way, through excessively mobile silicates in the first stage of the accretion disk, and by later being bombed by very large rocky bodies that were more likely to erode it. That is somewhat similar to the standard explanation of why Mercury is small but has a large iron core. The planets grow very quickly, and soon gravity binds all dust and small stones, then as it grows, gravity attracts objects that have grown further away, which perforce are large, but still significantly smaller than the main body in the zone.

Next post: how these rocky planets started to evolve to where they are now.

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Science in Action – or Not

For my first post in 2019, I wish everyone a happy and prosperous New Year. 2018 was a slightly different year than most for me, in that I finally completed and published my chemical bond theory as an ebook; that is something I had been putting off for a long time, largely because I had no clear idea what to do with the theory. There is something of a story behind this, so why not tell at least part of it in my first blog post for the year? The background to this illustrates why I think science has gone slightly off the rails over the last fifty years.

The usual way to get a scientific thought over is to write a scientific paper and publish it in a scientific journal. These tend to be fairly concise, and primarily present a set of data or make one point. One interesting point about science is that if it is not in accord with what people expect, the odds on are it will be ignored, or the journals will not even accept it. You have to add to what people believe to be accepted. As the great physicist Enrico Fermi once said, “Never underestimate the joy people derive from hearing something they already know.” Or at least think they know. The corollary is that you should never underestimate the urge people have to ignore anything that seems to contradict what they think they know.

My problem was I believed the general approach to chemical bond theory was wrong in the sense it was not useful. The basic equations could not be solved, and progress could only be made through computer modelling, together with as John Pople stated in his Nobel lecture, validation, which involved “the optimization of four parameters from 299 experimentally derived energies”. These validated parameters only worked for a very narrow range of molecules; if they were too different the validation process had to be repeated with a different set of reference molecules. My view of this followed another quote from Enrico Fermi: I remember my friend Johnny von Neumann used to say, “with four parameters I can fit an elephant and with five I can make him wiggle his trunk.” (I read that with the more modern density functional theory, there could be up to fifty adjustable parameters. If after using that many you cannot get agreement with observation, you should most certainly give up.)

Of course, when I started my career, the problem was just plain insoluble. If you remember the old computer print-out, there were sheets of paper about the size of US letter paper, and these would be folded in a heap. I had a friend doing such computations, and I saw him once with such a pile of computer paper many inches thick. This was the code, and he was frantic. He kept making alterations, but nothing worked – he always got one of two answers: zero and infinity. As I remarked, at least the truth was somewhere in between.

The first problem I attacked was the energy of electrons in the free atoms. In standard theory, the Schrödinger equation, when you assume that an electron in a neutral atom sees a charge of one, the binding energy is far too weak. This is “corrected”througha “screening constant”, and each situation had its own “constant”. That means that each value was obtained by multiplying what you expect by something to give the right answer. Physically, this is explained by the electron penetrating the inner electron shells and experiencing greater electric field.

What I came up with is too complicated to go into here, but basically the concept was that since the Schrödinger equation (the basis of quantum mechanics) is a wave equation, assume there was a wave. That is at odds with standard quantum mechanics, but there were two men, Louis de Broglie and David Bohm, who had argued there was a wave that they called the pilot wave. (In a recent poll of physicists regarding which interpretation was most likely to be correct, the pilot wave got zero votes.) I adopted the concept (well before that poll) but I had two additional features, so I called mine the guidance wave.

For me, the atomic orbital was a linear sum of component waves, one of which was the usual hydrogen-like wave, plus a wave with zero nodes, and two additional waves to account for the Uncertainty Principle. It worked to a first order using only quantum numbers. I published it, and the scientific community ignored it.

When I used it for chemical bond calculations, the results are accurate generally to within a few kJ/mol, which is a fraction of 1% frequently. Boron, sodium and bismuth give worse results.  A second order term is necessary for atomic orbital energies, but it cancels in the chemical bond calculations. Its magnitude increases as the distance from a full shell increases, and it oscillates in sign depending on whether the principal quantum number is odd or even, which results when going down a group of elements, that the lines joining them zig zag.

Does it matter? Well, in my opinion, yes. The reason is that first it gives the main characteristics of the wave function in terms only of quantum numbers, free f arbitrary parameters. More importantly, the main term differs depending on whether the electron is paired or not, and since chemical bonding requiresthe pairing of unpaired electrons, the function changes on forming bonds. That means there is a quantum effect that is overlooked in the standard calculations. But you say, surely they would notice that? Recall what I said about assignable parameters? With four of them, von Neumann could use the data to calculate an elephant! Think of what you could do with fifty!

As a postscript, I recently saw a claim on a web discussion that some of the unusual properties of gold, such as its colour, arise through a relativistic effect. I entered the discussion and said that if my paper was correct, gold is reasonably well-behaved, and its energy levels were quite adequately calculated without needing relativity, as might be expected from the energies involved. This drew almost derision – the paper was dated, an authority has spoken since then. A simple extrapolation from copper to silver to gold shows gold is anomalous – I should go read a tutorial. I offered the fact that all energy levels require enhanced screening constants, therefore Maxwell’s equations are not followed. These are the basic laws of electromagnetism. Derision again – someone must have worked that out. If so, what is the answer? As for the colour, copper is also coloured. As for the extrapolation, you should not simply keep drawing a zig to work out where the zag ends. The interesting point here was that this person was embedded in “standard theory”. Of course standard theory might be right, but whether it is depends on whether it explains nature properly, and not on who the authority spouting it is.

Finally, a quote to end this post, again from Enrico Fermi. When asked what characteristics Nobel prize winners had in common: “I cannot think of a single one, not even intelligence.”

Phlogiston – Early Science at Work

One of the earlier scientific concepts was phlogiston, and it is of interest to follow why this concept went wrong, if it did. One of the major problems for early theory was that nobody knew very much. Materials had properties, and these were referred to as principles, which tended to be viewed either as abstractions, or as physical but weightless entities. We would not have such difficulties, would we? Um, spacetime?? Anyway, they then observed that metals did something when heated in air:

M   + air +  heat        ÞM(calx) ±  ???  (A calx was what we call an oxide.)

They deduced there had to be a metallic principle that gives the metallic properties, such as ductility, lustre, malleability, etc., but they then noticed that gold refuses to make a calx, which suggested there was something else besides the metallic principle in metals. They also found that the calx was not a mixture, thus rust did not lead to iron being attached to a lodestone. This may seem obvious to us now, but conceptually this was significant. For example, if you mix blue and yellow paint, you get green and they cannot readily be unmixed, nevertheless it is a mixture. Chemical compounds are not mixtures, even though you might make them by mixing two materials. Even more important was the work by Paracelsus, the significance of which is generally overlooked. He noted there were a variety of metals, calces and salts, and he generalized that acid plus metal or acid plus metal calx gave salts, and each salt was specifically different, and depended only on the acid and metal used. He also recognized that what we call chemical compounds were individual entities, that could be, and should be, purified.

It was then that Georg Ernst Stahl introduced into chemistry the concept of phlogiston. It was well established that certain calces reacted with charcoal to produce metals (but some did not) and the calx was usually heavier than the metal. The theory was, the metal took something from the air, which made the calx heavier. This is where things became slightly misleading because burning zinc gave a calx that was lighter than the metal. For consistency, they asserted it should have gained but as evidence poured in that it had not, they put that evidence in a drawer and did not refer to it. Their belief that it should have was correct, and indeed it did, but this avoiding the “data you don’t like” leads to many problems, not the least of which include “inventing” reasons why observations do not fit the theory without taking the trouble to abandon the theory. This time they were right, but that only encourages the act. As to why there was the problem, zinc oxide is relatively volatile and would fume off, so they lost some of the material. Problems with experimental technique and equipment really led to a lot of difficulties, but who amongst us would do better, given what they had?

Stahl knew that various things combusted, so he proposed that flammable substances must contain a common principle, which he called phlogiston. Stahl then argued that metals forming calces was in principle the same as materials like carbon burning, which is correct. He then proposed that phlogiston was usually bound or trapped within solids such as metals and carbon, but in certain cases, could be removed. If so, it was taken up by a suitable air, but because the phlogiston wanted to get back to where it came from, it got as close as it could and took the air with it. It was the phlogiston trying to get back from where it came that held the new compound together. This offered a logical explanation for why the compound actually existed, and was a genuine strength of this theory. He then went wrong by arguing the more phlogiston, the more flammable the body, which is odd, because if he said some but not all such materials could release phlogiston, he might have thought that some might release it more easily than others. He also argued that carbon was particularly rich in phlogiston, which was why carbon turned calces into metals with heat. He also realized that respiration was essentially the same process, and fire or breathing releases phlogiston, to make phlogisticated air, and he also realized that plants absorbed such phlogiston, to make dephlogisticated air.

For those that know, this is all reasonable, but happens to be a strange mix of good and bad conclusions. The big problem for Stahl was he did not know that “air” was a mixture of gases. A lesson here is that very seldom does anyone single-handedly get everything right, and when they do, it is usually because everything covered can be reduced to a very few relationships for which numerical values can be attached, and at least some of these are known in advance. Stahl’s theory was interesting because it got chemistry going in a systemic way, but because we don’t believe in phlogiston, Stahl is essentially forgotten.

People have blind spots. Priestley also carried out Lavoisier’s experiment:  2HgO  + heat   ⇌   2Hg  + O2and found that mercury was lighter than the calx, so argued phlogiston was lighter than air. He knew there was a gas there, but the fact it must also have weight eluded him. Lavoisier’s explanation was that hot mercuric oxide decomposed to form metal and oxygen. This is clearly a simpler explanation. One of the most important points made by Lavoisier was that in combustion, the weight increase of the products exactly matched the loss of weight by the air, although there is some cause to wonder about the accuracy of his equipment to get “exactly”. Measuring the weight of a gas with a balance is not that easy. However, Lavoisier established the fact that matter is conserved, and that in chemical reactions, various species react according to equivalent weights. Actually, the conservation of mass was discovered much earlier by Mikhail Lomonosov, but because he was in Russia, nobody took any notice. The second assertion caused a lot of trouble because it is not true without a major correction to allow for valence. Lavoisier also disposed of the weightless substance phlogiston simply by ignoring the problem of what held compounds together. In some ways, particularly in the use of the analytical balance, Lavoisier advanced chemistry, but in disposing of phlogiston he significantly retarded chemistry.

So, looking back, did phlogiston have merit as a concept? Most certainly! The metal gives off a weightless substance that sticks to a particular gas can be replaced with the metal gives off an electron to form a cation, and the oxygen accepts the electron to form an anion. Opposite charges attract and try to bind together. This is, for the time, a fair description of the ionic bond. As for weightless, nobody at the time could determine the weight difference between a metal and a metal less one electron, if they could work out how to make it. Of course the next step is to say that the phlogiston is a discrete particle, and now valence falls into place and modern chemistry is around the corner. Part of the problem there was that nobody believed in atoms. Again, Lomonosov apparently did, but as I noted above, nobody took any notice of him. Of course, is it is far easier to see these things in retrospect. My guess is very few modern scientists, if stripped of their modern knowledge and put back in time would do any better. If you think you could, recall that Isaac Newton spent a lot of time trying to unravel chemistry and got nowhere. There are very few ever that are comparable to Newton.

Is science being carried out properly?

How do scientists carry out science, and how should they? These are questions that have been raised by reviewers in a recent edition of Science magazine, one of the leading science journals. One of the telling quotes is “resources (that) influence the course of science are still more rooted in traditions and intuitions than in evidence.” What does that mean? In my opinion, it is along the lines, for those who have, much will be given. “Much” here refers to much of what is available. Government funding can be tight. And in fairness, those who provide funds want to see something for their efforts, and they are more likely to see something from someone who has produced results consistently in the past. The problem is, the bureaucrats responsible for providing the finds have no idea of the quality of what is produced, so they tend to count scientific papers. This favours the production of fairly ordinary stuff, or even rubbish. Newbies are given a chance, but there is a price: they cannot afford to produce nothing. So what tends to happen is that funds are driven towards something that is difficult to fail, except maybe for some very large projects, like the large hadron collider. The most important thing required is that something is measured, and that something is more or less understandable and acceptable by a scientific journal, for that is a successful result. In some cases, the question, “Why was that measured?” would best be answered, “Because it was easy.” Even the large hadron collider fell into that zone. Scientists wanted to find the Higgs boson, and supersymmetry particles. They found the first, and I suppose when the question of building the collider, the reference (totally not apt) to the “God Particle” did not hurt.

However, while getting research funding for things to be measured is difficult, getting money for analyzing what we know, or for developing theories (other than doing applied mathematics on existing theories), is virtually impossible. I believe this is a problem, and particularly for analyzing what we know. We are in this quite strange position that while in principle we have acquired a huge amount of data, we are not always sure of what we know. To add to our problems, anything found more than twenty years ago is as likely as not to be forgotten.

Theory is thus stagnating. With the exception of cosmic inflation, there have been no new major theories that have taken hold since about 1970. Yet far more scientists have been working during this period than in all of previous history. Of course this may merely be due to the fact that new theories have been proposed, but nobody has accepted them. A quote from Max Planck, who effectively started quantum mechanics may show light on this: “A new scientific truth does not triumph
by convincing its opponents and making them see the light, but rather because its opponents eventually die.” Not very encouraging. Another reason may be that it failed to draw attention to itself. No scientist these days can read more than an extremely tiny fraction of what is written, as there are tens of millions of scientific papers in chemistry alone. Computer searching helps, but only for well-defined problems, such as a property of some material. How can you define carefully what you do not know exists?

Further information from this Science article provided some interest. An investigation led to what then non-scientists might consider a highly odd result, namely for scientific papers to be a hit, it was found that usually at least 90 per cent of what is written is well established. Novelty might be prized, but unless well mixed with the familiar, nobody will read it, or even worse, it will not be published. That, perforce, means that in general there will be no extremely novel approach, but rather anything new will be a tweak on what is established. To add to this, a study of “star” scientists who had premature deaths led to an interesting observation: the output of their collaborators fell away, which indicates that only the “star” was contributing much intellectual effort, and probably actively squashing dissenting views, whereas new entrants to the field who were starting to shine tended not to have done much in that field before the “star” died.

A different reviewer noticed that many scientists put in very little effort to cite past discoveries, and when citing literature, the most important is about five years old. There will be exceptions, usually through citing papers by the very famous, but I rather suspect in most cases these are cited more to show the authors in a good light than for any subject illumination. Another reviewer noted that scientists appeared to be narrowly channeled in their research by the need to get recognition, which requires work familiar to the readers, and reviewers, particularly those that review funding applications. The important thing is to keep up an output of “good work”, and that tends to mean only too many go after something that they more or less already now the answer. Yes, new facts are reported, but what do they mean? This, of course, fits in well with Thomas Kuhn’s picture of science, where the new activities are generally puzzles that are to be solved, but not puzzles that will be exceedingly difficult to solve. What all this appears to mean is that science is becoming very good at confirming that which would have been easily guessed, but not so good at coming up with the radically new. Actually, there is worse, but that is for the next post.

Volatiles on Rocky Planets

If we accept the mechanism I posted before is how the rocky planets formed, we still do not have the chemicals for life. So far, all we have is water and rocks with some planets having an iron core. The mechanism means that until the planet gets gravitationally big enough to attract gas it only accretes solids, together with the water that bonded to the silicates. There re two issues: how the carbon and nitrogen arrived, and if these arrived as solids, which is the only available mechanism, what happened next?

In the outer parts of the solar system the carbon occurs as carbon monoxide, methanol, some carbon dioxide, and “carbon”, which essentially many forms but looks like tar, is partially graphite, and there are even mini diamonds. There are also polyaromatic hydrocarbons, and even alkanes, and some other miscellaneous organic chemicals. Nitrogen occurs as nitrogen gas, ammonia, and some cyanide. As this comes closer to the star, and in the region of the carbonaceous chondrites, it starts getting hot enough for some of this to condense and react on the silicates, which is why these have the aminoacids, etc. However, as you get closer to the star, it gets too hot and seemingly the inner asteroids are mainly just silicates. At this point, the carbon is largely converted to carbon monoxide, and the nitrogenous compounds to nitrogen. However, on some metal oxides or metals, carbon forms carbides, nitrogen nitrides, and some other materials, such as cyanamides are also formed. These are solids, and accordingly these too will be accreted with the dust and be incorporated within the planet.

As the interior of the planet gets hotter, the water gets released from the silicates and they lose their amorphous structure and become rocks. The water reacts with these chemicals and to a first approximation initially produces carbon monoxide, methane and ammonia. Carbon monoxide reacts with water on certain metals and silicates to make hydrocarbons, formaldehyde, which in turn condenses to other aldehydes (on the path to making sugars) ammonia (on the path to make aminoacids) and so on. The chemistry is fairly involved, but basically given the initial mix, temperature and pressure, both in ready supply below the Earth’s surface, what we need for life emerges and will make its way to the surface. Assuming this mechanism is correct, then provided everything is present in an adequate mix, then life should evolve. That leaves open the question, how broad is the “right mix” zone?

Before considering that, it is obvious this mechanism relies on the temperature being correct on at least two times during the planetary evolution. Initially it has to get hot enough to make the cements, and the nitrides and carbides. Superficially, that applies to all rocky planets, but maybe not for the nitrides. The problem here is Mars has very little nitrogen, so either it has gone somewhere, or it was never there. If Mars had ammonia, since it dissolves in ice down to minus 80 degrees C, ammonia on Mars would solve the problem of how could water flow there when it is so cold. However, if that is the case, the nitrogen has to be in some solid form buried below the surface. In my opinion, it was carried there as urea dissolved in water, which is why I would love to see some deep digging there.

The second requirement is that later the temperature has to be cool enough that water can set the cements. The problem with Venus is argued that it was hotter and it only just managed to absorb some water, but not enough. One counter to that is that the hydrogen on Venus has an extremely high deuterium content. The usual explanation for this is that if water gets to the top of the atmosphere, it may be hit with UV which may knock off a hydrogen atom, which is lost to space, and solar wind may take the whole molecule, however water with deuterium is less likely to get there because the heavier molecules are enhanced in the lower atmosphere, or the oceans. If this were true, for Venus to have the deuterium levels it must have started with a huge amount of water, and the mechanism above would be wrong. An embarrassing problem is where is the oxygen from that massive amount of water.

However, the proposed mechanism also predicts a very large deuterium enhancement. The carbon and nitrogen in the atmosphere and in living things has to be liberated from rocks by reaction with water, and what happens is as the water transfers hydrogen to either carbon or nitrogen it also leaves a hydroxyl attached to any metal. Two hydroxyls liberate water and leave an oxide. At this point we recall that chemical bond to deuterium is stronger than that to hydrogen, the reason being that although in theory the two are identical from the electromagnetic interactions, quantum mechanics requires there to be a zero point energy, and somewhat oversimplifying, the amount of such energy is inversely proportional to the square root of the mass of the light atom. Since deuterium is twice the mass of hydrogen, the zero point energy is less, and being less, its bond is stronger. That means there is a preference for the hydrogen to be the one that transfers, and the deuterium eventually turns up in the water. This preferential retaining of deuterium is called the chemical isotope effect. The resultant gases, methane and ammonia as examples, break down with UV radiation and make molecular nitrogen and carbon dioxide, with the hydrogen going to space. The net result of this is the rocky planet’s hydrogen gradually becomes richer in deuterium.

The effects of the two mechanisms are different. For Venus, the first one requires huge oceans; the second one little more than enough water to liberate the gases. If we look at the rocky planets, Earth should have a modest deuterium enhancement with both mechanisms because we know it has retained a very large amount of water. Mars is more tricky, because it started with less water under the proposed accretion of water mechanism, and it has less gravity and we know that all gases there, including carbon dioxide and nitrogen have enhanced heavier isotopes. That its deuterium is enhanced is simply expected from the other enhancements. Venus has about half as much CO2 again as Earth, and three times the amount of nitrogen, little water, and a very high deuterium enhancement. In my mechanism, Venus never had much water in the first place because it was too hot. Most of what it had was used up forming the atmosphere, and then providing the oxygen for the CO2. There was never much on the surface. To start with Venus was only a bit warmer than Earth, but as the CO2 began to build, whereas on Earth much of this would be dissolved in the ocean, where it would react with calcium silicate and also begin weathering the rocks that were more susceptible to weathering, such as dunite and peridotite. (I have discussed this previously: https://wordpress.com/post/ianmillerblog.wordpress.com/833 ), on Venus there were no oceans, and liquid water is needed to form these carbonates.

So, where will life be found? The answer is around any star where rocky planets formed with the two favourable temperature profiles, and ended up in the habitable zone. If more details as found in my ebook “Planetary Formation and Biogenesis” are correct, then this is most likely to occur around a G type star, like our sun, or a heavy K type star. The star also has to be one of the few that ejects it accretion disk remains early. Accordingly life should be fairly well spaced out, which may be why we have yet to run into other life forms.

What do Organic Compounds Found on Mars Mean?

Last week, NASA announced that organic compounds had been found on Mars. The question then is, what does this mean? First, organic compounds are essentially chemicals formed that involve carbon, which means Mars has carbon besides the carbon dioxide in the atmosphere. The name “organic” comes from the fact that such compounds found by early chemists, with the exception of a very few such as carbon dioxide, came from organisms, hence there is the question, do these materials indicate that Mars had life? The short answer is, the issue remains unresolved. One argument is that if there were no organic compounds on Mars, it obviously did not have life. That it has taken so long to find organic compounds does not say anything about the probability, though, because the surface of Mars is strongly oxidizing, and had any been there, they would have been turned into carbon dioxide. The atmosphere already has a lot of that. The reason none has been found, therefore, is because most of the rovers have not been able to dig very deeply.

I shall try to summarise the results that were reported [Eigenbrode et al., Science 360, 1096–1101 (2018)]. One important point is that the volatiles analysed were obtained by pyrolysing the mudstone the rover dug up, so what was detected may not be the same that was in the rock. The first compounds were identified as aliphatic hydrocarbons, from C1 (methane) to C5, and these were stated to be typical of that obtained from Kerogen or coal on Earth. One problem I had with these data was there were odd-numbered masses, BUT they all indicated that the cause was a fractured hydrocarbon, i.e. the pyrolysis had chopped that bit off something else and produced a radical.

One big problem was they could not say whether nitrogen or oxygen was present ” because mass spectra are not resolvable in EGA and other molecules share the diagnostic m/z values. ” I really don’t understand that. First, the identification of aliphatic hydrocarbons was almost certainly correct, because they form series of signals that are very recognizable to anyone who has done a bit of this work before. They stick out like an organ stop, so to speak. However, the presence of nitrogen species in any reasonable amount should be just as easily identified because while hydrocarbons, and their like with oxygen, basically give even mass signals, nitrogen, because of its valency of 3, gives odd numbered mass signals that is 1 bigger than a hydrocarbon. Now, a few of the fragmentation patterns of hydrocarbons give odd numbered mass signals, but if you cannot tell where the molecular ion is, you do not know what the mass of your molecule is. If all you have are fragmentation ions, then the instrument was somewhat poorly designed to go to Mars. With any experience, you can also tell whether you have oxygenated materials because hydrocarbons go up by adding 14 to the basic ion, and the atomic weight of oxygen is 16. If it has oxygen, it abd the fragments containing oxygen have an entirely different mass.

Of course the authors did note the presence of CO2 and CO. These could arise from the pyrolysis of carboxylic acids and ketones, but that does not mean life. Carboxylic acids would pyrolyse at about 400 – 550 degrees C and ketones a bit higher. They also found aromatic hydrocarbons, thiophenes and some other sulphur containing species. These were explained in terms of sulphur –bearing gases coming in contact, and further chemical reactions then taking place, in other words, these sulphur containing species such as hydrogen sulphide do not necessarily provide any information regarding what formed the original deposit. The sulphurization, however, was claimed to provide a preservative function by protecting against mild oxidation. If it carried out that function, it would be oxidized, and none of the observed materials were.

Unfortunately, the material is not directly associated with anything related to life. The remains of life can give rise to these sort of chemicals, as noted by our crude oil, which is basically hydrocarbon, and formed from life, but then altered by tens of millions of years change. These Martian deposits are believed to be in rocks 3.5 billion years old. However, the materials were also obtained by pyrolysis at temperatures exceeding 500 degrees C. The original molecules could have rearranged, and what we saw was the sort of compounds that organic compounds might rearrange to. Nevertheless, the absence of nitrogen is not encouraging. Nitrogen is present in all protein and nucleic acids, and there tends to be high levels of these in primitive life. Pyrolysis would be expected to produce pyrazines and pyridines, and these should be detectable. Pyrazines, having two nitrogen atoms, tend to give even numbered ions, and give the same mass as a ketone, but since neither was seen, that is irrelevant. Had there been such signals, the fragmentation patterns are quite distinctive if you have done this sort of work before.

Other possible sources of organic compounds, besides carbon, are from chondrites that have landed, and geochemically. It is hard to assess chondrites, because we do not have other information. It is possible to tell the difference between oxygen from chondrites from oxygen from other places (because of the different ratios of isotopes of mass 17 and 18 compared with 16), but they never found oxygen. The materials could be geochemical as well. The same reaction used by Germany to make synthetic petrol during WW2 can occur underground, and make hydrocarbons. So overall, while this is certainly interesting, as is often the case it raises more questions than it answers.

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.