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I just have to say that in regard to the deteriorating situation with the
Soviet Union Russian Federation, it does not appear that either the EU or the US have their best thinkers working on it. I think US leaders have misunderstood Putin from the beginning and I see very little to convince me that Obama’s people, the Congress, or any other high level functionaries known to me have a clue how to get their arms around Russian behavior or a workable diplomacy.
Certainly recent (post-Ford) US incursions into foreign lands with troops or drones have taken us off the moral high ground in this regard. How can the US lecture Russia on the invasion of Crimea when we invaded Iraq based on lies, subterfuge, and outright errors?
Bush 43 and Clinton had historical opportunities to gain better alliance with Russia. But we supported Yeltsin in the Clinton years and ignored Putin’s offers of assistance after 9/11. The Russian people were mystified when the US supported Yeltsin, widely regarded as a drunken buffoon. Gorbachev’s memoirs paint a lackluster and untrustworthy picture of Yeltsin. And the US has done nothing but confirm Putin’s paranoia about US intentions by adding membership to NATO, ABM’s in Poland, petroleum wars in the middle east, and the general appearance of weakness by in-house political fratricide.
We have no use for milquetoast administrations like Obama’s, nor do we need rabid swingin’ dicks like John McCain or his hawkish brethren. We do need Russian and Slavic scholars who speak the language and understand the history of Russia at least back to Peter the Great. They can be immigrants from former Soviet territories of the ilk of Zbigniew Brzezinski, Madeleine Albright, or even a world savvy guy like Henry Kissinger. Who are the current brain trust for eastern European politics and is the CIA giving them good intelligence? Did the CIA predict the takeover of Crimea?
It is a misconception that renaissance alchemists were only concerned with the philosophers stone. Hermetic alchemy was an overlap of alchemical practice within a mystical or spiritual framework. This branch of alchemy and its practitioners are perhaps better known in the popular literature than the alchemists who might be regarded as more pragmatic experimentalists.
Many alchemists over history were very practical and quite occupied with their trade in medicaments, tinctures, distillates, and elixirs or with metallurgical and compounding endeavors. Paracelsus is regarded as an early practitioner of iatrochemical work, but within a hermetical framework. Agricola and Biringuccio were 16th century chroniclers of metallurgy that had a basis in earlier alchemical progress.
Consider an entry from a translation of The Laboratory, or School of Arts; in which are faithfully exhibited and fully explain’d, I. A variety of curious and valuable experiments in refining … VI. A dissertation on the nature and growth of saltpeter; … Translated from the German, by Godfrey Smith, published 1738. In this volume, available from ECCO, Eighteenth Century Collections Online, contains a passage under the heading of “To prepare Aurum Fulmina__s” (two letters obscured). I have retained the archaic character “f” in place of “s” for the reader to enjoy.
To prepare Aurum Fulmina__s
Take Gold that is refin’d with Antimony, beat it to thin Plates, put it into a Phial or Matrafs, pour Aqua Regis upon it, then fet the Phial or Mastrafs upon warm sand, till the Aqua regis is diffolv’d as much of the gold as it is able to contain, which you will knw when you fee the Ebullitions ceafe, pour your Solution by Inclination into another Glafs, and if you fee there remains any Gold in the Matrafs, dissolve it as before with a little frefh Aqua regis, mix your Diffolution, and pour to it five times as much common Water, afterwards drop into this Mixture, by Degrees, the Volatile Spirit of Sal Ammoniac, or Oil of Tartar, and you will see the Gold precipitate to the Bottom of the Glafs, let it reft a good while for the Gold to settle, then pour off the Water by Inclination, wafh your powder with warm Water, till grows infipid, dry it to the Substance of a Pafte, then form it in little round Corns, the Bignefs of a Hempfeed, dry them by the Sun, if you put one of them into a Fire, it will fly and difperfe with a terrible Noife, and beat about with great Violence. [Emphasis mine]
It seems likely that the worker is trying to refine the gold by dissolution of the Sb/Au blend by complete dissolution in aqua regia, followed by what we would now regard as a reduction of the gold solution. Quenching the aqua regia would be expected to cause the gold to reduce and fall out as the native metal. But gold chemistry is not what is interesting in this account.
The Spirit of Sal Ammoniac, meaning either ammonia itself or ammonium chloride, would do as follows: the ammonium would ion pair with nitrate and, upon drying, leave a residue of ammonium nitrate, which is an explosive. Simple open burning of small kernels material enriched in ammonium nitrate might be expected to deflagrate or pop, as indicated in the end of the description.
The Oil of Tartar, however, might have an altogether different fate when dissolved in aqua regia. Oil of Tartar is a concentrated aqueous solution of potassium (or Na) tartrate. In solution with aqua regia, one would reasonably expect the two hydroxy groups of tartaric acid to form the dinitro ester if appropriate nitrating species are present. A nitrate ester group is a common explosophore and consists of O2N-O-C comprising an oxygen linkage between NO2 and carbon. This linkage is sensitive to low levels of stimulus, making compounds with such linkages susceptible to rapid or explosive decomposition. The nitrite ester is listed as an explosophore as well.
The nitration of tartaric acid is described in US patent 1,506,728. This patent teaches the use of the standard H2SO4 catalyzed HNO3 nitration of the tartaric acid diol functionality to form a dinitro ester via the standard nitronium ion formation. In the case of aqua regia, the presence of NO2(+) is questionable. Aqua regia is known to produce nitrosyl chloride, ClNO which dissociates to Cl2 and NO. Literature on the nitration of alcohols to nitro esters in aqua regia is non-existant in Chemical Abstracts. There are a few citations describing aromatic nitration by aqua regia, but no clear description of nitro ester formation. Indeed, there are many descriptions of direct extraction of gold from aqua regia using isoamyl alcohol with no warnings of explosive or nitro formation.
There are, however, reports of the use of ClNO to produce organonitrites when reacted with a monohydroxy alcohol (Journal of the American Pharmaceutical Association (1912-1977) (1932), 21, 125-8). It is possible that a tartaric nitrite was formed which may be energetic to some extent.
But perhaps the application of Occams Razor is needed. Potassium or sodium tartrate would be mildly basic and upon addition to a mineral acid solution, it would neutralize the acid in sufficient quantities, affording potassium or sodium nitrate (saltpeter). On evaporation of water, the saltpeter residues would be comingled with tartaric acid, comprising a fuel/oxidizer mixture.
Small quantities of crude nitrate esters, nitrite esters, or nitrate salts could have been present in the dried paste, giving the pyrotechnic effect described. The formation of energetic materials was not the primary purpose of the procedure, although the observed behavior of the residues was apparently compelling enough to document.
Lots happening but, sadly, nothing I can blog about. I need to get some RC1 experiments done before I head off to San Diego for the ACS National Meeting and Research Pageant. I really like this Mettler-Toledo RC1 and the sales and support staff. Pretty helpful folks in my experience. The Swiss make some fine equipment.
I spent the weekend reading about the very early history of gunpowder or Huo Yao (China, ca 850 AD). Turns out that the earliest clear description of a gunpowder-like composition was described in a document produced during the Tang Dynasty. A document titled “Classified Essentials of the Mysterious Tao of the True Origins of Things” contained a list of particularly dangerous elixirs.
Within this list of hazardous compositions, a warning was offered citing the dangers of mixing and heating together realgar, salt peter, sulfur, and honey. The document tells of alchemists mixing this combination and heating it resulting in a deflagration leading to burnt beards, faces, and hands as well as the loss of the structure to fire. This mix was called “fire-drug”.
There are earlier references to compositions that produced a violent effect, but the compositions are not disclosed. The information in the 850 AD document clearly describes the components of classic gunpowder- a nitrate oxidizer, sulfur for low ignition temperature, and a carbohydrate carbon source- honey. Carbohydrates readily dehydrate to afford fairly concentrated carbon.
The realgar present in the mix is puzzling. It is not unreasonable to guess that the composition may have been intended for some medicinal application. Realgar is tetraarsenic tetrasulfide. This may have been an common apothecary ingredient of the age.
In his 1736 publication Smegmatalogia, or the Art of Making Potashes and Soap, and Bleaching of Linens, James Dunbar describes a process for the preparation of potash. The intended user of the process was the common Scottish farmer. Dunbar was anxious to imbue the common Scot with the ability to “bleach” his own linens. It is important to realize that the meaning of the word bleach in the early 18th century is different from contemporary use. The modern use comprises notions of decolorization through oxidation of color bodies to produce a white appearance. The 18th century concept involves the apparent cleansing and subsequent lightening of a fabric.
The book begins by detailing the preparation of a solution or extract from ashes called Lee. To obtain this solution, the “Country-Man” would carefully collect Scottish vegetables such as the wood of oak, ash, beech, “thorns”, juniper trees, and “whins”. Suitable herbs included fern, breckens (or brackens), wormwood, thistles, stinking weed, and hemlock.
Dunbar is careful to instruct that the vegetation should be burned in the shelter of a house but in such a way as to avoid burning down the house. The purpose of burning the vegatation in a shelter is to avoid having rainwater come into contact with the ashes. My interpretation of this is that runoff carries away soluble potash.
The ashes are placed in a container and covered with water. The ashes are soaked in water until such time that the Lee “carries an egg on its surface”. What Dunbar is telling us is that the extraction of the ashes needs to go until the worker obtains in the solution a particular specific gravity- this is a specification. There is some minimum specific gravity of the Lee that will float an egg. And the higher the specific gravity, the more volume of the egg rises from surface of the Lee. The specification herein is required for the next operation. In order to carry out a successful saponification of tallow, the Lee solution must be sufficiently concentrated.
Dunbar then describes steps where the Lee is combined with the ashes of ash, beech, or fern followed by boiling the water off to afford “thickens of pottage“. The residue is shaped into balls which are then calcined in a fire to afford a substance that may be stored in a dry container for the purpose of making soap.
The discovery of chlorine in 1774 by Scheele and the subsequent of discovery of chlorine bleaching by Berthollet gave us our modern conceptual notion of bleach and bleaching. The develoment of bleaching powder was made by Scottish chemist Charles Tennant who took a patent in 1799. Tennant’s associate, Charles MacIntosh, is thought to be a contributor to this invention. Bleaching liquors and powders soon became an important raw material for the bleaching of paper and fabric.
The procedure described by Dunbar is a chemical process. It tells the user when the extraction is complete, qualitatively at least, by a folksy means of specific gravity determination. This is really very clever- it uses a common object to do the test and the result is readily apparent. Bleaching in the early 18th century involved the use of soaps and of urine treatment and bleaching fields- a far cry from what we now think of as bleaching.
We tend to think of some things as being relatively new. I’m thinking of the gas and oil extraction technique of fracturing, or fracking. In the 1884 third edition of The Modern High Explosives, Nitro-glycerine and Dynamite by Manuel Eissler, p 311, there is a mention of the practice of exploding nitroglycerine charges at the bottom of oil and water wells to renew or increase the flow. The author states that this is a popular technique in Pennsylvania at the time of writing.
On p 318 of the same book, Eissler describes the economics of blasting stumps. In general, the process of removing stumps was called “grubbing”. Enterprising fellows knowledgeable with nitroglycerine took little time in applying the explosive power of this oily liquid to clearing the land of stumps.
Eissler describes the economics of explosive grubbing as follows: Three pounds of No. 1 dynamite cost $1.50, labor cost 20 cents per hour, 25 ft of fuse cost 1 cent per foot, and 17 percussion caps cost 1 cent each. Grubbing 17 oak stumps cost $22.52 with 99 man hours for chopping and piling the pieces. Grubbing with an axe took 142 man hours and cost $28.40. No. 1 dynamite was comprised of 75 % nitroglycerin and 25 % absorbent.
Bertholet’s discovery of potassium chlorate (oxygenized muriate of potash) happened in 1785. He observed
“that it appears to include the elements of thunder in its particles; and Nature seems to have concentrated all her powers of detonation, fulmination, and inflammation in this terrible compound”.
Eissler goes on to say that attempts to prepare gunpowder or blasting powder with potassium chlorate lead only to loss of life and limb for the luckless experimenters with this compound. Two of Bertholet’s artisans employed to do experiments with this material were killed in 1788. The hazards associated with both manufacture and use of compositions of potassium chlorate were too great to allow this substance to see much commercial application by the 1880’s.
The Black Hills are a mountain range that stand in the southwest corner of South Dakota and extend a bit into northeastern Wyoming. The area is known for the natural beauty of its forested mountains and green meadows. The relatively low population density along with the dramatic monuments and natural wonders make this a satisfying destination. In rather stark contrast to the panoramic beauty of the area, however, is a geopolitical history that is quite a bit less than pristine.
After decades of expansive settlement from the US in the east and the corresponding conflicts, a treaty was forged in 1868 between a confederation of northern plains Native tribes and the US government. This treaty deeded the Black Hills region to the Native confederation.
Within a few years the Native American confederation lost possession of the land granted to them by the Treaty of Ft Laramie. It seems to have happened not so much by the US government backing out of its obligations, but by lack of decisive government enforcement of the terms of the treaty.
The discovery of gold in 1874 by the Custer expedition and the prompt announcement of this discovery lead to an irreversible economic migration to the area by gold seekers and those who would follow them. Many of the gold seekers were miners and entrepreneurs from other gold fields seeking new opportunity. Custer met his end in battle, hopelessly outnumbered by Indian forces.
Today the Black Hills of South Dakota are a locus of tourism, gambling, and recently, neutrino physics. Native Americans reside on a handful of reservations scattered throughout the eastern plains.
It is a curious contrast to behold. Today automobiles and tour buses disgorge well fed tourists by the hundreds of thousands each year to marvel at the spectacle of Mt Rushmore, buy souvenirs, and to rejoice in nationalistic self satisfaction.
Bikers make the annual sojourn-in-leather to nearby Sturgis in part to celebrate the freedom of motorcycling. All of this celebration of freedom in an area where the lust for gold has trumped the freedom of a hunter-gatherer society by those who had mastery of explosives, metallurgy, and steam energy. I suppose it was inevitable.
Th’ Gaussling and family splurged (Yoww!!) on a helicopter tour of the Mt Rushmore and Crazy Horse area. It was just spectacular. The heliport was a mile from the Crazy Horse Monument so we were treated to two visits to the site.
Gutzon Borglum launched his ambitious monument project on a mountain the locals called Mt Rushmore. The final form differed somewhat from early models.
A great deal of resources and effort went into the Mt Rushmore monument. It features a parking garage, gift shops, museum, two indoor theaters, an amphitheatre, cafe, and Borglums studio. The visior is free to simply sit and ponder the monument or dive into the historical details of its construction.
Borglum fabricated scale models of the subject faces in his workshop below the site and used a geometric device to transfer the dimensions to the mountain. A plumb bob hung below a protractor-style device mounted on the model. A rudimentary coordinate system would provide a basis for scale-up.
Borglum died of complications from surgery in March of 1941. Gutzon’s son Lincoln Borglum carried on with the project after his death. However, Lincoln left the project substantially in the form left by his father. The project was officially halted later in 1941 owing to a lack of funding.
Mt Rushmore is a spectacular thing and everyone should see it. All of the fellows captured in stone had attributes worthy of meditation. The timeline between them and we of the present day is jam packed with fantastic events that they had a hand in initiating. I’m certain that they would say that our technology is different but human nature is the same.