Chimica Arcana

To grasp the invisible elements, to attract them by their material correspondence, to control, purify and transform them by the living power of the spirit, this is true alchemy. 

~Paracelsus (1493-1541)

Before any sort of chemical bonding was even thought of there were charts of so-called affinities.  I found this interesting chart dating from 1718 on Wiki. It teaches how the then-known "elements" combined with each other. The top row identifies an element and the columns contain those elements with which it combines. Note that sulfur (middle column) was considered the most promiscuous element, consistent with its primacy as the "soul" of matter according to alchemy. Also bear in mind that this simple chart condenses the then known science of chemisty, ca. 1718.  I like the arcane symbols and could see using some them as avatars depending on my mood:

Click to enlarge or see link above

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Here are my translations of the "elements."

Esprit acides : Acidic (acerbic) spirits

Acide du sel marin: Lit. acid of sea salt, HCl (which was thought to contain oxygen until Davy showed otherwise: link)

Acide nitreux: Nitric and nitrous acids, HNO₃, HNO₂

Acide vitriolique: Sulfuric and sulfurous acids, derived from oleum & vitriol.

Sel alcali fixe: Sodium & potassium hydroxides and carbonates.

Sel alcali volatil: Sal ammoniac, NH₄Cl, which sublimed and was endlessly fascinating.

Terre absorbante: Silicates (sand) and diatomaceous earth.

Substances metalliques: Metallic substances

Mercure: Mercury was considered to be the spirit of matter.

Regule d'Antimoine: Regulus of antimony--metallic antimony. Regulus means "little King"

Or: Gold

Argent: Silver

Cuivre: Copper

Fer: Iron

Plomb: lead

Etain: Tin

Zinc

Pierre Calaminaire: Lit. calamine stone, i.e., calamine ore. Note the French place name.

Soufre mineral: Sulfur or brimstone.  This material held a special place in alchemy, along with mercury and salt.

Principe huileux ou Soufre: The oily essence of organic substances from plants, also called the "sulfur." See the interesting discussion under Spagyric.

Esprit de vinaigre: Vinegar or acetic acid

Eau: water

Sel: Salt held a special place in alchemy along with mercury and sulfur.  

Esprit de vin et Esprit ardents: Any of the flammable alcohols derived from fermentation, e.g., ethanol, methanol, etc.

"Don't call it transmutation. They'll have our heads off as alchemists"

The transmutation of elements was an ancient, discredited notion promulgated by alchemy (alchemy is to chemistry what astrology is to astronomy). Alchemists sought to turn base metals like lead into gold. They failed or were quacks and charlatans. And yet transmutation has always occurred naturally and has been practiced since 1917.

Natural transmutation was first discovered when Frederick Soddy, along with Ernest Rutherford, proved that radioactive thorium converted to radium in 1901. At the moment of realization, Soddy later recalled shouting out: "Rutherford, this is transmutation!" Rutherford snapped back, "For Christ's sake, Soddy, don't call it transmutation. They'll have our heads off as alchemists."

Transmutation became a fait accompli. But it was one thing to discover that atoms could naturally and spontaneously lose little pieces like an alpha particle or a beta particle or even a gamma ray. It was quite another thing to discover that atoms could add little pieces too.

In 1917, Rutherford projected alpha particles from radium decay through air and discovered a new type of radiation which proved to be hydrogen nuclei (Rutherford named these particles protons). Further experiments showed the protons were coming from the nitrogen component of air, and he deduced that the reaction was a transmutation of nitrogen into oxygen:

¹⁴N + α → ¹⁷O + proton

This was also the first demonstrative proof of artificial transmutation and the proton's existence.  All that was needed now was the neutron which led to division and multiplication.

Arsenic And Old Lies

Alchemist's symbol for Arsenic

Some credit Arsenic with being present at the miraculous birth of organometallic chemistry. He was not.* Let me explain.

Organometallic chemistry is the mystical, covalent union of metallic elements with non-metallic elements--mainly carbon with metals. Saying that Arsenic is a metal is a bit like saying that Barack Obama is black. Arsenic, like phosphorus and sulfur, has different allotropes which is more a mark of non-metallic character.

The element has been known since at least 1250 A.D, but it was known much earlier as its sulfide and its affinity for sulfur is the chief cause for its toxicity. It binds to vital sulfur-containing proteins in cells and shuts them down.

Only about a dozen or so elements are poisonous (not including radioactive ones); the dirty dozen are (in alphabetical order): Aluminum, Antimony, Arsenic, Barium, Beryllium, Cadmium, Chromium (hexavalent), Lead, Mercury, Osmium, Thallium, and Vanadium.

Each name has its own story and its own LD₅₀--some are much worse than others.
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*He because the word Arsenic derives from a Greek word corresponding to male potency. Link

Think Zinc!

Elemental zinc is used like electronic paint. The element is always found as Zn²⁺, but it may be coaxed into taking back two electrons. The word "zinc" entered the lexicon via German, Zink, presumably when it was discovered by alchemists. The usual sources viz., van der Krogt and the OED are silent regarding a hunch of mine--that it was so named because of its toothy appearance. My trusty Duden Vol 7 confirms that the word Zink is distantly related to the German word for tooth, Zahn--apparently from the metal's appearance when freshly prepared.

We've all seen how zinc appears when coated on sheet metal. The pattern is called spangling and comes from the underlying crystalline zinc which to me also looks "toothy."

A thin layer of zinc oxide/carbonate passivates the underlying steel from oxygen, but even if the coating is scratched, the exposed iron will not corrode because adjacent zinc offers up its electrons instead. This basic notion was first conceived by Sir Humphry Davy in the context of protecting copper sheathing on ship's hulls. link  In the days of iron rails, little zinc spikes were hard-wired to rails and served the same purpose. Rail workers only needed to come by periodically and replace the spent zinc anodes and check the wiring. Nowadays, aluminum and magnesium anodes are also used, depending on the application.

Cut the vitriol, are those D's for real or not?

Here's the problem in a nutshell:

Elements 1 through 20 are theoretically supposed to build molecular structure using just those spherical and dumbell shaped thingies: the s- and p-orbitals. Theoretically speaking, no more than eight valence electrons should ever surround those atoms. This is the octet rule, and also explains why no more than four atoms ever surround those elements. The octet rule is supposed to apply to phosphorus, sulfur, and chlorine. And yet...

Fact: PF₅ and SF₆ exist, in apparent violation the octet rule. PF₅ has ten valence electrons (2 in each bond) and SF₆ has twelve. Also, some pretty common species like phosphate, sulfate, and perchlorate, appear to violate the octet rule. Those are pretty serious charges. Good men may have even killed themselves over the very issue. Link

Look, intelligent people disagree on many topics. As an aside, the ancient name for sulfuric acid was vitriol, which nowadays mostly means nasty rhetoric. But consider the word's origins. According to the OED, vitriol, H₂SO₄, was so-named because of the glassy-like appearance of concentrated sulfuric acid. I love how so many words are, in the end, just metaphors. Vitriol is an ancient substance, and came to us by way of alchemy. By the way, we spell it "sulfuric" and the Brits spell it "sulphuric."

Bored yet?

You should have seen what I was going to post on this topic. Something about D-orbitals.

The State of Chymistry in 1728

 

Let us take the Road. 

Hark! I hear the Sound of Coaches!

The Hour of Attack approaches,

To your Arms, brave Boys, and load.

See the Ball I hold!

Let the Chymists toil like Asses,

Our Fire, their Fire surpasses,

And turns all our Lead to Gold! 

John Gay, The Beggar's Opera Act II, Scene I

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Silver and gold are back in the news again today. I mentioned them back here. The Beggar's Opera (1728) underscores man's perpetual lust for gold and also shows how as late as 1728 "chymistry" was still regarded as a mere quest for transmutation of base metals into gold. 

The Beggar's Opera later inspired Bertold Brecht and others. According to the Wiki:

Instead of the grand music and themes of opera, the work uses familiar tunes and characters that were ordinary people. Some of the songs were by opera composers like Handel, but only the most popular of these were used. The audience could hum along with the music and identify with the characters. The story satirised politics, poverty and injustice, focusing on the theme of corruption at all levels of society. 

 We need a popular comeback of The Beggar's Opera.

Sir Humphry Davy Also Bleached The French

Muriatic Acid: a synonym for hydrochloric acid. Muriatic † pert. to brine; ‘marine’ (acid), hydrochloric. XVII. — L. muriāticus, f. muria brine (the acid being obtained by heating salt with sulfuric acid).

Chemistry is fraught with confusing synonyms and antiquated terms. "Muriatic acid" is such an example. The acid itself was known to medieval alchemists who concocted it from vitriol and sal ammoniac (the salt of Ammon). They discovered that it (in combination with lesser parts of nitric acid) would dissolve gold--whence the fanciful name aqua regia.

We owe the modern name hydrochloric acid to Sir Humphry Davy, who also dealt a great blow to French scientific pride. Davy (1778-1829) dealt with the nature and definition of acids which was the cutting edge of chemical knowledge in his day:

French chemists, following Lavoisier, argued that all acids must contain oxygen (which means 'acid producer') and that therefore muriatic acid contained oxygen. Davy showed that muriatic acid gas was a chemical element which he named chlorine and that muriatic acid was a compound of hydrogen and chlorine (hydrochloric acid, HCl) containing no oxygen.

--Frank A.J.L. James Michael Faraday: A Very Short Introduction, Oxford University Press (2010)

Davy gave the name chlorine to the element because of its color:

As the new compound in its purest form is possessed of a bright yellow green colour, it may be expedient to designate it by a name expressive of this circumstance, and its relation to oxymuriatic gas. As I have named that elastic fluid Chlorine, so I venture to propose for this substance the name Euchlorine, or Euchloric gas from ευ and χλωρος. The point of Nomenclature I am not, however, inclined to dwell upon. I shall be content to adopt any name that may be considered as most appropriate by the able chemical philosophers attached to this Society. link 

Phosphorus, The Miraculous Bearer Of Light

"The Alchymist" by Joseph Wright of Derby (1771)

Several elements -- gold, silver, copper, mercury, lead, iron, tin, sulfur, and carbon -- were known since ancient times. Three more were discovered during the Dark Ages: antimony, arsenic and zinc. Phosphorus was first isolated in 1669 during the pre-dawn hours of the Enlightenment and it was the first element whose discovery was recorded in modern times. After a lapse of about a hundred years, new elements were rapidly discovered up until the last one, Francium, was found in 1939. New elements were of course still synthesized afterwards.

Van der Krogt retells the amazing story of Henning Brandt's discovery of phosphorus and its subsequent naming as the "light bearer" -- it's well worth a read. The above painting, called "The Alchymist" by Joseph Wright of Derby, depicts the special property displayed by elemental phosphorus: its chemiluminescence as it slowly burns in air. I once provoked a challenge over at Trooper York's as to whether Brandt had really discovered phosphorus. You can read that here. I think the notion that medieval alchemist Paracelsus actually discovered phosphorus is a Montana Urban Legend. Incidentally, I did learn researching this blog post that glowing phosphorus may indeed be an ancient phenomenon: see the story of the "will o' the wisp" here.

The Wright painting also reminds me of the covers of the old Aldrich Chemical Company catalogs. I wish that Alfred Bader would publish a collection of all the past covers. More of what I'm talking about can be found here.

Since the time of Brandt, better sources than putrefied urine have been found for the element, namely, bone.  Did you know that we may one day face a phosphate shortage?  Perhaps the time will come when we start to recycle people's bones.

I'll end with a recipe à la Trooper York for elemental phosphorus:

How to Make Phosphorus (ref)

1. Allow urine to sit in an open container for 7 days.

2. Mix two tablespoons of finely-powdered charcoal and two tablespoons of powdered cinnamon* into the urine and stir.

3. Pour the urine/charcoal dust and cinnamon mixture into a glass retort with a glass tube leading into a second beaker filled with plain water.

4. Heat the retort containing the urine mixture using your torch. Be sure to wear protective clothing, eye protection and a breathing mask.

5. Allow the vapors from the urine mixture to bubble through the plain water. A yellow or white waxy substance will collect in the bottom of your water beaker. This is phosphorus. Do not expose it to the air or it may ignite spontaneously. After being exposed to light your phosphorus should glow very brightly in the dark for several hours.
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* I'm not at all sure of the role of cinnamon here--perhaps as an anti-oxidant or an odor-masking agent for a very unsavory process.

The Basics Of How Chemistry Is Like Sex

Anyone who has cleaned with Windex has whiffed ammonia, a substance with a rich and interesting history that includes its very name: link.  Note that ammonia was once called animal alkali. Muslims-in-science scholars should take note of the origin of the word alkali, but should take care not to get the concept of alkaline bases etymologically confused with that other Arabic word meaning base.

Ammonia gas easily condenses into a liquid when compressed (Albert Einstein and his erstwhile student Leó Szilárd once patented a refrigerator with no moving parts that used ammonia instead of freon). If Szilárd's idea had gone anywhere, he may not have bothered to have conceived the atomic bomb.

Ammonia has been variously depicted as NH₃ or better as :NH₃ or better still with its electron "lone pair" on full display, as:

The lobe-like appendage sticking up is called a "lone pair" because there are two electrons in the orbital and because they're not associated with any atom except nitrogen.  Some depictions of ammonia omit the lone pair but here I prefer the "fig leaf is off" depiction.

Ammonia is perpetually in search of an acid to quench its baser instincts. Given a proton like H⁺, ammonia and the proton instantly couple to make ammonium NH₄⁺ in which all four H's become equivalent. In a real sense, the incoming acid polarizes the other three H's, sucking electrons away from them, making them all more acidic.

The Essence of Distillation

Distillation is an ancient art, bequeathed to the Western world by medieval alchemy. If someone were serious about Muslim contributions to science, I suggest starting with the alchemists.

I once wrote the blogger vbspurs a mini-lesson on coffee making using a stovetop espresso maker:

Yes. BTW, the different aesthetic designs of those things actually hide the true inner beauty: upwards steam extraction of oils and essences, a short retort, and then a gentle collection cup, shielded from direct heat. We've own[ed] several designs, but they're really all the same. link

Many substances won't distill and the technique is really only useful for liquids in a chemistry lab or at an oil refinery. I found a totally cool description of how petroleum distillation works here.

The essence of an idea can be distilled from crude thought too. All it takes is a little focused energy--just enough to set it free from context--and a little care in gathering and enjoying it.