Thursday, October 28, 2010

Newlands' Law of Octaves

John Newlands was a 19th century chemist, inglese italianato, and an avid musician. He was among the first to see underlying rhyme and reason in the matter of the elementseven before Mendeleev did. But he mistook his insight as a fundamental harmony like the one between musical notes and for this he was rebuffed by his peers at the time.

Newlands arranged the then known elements in order of increasing atomic weight. He noticed that the eighth element (fluorine) resembled the first one (hydrogen), and that the ninth element (Na) resembled the second one (Li), and so forth. His observation that every eighth element had similar properties led him to compare his "chemical octaves" with musical octaves, and he called it his law of octaves. The first two octaves of elements behaved:

Do    Re    Mi    Fa    So    La    Ti     Do 
H      Li     Be     B      C      N      O     F
F      Na    Mg   Al     Si     P       S     Cl

One obvious problem with Newlands' octaves is that he left no room for the noble gases (which hadn't been discovered yet). So what Newlands described was not a law of octaves but rather a law of "nonaves":
Another problem with Newlands' scheme was that he tried to fit elements beyond chlorine into his scheme, including some known transition metals and he made some real errors. But give the man some credit.  Like Theo Boehm tweeted to me:

Well, Newland was on to *something* Just that musical analogy didn't quite make it. Tricky to work music into other areas! link

Imagination Sufficed

Click twice to magnify & to read the text about Titanic

That drawing is from Logan Marshall's The Sinking of the Titanic and Great Sea Disasters and has intrigued me since I was kid, especially the little stick figures tumbling off the stern. It affected me the same way the jumpers from the Twin Towers affected some people. But as a kid I didn't need such graphic "reality" footage.  Imagination alone sufficed to horrify.

Monday, October 25, 2010

Neon Rhymes With Helium*

Nothing says periodicity like neon and the other six noble gases. From top to bottom, they shore-up the whole right-hand side of the Periodic Table:

click to enlarge
A noble gas appears at the end of each row like a rhyming element. There are seven complete periods (rows) in the table above. Work has begun on the 8th period.  Don't let the gaps in the table fool you; they are just an artifact of our Cartesian thinking: link.

At the very bottom right of the table is Ununoctium, the last noble gas. Only a few atoms of Uuo have been made, not enough to characterize in detail, but I'm sure that the properties of Uuo would make radon (Rn) look tame. Most transactinide elements are not of this earth.

Back to earth. Neon's colorful history and etymology are covered here by van der Krogt.  The entire noble gas family eluded scientists for decades and for good reason. Interestingly, Neon's name was suggested by its discoverer's 13 year old child.

I think neon signs are cool. I didn't know until today that there's a Museum Of Neon Art (MONA) in Los Angeles link.  I'll have to add it to my list of places to see.
*The name "Helium" is a bit of misnomer. It should called Helion. The suffix "ium" really and truly belongs to metallic elements. At the time of helium's discovery on the sun, it was assumed that helium was metallic.

Letters Home: #31

October 25, 1952
Fliegerhorst Kaserne
Sat morning

Dear Mom,
We are getting ready to go on a road march with the tanks. We have to load them on flatcars and take them to the Russian border. [1]  It will be about 2 week before we get back. 400 miles round trip.
Last Sunday I went to Sababurg to see the castle. It was just like the ones you see in the movies. High walls, and a moat around it. Looked something like a fort.
I haven't been to Frankfurt lately. I am going in before December and get some things to send home. Tell R. I will write him, one of these days.
I bet dad would really cuss if he was over here. It rained 42 out of the last 54 days. It's been cool here, but no snow yet.
How is Jr. coming along? Has he got that new pick up yet? I hope I can save enough money to get a new car when I get out. At least the down payment.  How much does John want for a Hudson Hornet? [2] I suppose around $3,000.  I won't have any new a.p.o. number, it's still 46.
I sure was surprised to hear Donna B. and Skip C. and Bill K. got married. Things sure will be changed before I get back. So Vern and Ilene are supposed to get hitched too, but the last time I heard Ilene's mother wouldn't sign for her. I think there all foolish to get married the way the world is now. You always got the Draft Board to face.
I heard they wasn't going to draft any more 19 year olds till they got all the 20-21 year olds. R. might not have to worry for year. I hope he don't have to come. I know he would hate it worse than I do. I'm just easy going enough to put up with it. Just waiting till they cut me loose. The 29th of this month and I've been in 1 year, and still a private. Ha! Ha!  Sure different than Jr. I don't care myself if I get anything.

Love, V.

[1] I found a link with several photos contemporaneous with my father's service here.
[2] Ah, the Hudson Hornet. He must have been smitten back here. (footnote 2).

Sunday, October 24, 2010

Resonance is in the Air

I came across the following last night which resonated with me:
When you have two guitars tuned alike you also experiment with the phenomenon of resonance or sympathetic vibration. If you pluck one string on one guitar, and the second guitar is just a short distance away, the second guitar's similar string and only that string will sound softly and mysteriously without being plucked.
~Mary Ellen Bowden & Theodor Benfey writing in "Robert Burns Woodward and the Art of Organic Synthesis"
Nancy Duarte wrote a fascinating piece about resonance and public speaking here.  She wrote:
The audience does not need to tune themselves to you—you need to tune your message to them. Skilled presenting requires you to understand their hearts and minds and create a message to resonate with what’s already there. Your audience will be significantly moved if you send a message that is tuned to their needs and desires. They might even quiver with enthusiasm and act in concert to create beautiful results.
We have a real dissonance coming out of Washington D.C. We have public figures and radio personalities demanding that we tune to their frequency, rather than the other way around.  We are not a captive audience.

Friday, October 22, 2010

Past and Present: Now The Twain Shall Meet

Now, if I wanted to be one of those ponderous scientific people, and `let on' to prove what had occurred in the remote past by what had occurred in a given time in the recent past, or what will occur in the far future by what has occurred in late years, what an opportunity is here! Geology never had such a chance, nor such exact data to argue from! Nor `development of species', either! Glacial epochs are great things, but they are vague--vague. Please observe. In the space of one hundred and seventy-six years the Lower Mississippi has shortened itself two hundred and forty-two miles. This is an average of a trifle over one mile and a third per year. Therefore, any calm person, who is not blind or idiotic, can see that in the Old Oolitic Silurian Period, just a million years ago next November, the Lower Mississippi River was upward of one million three hundred thousand miles long, and stuck out over the Gulf of Mexico like a fishing-rod. And by the same token any person can see that seven hundred and forty-two years from now the Lower Mississippi will be only a mile and three-quarters long, and Cairo and New Orleans will have joined their streets together, and be plodding comfortably along under a single mayor and a mutual board of aldermen. There is something fascinating about science. One gets such wholesale returns of conjecture out of such a trifling investment of fact.
~Mark Twain, The Atlantic Monthly, 36, 193 (1875)
Mark Twain's autobiography is finally coming out after 100 years of waiting: link.  I'm expecting the unexpected, based on conjecture.

Umpolung: The Strange Case of Dr. Proton and Mr. Hydride

Umpolung is a chemistry term meaning "reversal of polarity." This is a useful trick, to change something from having a plus charge to having a minus charge. Hydrogen is the simplest example and shows how the same element behaves differently depending on whether it is cloaked in electrons or not.

The promiscuous proton, H+, flits from base to base in water. But hydride (written as H-), laden with two electrons, usually seeks an electrophile with which to couple irreversibly. If proton and hydride get together, they make little H2's.

Hydrogen usually appears on the upper far left side of the Periodic Table sitting above Li, Na, K,.., emphasizing its usual cationic (H+) character.  But umpolung explains why it's sometimes useful to think of hydrogen as belonging on the upper right side (next to He), sitting above the halogens, F, Cl, Br,.., emphasizing its anionic H- = hydride ~ halide character.

Saturday, October 16, 2010

Something Only A Man Would Think...

In chemistry, one's ideas, however beautiful, logical, elegant, imaginative they may be in their own right, are simply without value unless they are actually applicable to the one physical environment we have--in short, they are good only if they work!  I personally very much enjoy the very special challenge which this physical restraint on fantasy presents. 
~Robert Burns Woodward

I liked that quote so much (found here) that I read it aloud to my wife.  She immediately snarked that "only a man would even think to write such a thing."

Friday, October 15, 2010

Letters Home: #30

October 14, 1952

Dear Mom,

I guess I owe you a letter. I haven't got that one from R. It's been a bad day. Raining. We stayed inside and had map reading. We won't be going to the field till the 26th.
They're trying to teach us what way to go if we get lost.
Say can you send me my boots? The pair in my box with the Zippers.
If you send them by airmail I don't think it would cost to much. If you need any money for anything use my money.
Has Dad got a job yet?
I got one tomorrow. K.P. It comes once a month as sure as the sun rises.
By the way, we are 7 hours ahead of you.  At noon here, you're just getting up.
I met a kid from Sun Prairie today.
I think Don E. is over here isn't he? The last time I saw him he said he was going to Germany.
There just ain't a darn thing to write about. It rains all the time. 23 days out of September.
The leaves are just starting to fall. Some parts of Germany had snow already. The higher places.
I guess I will have to sign off for this time.

Love, V.

My father on the left, age 20 yrs

P.S. Didn't go to town this weekend. we had a P.T. test. I passed. Done 35 pushups. 7 pull ups. I had a score of 300. 250 was passing.

Saturday, October 9, 2010

Diamond Soufflé

Graphite (as graphene)

Isn't it obvious looking at their structures why so many attempts to make synthetic diamonds fall flat and make graphite instead?

This is backed by thermodynamic data so argue only if you dare.

Friday, October 8, 2010

A Girl's Best Friend is the Blue Diamond*

The structure of graphene got me to thinking of that other form of carbon, viz., diamond:

3D movie: link

Why is diamond so tough, so adamant, so opposed to physical change? I think the answer is called "perfect covalency" but not in an electron sharing sense:
The paradox of the diamond is interesting. Its atoms are not arranged in a tight, closest-packing order. They lack the triangulation of sound architecture. In order for its remarkable rigidity to be understood, I assume that the electrons which surround this meager structure supply it with its resistance to deformation. This is one reason why I cannot assume that electron clouds can infiltrate one another like vapors or ghosts. link
Pure diamond is also colorless and transparent, so what gives fancy (colored) diamonds their colors? The answer is not simply: "there must be something blue inside." An impurity is involved, but not the usual colored metal atoms like iron or chromium found inside other gemstones. The impurities in blue and yellow diamonds are carbon's left- and right-hand periodic neighbors--boron and nitrogen--playing little tricks on the lattice electrons.

Take the perfect 3D lattice of carbon atoms pictured above. Now suppose that we could randomly go in and replace every millionth carbon atom with a boron atom without perturbing anything else. What we get is a boron-doped diamond lattice. Because boron has one less electron than carbon, the entire lattice structure of the diamond is riddled with electronic "holes."

Now it just so happens that reddish-orange light has just the right energy match to promote an electron on an adjacent carbon atom into a "hole" next door. That jump in turn creates a new "hole" and so the next neighbor carbon jumps at the chance to fill the new hole and so on and so forth throughout the entire diamond lattice. Really, a blue diamond is rather like a doped silicon p-type semi conductor. In fact, blue diamonds are semi-conductors--albeit rather expensive ones!

Because only reddish-orange light is absorbed, the remaining visible light appears bluish to our eye because the white light lacks its reddish-orange component: remember the color wheel and complimentary colors!

Likewise, water in a white bathtub appears bluish because it absorbs some of the reddish component of the incident white light. That's also why heat lamps are red too--they are more or less tuned to the wavelength (infrared) that water in food absorbs and converts to heat. Microwave ovens are even better at this.

So what makes yellow diamonds? The answer is slightly more complex. If nitrogen atoms, carbon's other nearest neighbor, are doped into the diamond lattice instead of boron, each nitrogen brings an extra electron into the lattice which is easily promoted to the existing conduction band of diamond by violet light--ergo yellow appearing diamonds. Yellow diamond is analogous to an n-type semiconductor. Here's a link explaining in more detail why blue diamonds are blue and why yellow diamonds are yellow: Link.

Meanwhile, here's a very pretty picture of the Hope Diamond:

*I don't mean "blue diamond-shaped" Viagra either.

Thursday, October 7, 2010

50 Years Of MyTunes: 1967

One man's opinion:
There were three essential albums in the Magic Summer of '67: Sergeant Peppers's by The Beatles, Surrealistic Pillow by The Airplane, and The Doors by Robbie Krieger, Ray Manzarek, John Densmore, and Jim Morrison--and in some ways, it is only the last of these that seems far away in time, as if we remember it from another world and another lifetime.
~Bruce Harris (1972)
Another man's opinion: Are You Experienced? ~ Jimi Hendrix

A few of my favorite Singles:

Purple Haze ~ The Jimi Hendrix Experience
White Rabbit ~ The Jefferson Airplane
Time Has Come Today ~ The Chambers Brothers
Brown Eyed Girl ~ Van Morrison
Tears Of A Clown~ Smokey Robinson & the Miracles
Get Together ~ The Youngbloods
I Think We're Alone Now ~ Tommy James & the Shondells
Lucy In The Sky With Diamonds ~ The Beatles
Gentle On My Mind ~ Glen Campbell
San Francisco ~ Scott McKenzie
Break On Through ~ The Doors
Incense And Peppermints ~ Strawberry Alarm Clock
Spooky ~ Classics IV
Tuesday Afternoon ~ The Moody Blues
Strange Brew ~ Cream
Pictures Of Matchstick Men ~ The Status Quo
Itchycoo Park ~The Small Faces
Both Sides Now ~ Judy Collins

Some people really dislike "Incense and Peppermints" but I have this fantastic indelible memory of running around in the backyard when I was 7 or 8 singing:
Beatniks and politics nothing is new, a yardstick for lunatics, one point of view


The end of summer brings a gradual respite from arduous work. October, with its golden days and hazy blue atmosphere, is signalized in some German communities with a harvest festival on the first Sunday of the month. For forty-five years such an event has been observed annually in Sheboygan and Milwaukee by Bavarian societies. Less regularly but over a longer period smaller German settlements have kept up the custom. It is a Thanksgiving event, religious in background, colorful with Old World civic ceremonials. Among the older Germans it is still known as the 'Münchner October Fest.'
~Fred L. Holmes, "Freiheit Ist Meine" Old World Wisconsin (1944)

Wednesday, October 6, 2010

One Step At A Time

Consider again an uphill change from A to B with a steep barrier (tipping point): link

When faced with such a high barrier, it helps to break the uphill slog into steps. Catalysts (enzymes included) employ this strategy, breaking a reaction into one or more steps.*

Linus Pauling, that greatest of American chemists, introduced the profound notion that enzymes work by stabilizing tipping points (transition state energies in the parlance) and thereby speed things up:

Some of the acceleration occurs because requisite energy is just smoothly shaved off the peak, but sometimes a transient intermediate, labelled C above, appears. Thus we have a "stepwise" versus a "concerted" process.
*The 2010 Nobel prize was awarded to three inventors of a family of very similar catalysts.

Tuesday, October 5, 2010

Letters Home: "I hope the other outfits over here are combat ready because we're not"

Click To Enlarge

October 6, 1952
Fliegerhorst Kaserne
Dear Mom,
Well we finally got moved. I don't like this camp as well as the other one. This used to be a town. The barracks look like a college or high school. Long hallways and rooms. I'm in a 3 man room. Number 17.
I'm about 3 miles from Hanau and 15 from Frankfurt. Only 20 miles to the Russian border. [1] We are going there on patrol about the 13th.
I got your letter today. I think Marvin is stationed about 5 miles from here but I don't know his address.
What kind of deal will Le Vake give Dad for the Mercury? I don't think he should trade it before winter. It needs a bigger battery.
I gave Les Jim's address. I doubt if I will write to him. I don't like to write. I'll talk to him when we both get back.
It's not too cold here yet. It will be this winter though. I'll be camping out most of winter I suppose. In Dec. we fire the 90 m.m. for the first time. [2] I think if Russia ever attacked the 141st would have to run. I hope the other outfits over here are combat ready because we're not. [3]
Put plenty of mothballs on my leather jacket and tankers jacket, because I will be wanting them when I get back next Fall.
I go to the show every time it changes. It costs 20 cents; I think the price is going up to 25 cents after awhile.
I took a carton of cigarettes to town and sold them to a German for 15 marks ($3.75).  They only cost us $1.00 a carton but I still can't afford to smoke. I can't see it anyway. You have to be careful who you sell them to because that's Black market. Coffee sells for $2.50 a pound.

[1] He was stationed near the Fulda Gap, then strategically considered the most likely flashpoint of a shooting war between the US and the USSR.  The Fulda Gap was defended on our side (in part) by the 3rd Army Armored Division. On the other side was Russia's 8th Guards Army, defending a still prostrate Eastern Germany.

[2] The new Patton tanks were equipped with 90 mm cannons.

[3] I wondered what may have caused this momentary shudder in confidence. Nixon's Checkers Speech? The Brits going nuclear?  I think what may have been bothering him was a sense that Eisenhower really was going to be elected.  Ike was leading in the polls at the time. For a young soldier, this meant that the leadership at the very top was about to change--and that change would come on his watch when Ike took office in January the following year.  What effect could that have had on his mind?  Eisenhower after all had been a very successful general--a European war general.

Graphene is Wavy Gravy

Andre Geim and Konstantin Novoselov, both from the University of Manchester in Britain, won the 2010 Nobel Prize in Physics on Tuesday.

The two were awarded for  "groundbreaking experiments regarding the two-dimensional material graphene"


(Chemistry should be tomorrow)

Fluorine Gave Uranium Wings*

Fluorospar or Fluorite

Fluorine gas is wretched stuff.  Nothing can tear-out valence electrons like elemental fluorine can. Watch it corrode solid brick here: link  There's another video link along the sidebar there of fluorine eating through a dead chicken. Fluorine was too hot to handle for WW I trench warfare, and even Fritz Haber had to settle for chlorine, the next lower (and less reactive) halogen. Fluorine is superlative in a number of other ways: Uberchemist Martyn Poliakoff explains here: link
[added: an updated video here: link]

The name came from the rock in which it was found, and that mineral, fluorspar, was so named because it helped molten metal flow, a property known since the Middle Ages. Calcium fluoride is still used in welding flux. Fluorospar also glows blue when heated, and that property gave us the term fluorescence.

Fluorine and its heavier halide brethren are the polar opposites of the alkaline earths: Li, Na, K, Cs, etc. Here's some raw video of two polar extremes going at it: link  making salt (halogen means salt-forming in Greek) and a bunch of energy.

Hydrofluoric acid (HF) burns are particularly nasty: a decent amount of it burns right through flesh, overpowering the natural buffering system, and it keeps burning through flesh until it finds bone because calcium is the natural bonding partner of fluorine (as in fluorospar). I once witnessed the aftermath of a grad student who suffered an HF burn: he had to be med-evaced to Denver.

During WW II, uranium hexafluoride (or "hex" as it was so aptly nicknamed) became the vehicle of choice for the gaseous diffusion of uranium isotopes. Consider that nearly every single atom of U-235 that went into "Little Boy" was first borne aloft by six little fluoride wings (as volatile UF6) before the Enola Gay carried them aloft en mass for Hiroshima. Teflon (polytetrafluoroethylene) was used by chemists during WW II to enable the safe handling of UF6 during isotope separation.
UF6 was also of early interest to the Manhattan Project, as told to me by Jacob Bigeleisen: link
*The title is my homage to Ludwig Mond who in the words of Lord Kelvin "gave metal wings," referring to Mond's discovery of nickel tetracarbonyl, Ni(CO)4, a volatile compound so insidiously poisonous that it packs a double whammy if inhaled: it nickel plates your lungs while poisoning you with carbon monoxide.