Isambard Kingdom Brunel: A Ghost Of Britons Past

Separated at birth?  Kenneth Branagh channels Isambard Kingdom Brunel:

Kenneth Branagh at the 2012 London Olympics

Isambard Kingdom Brunel

The likeness was intentional. More on Brunel here

Рутений Made It Possible

Ruthenium, or Рутений in Russian, was named for Russia. We should call the element russium--that would at least be more historically descriptive--but ruthenium it is.* The first detectable amounts came from platinum ores in the Ural mountains--first discovered in the 1820's. The element is exceedingly rare--and thus expensive--and yet it too has its unique chemical niche. 

Ruthenium is the first element in the series 1 to 44 which can be fully stripped of 8 electrons to give a stable oxidation state of VIII.** Step just one atomic number backwards, to technetium, and there aren't 8 valence electrons to lose--only 7; step one element to the right, to rhodium, and the nucleus is already too electronegative to give up more than 6 electrons.  This makes ruthenium special--its willingness to fully yield to rapacious oxygen.

Ruthenium isn't really famous for much. It enjoyed brief fame in 1952 when ruthenocene was prepared by analogy to ferrocene, but it always seemed a little under-represented in catalysis until a chemist named Robert Grubbs (originally from Possum Trot holler in Kentucky), put ruthenium on the map with his Nobel-prize winning work centered around olefin metathesis.

"Olefin metathesis" has interesting history as a term--taken apart, "olefin" comes from oléfiant which means oil-forming and which ultimately comes from the roots oleum + facere. Olefin is an old word as chemistry words go--not so old to be practically archaic like oleum or vitriol, but still old. The modern term for olefin is alkene--organic hydrocarbons having one or more unsaturated double bond. The terms "polyunsaturated fat" and "trans fat" refer to olefins, FWIW.

Metathesis is a special word meaning rearrangement. There's a grammatical sense of the word which means transposition, and the chemical sense is just a metaphor. If we let the equal sign be a double bond, olefin metathesis refers to

a=b + c=d --> a=c + b=d.

See what happened there? Transposition.
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*Ruthenia corresponded to a much smaller region of what is now in the Ukraine. The Ural region was unknown to the Romans.
**Wikipedia notes claims to the existence of Fe(VIII) as in FeO₄ but the claim is tentative.

Selènè mooned the Xerox machine*

Selene, the moon goddess

Every element has its schtick, meaning that each one seems uniquely good at something. Selenium is particularly good at mediating light and electricity via photoconductivity, a property discovered early in its history: shine light on selenium and it conducts electricity better.

Chester Carlson put selenium's photoconductivity to practical use by inventing xerography and founding the Xerox corporation. Carlson patented xerography (which means dry writing in Greek) in 1942 and commercialized it. Selenium's role in xerography was to hold an electrostatic image long enough to attract toner ink for transfer to paper--and then to quickly forget what it saw. Selenium is no longer used in commercial copy machines, but the first ones did. A good historical read is here. Television, then a nascent technology, also used selenium early on. link

Though right next door to arsenic, selenium is not nearly as toxic--though its smell can be nauseating. Selenium disulfide puts the stink in dandruff shampoos, though I'm not sure if it's the selenium or the sulfur--both are chalcogens. Toxic in large doses, selenium is also an essential micro-nutrient, replacing sulfur in amino acids like cysteine and methionine and serving as an anti-oxidant.
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*Element 34, Selenium was named for Σεληνη [Selènè], Greek for Moon. Van der Krogt gives more history of the element's naming. Link

Amba Schooled Me (again)

Isambard Kingdom Brunel (1806-1859)

While on the topic, the man who built the SS Great Eastern (and the Great Western before her) was Isambard Kingdom Brunel.  There he is, pictured above, in a photo which might have stoked the rage and scorn of Dickensian socialists. Yet today, Brunel ranks highly in polls of "Greatest Britons."

I put this here to celebrate another wealth maker and also to note how Brunel exploited something which Amba schooled me on a few months ago: Surface area to volume ratio.  As a shipbuilder, Brunel understood that the carrying capacity of a ship increases by volume, while the water resistance (friction) only increases with the submerged area of its dimensions. This meant that large ships were intrinsically more fuel efficient, which was very important for long voyages across the Atlantic.

Ludwig Mond Gave Metal Wings

Ludwig Mond (1839-1909) founded Britain's ICI.

Ludwig Mond was another wealth maker who changed chemistry and in so doing, changed the world. Am I giving him too much credit?  Perhaps. Mond discovered nickel tetracarbonyl--an insidious poison--and turned its making into a process for refining ultra pure nickel--mostly Canadian nickel from the Sudbury Basin. Such nickel went into steel to make armor plating for ships. I'm sure that some still sits in the sunken battleship USS Arizona at Pearl Harbor.* Hardened steel armor was also the reason the US Treasury had to pull nickel from circulation during World War II, replacing it with less precious silver. link

Mond found (by accident) that nickel combines with four molecules of carbon monoxide to give nickel tetracarbonyl,
Ni(CO)₄:
 

Nickel tetracarbonyl is volatile and can be distilled. In a sense, the four carbon monoxides bear a metal atom aloft. To paraphrase Lord Kelvin: Mond gave wings to metals (I used Kelvin's metaphor to describe how fluorine "gave uranium wings" back here).
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*Kruppstahl as it turns out. I suspected this after having seen one of the Arizona's turrets still half submerged in warm seawater after nearly 70 years!

Blessed Are The Wealth Makers

Wallace Hume Carothers (1896-1937)

DuPont made a fortune selling things like gunpowder and nitrocellulose to warring governments (mainly to our own) up through and including the First World War. During the roaring 1920s (and flush with cash before the crash) they decided to pursue pure research into material science and established a new division at their fledgling Experimental Station located near Wilmington, Delaware.

The company hired a young PhD chemist named Wallace Carothers to start up a new group. Carothers was fascinated by long chain macromolecules ubiquitous in nature but which had only recently been recognized as "polymers." With the exception of Bakelite, the first synthetic plastic,* other synthetic polymers were unheard of, let alone commercially successful.

DuPont's research gamble paid off and Carothers and his group brought the company enormous success, first with the serendipitous discovery of neoprene, the first synthetic rubber, and then with nylon. Neoprene and nylon were tangible wealth creation: making things of value from what were, at the time, essentially waste products.

Nylon was Carothers' baby. Not only did he invent a synthetic replacement for silk, he purposefully developed a new method of making polymers called step-growth polymerization. He used the same durable type of linkages used by proteins (amide bonds), mimicking nature. Nylon was the first synthetic fabric and was commercialized around 1938, just in time to replace Asian silk which, along with natural rubber, went missing during the Second World War.

We have a lot to thank Carothers for but he didn't stick around. He checked out early, killing himself in 1937.
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* I have two items made from Bakelite: One is a late 1940's era Viewmaster device and the other is my father's old Kit-Cat clock which I described here. Both of these items have the characteristic fragility and tendency to chip common to Bakelite.

Meet the Priest who invented Flubber

Remember the storyline from Walt Disney's The Absent Minded Professor(1961)?  Fred MacMurray played a small Midwestern college chemistry professor who invented a miraculous substance which he named Flubber. He saved the football team and got the girl in the end. I think I found the real-life embodiment-well, forget the getting the girl part and focus on the chemistry and small midwestern university parts.

Reverend Julius Nieuwland (1878-1936)

I ran across the name Julius Nieuwland recently. Nieuwland was a priest and professor at Notre Dame University. As part of his Ph.D research, Nieuwland discovered Lewisite which was produced in tonnage quantitites by the U.S. during World War I as a poison gas.  Nieuwland had nothing to do with this application and distanced himself from the molecule (it's named for an enthusiastic supporter of gas warfare, named Lewis). Later, as a professor of organic chemistry at Notre Dame, Nieuwland successfully polymerized acetylene into divinylacetylene, laying the groundwork for the discovery of neoprene by Du Pont.

One of Nieuwland's more famous students was Knute Rockne, which even explains the football part of the otherwise bizarre Flubber story.

Karl Ziegler: "Consequences and Development of an Invention"

Karl Ziegler, German chemist (1898-1973)

Karl Ziegler, then director of the Max-Planck-Institute-for Coal Research, describing what he and co-workers discovered ten years prior to winning the 1963 Nobel Prize in Chemistry:

The catalyst is prepared simply by simultaneously pouring, with exclusion of air, two liquid materials into about two liters of a gasoline-like hydrocarbon, after which ethylene is introduced, while stirring. The gas is absorbed quickly; within an hour one can easily introduce 300-400 liters of ethylene into the two liters of liquid. At the same time, a solid substance precipitates, and can scarcely be stirred anymore. If the brown catalyst* is then destroyed, by the addition of some alcohol and by the introduction of air, the precipitate becomes snow-white and can be filtered off. In its final state it will accumulate in amounts of 300-500 g, as a dry, white powder.

~Karl Ziegler "Consequences and development of an invention"

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*The two co-catalysts were titanium and aluminum chlorides

Polyethylene had been known earlier. A British company, ICI, held patents for what they called "polythene" (hmm, maybe related to the Beatles' "plasticene"?), but ICI's polyethylene was different animal than Ziegler's polyethylene. The difference is at the atomic level. Though both plastics were polymers of ethylene, the older, inferior product was highly branched:

Ziegler's new process for making polyethylene essentially made perfectly linear chains of polymer with very little branching. The bulk properties of the two were markedly different. The density differences are akin to what one expects from trying to pack together a bunch of branches versus bunches of straight sticks.

Ziegler and his Institute became independently wealthy as the plastic age began in earnest.