Thursday, July 24, 2008

Manganese thermite based on blends of MnO and Mn2O3

Making manganese metal by thermite reduction of manganese oxides is one of the more frustrating oxide reductions I've ever carried out.

To get a better understanding of what the issues are I'd firstly recommended reading my blog post on this subject.

The issue with manganese thermite, especially from the higher oxides MnO2 and Mn3O4, is that these reactions generate so much heat that in adiabatic conditions the temperature of the reaction products will exceed the boiling point (BP) of Mn (2,061 C, 2,334 K). It's this characteristic that causes MnO2 thermites to deflagrate often violently, almost 'explosively'. The end-temperature of a thermite reaction (in adiabatic conditions) can be estimated quite accurately from the molar reaction heat (ΔH, reaction enthalpy), and the molar heat capacities and molar heats of fusion of the reaction products, basically by applying Hess's Law. If of interest to readers I can give an example of such a calculation (on request).

The obvious solution to the problem would be to create conditions in which the reaction enthalpy is either lower or partly dissipates away (non-adiabatic conditions) but there's another problem complicating this approach.

For a thermite reaction to yield liquid metal, separated from the liquid slag (both solidify on cooling of course), the melting point (MP) of both (whichever is highest) the produced metal and the by-product alumina (Al2O3) has to be reached at the end of the reaction. For alumina the MP is 2,327 K (2,054 C), for Mn, 1,519 K. But as stated before, the BP of Mn is also only 2,061 C, perilously close to the MP of alumina.

This creates a real lose-lose situation: to achieve metal-slag separation of Mn/Al2O3 this mixture has to reach a temperature that's really close to the BP of manganese metal. Even higher temperatures will cause much of the Mn metal to simply boil off. At temperatures somewhat below the MP of alumina, the vapour pressure of the Mn will be less but metal/slag separation will not be able to occur, resulting in powdered, sintered metal frozen in the slag.

Accurate control of the end-temperature in near-adiabatic conditions is thus essential to obtain any lump metal from such a reduction.

I therefore started out on a series of experiments designed to cool the MnO2 thermite by co-reducing MnO2 and MnO. The reaction enthalpies per mol of oxide for both reductions are respectively - 597 kJ per mol of MnO2 and - 173 kJ per mol of MnO. Initial results with a blend of 1 mol MnO and 0.4 mol MnO2 and a high level of CaF2 (calcium fluoride, fluorite, fluorspar) as a heat sink and slag fluidiser, showed that this kind of mix with a stoichiometric amount of Al powder is capable of making nice blobs of clean Mn metal, albeit at low yields.

In the mean time I've switched from MnO2 to Mn2O3 because thermochemical calculations show that an Mn2O3 runs a little cooler than the corresponding MnO2 reaction, mainly because the Mn2O3 reaction generates more moles of reaction products (per mol of Mn2O3, 2 mol of Mn and 1 mol Al2O3, against 1 mol Mn and 2/3 mol Al2O3 for MnO2).

I've run several small (20 g and 50 g batches) thermites using blends of Mn2O3 and MnO, always using a high level of CaF2. I set the level of CaF2 as a constant molar ratio of CaF2/Al = 0.225, the alumina slag therefore contains always the same molar fraction of CaF2.

On the whole the results indicate that obtaining yields (recovered metal/metal present in the oxide x 100 %) is hard to push much beyond 35 % or so. The last two batches, both with 50 g stoichiometric (and CaF2 = 0.225 molar ratio) mixes, gave the following yields:



Yield....................37 %...................19 %

The 1/0.5 blend gave the highest yield of Mn metal I've ever achieved (out of probably over 20 or so reactions) and the metal is clean skinned and solid. The largest regulus was 7.3 g. Both reactions ran well-contained, leaving a molten slag/metal puddle at the bottom of the crucible. The 1/0 batch yielded metal that was significantly more oxidised, yet on the whole of passable quality.

It's clear though although these results constitute a great improvement to the usual 'explosive' MnO2 thermite, there is only so much cooling the Mn2O3 thermite by blending it with the much cooler MnO can actually achieve in terms of yield improvement.

The only real solution to reducing Mn oxides (or halides) with higher yields is by using a reductant with a much lower melting oxide (or halide).

One such reaction that springs to mind is the reduction of anhydrous MnCl2 with Mg. The reaction enthalpy of MnCl2 + Mg ---> Mn + MgCl2 is unfortunately only a measly - 161 kJ/mol of MnCl2, about a 100 kJ short of success. Thermocalcs show that in adiabatic conditions the reaction products would be heated to about 1,200 K, well above the MP of MgCl2 (987 K) but about 300 K short of the MP of Mn (1,519 K). Pre-heating the mixture by about 300 K or simply heating it to spontaneous ignition could work to obtain liquid Mn and liquid MgCl2. It may also be possible to use the reaction Mg + I2 ---> MgI2 (ΔH = - 367 kJ/mol) as a heat-booster system, by adding extra magnesium and iodine to the reagent mix.

As regards using a reductant with an oxide of lower MP, that excludes both Mg and Ca, as both have oxides with insanely high MPs. That then really only leaves the alkali metals, in particular Li and Na.

Thermochemical calculation for the reaction Mn2O3 + 6 Li ---> 2 Mn + 3 Li2O (ΔH = - 838 kJ per mol Mn2O3) shows that in adiabatic conditions the estimated end-temperature would be 2,320 K which is still too high and too close to the BP of Mn.

But here we could blend with MnO again. Setting a target end-temperature of 2,000 K (well above the MP of Mn, yet well below its BP as well), the blend composition of a stoichiometric mix has been estimated to be about 1 mol Mn2O3 + 2.6 mol MnO.

One small problem: I haven't got any Li...

Sodium, with a ΔH = - 295 kJ per mol Mn2O3 for Mn2O3 + 6 Na ---> 2 Mn + 3 Na2O could also be a good candidate... Haven't got any Na either...

Sunday, July 20, 2008

Bill O'Liely, Viagra and Birth control...

Where Billy contends Viagra is for a medical condition and birth control is a choice... Stooopid "planned parenthood fanatics" (dixit BOR) for not cottoning on to that earlier: it's so damn self-evident... Also features McCain with a mouth full of nothing. BOR will later claim it was all pulled out of context, but McCain won't be able to contend that: he said nuttin'...

At least it sheds light on an old mystery: how do Conservatives reproduce? With paid Viagra, without birth control and mostly in the dark...

Saturday, July 19, 2008

Boffins, Elements and Videotape...

SodiumThe University of Nottingham, guided by chemboff supreme professor Martyn Poliakoff, has brought out a 118 part video guide to the chemical elements, somewhat predictably called The Periodic Table of Videos. Interesting. And a bit British: somewhat low budget and endearing. Element boffins, nerds and anoraks (like me) will love it... Predictably sodium and lithium get dunked in water but scientists are only big kids, like most other adults. (Photo: chunks of sodium metal)

Saturday, July 12, 2008

Seven Questions: What Iran Wants

By Karim Sadjadpour

Foreign Policy, July 10, 2008

Calling for dialogue one day and firing off missiles the next, Iran has baffled many observers with its seemingly erratic behavior of late. Karim Sadjadpour, an Iran expert at the Carnegie Endowment for International Peace, explains how the Islamic Republic responds to pressure, why Mahmoud Ahmadinejad laughs in the face of danger, and what Tehran’s hard-liners think of Barack Obama.

Foreign Policy: Last week, Iran sounded conciliatory notes when Foreign Minister Manouchehr Mottaki hailed a “new trend” in negotiations with the West over the nuclear issue. But this week, Iranian officials vowed to strike back against any U.S. or Israeli attack and test-fired missiles that they claim can hit Tel Aviv. What explains this shift in tone?

Karim Sadjadpour: The last two weeks have been very representative of the worldview of Supreme Leader Ayatollah Ali Khamenei and his modus operandi of neither confrontation nor accommodation with the West. Last week, we saw conciliatory signals from Tehran, saying: “We’re capable of being diplomatic.” And this week, Iran was sending signals to the Israelis and Americans saying, “If you want to escalate, we have the means to reciprocate.” Khamenei wants to send a clear signal: “Don’t think that pressure is going to moderate our behavior,” because he has always believed that if you give in to pressure, you only invite more of it.

FP: Also this week, Iranian President Mahmoud Ahmadinejad dismissed the possibility of an attack on his country as a “funny joke.” What do you think he’s trying to accomplish?

KS: He’s always genuinely thought that the likelihood of an attack is very slim, and his reading of U.S. domestic politics is that the Democrats won the 2006 midterm elections precisely because the U.S. public doesn’t have any appetite to embark on any more Middle East adventures. So, he believes that U.S. politicians have their hands tied.

That said, a U.S. military attack would be more carrot than stick for Ahmadinejad. There are two things that would really rehabilitate his presidency: One is a U.S. attack on Iran, and the second is a major U.S. diplomatic overture to Iran. I think the United States should not offer him either.

FP: What about an Israeli attack?

KS: I think the odds are very low. When Israel bombed Osirak in 1981, and when they bombed Syria more recently, there was “radio silence” before and after the operation. Whereas now with Iran, it’s been a much more public campaign. If the Israelis were serious about doing it, there would be a much more studied silence. I don’t think they want to do it and are hoping to intimidate Iran into compromise.

FP: Some analysts argue that, under certain circumstances, an attack might cause Iranians to blame Ahmadinejad for miscalculating.

KS: I would disagree with that. After the fall of the Taliban, there was a great deal of romanticism in Iran about the prospects of some type of 24-hour U.S. regime-change operation. But after what they’ve seen on a daily basis—and this is one thing the regime has done very effectively, broadcasting the carnage taking place next door in Iraq—I don’t see any scenario whereby Iranians would put the onus on their own leaders rather than the United States or Israel. Keep in mind, upwards of 80 percent of the Iranian public gets their news directly from official state television. You would have a segment that would blame their own leadership, but they’re marginalized politically. Iran’s liberal elite stay on the sidelines.

FP: What does Iran wants to see in Iraq right now? Is Iran pushing the Maliki government to impose a timetable for the withdrawal of U.S. troops?

KS: For the moment, the status quo in Iraq works quite to Iranian leaders’ advantage because they have their friends, their Shiite coreligionists, in a position of power, and they have their main adversary, the United States, bleeding very heavily.

But over the long term, there are actually a lot of overlapping interests between the United States and Iran with regard to Iraq. Both want to see its territorial integrity preserved. Iran supports the democratic process in Iraq probably more than any of Iraq’s neighbors, given that the Shiites are the demographic majority. And remembering what happened in Afghanistan, the last thing Iranian leaders want is for Iraq to break down into an al Qaeda-infested, failed state.

FP: Seymour Hersh recently reported in the New Yorker that the United States is working with ethnic minority groups to stir up trouble for the Iranian government. If Hersh’s allegations are true, how do you think Iranians will react?

KS: Iranian officials have been saying for a while now that they have concrete intelligence proving that the United States is trying to foment ethnic and sectarian unrest within Iran. Any type of U.S. policy along those lines would be unequivocally disastrous, and it would alienate just about every single Iranian. You have to remember: Iran is not a post-Ottoman entity that was drawn on a cocktail napkin by Winston Churchill. It has more than 2,000 years of being a nation state. Whether you’re Persian or Azeri or Kurdish or even Baluchi, there’s a strong sense of attachment to the soil of Iran. So, if Washington’s goal is truly to bring about a more democratic Iran, you’re going to tremendously alienate the Iranian nationalists and democrats that you want to see one day come to power if they perceive that you’re trying to tear the country apart.

FP: What do Iranians think about the U.S. presidential election and John McCain versus Barack Obama?

KS: There’s far more intrigue about Obama than about McCain. Apart from the fact that he advocates dialogue with Iran, he’s African-American and his middle name is Hussein, who is the paramount figure in Shiite history and culture. If Obama were to win, it would be much more difficult for Iran to constantly paint the United States as this grand oppressor. It’s interesting to note that a few days after the hostages were taken at the U.S. Embassy in Tehran, the Iranians released all the women and blacks because they said these groups were historically oppressed by Americans.

An Obama victory in November could tremendously change the dynamics in U.S.-Iran relations. If you’re a hard-liner in Tehran and you survive in isolation, like Ayatollah Khamenei, it presents far more of a quandary for you to have a president in Washington who says “Let’s be friends” than one who says “Let’s be enemies” and essentially continue the status quo. I would wager the vast majority of Iran’s political elite, who do want to see some sort of reconciliation, support Obama. But then you have a small, but powerful minority who survive in isolation, much like Fidel Castro in Cuba. They see Iran opening up to the world as a threat to their interests, and I’m sure they would much prefer John McCain to be president.

Friday, July 11, 2008

Lillian Ladele: state sanctioned religious bigotry

CosmoDaddy rebutts The Daily Mail's position on Lillian Ladele and the civil partnership kerfuffle...
“A Victory for Britain’s Quiet Majority“

Britain’s acceptance of those from different racial, social or religious backgrounds has long been an attractive aspect of our national character.

But this culture of tolerance has come under pressure from politicians and the courts, who have put the often stridently expressed demands of minorities ahead of the rights of the majority.

No case has so clearly illustrated this as that of Lillian Ladele, the registrar whose Christian beliefs - beliefs incidentally that in the broader sense shaped the DNA of this country - led her to refuse to perform same-sex civil partnerships.

The Mail supports the right to undertake civil partnerships, but not to force others to participate in ceremonies with which they may profoundly disagree.

But Miss Ladele’s bosses at Islington council, always ready to leap to the defence of the gay community, concluded that she was prejudiced, and insisted that she change her mind.

So she took them to an employment tribunal and - to the amazement of all those who have given up on the ability of our legal system to stand up for ordinary Britons - she won.

The tribunal concluded that Miss Ladele had been discriminated against, that the council had allowed the rights of homosexuals to trump her religious beliefs, and that it was utterly wrong.

The battle is far from over. Islington may appeal against the judgment. And we should never underestimate the sheer zeal of the commissars of political correctness to get their way.

I remember the Daily HateMail in the 80s, stirring up hate against ‘loonies’ and the ‘left’, as though standing up for, promoting and funding equality was only something which those with diseased minds would do. This paper has never accepted difference. They have railed incessantly against gay people, asylum seekers, foreigners and others, and in addition to their Nazi-supporting past have run appalling, personal campaigns against politicians such as Ken Livingstone who have had the temerity to stand up to them.

Their claim that the case against Lillian Ladele was a demand by a ’strident’ minority against the ‘rights’ of the majority is an outright deceit. Noone has suggested for a moment that gay rights should trump those of straight people or even the religious - that would be ridiculous because they are not fundamentally in opposition to one another. However the stridently religious believe that gay people are not equal - Lillian Ladele said she couldn’t fulfil her job description for gay people because of her ‘religious beliefs’. To allow belief as an excuse for enforcing in equality would be as dangerous as it is monstrous. In effect she demanded an opt out from the social norms which we are all now bound by, but against which the Daily HateMail continues to campaign. Her religion is not fundamentally opposed to gay people or homosexuality, whatever hysterical theists like Iris Robinson would have you believe, and to enshrine such an opt out under the law would be to misrepresent even her religion.

The HateMail suggests that this is ‘political correctness’, as if a local council standing up for equality before the law (and Ladele’s job description was bound by at least two laws) were something undesirable. It makes no difference whether or not the council could fulfil its remit to provide civil partnerships without her - the argument was whether or not the stridently religious could get special treatment in employment, treatment which allowed them to discriminate in the world of work, based merely on belief and not on the law which is supposed to apply to the rational majority. That Lillian Ladele has (for now) succeeded is a slap in the face for the real majority, who are not in any way connected to the bigoted, small-minded, xenophobic and hateful DNA of the country which the HateMail thinks it appeals to.

Bigotry is not a ‘right’ held by the majority, whatever else the tabloid would have you believe; Iris Robinson didn’t have this right, nor does Lillian Ladele. Thankfully our thoughts can’t (yet) be controlled, but we do not have the ‘right’ to impose our darker thoughts on those different to us, or those whom we dislike or disapprove of, at least not in the world of work. The law has, in this instance, said that belief trumps the rule of law, that Islington Council was wrong, despite having equality policies which Lillian Ladele was bound by, and laws governing the conduct of her job, to enforce her job description for all, not just some. It’s an outrageous decision, based on a flawed interpretation of the law, and it must be challenged for all our sakes.

Thursday, July 10, 2008

Manganese thermite based on manganese (II) oxide

I've run many thermite reactions in the past, including silicon thermite and titanium thermite, as well as many others that I haven't written about, namely iron, chromium, vanadium, cobalt, copper, ferrotitanium, ferrosilicon, ferrochromium, ferrovanadium and copper titanium bronze. But manganese thermite has been the object of many failed attempts, basically up to now.

Those familiar with thermite reactions may wonder what I mean by 'failed' in the manganese thermite context. Well, it isn't my primary objective to put on a good fireworks display, something that any backyard scientist in possession of any of the higher oxides of manganese can attain. The classic manganese dioxide thermite reaction:

MnO2 + 4/3 Al ---> Mn + 2/3 Al2O3

is one of the most exothermic pyrometallurgical reactions in the entire series of thermites: it's reaction enthalpy (per mol of MnO2 and at 298 K) is - 597 kJ. That's enough to cause any well proportioned and well ignited mixture of fine manganese dioxide and aluminium powder to cause a dazzling display of extremely high temperature.

ManganeseAnd that's precisely the problem with the aluminothermic reduction of MnO2 (manganese (IV) oxide, manganese dioxide): in adiabatic (or near-adiabatic) conditions it runs far too hot. The reaction is often described on Internet posts as 'explosive' (although I can assure you that only if the burning mixture is contained - in a bomb like enclosure e.g. - is there a serious risk of an actual explosion in the strict sense of the word). My own experience with MnO2-based thermites confirms that these mixtures have a tendency to deflagrate, or 'throw their toys out of their pram'. Often one ends up with a completely empty crucible, with the formed metal and alumina (Al2O3, here also referred to as 'the slag') thrown out of it. Needless to say, if producing small quantities of relatively pure manganese metal is the objective then that objective cannot be attained this way.

The problem becomes clear when comparing the heat generated by the reaction, the heat required to melt both the nascent metal and alumina and bearing in mind the melting points of both the alumina and the manganese metal. Pyrometallurgical extraction of metals from their oxides (or halides) depends on the reaction products to achieve the molten state, so that the metal can separate out from the molten slag/metal mix, much like oil separates out from an oil/water mixture. The melting point of alumina is 2,054 C (3,729 F) and the melting point of manganese is 1,246 C (2,275 F), so basically we need to reach 2,054 C to obtain both the alumina and manganese in molten form and for the slag/metal separation to be able to occur. Below this temperature, powdered metal would be frozen in a powdered, sintered slag pile.

The reduction of MnO2 with aluminium powder generates as said above about 600 kJ per mol of oxide reduced (at 298 K). Thermochemical data (typically from NIST) shows that to heat and melt 1 mol of manganese metal to 2,054 C requires about 85 kJ and the heat to melt 1 mol of alumina to 2,054 C requires about 393 kJ (these values include also the actual heats of fusion required). From the reaction equation MnO2 + 4/3 Al ---> Mn + 2/3 Al2O3 can be gleaned that the reduction of 1 mol of manganese dioxide yields one mol of manganese metal and 2/3 mol of alumina, requiring 85 + 2/3 x 393 = 347 kJ to reach 2,054 C.

At first glance this is excellent news because in adiabatic conditions (all heat generated by the reaction is used to heat up the reaction products and no heat is lost to the environment - these conditions more or less exist provided the reaction proceeds very quickly, because heat transfer takes time) the reaction produces considerably more heat (600 kJ) than is needed to heat up the reaction products past the melting point of alumina (347 kJ). The manganese dioxide thermite (in more or less adiabatic thermite conditions) will heat up well beyond the minimum requirement of 2,054 C, necessary to obtain slag/metal separation and thus solid reguli of metal after the reacted mass has cooled down.

Unfortunately there's a snake in the grass. Manganese doesn't only have a relatively low melting point, its boiling point is only 2,061 C (3,742 F) and thus only barely higher than the melting point of alumina. Since as we've shown the manganese (IV) oxide thermite reaction to well exceed the melting point of alumina, it's reasonable to assume the reactive mix will reach temperatures that exceed the boiling point of manganese metal (a precise estimate of the end-temperature of such a reactive mix is possible and shows it will in fact exceed 2,500 C, well above the 2,061 C boiling point of manganese).

This then explains why almost no backyard scientists have ever obtained manganese metal from a manganese (IV) oxide based thermite reaction. On one occasion I found tens if not hundreds of fine (sub mm) globules of manganese metal around the reaction crucible: the metal had boiled off and it really was raining manganese that day! It also explains why manganese thermite is often referred to (somewhat erroneously) as 'explosive'.

And it begs the question how to run this thermite cooler, so that its maximum end-temperature stays (ideally) in the 2,054 - 2,061 C area...

One fairly obvious way would be to run the thermite in strongly non-adiabatic conditions, in plain English: by cooling it down a lot. But for backyard scientists cooling such a hot object to a fairly narrow window of temperature is easier said than done. Open reaction vessels with extensive cooling fins at the bottom end of the reactor, pre-cooling the reaction mix prior to ignition and such like are possibilities that could be explored but would require in my opinion a great deal of hit-and-miss and costly experimentation.

Using coarser rather than very fine ingredients is also a possibility because heterogeneous reactions tend to run much slower with coarser reagents and this allows the reacting mix to exchange more heat with the environment (assuming an open reactor set-up), thus running cooler. But the relation between mix granulometry and reaction temperature (in non-adiabatic conditions) is complex and hard to establish in a reliable and reproducible way.

Another possibility is the use of heat sinks mixed in with the reagents, prior to ignition. One such heat sink is routinely used by pyrometallurgists and backyard thermite enthusiasts alike: calcium fluoride (CaF2, fluorite or fluorspar) has a relatively low melting point (1,402 C or 1,675 F), is completely inert (it doesn't take part in the reaction and doesn't decompose to any appreciable degree) and requires about 166 kJ per mol to melt and heat to 2,054 C. It not only therefore absorbs some of the reaction heat, thereby reducing the end temperature of the mix somewhat but its relatively low melting point also ensures that at the melting point of alumina, molten fluorite is highly fluid (low viscosity) and for that reason is often referred to as a slag fluidiser. It also forms a relatively low melting eutectic with alumina (unfortunately at the fluorite end of the alumina-fluorite mixture). Fluorite is a very popular ingredient in thermite mixtures for that reason. But cooling a manganese thermite sufficiently simply by slagging it with high amounts of CaF2 doesn't work because too much of the good stuff interferes with the reaction kinetics, thereby impeding ignition or leading to fizzling mixtures.

The fourth possibility, fairly obvious at first glance, is the use of another manganese oxide, other than manganese (IV) oxide, one for which the reduction reaction yields much less heat than MnO2 reduction does. Again, this is easier said than done: detailed calculations show that most other oxides of manganese including manganese (III) oxide (Mn2O3) and manganese (II, III) oxide (Mn3O4) suffer from the same problem as manganese (IV) oxide: the reaction enthalpies of the reductions of these oxides is so high that in adiabatic conditions the mix will run to temperatures that well exceed the boiling point of manganese metal.

That then leaves one oxide, the lower oxide manganese (II) oxide, MnO. For the reduction reaction MnO + 2/3 Al ---> Mn + 1/3 Al2O3 the enthalpy of reaction (at 298 K) is much lower: - 173 kJ (per mol of MnO). Since as the reaction products comprise of 1 mol of Mn and 1/3 mol of Al2O3, the heat needed to melt and heat this mixture to 2,054 C, according to above, is: 85 + 1/3 x 393 = 216 kJ.

Since as the heat generated during the reaction (173 kJ) is lower than the heat required to heat the reaction products to the melting point of alumina (216 kJ), this reaction is considered as heat starved and cannot lead to a liquid slag/metal mix and gravitational separation of the metal from the slag. In order to obtain both metal and slag in liquid conditions using the reduction of MnO as a heat source, extra heat has to be applied. There is of course an easy way of doing this: by adding manganese (IV) oxide; the heat of that reduction will be sufficient to reach 2,054 C, without overshooting the target temperature and ending up with boiling manganese metal. A blend of MnO and MnO2 in the right proportions is therefore called for.

A simple but detailed calculation based on the reaction heats of both reductions and the required heat to heat the reaction products to 2,054 C shows that this optimum, in strictly adiabatic conditions, lies somewhere near a molar ratio of MnO / MnO2 = 1 / 0.30 (or a 3.333... ratio). In the formulation, stoichiometry and the use of a fairly high level of CaF2 were also taken into account and the resulting target formulation expected in adiabatic conditions to produce an end temperature close to 2,054 C is as follows:

MnO ..............1 mol
MnO2 .............0.3 mol
Al ..................1.0666... mol
CaF2 ............. 0.24 mol

That leaves one 'minor' problem: MnO is not near as readily available as the other manganese oxides. I therefore had to resort to home brewing it, which will be the subject of a separate post, by thermal decomposition of manganese (II) carbonate to manganese (II) oxide in the absence of air, according to MnCO3 ---> MnO + CO2.

A first attempt to light up an 'MnO only' (no MnO2 at all - as a baseline) showed that the thermite based on manganese (II) oxide alone burns only with great difficulty and very coolly, confirming the low reaction heat on which the new manganese thermite mixture is founded. The slag/metal mix after cooling is of the spongy 'muffin' type with the metal trapped inside in powder form.

A second attempt, using the formulation above in a 20 g batch was already very near successful: the thermite burned well, not very fast but hot enough for the molten slag/metal mix to mostly collect at the bottom of the crucible (I use egg cups for these small developmental reactions). Breaking open the slag heap revealed multiple small manganese reguli, some a few mm across, many about 1 mm and many more sub mm. The metal breaks away clean from the alumina/fluorite slag and reacts very vigorously with strong hydrochloric acid, as chemically it's expected to do.

Reasoning the reaction probably still ran a little too cool, I decided to increase the amount of MnO2 to about 0.4 mol, the formulation then becoming MnO = 1 mol, MnO2 = 0.4 mol, Al = 1.2 mol, CaF2 = 0.27 mol and another 20 g test batch was mixed and ignited. Predictably, it ran faster and a little hotter and yielded more and larger globules of manganese metal. Based on the amount of metal recovered yield was still only a measly 25 % but already this is about twice as high as what I previously obtained with the most successful efforts with pure manganese (IV) oxide.

The hunt is now on to further optimise the MnO / MnO2 ratio, run larger reactions and obtain better yields. Other thermites show that in open reactor conditions and relatively small batches, yields of 50 % or more can reasonably be expected.

The obtained results so far show conclusively that backyard manganese thermites based on blends of manganese (II) and manganese (IV) oxides can run 'well behaved', without deflagration of the mix or boiling off the metal.

Note: this article is followed up by a report on manganese thermites based on blends of Mn2O3 and MnO.

Wednesday, July 09, 2008

Believe Me, It’s Torture

What more can be added to the debate over U.S. interrogation methods, and whether waterboarding is torture? Try firsthand experience. The author undergoes the controversial drowning technique, at the hands of men who once trained American soldiers to resist—not inflict—it.

by Christopher Hitchens (View a video of Hitchens’s waterboarding experience) July 2008

Here is the most chilling way I can find of stating the matter. Until recently, “waterboarding” was something that Americans did to other Americans. It was inflicted, and endured, by those members of the Special Forces who underwent the advanced form of training known as sere (Survival, Evasion, Resistance, Escape). In these harsh exercises, brave men and women were introduced to the sorts of barbarism that they might expect to meet at the hands of a lawless foe who disregarded the Geneva Conventions. But it was something that Americans were being trained to resist, not to inflict.

Exploring this narrow but deep distinction, on a gorgeous day last May I found myself deep in the hill country of western North Carolina, preparing to be surprised by a team of extremely hardened veterans who had confronted their country’s enemies in highly arduous terrain all over the world. They knew about everything from unarmed combat to enhanced interrogation and, in exchange for anonymity, were going to show me as nearly as possible what real waterboarding might be like.

It goes without saying that I knew I could stop the process at any time, and that when it was all over I would be released into happy daylight rather than returned to a darkened cell. But it’s been well said that cowards die many times before their deaths, and it was difficult for me to completely forget the clause in the contract of indemnification that I had signed. This document (written by one who knew) stated revealingly:

“Water boarding” is a potentially dangerous activity in which the participant can receive serious and permanent (physical, emotional and psychological) injuries and even death, including injuries and death due to the respiratory and neurological systems of the body.

As the agreement went on to say, there would be safeguards provided “during the ‘water boarding’ process, however, these measures may fail and even if they work properly they may not prevent Hitchens from experiencing serious injury or death.”

On the night before the encounter I got to sleep with what I thought was creditable ease, but woke early and knew at once that I wasn’t going back to any sort of doze or snooze. The first specialist I had approached with the scheme had asked my age on the telephone and when told what it was (I am 59) had laughed out loud and told me to forget it. Waterboarding is for Green Berets in training, or wiry young jihadists whose teeth can bite through the gristle of an old goat. It’s not for wheezing, paunchy scribblers. For my current “handlers” I had had to produce a doctor’s certificate assuring them that I did not have asthma, but I wondered whether I should tell them about the 15,000 cigarettes I had inhaled every year for the last several decades. I was feeling apprehensive, in other words, and beginning to wish I hadn’t given myself so long to think about it.

I have to be opaque about exactly where I was later that day, but there came a moment when, sitting on a porch outside a remote house at the end of a winding country road, I was very gently yet firmly grabbed from behind, pulled to my feet, pinioned by my wrists (which were then cuffed to a belt), and cut off from the sunlight by having a black hood pulled over my face. I was then turned around a few times, I presume to assist in disorienting me, and led over some crunchy gravel into a darkened room. Well, mainly darkened: there were some oddly spaced bright lights that came as pinpoints through my hood. And some weird music assaulted my ears. (I’m no judge of these things, but I wouldn’t have expected former Special Forces types to be so fond of New Age techno-disco.) The outside world seemed very suddenly very distant indeed.

Arms already lost to me, I wasn’t able to flail as I was pushed onto a sloping board and positioned with my head lower than my heart. (That’s the main point: the angle can be slight or steep.) Then my legs were lashed together so that the board and I were one single and trussed unit. Not to bore you with my phobias, but if I don’t have at least two pillows I wake up with acid reflux and mild sleep apnea, so even a merely supine position makes me uneasy. And, to tell you something I had been keeping from myself as well as from my new experimental friends, I do have a fear of drowning that comes from a bad childhood moment on the Isle of Wight, when I got out of my depth. As a boy reading the climactic torture scene of 1984, where what is in Room 101 is the worst thing in the world, I realize that somewhere in my version of that hideous chamber comes the moment when the wave washes over me. Not that that makes me special: I don’t know anyone who likes the idea of drowning. As mammals we may have originated in the ocean, but water has many ways of reminding us that when we are in it we are out of our element. In brief, when it comes to breathing, give me good old air every time.

You may have read by now the official lie about this treatment, which is that it “simulates” the feeling of drowning. This is not the case. You feel that you are drowning because you are drowning—or, rather, being drowned, albeit slowly and under controlled conditions and at the mercy (or otherwise) of those who are applying the pressure. The “board” is the instrument, not the method. You are not being boarded. You are being watered. This was very rapidly brought home to me when, on top of the hood, which still admitted a few flashes of random and worrying strobe light to my vision, three layers of enveloping towel were added. In this pregnant darkness, head downward, I waited for a while until I abruptly felt a slow cascade of water going up my nose. Determined to resist if only for the honor of my navy ancestors who had so often been in peril on the sea, I held my breath for a while and then had to exhale and—as you might expect—inhale in turn. The inhalation brought the damp cloths tight against my nostrils, as if a huge, wet paw had been suddenly and annihilatingly clamped over my face. Unable to determine whether I was breathing in or out, and flooded more with sheer panic than with mere water, I triggered the pre-arranged signal and felt the unbelievable relief of being pulled upright and having the soaking and stifling layers pulled off me. I find I don’t want to tell you how little time I lasted.

This is because I had read that Khalid Sheikh Mohammed, invariably referred to as the “mastermind” of the atrocities of September 11, 2001, had impressed his interrogators by holding out for upwards of two minutes before cracking. (By the way, this story is not confirmed. My North Carolina friends jeered at it. “Hell,” said one, “from what I heard they only washed his damn face before he babbled.”) But, hell, I thought in my turn, no Hitchens is going to do worse than that. Well, O.K., I admit I didn’t outdo him. And so then I said, with slightly more bravado than was justified, that I’d like to try it one more time. There was a paramedic present who checked my racing pulse and warned me about adrenaline rush. An interval was ordered, and then I felt the mask come down again. Steeling myself to remember what it had been like last time, and to learn from the previous panic attack, I fought down the first, and some of the second, wave of nausea and terror but soon found that I was an abject prisoner of my gag reflex. The interrogators would hardly have had time to ask me any questions, and I knew that I would quite readily have agreed to supply any answer. I still feel ashamed when I think about it. Also, in case it’s of interest, I have since woken up trying to push the bedcovers off my face, and if I do anything that makes me short of breath I find myself clawing at the air with a horrible sensation of smothering and claustrophobia. No doubt this will pass. As if detecting my misery and shame, one of my interrogators comfortingly said, “Any time is a long time when you’re breathing water.” I could have hugged him for saying so, and just then I was hit with a ghastly sense of the sadomasochistic dimension that underlies the relationship between the torturer and the tortured. I apply the Abraham Lincoln test for moral casuistry: “If slavery is not wrong, nothing is wrong.” Well, then, if waterboarding does not constitute torture, then there is no such thing as torture.

Sunday, July 06, 2008

How Relevant Is Patriotism? Go Ask France

On the blog of my Right Honourable Fellow blogger and personal friend Cookie I found a piece, written by Thomas Sowell, reprinted there in the spirit of July 4th, which struck as grossly out of character for an author otherwise known for his often original and varied thinking, deeply steeped in empiricism. That's assuming the Thomas Sowell quoted by said blogger and this Thomas Sowell are one and the same. I can't be sure of it because although I don't agree with a lot of Sowell's thinking, it's always struck me as well-researched, well-reasoned and underpinned by empirical evidence (the interpretation of which often remains nonetheless more a question of historicism than actual objectivity). So it came somewhat as a surprise to find Sowell presenting a piece on patriotism that's frankly as self-serving as any other piece of propaganda and is on the whole extremely selective in its choice of presented evidence and selected arguments. An uninterrupted version of the entire (and relatively short) piece can be found here. Here I'll comment on various blocks from the essay.

How Relevant Is Patriotism? Go Ask France

The Fourth of July is a patriotic holiday, but patriotism has long been viewed with suspicion or disdain by many of the intelligentsia. As far back as 1793, prominent British writer William Godwin called patriotism "high-sounding nonsense."

Right from the off, Sowell completely fails to recognise that patriotism, much like any other idea or ideology, can indeed be grossly misused and that most of his essay would not have been written if Nazi Germany's own monstrous manifestations of nationalistic and patriotic pride hadn't brought Europe to the brink of oblivion. And all throughout Europe's long and bloody history, frequent eruptions of nationalistic and patriotic fervour were the cause of perpetual, almost endless bloodletting.

Internationalism has long been a competitor with patriotism, especially among the intelligentsia. H.G. Wells advocated replacing the idea of duty to one's country with "the idea of cosmopolitan duty."

In one short paragraph Sowell relegates an entire movement, inspired rightly by Europe's belligerent past and the sheer misery it rained upon many of its peoples, to the dustbin, painfully ignoring the root causes of 'internationalism and pacifism'. Conservatives, even if economists or wannabee historians, were never that good with root causes (which they would probably dismiss as 'root-causism').

French soldiers in World War I's Battle of Verdun went from heroes to victims after pacifists got a hold of the history books.

Here the piece takes on a veritable cartoonesque quality. Sowell, eager to get his presumably mainly conservative audience on board, brings up the French, in the full knowledge that rife populist US francophobia will prick up ears and make attentions focus.

Perhaps nowhere was patriotism so downplayed or deplored than among intellectuals in the Western democracies in the two decades after the horrors of the First World War, fought under various nations' banners of patriotism.

At last, a fleeting glimmer of insight as to why this alleged pernicious internationalism and pacifism came about: as a reaction to the horrors of the Great War. Well, I'll concede that half-point because it's true that in the wake of World War I, when on every cenotaph on the European continent the words "Never Again" (or words to that effect) were carefully chiseled in stone, there was indeed a feeling of having reached a turning point in European history. What Sowell conveniently fails to mention is that that feeling is rather the sum total of revulsion at Europe's history of internal and external belligerency, imperialism, colonialism and brutal rivalry and warfare. And I put it to American readers of this post that if only a tenth of blood and treasure spilt on European soil during its entire history had been spilt in America's relatively short history and most importantly on its own soil, American patriotism and glorification of its military would be nothing near what it is today...

A bad British joke refers to the Americans as 'always late for the war'. But both these British wannabee-comedians and people like Sowell should understand that it was the all too fresh memory of massive sacrifice of American blood and treasure during the 1914 - 1918 war that made Americans barely 20 years later understandably reluctant to join yet another European fray...

In France, after the First World War, the teachers' unions launched a systematic purge of textbooks, in order to promote internationalism and pacifism.

Books that depicted the courage and self-sacrifice of soldiers who had defended France against the German invaders were called "bellicose" books, to be banished from the schools.

Textbook publishers caved in to the power of the teachers' unions, rather than lose a large market for their books. History books were sharply revised to conform to internationalism and pacifism.

Here Sowell resorts to very selective use of evidence, combined with over-simplification and use of loaded terms like "purge" and "revised". But that many in French society, and not just French teachers - in Sowell's piece essentially code for 'lefty US state school teachers', sought to point out the atrocity of the first large scale mechanised war in world history is correct and they were right to do so.

The once-epic story of the French soldiers' heroic defense against the German invaders at Verdun, despite the massive casualties suffered by the French, was now transformed into a story of horrible suffering by all soldiers at Verdun — French and German alike.

At this point one wonders when Sowell wrote this: in modern day eyes Verdun can only be seen as a horrible massacre and a rather futile one at that. Most modern Nation states are equipped to learn the lessons from Verdun and to ensure that, even in the midst of military confrontation, this kind of massive, wholesale and futile slaughter can be avoided.

In short, soldiers once depicted as national heroes were now depicted as victims — and just like victims in other nations' armies.

Children were bombarded with stories on the horrors of war. In some schools, children whose fathers had been killed during the war were asked to speak to the class, and many of these children — as well as some of their classmates and teachers — broke down in tears.

In Britain , Winston Churchill warned that a country "cannot avoid war by dilating upon its horrors."

In France , Marshal Philippe Petain, the victor at Verdun , warned in 1934 that teachers were trying to "raise our sons in ignorance of or in contempt of the fatherland."

Ah oui, le bon Maréchal Pétain, that lovely fellow, after WW II convicted and sentenced to death for treason, which was commuted to life imprisonment. A true example of a patriot...

But they were voices drowned out by the pacifist and internationalist rhetoric of the 1920s and 1930s.

Did it matter? Does patriotism matter?

France, where pacifism and internationalism were strongest, became a classic example of how much it can matter.

During the First World War, France fought on against the German invaders for four long years, despite having more of its soldiers killed than all the American soldiers killed in all the wars in the history of the U.S. put together.

But during the Second World War, France collapsed after just six weeks of fighting and surrendered to Nazi Germany. At the bitter moment of defeat, the head of the French teachers' union was told, "You are partially responsible for the defeat."

The fact that the French teachers' union (read 'leftard US state school teachers') were told this of course must actually make it true.

Never mind the fact that finger pointing, general hysteria, confusion and knee-jerking always run rife in national post-debacle circumstances - see also the US's own disastrous decision to wage war on Iraq on false pretenses in the wake of their very own National disaster - 9/11. Or was it just oil - I get a tad confused at times...

Never mind the fact that European armies were indeed no match for Nazi Germany's war machine and their innovative approach of massive mechanised troop movements and use of heavy weapons up front, colloquially known as the Blitz Krieg.

Never mind the fact that French troops did fight very bravely when securing a relatively secure perimeter for Dunkerque, thereby averting the disastrous retreat of the British Expeditionary Force becoming a wholesale massacre.

Never mind the fact that if it hadn't been for the channel, German tanks would have rolled into London virtually unopposed shortly after the fall of northern France, as Britain was as ill-prepared for war as was any major (and minor) European country. I guess we'll have to blame British teachers' unions for that, eh Sowell? But you wouldn't do that to us, would you? Special Relationship and all that. Better (safer at least) to pick on the Frogs instead...

Charles de Gaulle, Francois Mauriac and other Frenchmen blamed a lack of national will or general moral decay for the sudden and humiliating collapse of France in 1940.
At the outset of the invasion, German and French generals assessed French military forces as more likely to gain victory, and virtually no one expected France to collapse like a house of cards — except Adolf Hitler, who had studied French society instead of French military forces.

Yawn... Lack of national will... general moral decay... blahdiblah...

And Hitler, mediocre mind, poor military strategist, general coward and self-aggrandiser of his petty role (of a bicycled messenger boy) in WW I, deeply superstitious, seriously interested in the occult, a deeply irrational character and anti-Semite supreme... studied "French society", not "French military forces" (and of course not wholesome English fellow Anglosaxons - in Sowell's book above reprieve just for speaking English).

Did patriotism matter? It mattered more than superior French tanks and planes.

Which superior French tanks and planes? Superior to Nazi Germany's??? Which, pray, tell... Does Sowell feel it was lack of 'moral fibre', rather than lack of firepower that made France fall?

Most Americans today are unaware of how much our schools have followed in the footsteps of the French schools of the 1920s and 1930s, or how much our intellectuals have become citizens of the world instead of American patriots.

Our media are busy verbally transforming American combat troops from heroes into victims, just as the French intelligentsia did — with the added twist of calling this "supporting the troops."

Be scared, very, very scared: the 'librul mejuh', the intelligentsia and assorted leftards are trying to do a 'Frenchie'. Following in the frog's webbed pawmarks can only lead to ruin!

Let those who advocate nationalism, patriotism and indiscriminate flag waving realise how many times in past human history these have lead to massive bloodletting. Let them perhaps read Benedict Anderson's excellent Imagined Communities and see for themselves how flimsy the rational basis for nationalistic thinking actually is.

The author, in stark contrast with previous writings of his that I've read, in this piece shows himself essntially as a bought pamphleteer.
Sowell, with this piece of boring and inaccurate agitprop you've lost a lot of respect and credit in my eyes...