Sunday, April 29, 2012

La Dolce Salsa

Cross-posted at Trooper York, a speakeasy blog (invitation only) I frequent:
It is sarsa time in Madison. The hot August sun has ripened the tomatoes, and Monona Bay that skirts 'Little Italy' seems congealed in silver silence. It is the season before the gnat invasion.
All along lower Regent Street, in adjoining backyards and open spaces off Milton Street, Italian housewives are vigilantly guarding the sarsa boards from the threat of rain. Within the homes the kettles are boiling—big kettles filled with sliced red tomatoes. When after an hour the cooking has turned the bubbling pulp into a thin red sauce, the contents are strained. Then the squishy mass is poured on clean white sarsa boards and placed in the sun to evaporate. Every hour, or oftener, the thickening nucleus is spread and respread until it takes on a richer shade and becomes a heavy relish. As it is packed away in jars, olive oil is poured on top—enough to form an air-proof covering. The finished product is then ready for use—all fall, all winter, all spring—until another crop of red tomatoes can be harvested.
~from Old World Wisconsin by Fred L. Holmes, published in 1944. Other nationalities are at the "Old World Wisconsin" tag.

"Sarsa" is Sicilian dialect for salsa.

Here's a link to a photo of a woman preparing "sarsa" in Madison. link

I especially like the simple trick of pouring oil over the sarsa to keep out air. That's exactly how commercial sodium and potassium metals (both air and moisture sensitive) are sold--submerged in oil to protect them.

Ignore The Skidmarks

Thirty years ago and I still recall a problem on a physics final exam at UW-Madison. It went something like this:
A tire is rolling at a constant speed along a pavement. A brake is suddenly applied, bringing the tire to a screeching halt. If the initial temperature of the tire is To, what is the final temperature of the tire? You may ignore heat exchange between the tire and road. 
The solution required a couple more pieces of info like the tire's velocity and mass, as well as the heat capacity of the tire.  I omitted those details. I remembered the problem because it was such a nice example of the first and second laws of thermodynamics.

First--all of the kinetic energy (called angular momentum) of the rolling tire changes into thermal energy (heat) as the tire skids to a halt. Nothing is "lost." The rubber in the tire heats up accordingly.*

Second--entropy increases for the energy transformation, meaning that all the well-ordered motion of the rolling tire transforms into the chaotic thermal vibrations of the warmer tire. The second law says that the reverse will not occur. In other words, a rolling tire can suddenly stop and heat up, but heating a tire will never make it roll.
James Joule spent part of his honeymoon in Switzerland measuring temperature differences between the tops and bottoms of waterfalls. His hypothesis was that the water should be warmer after the kinetic energy of the falling water is converted into heat. There were no forthcoming reports of frictional experiments with his bride.

Friday, April 27, 2012

Boredom Creates Friction

Count Rumford (1753-1814)
Benjamin Thompson (born in Woburn, MA) was the American anti-Franklin. He was a prolific inventor and scientist but sided with Britain during the Revolution and left America after the War and lived abroad thereafter. He eventually settled in Bavaria where he changed his name to Count Rumford and then changed our understanding of the science of heat. And he did all this in the service of practical pursuits.

Rumford oversaw the boring of iron cannon from iron cylinders using a horse-driven drill. He was impressed by how much heat the drilling friction gave off and he designed experiments to measure this. With insulated cannons and submerged drilling experiments, he carefully measured temperature increases. He found that sustained drilling could heat and boil cold water! Collecting and weighing the iron filings, he established that the metal shavings had the same weight and properties as the unbored metal, so nothing had been "given off" as was then currently thought. Rumford concluded that the mechanical work by the horses was converted into heat. Rumford showed that mechanical action can generate indefinitely large amounts of heat, thus directly challenging the caloric theory of the great Frenchman, Lavoisier. 

Lavoisier, a contemporary, didn't live to appreciate Rumford's work--he was guillotined in the French Revolution--ironically for Royalist sympathies. Rumford wound up marrying his widow, Marie-Anne Paulze who was an unappreciated chemist in her own right.

Tuesday, April 24, 2012

Boomer Alert II

Posting this because I was just thinking about the lyric:
Now there's a look in your eyes, like black holes in the sky.

Friday, April 20, 2012

Chemical Gnomonclature*

Scotoma is the technical term for the blind spot in our field of vision. Our brains interpolate the missing data so we don't perceive a black spot, but in fact we have two scotomas, caused by the lack of retinal cells where the optic nerve joins the retina (see link).

The Periodic Table is a reticulated array of data. In the mid 1930's, element 43 was still conspicuously lacking. Dmitri Mendeleev, that great Russian seer of visions and father of the Periodic Table, foresaw its existence and called it eka-manganese, meaning "one-after-manganese." Here's what the family of transition metals looked like in the mid 1930's:

Chemists sought eka-manganese unsuccessfully for 75 years after Mendeleev's prediction: their efforts are nicely summarized by van der Krogt. Of the fruitless efforts, those of Noddack et al. came closest, and they proposed the name masurium in 1925. Several Periodic Tables from that era even included Ma beneath manganese.

Unequivocal proof for element 43 appeared in 1937, after an Italian team led by Emilio G. Segrè  isolated it from radioactive samples of next door molybdenum which had been bombarded with deuterium nuclei at Berkeley. They named the new element technetium from the Greek τεχνητος, meaning artificial.
*Gnomonclature is an homage to James Joyce who invented a literary device called gnomon to accentuate character or story element.  In the words of his character Stephen in A Portrait of the Artist as a Young Man:
Absence is the highest form of presence.
The absence of eka-manganese drove generations of chemists to search for it because it was there--somewhere.

Tuesday, April 17, 2012

Boomer Alert!

I ran across this video of The Who circa 1970 playing a live version of "Young Man Blues." It's very similar to the one on their "Live At Leeds" LP. It's easy to see how visually distracting Keith Moon was to watch. And I like John Entwistle's skeleton suit--he rocks on this song--standing so motionless as he always did, putting all his energy into his fingers on the fretboard.

Ron (the commenter) once noticed how the surviving members of The Beatles and The Who compliment each other perfectly and could form a band to replace their missing members: Ringo for Moon and McCartney for Entwistle. Ron suggested calling them "The Whotles."

Sunday, April 15, 2012

Titanic Centennial: What Really Happened?

I think it's rare when a controversial book bucks conventional wisdom and gets high marks from both professional and amateur reviewers. David G. Brown's book, "The Last Log of the Titanic: What Really Happened on the Doomed Ship's Bridge?" seems to be one of those.

Titanic never goes out of style for me and I just ordered a copy.

Friday, April 13, 2012

Titanic Centennial: Lightoller and the Mechanics of Sinking

EBL linked a great video showing exactly how Titanic actually sank here: link

Charles H. Lightoller was the highest ranking officer to survive the sinking. His stories and testimony were given considerable weight at the subsequent hearings (at the Waldorf-Astoria Hotel).  Here is his harrowing account of the sinking. Some of his recollections are inconsistent with the simulated sinking as noted.
I stuck to the ship until the water came up to my ankles. There had been no lamentations, no demonstrations either from the men passengers as they saw the last life-boat go, and there was no wailing or crying, no outburst from the men who lined the ship's rail as the Titanic disappeared from sight.
The men stood quietly as if they were in church. They knew that they were in the sight of God; that in a moment judgment would be passed upon them. Finally, the ship took a dive, reeling for a moment, then plunging. [1] I was sucked to the side of the ship against the grating over the blower for the exhaust. There was an explosion. It blew me to the surface again, only to be sucked back again by the water rushing into the ship.[2]
This time I landed against the grating over the pipes, which furnish a draught for the funnels, and stuck there. There was another explosion, and I came to the surface. The ship seemed to be heaving tremendous sighs as she went down. I found myself not many feet from the ship, but on the other side of it. The ship had turned around while I was under the water. [3]
I came up near a collapsible life-boat and grabbed it. Many men were in the water near me. They had jumped at the last minute. A funnel fell within four inches of me and killed one of the swimmers. [4] Thirty clung to the capsized boat, and a life-boat, with forty survivors in it already, finally took them off. [5]
George D. Widener and Harry Elkins Widener were among those who jumped at the last minute. So did Robert Williams Daniel. The three of them went down together. Daniel struck out, lashing the water with his arms until he had made a point far distant from the sinking monster of the sea. Later he was picked up by one of the passing life-boats.
The Wideners were not seen again, nor was John B. Thayer, who went down on the boat. 'Jack' Thayer, who was literally thrown off the Titanic by an explosion, after he had refused to leave the men to go with his mother, floated around on a raft for an hour before he was picked up.
Here is a video link to a slightly different take on the mechanics of the sinking: link
[1] Lightoller testified that she did not break in two. This contradicts fact and it's difficult to reconcile his testimony. One reason, perhaps, is that Lightoller saw Jack Thayer's depiction of the breakup and decided it wasn't what he saw. Thayer's description, depicted here, shows the bow section magically refloating after being submerged. The chaos of the sinking led to a Roshomon effect.

[2] As the ship sank, many air vents become inlets for water. A suction effect could have trapped him against a vent grating. Occasionally, trapped air would have to escape, sometimes violently. Also, though the boiler fires were raked down, they were not extinguished. Cold seawater would have produced pockets of steam.

[3] Underwater gyrations from breaking in two could have caused this.

[4] This seems to have happened much earlier in the simulation video than Lightoller's description. The other stacks are shown to remain in place until she submerged.

[5] The men actually stood on the capsized boat for several hours until they were picked up.

Time For Cocktails: The Astoria

2 oz Gin
1 oz dry Vermouth*
2 dashes Orange Bitters
Shake over ice and strain into chilled martini glass
Garnish with lemon twist or olives.

This cocktail was allegedly invented at the original Waldorf-Astoria Hotel, located on 5th Ave, where the Empire State Building is now. The original Astoria hotel was built by John Jacob Astor IV, who went down with the Titanic. Astor was the wealthiest man aboard Titanic, but he was supposed to have been one-upped by J. Pierpont Morgan, who cancelled at the last minute. White Star Line Managing director J. Bruce Ismay took J. P. Morgan's luxury suite of cabins for the maiden voyage.

Astor was accompanied on Titanic by his very pregnant bride, Madeleine, who survived the sinking and gave birth to a son, John Jacob VI, four months later. Both wife and son's lives had sad endings.
*Some mixers transpose the amounts of gin and vermouth.

Saturday, April 7, 2012

Does This Answer Your Question?

An experiment is a question which science poses to Nature and a measurement is the recording of Nature's answer. 
~Max Planck
If you've done real experiments, you know that sometimes you have to keep asking until you get the question right.

Friday, April 6, 2012

RIP Jim Marshall (1923-2012)

I wrote about him back here.

Here's an iconic photo by the other Jim Marshall of another James Marshall kneeling next to a Jim Marshall amp:

Three Jim Marshall's went into that photo--now they're all gone.

Wednesday, April 4, 2012

Conversations with Henry

Henry: You forgot to mention Allen and Senoff.

Me: Who? 

Henry: Allen and Senoff. They made the first dinitrogen complex from ruthenium, [Ru(NH3)5(N2)]2+. That news caused quite a stir back in 1965. Ruthenium rhymes with iron, so you're also speculating about molybdenum. It could be iron doing the fixing in nitrogenase.  Never sell iron short.

Me: *gulps*

Henry: I'm glad to see that you're reading and keeping up with newer stuff. Barry told me you'd be back.

Molybdenum Fixes Nitrogen

Molybdenum's odd-sounding name comes from its resemblance to lead ores. That makes three elements: plumbum (lead), carbon (plumbago), and now molybdenum named after lead. Perhaps it's not so much the color as the texture:

Native ore: MoS2

Native plumbago (graphite)

Native lead (Galena, PbS)
Molybdenum's role in life is anything but leaden. Mo is in nitrogenase, an enzyme absolutely essential for life. Nitrogenase-containing bacteria "fix" nitrogen, turning thin air into solid plant food (ammonium), a feat no less remarkable than photosynthesis. The bacteria in turn get first dibs on the sugars made by the plants in perfect symbiosis.

If artificial photosynthesis is cool--making sugars and fuels from CO2--nitrogen fixation is even more exciting because we're about a third of the way there.*  Bacteria make about 2/3 of the world's fixed nitrogen, and the ancient Haber-Bosch process does the rest.  The Haber-Bosch process, first developed in 1913, enabled Germany to fight the First World War. Today it helps feed about a third of the world's population but it also consumes about 1-2 % of the world's annual energy supply. We can do even better, perhaps by learning from nature.

Nitrogenase manages to fix nitrogen under much milder conditions than Haber-Bosch, though like many natural processes, the yield is diffuse and unusable industrially. Molybdenum's connection to nitrogen fixation was first noted in 1930 when bacteria raised on ammonia showed no need for the element while those raised on nitrogen did (before the enzyme nitrogenase had even been identified). When nitrogenase was found, the next step was to crystallize it and determine its structure. This happened in 1992, at a time when molybdenum and the heavier tungsten were already famous for loosely binding things like H2 and N2 in synthetic tungsten compounds. Some thought perhaps nature had gotten there first. Alas, the structure gave few clues as to where and how nitrogen is activated, except that it happened stepwise, using protons and electrons instead of H2.

Another really cool thing about the nitrogenase X-ray crystal structure was the revelation of a mystery element "X" which could be either a C, an N, or an O atom. Several contact points surround the mystery element X which makes that a "Texas" atom.  More recent work, published last year in Science, says it is carbon (link). More on that later.
*There are vanadium-dependent nitrogenases which convert CO to alkanes--just like Fischer-Tropsch catalysts do: link  That would be so cool if the X-factor were a Texas carbide.

Tuesday, April 3, 2012

Titanic Centennial: Murdoch's Suicide

"...even the most respected history of an event is at best an approximation." 
~James Cameron, writing in the preface to The Titanic Disaster Hearings
"The whole incident can’t be verified, yet can’t be dismissed."
~Walter Lord, referring to the alleged suicide of William Murdoch.

Perhaps nothing is more controversial regarding Titanic (even today) than exactly why she steamed headlong into disaster. And not just into an iceberg but into an enormous ice field--that fact was clearly established in both the US and British inquiries and by reconstruction of extant the facts from other ships in the vicinity of the disaster. Here's a good visual of what Titanic came upon that night:

The sworn testimony of several witnesses clearly established that Captain Smith knew of the ice danger via wireless messages (marconigrams) as early as noon the day of the accident, April 14th. He even knew the expected arrival time at the ice field based on coordinates, direction and travel speed--between  11 PM and midnight (the mishap occurred at 11:40 PM). Smith did order a change of course slightly more to the south but the reason why he didn't slow Titanic down went down with him to the sea bottom. Surely he was not that stupid. Afterwards, meddling interference by White Star Line Managing Director J. Bruce Ismay was floated as a likely reason (Ismay wanted to set a record crossing time and he never lived down those suspicions, though he was never officially charged). Clearly negligence was a factor. But the chain of command puts William T. Murdoch in charge and the whole story looked even worse shortly after the sinking.

In the initial days following the disaster, a Titanic crew member alleged that the bridge had ignored 15 minutes of warnings from the crow's nest.  From the book, The Sinking Of The Titanic And Great Sea Disasters, published in 1912 (I've footnoted subsequent historical challenges):
SUNDAY night the magnificent ocean liner was plunging through a comparatively placid sea, on the surface of which there was much mushy ice and here and there a number of comparatively harmless-looking floes. The night was clear and stars visible. First Officer William T. Murdock was in charge of the bridge.[1] The first intimation of the presence of the iceberg that he received was from the lookout in the crow's nest. 
Three warnings were transmitted from the crow's nest of the Titanic to the officer on the doomed steamship's bridge 15 minutes before she struck, according to Thomas Whiteley, a first saloon steward (waiter). 
Whiteley, who was whipped overboard from the ship by a rope while helping to lower a life-boat, finally reported on the Carpathia aboard one of the boats that contained, he said, both the crow's nest lookouts. [2] He heard a conversation between them, he asserted, in which they discussed the warnings given to the Titanic's bridge of the presence of the iceberg.    
Whiteley did not know the names of either of the lookout men and believed that they returned to England with the majority of the surviving members of the crew.
'I heard one of them say that at 11.15 o'clock, 15 minutes before the Titanic struck, he had reported to First Officer Murdock, on the bridge, that he fancied he saw an iceberg!' said Whiteley. "Twice after that, the lookout said, he warned Murdock that a berg was ahead. They were very indignant that no attention was paid to their warnings.'  Murdock's tardy answering of a telephone call from the crow's nest is assigned by Whiteley as the cause of the disaster.[3] 
When Murdock answered the call he received the information that the iceberg was due ahead. This information was imparted just a few seconds before the crash, and had the officer promptly answered the ring of the bell it is probable that the accident could have been avoided, or at least, been reduced by the lowered speed.

The lookout saw a towering "blue berg" looming up in the sea path of the Titanic, and called the bridge on the ship's telephone. When, after the passing of those two or three fateful minutes an officer on the bridge lifted the telephone receiver from its hook to answer the lookout, it was too late.

The speeding liner, cleaving a calm sea under a star-studded sky, had reached the floating mountain of ice, which the theoretically "unsinkable" ship struck a crashing, if glancing, blow with her starboard bow.

Had Murdock, according to the account of the tragedy given by two of the Titanic's seamen, known how imperative was that call from the lookout man, the men at the wheel of the liner might have swerved the great ship sufficiently to avoid the berg altogether. At the worst the vessel would probably have struck the mass of ice with her stern.

Murdock, if the tale of the Titanic sailor be true, expiated his negligence by shooting himself within sight of all alleged victims huddled in life-boats or struggling in the icy seas.[1]

When at last the danger was realized, the great ship was so close upon the berg that it was practically impossible to avoid collision with it.
The first officer did what other startled and alert commanders would have done under similar circumstances, that is he made an effort by going full speed ahead on the starboard propeller and reversing his port propeller, simultaneously throwing his helm over, to make a rapid turn and clear the berg. The manoeuvre was not successful. He succeeded in saving his bows from crashing into the ice-cliff, but nearly the entire length of the under body of the great ship on the starboard side was ripped. The speed of the Titanic, estimated to be at least twenty-one knots, was so terrific that the knife-like edge of the iceberg's spur protruding under the sea cut through her like a can-opener.
The Titanic was in 41.46 north latitude and 50.14 west longitude when she was struck, very near the spot on the wide Atlantic where the Carmania encountered a field of ice, studded with great bergs, on her voyage to New York which ended on April 14th. It was really an ice pack, due to an unusually severe winter in the north Atlantic. No less than twenty-five bergs, some of great height, were counted.
Icefield in the vicinity of the Titanic sinking April 15, 1912. original

[1] Murdoch did not survive. Several books and movies portray him committing suicide, including James Cameron's 1997 Titanic. Walter Lord, the first Titanic historian, had discounted Murdoch's suicide in his 1955 book A Night To Remember but reversed his opinion when letters written by survivors to family members surfaced. Lord was a technical consultant to Cameron's 1997 film and passed away in 2002. Interestingly, when Murdoch's living descendants complained of Murdoch's portrayal in Titanic and threatened to sue, Cameron responded by endowing a scholarship in Murdoch's Scottish hometown. The facts of the alleged Murdoch suicide are explored in most detail here. <-- a website devoted to Murdoch.

[2] The lookout on duty, Fredrick Fleet, survived in lifeboat No. 6. He was subpoenaed at both the US and British inquiries. He denied Whiteley's claims. The other lookout, Reg Lee, was saved in lifeboat No. 13. and subpoenaed at the British hearings. He also denied the claims.

[3] This has been factually contested. Whiteley was not picked up in life boats No. 6 nor No. 13 which contained the two lookouts. Instead he appears to have been saved by climbing aboard overturned collapsible boat B. Whiteley is an interesting character and appears to have gone on to have some interesting Rose Dawson-like adventures: flying ace, & stage and film actor. He has no Wikipedia page entry but is covered by Encyclopedia Titanica here. Whiteley actually sued the White Star Line in 1914 for "steering error" and negligence, but the suit never went to trial.