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Sunday, May 04, 2008
Unbibium or Unbelievium?
Wow... Scientists at the University of Jerusalem have made an extraordinary claim. If correct it would be the science scoop of this young century, if it fizzles out it would be a more spectacular science blooper than cold fusion and polywater combined... Much is at stake here!
Amnon Marinov and co-workers claim to have found a new chemical element and not just any either: their temporarily baptised Unbibium (aka eka-Thorium) would be the first super-heavy element to have been found in nature (and not synthesised by atom bashing, like so many other transuranium and some transactinide heavy elements). Marinov et al sifted through a pile of Thorium atoms, one at a time, using an advanced mass spectrometer. Alongside various super-heavy species, usually combinations of heavy atoms, inter-metallics, oxides and hydrides that all form as a kind of side-show when mass spectrometry is used, they also encountered a species with an alleged atomic weight of 292 and atomic number of 122. If this proves to be a single-atom-species (and not the sort of multi-atom-species that are often found inadvertently when using this kind of measurements) then it would indeed be a new chemical element and one that has in fact been predicted from quantum mechanical theory (see for example the much studied so-called 'island of stability').
Marinov and his group, hopefully not prematurely, claim to have been able to exclude any rival species for which the alleged (Z = 122, W = 292) new element could easily be mistaken.
Personally I find the claim both fantastical and plausible at once and hope sincerely that Marinov and his colleagues aren't about to burn their fingers in a manner so spectacular that few scientists before have, because of the extreme importance of this to-be-corroborated discovery.
Lemmesee, Unbibium (from Latin: 1 = un, 2 = bi, so 122: Un-bi-bi-um) would:
be the first period 8, g-block element of the periodic table of the elements to be found or synthesised,
be extremely stable: Marinov et all calculated a radioactive half-life of over 100 million years (a claim that's hotly contested by some),
be rare, yet not that rare: the prospect of preparing the element in milligram amounts (way more than modern chemists need to determine its chemical properties) would be very real, owing also of course to its nuclear stability,
be a member of a new group of elements, analogous to the lanthanides and actinides, which could be dubbed the eka-actinides or super-actinides,
be chemically analogous to Thorium (hence the alternative name eka-Thorium), although with such a massive electron cloud chemical properties of the element may deviate from simple predictions, due to relativistic effects,
be another crowning tribute to the predictive power of nuclear quantum physics.
It's unlikely I'll be able to buy some Unbibium dioxide (UbbO2) in my life time for backyard chemical experimentation. For now, I'll maintain the healthy scepticism that's appropriate and call the elusive element Unbelievium. But let science provide the compelling evidence needed to turn me into a believer...
Rolf-Dietmar Herzberg, of the University of Liverpool, is almost hostile to the discovery:
Researchers at Lawrence Livermore National Laboratory, California, who helped confirm the detection of element 118 in 2006, told Chemistry World they were too busy to check through Marinov's research.
'The popular vote is one of ridicule and I cannot fault that,' Herzberg sums up.
Marinov says he has submitted the article to the journals Nature and Nature Physics, but both turned it down without sending it for peer review. 'I am not changing the article and hope to get it published in another journal.'
The latter is confirmation that Marinov's paper hasn't been peer reviewed yet (there appeared to be some confusion about that). Looks like he will have his work cut out convincing the science community of the validity of his claims...
A recent comment on my previous post about Expelled, the movie caused me to revisit that subject by checking out the excellent rebuttal site Expelled Exposed. In the interest of fairness, anyone who's seen the movie, regardless whether they liked it, hated it or had no opinion on it, should really scrutinise this website because it shows just what a flaky flunkie Ben Stein actually is.
One of my main objections to Steins' crock of shit is the almost inverted anti-Semitism it displays: Stein, to bring home his fake message, will have us believe that "Neo-Darwinism" (whatever the f*ck that is, this Americano-speak that doesn't make an iota of sense) led to the Holocaust. Stein, being himself Jewish, should be deeply ashamed to point the finger to the wrong guys, as also the Anti-Defamation League accepts (see a little lower). The deeply annoying super-trailer has been appended near the bottom of this post, so see for yourself how Ben quite literally can't wait to start cackling about the Nazis, in order to make that pernicious connection: "Darwinists" (sorry, but I use inverted comma's here, because contrary to a widespread belief the scientific paradigm we correctly call Evolutionary Biology is not an ideology, it's not an -ism, it's simply science...) = the Nazis. Expelled Exposed does a good job at dispelling this ludicrous connection. Hitler & Eugenics
Summary
Expelled’s inflammatory implication that Darwin and the science of evolution “led to” eugenics, Nazis, and Stalinism is deeply offensive and detrimental to public discussion and understanding of science, religion, and history.
The Claim
“Darwinism” “led to” Nazism, the Holocaust, and other heinous historical events.
The Facts
Since the 1920’s, a narrow group of Christians who rejected the modernizing changes made by mainstream Protestants, have wrongly tried to blame evolution for the ills of modern society. World War I, atheism, and communism have all been attributed to evolution. After World War II, this narrow group added Nazism and Fascism to the horrors supposedly caused by evolution. Such claims occur in the writings of the young-earth creationist Henry M. Morris, a founder of the modern creation science movement, and have been repeated by “intelligent design” promoters and creationist Christian organizations such as Answers in Genesis, the Institute for Creation Research, and Coral Ridge Ministries.
Understanding the history of Nazi Germany and how the Holocaust could happen is obviously a very serious, and, in an era when ethnic cleansing and genocide are resurgent, a critically important subject. The public interest is not well-served by the efforts of sectarian groups to advance their own narrow agendas through distorted and simplistic explanations of horrific events.
Any serious attempt to understand the Nazis’ rise to power in the 1920’s would consider the devastation suffered by all of the belligerent countries in World War I, especially Germany, and the resulting deep political, social, and economic crisis in that country. The huge military losses (more than 2 million soldiers killed), the extraordinary number of civilian casualties, the fragmentation of German politics, the economic consequences of reparations Germany was required to pay to the war’s victors, the intensification of nationalism, and the exploitation of deeply rooted anti-Semitism are some of the factors that a serious history would address.
Anti-Semitic violence against Jews can be traced as far back as the Middle Ages at least, 7 centuries before Darwin. As Hitler and the Nazis rose to power in Germany in the aftermath of World War I, they distorted and abused anything they could in their despicable campaigns to foment hatred of Jews and others they stigmatized as “asocial” or “outside society.” The Nazis appropriated language and concepts from many sources, including evolution, genetics, medicine (especially the germ theory of disease), and anthropology as propaganda tools to promote their perverted ideology of “racial purity.”
On April 29, 2008, the Anti-Defamation League (ADL) issued this statement about Expelled:
The film Expelled: No Intelligence Allowed misappropriates the Holocaust and its imagery as a part of its political effort to discredit the scientific community which rejects so-called intelligent design theory.
Hitler did not need Darwin to devise his heinous plan to exterminate the Jewish people and Darwin and evolutionary theory cannot explain Hitler’s genocidal madness.
The ADL press release also said, “Using the Holocaust in order to tarnish those who promote the theory of evolution is outrageous and trivializes the complex factors that led to the mass extermination of European Jewry.”
Expelled erroneously implies that the theory of evolution necessarily “leads to” eugenics. While some geneticists were supporters of eugenics in the early 20th century, the movement drew on support from many sources. As the United Methodist Church recently stated in an apology for its support for eugenics:
Ironically, as the Eugenics movement came to the United States, the churches, especially the Methodists, the Presbyterians, and the Episcopalians, embraced it. Methodist churches around the country promoted the American Eugenics Society “Fitter Family Contests” wherein the fittest families were invariably fair skinned and well off. Methodist bishops endorsed one of the first books circulated to the US churches promoting eugenics. Unlike the battles over evolution and creationism, both conservative and progressive church leaders endorsed eugenics.
Opposition came from many quarters as well; some clergy, secular critics, and scientists spoke out against eugenics on social and scientific grounds. Clarence Darrow, famous for defending the teaching of human evolution in the 1925 Scopes trial, wrote this 1926 in a scathing repudiation of eugenics called “The Eugenics Cult”:
We have neither facts nor theories to give us any evidence based on biology or any other branch of science as to how we could breed intelligence, happiness, or anything else that would improve the race. We have no idea of the meaning of the word “improvement.” We can imagine no human organization we could trust with the job, even if eugenists [sic] knew what should be done and the proper way to do it. (Clarence Darrow, “The Eugenics Cult.” The American Mercury vol VIII, June 1926, p. 137)
Darrow concluded his article by writing:
Amongst the schemes for remolding society this is the most senseless and impudent that has ever been put forward by irresponsible fanatics to plague a long-suffering race. (Clarence Darrow, “The American Spectator” vol VIII, June 1926, p. 137)
By the 1930s, scientific support for eugenics continued to wane in the United States as it became clear that human genetics was far more complex than had been realized thirty years earlier. Evolutionary biologists were in the forefront of developing this understanding, another fact which Expelled ignores.
In recent decades, Harvard evolutionary biologists Richard Lewontin and the late Stephen Jay Gould have been among the most outspoken critics of crude biological determinism and eugenics. Gould’s book, The Mismeasure of Man (1981, 2nd ed. 1996) is an excellent and readable account of the history of misuses of science to support racist ideologies, and why modern evolutionary biology does not support these ideologies. Not in Our Genes, by Lewontin et al. argues for extreme caution in making claims about the genetic basis of behavior.
Controlling Human Heredity, 1865 to the Present, by Diane B. Paul (1998) gives a full and critical account of the eugenics movement in the United States and internationally. See also In the Name of Eugenics (1985, 1986, 1995) by Daniel Kevles and Preaching Eugenics: Religious Leaders and the American Eugenics Movement (2004) by Christine Rosen.
The Claim
Charles Darwin advocated eugenics in the Descent of Man.
The Facts
In Expelled, Ben Stein reads a passage (omitting ellipses) that was also read by anti-evolutionist William Jennings Bryan in the Scopes trial:
With savages, the weak in body or mind are soon eliminated. We civilized men, on the other hand, do our utmost to check the process of elimination. We build asylums for the imbecile, the maimed and the sick, thus the weak members of civilized societies propagate their kind. No one who has attended to the breeding of domestic animals will doubt that this must be highly injurious to the race of man. Hardly anyone is so ignorant as to allow his worst animals to breed.” (Charles Darwin, The Descent of Man, 1871.)
But Stein does not quote the very next passage in the Descent of Man which makes clear that Darwin was not advocating eugenics. Rather, he remarked, “The aid which we feel impelled to give to the helpless is mainly an incidental result of the instinct of sympathy, which was originally acquired as part of the social instincts, but subsequently rendered, in the manner previously indicated, more tender and more widely diffused. Nor could we check our sympathy, if so urged by hard reason, without deterioration in the noblest part of our nature.” (emphasis added)
These are hardly the words of someone arguing for the sort of totalitarian eugenics practiced by the Nazi state, as implied by Expelled. The super trailer:
And if all this depressed you, here's great spoof: SEXpelled: no SEX allowed!
Googling for some thermochemical data on calcium sulfide (CaS) I came across a story that illustrates the kind of progress that's been made in terms of protecting the environment (as well as humans and other life forms that inhabit it) from wasteful activities by industrial scale chemistry. The story's main protagonist is a waste product that was generated in large quantities around the turn of the 19th century, called galligu (a neologism that reflects the black, gooey and stinky nature of that hitherto unknown waste product), in which calcium sulfide features as a prime component. Ironically, my backyard process for producing titanium by means of sulfate boosted thermite reactions generates some calcium sulfide by-product too, albeit in much smaller concentrations and in a dry, fused and much less smelly form (hence my interest in CaS...) Britain has numerous former industrial sites that contain massive deposits of this seriously soil-contaminating waste product (galligu) and we're in a sense still dealing with the legacy of the 'alkali wars'.
The account is that of one of the first industrial chemical processes for the production of a chemical that still today is much sought after: soda ash, aka soda, washing soda, chemically sodium carbonate (Na2CO3). Soluble alkali carbonates had previously for centuries been produced only on a medium scale with more artisan methods, in particular the extraction (leaching with water in designated pots) of potash (potassium carbonate or K2CO3, from which the English word potassium is derived) from wood, plant or kelp ashes (these ashes are quite literally the calcined remains of plant metabolisms).
But demand for soluble alkali (sodium or potassium) carbonates grew exponentially and fueled the need for an industrial conversion of more readily available soluble sodium sources like sodium chloride (sea salt or kitchen salt) to carbonates.
And so in 1791, the Frenchman Nicholas Leblanc patented a process that could accomplish just that: converting abundantly available sea salt, combined with equally cheap-as-chips limestone, coal and sulfuric acid with some creative chemistry into that prized commodity: soda.
The Leblanc process must go down in history as one of the most polluting and wasteful industrial processes ever to have been put to massive use: this source here claims totally plausibly that:
In 1862, 1,834,000 tonnes of raw material were used to produce just 280,000 tonnes of saleable product, a ratio of more than 6:1. For every tonne of salt used in the process, three tonnes of coal were burned. It is estimated that one million tonnes of coal were burned annually at the height of Leblanc production. Furthermore, it is known that for every tonne of soda ash produced, two tonnes of waste material (galligu) were generated [...]
It's wastefulness would have been more of an economic problem than anything else, if it hadn't been for the extreme smelliness, indeed toxicity of its waste streams, which in those days were quite unceremoniously dumped, mostly where the factories stood.
The galligu itself contains large quantities of calcium sulfide, which due to hydrolysis in the presence of water (galligu is in fact a watery slurry!) generates hydrogen sulfide (H2S), aka rotten eggs or stink bomb gas. Apart from the repulsive odour, perceptible even in trace amounts, H2S is also toxic, more toxic in fact than hydrogen cyanide... In today's terms, Leblanc plants and environs must have been some of the smelliest and toxic places in this green and pleasant land! An 1839 suit against soda works alleged:
"the gas from these manufactories is of such a deleterious nature as to blight everything within its influence, and is alike baneful to health and property. The herbage of the fields in their vicinity is scorched, the gardens neither yield fruit nor vegetables; many flourishing trees have lately become rotten naked sticks. Cattle and poultry droop and pine away. It tarnishes the furniture in our houses, and when we are exposed to it, which is of frequent occurrence, we are afflicted with coughs and pains in the head ... all of which we attribute to the Alkali works."
But there's more. Another, this time gaseous waste product of the Leblanc process is hydrogen chloride (HCl), aka hydrochloric acid, spirit of salt or muriatic acid. Incredibly, back then HCl had no real residual value and Leblanc operators gaily pumped this highly corrosive, pungent smelling and toxic gas through smoke stacks straight into the free atmosphere!
Under pressure from legislators, to this problem a rather hasty and half-hearted solution was found by using primitive gas scrubbers which absorbed the HCl into water, thereby obtaining a dilute solution of hydrochloric acid... which was then simply allowed to flow into nearby water streams with predictably deleterious effects on the water's fauna and flora...
And upstream from the Leblanc process lay an equally polluting process: the production of one of Leblanc's feedstocks: sulfuric acid, back then produced mainly by burning pyrite ores (aka fool's gold, FeS2) that often contained dangerously high levels of heavy metals, among others arsenic, nickel, zinc and chromium...
Not so much later, the Belgian chemist and founder of the Solvay chemical empire, Ernest Solvay, developed a sulfurless means of soda production (the Solvay process) which was overall almost squeaky clean and fairly quickly replaced all Leblanc capacity.
Those who today still believe that G-d's green Earth has an infinite capacity for healing and that it's therefore OK to pollute to one's heart's content should accepts that careless and wasteful (albeit also highly useful) industrial activity can lay waste to large areas of the human environment for decades...
Ferrofluids, Anne Marie Helmenstine and plagiarism...
Upon my many Internet travels I was recently reminded of those strangely behaving paramagnetic fluids, known as ferrofluids or ferroliquids (see a demo below). Easy to make at home, they provide an ideal party trick and something that will enchant young and old. Unfortunately my surfing also lead me to a case of plagiarism so blatant, I haven't seen one like it in a long time...
Google searching a little for ferrofluid, I came across this little hub on home made magnetic fluids, written by a Anne Marie Helmenstine, Ph D, who provides About.com's guide to Chemistry since 2001. The author's 5 page article on ferroliquids is well written and provides a step-by-step approach to safely making your own.
Except, Mizz Anne Marie Helmenstine's method and much of her text isn't really her own. Scrolling down just a little in Google's search results I found another detailed web page describing the home production of such ferrofluids, at Sci-Spot.com and which clearly provided the inspiration, to put things very, very mildly, for Helmenstine's piece.
Anne Marie Helmenstine, "Ph D", has lifted entire passages from Sci-Spot.com's original text, almost verbatim. Read both texts in parallel and see for yourself. You'll also conclude that Anne Marie has probably never ever actually conducted a ferrofluid experiment in her life: the only photo of a ferrofluid in action is a photo lifted from Wiki (but with credit at least). For someone making a living from writing a science column, that's truly appalling and amounts to intellectual property theft, nothing less.
Please don't also forget that About.com generates web content, in this case provided by a paid writer, because said web content provides advertising space and revenue for About.com... that, and that alone, is their raison d'être.
What's more, she could have avoided all this simply by proving proper credit to Sci-Spot.com, she chose not too. Of course being a purely commercial resource, About.com would rather be seen dead than sporting a non-paid external link, so screw Sci-Spot.com, who, after all, are they? Something somewhat similar happened to me sometime ago and I didn't feel happy about it either...
Edit: Lauren Leonardi (Manager, Guide Operations, About.com - see comment section of this blog post) claims Hemelstine does link to Sci-Spot.com. Well, I'll take her word for it but cannot find this link.
Mizz Helmenstine's condescending defense of her actions, presented at Sci-Spot.com as a reply to one of their emails, is also worth noting:
"Yes, your article is one I read when I wrote that tutorial. It was not, however, the only one, and I haven't copied you...
You haven't been plagiarized. You have a one-page recipe for a ferrofluid. I have a 5-page resource, with background information and information on what to do with a fluid. I think it's obvious I didn't lift your text.
Best wishes, Anne Helmenstine, Ph.D. About Chemistry"
A 5-page resource... as opposed to a measly 1 page recipe... I challenge anyone to tell me what exactly About.com has added to Sci-Spot.com's original content that isn't simply advertising space and some irrelevant fluff. No, Anne Marie Helmenstine, the lifting is so obvious it's blinding and you're the empress with no clothes on (perish the thought...) Helmenstine strikes me as one of these people that, when faced with personal and genuine criticism, would retort: "Do you know who I am?"
I wonder if About.com has a page about plagiarism...
Sci-Spot.com's response to all this, to invite readers of their web page to contact Anne Marie, is of course a plaster on a wooden leg. They should sue About.com, period.
Update:
The plot thickens somewhat. Because I want to make some ferrofluid too but having no OTC source of oleic acid, one of the vital ingredients in the mix, I decided to make oleic acid by extracting it from its source material, olive oil, via alkaline route. I envisaged a purification step that involves converting the oleic acid to ammonium oleate and decided to Google a bit to see if I could find some more information on this substance.
On page 3 of Google.co.uk's search results for ammonium oleate I found in positions #23, #24 and #25 (at the time of writing) three texts that all share entire sections with Helmenstine's About.com piece and Sci-Spot.com ferrofluid page: This one cites Helmenstine's piece, but in a strange twist uses the same format as Sci-Spot.com:
This now really begs the question: which is the actual source text? Mentoring Advanced Placement can be excluded as they have at least the courtesy of citing their source (Helmenstine). But whether Sci-Spot.com's claim that Helmenstine's piece lifted theirs holds up to scrutiny isn't clear because it's impossible to establish whether they really were the trailblazers here or whether the phy.hr web page really provided the original information and Sci-Spot.com failed to cite that text. The phy.hr pdf version makes no claims to originality but cites no source at all.
The pdf version of the AP Mentoring web page however is quite revealing: part of the pdf document is simply Sci-Spot.com's web page converted into the pdf format. And in the middle of page 2 of the AP Mentoring pdf there's a bizarre link that compounds Helmenstine's About.com page with Sci-Spot.com's page... On a lighter note, watch this highly arty demo with sophisticated use of a ferrofluid (turn on the audio). Art, electromagnetism and fluid mechanics all rolled into one. Creepy, isn't it?
Many a backyard scientist has experimented with thermite reactions, including one of the harder reactions, that of silicon dioxide (silica, SiO2) and aluminium (Al) to produce silicon metal(loid) and alumina. These reactions present great pyrotechnical displays and with a little luck leave you with some lumps of metal as a memento. Because of the metal produced, thermite reactions also find widespread use in aluminothermic metal extraction processes for the preparation of specialist high purity metals and alloys.
Although the reaction 3 SiO2 + 4 Al ---> 3 Si + 2 Al2O3 is thermodynamically favourable, this reaction does not propagate by itself, presumably because the heat of reaction isn't enough to overcome the activation energy it needs. Straight mixes of a silica source and aluminium powder therefore fizzle out or can't be ignited.
To make the reaction self-sustainable, the most used method by backyard scientists (and fellow travellers) is to add a booster mix of aluminium powder and sulfur, which reacts according to 2 Al + 3 S ---> Al2S3 with great development of heat with great development of heat (ΔH ≈ -5.3 kJ/g of stoichiometric mix). This heat provides the missing activation energy and makes the reduction of silica to silicon with Al self-sustaining.
A typical sulfur boosted silicon thermite mixture is silica/Al/S = 100/111/133 (9:10:12) but I've also successfully used mixes much lower in S, such as 100/72/21.
Apart from yielding a self-sustaining reaction, S-boosted silicon thermites have also other advantages:
• Quite easy to ignite, using magnesium (Mg) ribbon (e.g.). • The resulting slag is a mix of alumina and aluminium sulfide (Al2S3). The much lower MP of the sulfide (around 1,100 C) causes the slag mix to be more fluid than pure alumina, which freezes at around 2,000 C. This greatly helps slag/metal separation, as the slag/metal mix remains liquid longer, allowing it to collect in the bottom of the crucible and the metal to coalesce out. And a mix of alumina and aluminium sulfide is also much softer than pure, fused alumina, making the slag easier to break up mechanically. • The alumina/aluminium sulphide slag mix reacts readily with water through hydrolysis of the sulphide: Al2S3 + 6 H2O ---> 2 Al(OH)3 + 3 H2S. This breaks up the slag into a (stinky) hydrated alumina slurry (or mud), giving easy access to the metal globules.
But that's the good news and there's some bad news too: the aluminium sulfide is so prone to hydrolysis, that even the newly fused slag positively reeks of H2S, in plain English: rotten eggs. Needless to say, adding water or a mineral acid to it, seriously aggravates the problem. Not only does H2S stink terribly, it's also toxic and it's perceptible even in trace amounts.
(Tip: if you're going to treat an alumina/aluminium sulfide slag mix with water, use copious amounts of bleach instead of pure water: the sodium hypochlorite in the bleach will convert much of the H2S to elemental sulfur, which is even recoverable).
In a nutshell, I got so fed up with the smell of rotten eggs, I decided to try and replace the S-booster mix with a sulfur-free system. I chose to investigate a potassium chlorate/Al mix, which reacts according to 2 Al + KClO3 ---> Al2O3 + KCl with an estimated ΔH ≈ 7.11 kJ/g (of stoichiometric mix) heat generated. I had used such mixes before for lighting thermites.
Initial tests with a silica/Al/KClO3 = 100/72/27 mix showed clearly that the reaction proceeded self-sustainingly and that Si metal was formed, in a hard, porous alumina matrix. I gradually stepped up the amount of booster mix to 100/84/57 and later to SiO2/Al/KClO3 = 100/96/81, to find that progressively more of the slag ends up at the bottom of the crucible (I used mostly 20 g mini batches for the development work) because of the increasingly high peak temperatures during the reactions.
The main problem remains slag/metal separation, both in situ and after the reaction products have cooled down: the pure, fused alumina freezes up quickly into a very, very hard mass. 32 w% HCl doesn't even begin to dent it and forget about mechanical separation: this stuff is HARD!
I then proceeded to test calcium fluoride (Fluorite, CaF2, calcium fluoride) as a potential flux, at 20 w% added to the promising 100/96/81 formulation (this then became 100/96/81/55 - with 55 the CaF2) . Although it made a world of difference in the sense that much larger globules of Si metal form, the slag remains extremely hard and insensitive to HCl. Another test at 40 w% CaF2 showed that at that level the reaction was being slowed down, probably due to adding so much inert material, and hence slag metal separation deteriorated again due to lower peak temperatures.
The purpose of the CaF2 is essentially that of slag fluidiser. Fluorite is inert in these conditions and takes no part in any chemical reactions but has a much lower melting point than pure alumina: 1402 C (2555 F) for fluorite against 2054 C (3729 F) for alumina. Adding relatively small amounts of the lower melting fluorite to the thermite mix therefore helps keeping the slag as fluid as possible for as long as possible, thereby allowing the slag metal mix to collect at the bottom of the crucible and the metal and slag to separate out by gravity.
So far the best formulation has been found to be SiO2 / Al / KClO3 / CaF2 = 100 / 96 / 81 / 55 (all parts by weight), which has been tested in a 100 g thermite mix with good results, although there is room for improvement. Slag/metal separation is generally good with large blobs of pure silicon metal being formed but adhesion of the slag to the metal remains a problem. Further attempts at optimising will include increasing the portion of booster mix and flux to obtain a mix that runs even hotter and should by rights lead to even better slag/metal separation. Another possibility is to use a flux that is even lower melting, such as Cryolite (Na3AlF6, sodium hexafluoroaluminate). Expect updates!
The principle of chlorate-boosted thermite reactions has in the mean time also been successfully deployed on an even more notoriously difficult reaction, that of extracting titanium metal from titanium dioxide. And the production of ferrotitanium (60 w% iron - 40 w% titanium) without any booster has also been demonstrated separately.
A simple but effective thermodynamical model of what goes on thermally inside a thermite mix has also been developed and has been shown to be accurate in estimating the peak temperatures during reaction. More on that in a dedicated post to come soon.
This is Easter, the day Christians everywhere set aside to celebrate the day they were hoaxed by a gang of Middle Eastern charlatans into believing a local mystic rose from the dead. Zeno finds that this year it's also a day to remember another flop: the cold fusion debacle.
It's been 19 years since Pons and Fleischmann announced their purported discovery of a mechanism for generating energy from a room-temperature fusion cell. Unlike the resurrection, I was actually there for that one. I was a post-doc at the University of Utah at that time, in the building right next door to where Pons and Fleischmann worked, and I attended the various events associated with the "discovery".
Even then, there was reason to doubt: I remember being mystified that they'd chosen to announce it via press release rather than a scientific publication (a strategy that you'll notice the Discovery Institute has expanded upon), and when I attended Pons lecture on the phenomenon, I was bothered by the lack of mechanism and the uncontrollable variability in the experiments — it was basically a laundry list of experiments done, some of which did nothing, some that got a trickle of excess energy output, and others that exploded. It was exciting and interesting, and we all hoped that this was real, but it wasn't science yet.
And it still isn't. I guess some people are still puttering away at it, but it's still an inconsistent phenomenological collection of anecdotes.
If only Pons and Fleischmann had thought to make a religion of it, that wouldn't be a problem.
A couple of weeks ago I had adjusted the best-so-far SiO2/Al/KClO3/CaF2 = 100/96/81/55 formulation to TiO2/Al/KClO3/CaF2 = 100/72/61/47 and tried it with my home brewed 'emulsion paint' TiO2 and it burned but somewhat sputteringly and of course no metal. The home made TiO2 undoubtedly contained residues of paint resin and possibly other white pigments. Without concentrated sulfuric acid, it is difficult to purify it.
But I recently bought a good grade of pure TiO2, Anatase "99 %", so I decided to stick that in there too, as well as in an adjusted formulation with magnalium (a 50/50 alloy of aluminium and magnesium - denoted MgAl) . The total charge in both cases was 20 g, contained in an egg cup and embedded in a sand-filled steel bucket. Materials used: very fine Anatase 99 %, 400 mesh Al powder, potassium chlorate reagent grade, ground Fluorite for CaF2. Ignition with a stoichiometric mix of Al/KClO3 mix and an Mg ribbon fuse. The experimental set-up is very similar to the silicon thermite described here.
The Anatase formulation burns like hell: very fast and furious, very regular: it's completely on a par with its SiO2 analog. Immediately after the reaction had finished I went over to look and saw three quite large, darker regions at the bottom of the white/yellow hot crucible (eggcup). Darker regions in the hot slag are an indication of materials with higher heat conductivity (such as metals), I've seen this happen many times before.
But at that point I didn't even dare to hope too much and decided to light the magnalium version (TiO2/MgAl/KClO3/CaF2 = 100/82/61/49). That basically exploded! I knew it was going to be fast, possibly too fast, so I ran away after lighting the Mg ribbon and the whole thing went "poof!" while I still had my back to it, throwing content as far as a meter away from the test point!
But after the straight Al test had cooled down it became clear that the darker regions were indeed titanium metal: oxidised (only slightly) on the outside on the top and lightly covered in dark slag at the bottom, a little buffing up with rough sanding paper revealed the hard, shiny metal. It has a slight golden tinge to it. I'm now the proud owner of three 4 - 6 mm blobs of home made titanium metal, total weight about 1.9 g.
Interestingly, slag/metal separation was simply exemplary: most of the metal neatly at the bottom, easily separable from the slag mix. It appears to me a lot of the slag had been blown off, covering the globules only in a slight oxide/slag coating. The metal had also passivated, like Al does.
Tonight I'll be running a larger test to confirm.
It may also prove difficult to get chemical confirmation of the metal's identity: Titanium only really dissolves in concentrated acids like sulfuric or nitric, also apparently HF. Nice one... I haven't got any of those...
Update:
Another test using the same formulation but this time with a larger batch size (92 g) also yielded good metal, including one blob of 11.5 g, the thickness of a pound coin but larger in surface. Some smaller globules were spewed out of the crucible, so it's probably running a little too hot.
While pure titanium is much more resistant to 32 w% HCl than say steel, it does dissolve slightly, given a bit of time and temperature. The resulting solution is a nice Amethyst type purple, due to aqueous Ti3+. The solution tests positive for Ti with hydrogen peroxide according to this test here. There is therefore no reasonable doubt left that the metal produced is in fact elemental titanium metal.
The reduction of titanium dioxide with Al powder has also been used twice to produce a ferrotitanium alloy (in my case approx. 60 w% Fe and 40 w% Ti) by co-reducing Fe2O3 (iron (III) oxide, Hematite) and TiO2 (here Anatase) with Al powder. The oxide mix was composed of 1 mol of TiO2 and 0.85 mol of Fe2O3. Here, no chlorate-booster is needed because the reduction of Fe2O3 to Fe metal provides the heat needed to sustain the reaction and to ensure the reaction products are obtained in molten form. CaF2 was used as a fluxing agent. Two 20 g reactions were carried out, both yielding exemplary slag/metal separation and clean 5 g reguli of the ferrotitanium alloy.
Without a shimmer of doubt this process can be applied to make other pure titanium alloys of precise composition.
And other heat booster systems besides the potassium chlorate/aluminium powder system have also been tested successfully. A booster system for thermites usually comprises of aluminium and an oxidiser. In the conditions of high temperature that exist inside an ignited thermite mixture, the oxidiser oxidises the aluminium to alumina and the formation of this oxide is accompanied by great release of heat, which is used to keep the thermite 'burning', as well as reach a sufficiently high end temperature. The latter is necessary to ensure the reaction products, the target metal and slag, are obtained in liquid form and can separate out, thereby obtaining the pure metal as a solid (after cooling).
Other well-known oxidisers for aluminium are nitrates and sulfates. For sodium nitrate the booster reaction is:
NaNO3 + 2 Al ----> Na + 1/2 N2 + Al2O3
This reaction produces about 700 kJ of reaction heat per mol of nitrate.
A typical sulfate is calcium sulfate, used extensively in plaster of Paris, wall fillers, writing chalks and other OTC products and it reacts with aluminium according to:
CaSO4 + 8/3 Al ---> CaS + 4/3 Al2O3
It releases nearly 1,300 kJ of heat per mol of sulfate.
I have used both sodium nitrate/aluminium and calcium sulfate/aluminium with success as heat boosters in titanium metal producing thermites (and I've got the metal to prove it!)
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And so in 1791, the Frenchman Nicholas Leblanc patented a process that could accomplish just that: converting abundantly available sea salt, combined with equally cheap-as-chips limestone, coal and sulfuric acid with some creative chemistry into that prized commodity: soda.
The galligu itself contains large quantities of calcium sulfide, which due to hydrolysis in the presence of water (galligu is in fact a watery slurry!) generates hydrogen sulfide (H
