The Chemistry of Politics

Politics and chemistry share many concepts and even words: coming together vs. falling apart; donor vs. acceptor; tipping point & transition state; polarized vs. neutral; vitriolic & caustic vs. neutral; litmus test; right vs. left; purity vs. impurity; structure & status quo vs. change & kinetics; majority vs. minority; and resonance to name a few off the top of my head. The words "electron" and "election" even look related but are in fact unrelated; electron comes from the Greek word for amber, while the word elect comes from the word to pick and choose.

Years ago, I hypothesized (and published with evidence) that a well-known (but poorly understood) chemical reaction was governed by repulsion: Electronic repulsion at its very core.  Briefly, a catalyst separately held the same substrate in two different ways; an incoming hydrogen molecule would then chose which of the two configurations to ride over the barrier hump while melding into stable products, corresponding to what could be dubbed right and left-handed versions of the same thing. Now, the rate of hydrogen's addition to (choice of) one of two configurations was the deciding factor; it was the deal clincher. Moreover, the two configurations were present in vastly unequal amounts from the start -- around a 10:1 ratio. Prior studies had shown that the incoming hydrogen preferred the minority configuration. That's where I came in. I said that incoming hydrogen was repelled by the major substrate-catalyst complex -- the one with the clingier hangers-on. In effect, I said that substrate binding (clinginess) killed reactivity by swelling a repulsive lobe on the catalyst.

A catalyst is rather like a politician. Its job is to bring us lowly substrates together to make something more stable. But just like my chemistry example, the favored politician with the clingier hangers-on can be the kinetic loser.  It's the repulsion, stupid.

Inspired By Amba

Amba wrote this a while back on her blog Ambiance:

Matter is a corrective. Matter exerts a resistance, a counterforce, like wood to a carving knife or water to a ship’s keel or air under an airplane’s wings, that paradoxically enables us to get somewhere by making it more difficult. link

To which I responded:

OK, this is way off-topic and perhaps I should write it as another “inspired-by-Amba” blogpost, but I had to mention two connections this triggered for me. The first was the old-fashioned way that nations used to settled trade imbalances: there might be trade exchanges in one direction: goods or services for example. At the end of the day, there would be a reckoning and something like gold would flow in the other direction. In this way gold, having gravitas, kept thing[s] grounded. 

The second was the way chemical reactions occur. Chemistry is valence electrons exchanging and rearranging. The nuclei hardly change at all (unless we’re talking nuclear chemistry). Anyways, electrons, being flighty and fleet, are forever waiting around for the heavier nuclei to get into the right configurations for exchange. When the laggard atoms finally are…zip…the electrons are already there like magic. link

She responded:

Anyways, electrons, being flighty and fleet, are forever waiting around for the heavier nuclei to get into the right configurations for exchange. When the laggard atoms finally are…zip…the electrons are already there like magic. 

That is totally what it’s like to write, or perhaps to create in any medium. You have to do the heavy, lumbering work of getting yourself properly aligned, then–inspiration is there. link 

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For too long I've behaved like water or electricity -- always seeking the path of least resistance. If I wish to channel my thoughts -- to steer them in a meaningful direction-- I must also do the work of building the embankments to contain them. I'll have to move a few atoms. I've done this before and so am no stranger.

More notes on "The Disappearing Spoon"

[continued from previous post]

Part I   "Orientation: Column By Column, Row by Row"

1. Geography Is Destiny: H, He, B, Be, Sb
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Page 21, bottom of page:

Egyptian women were applying a different form of antimony as mascara, both to decorate their faces and to give themselves witchlike powers to cast the evil eye on enemies.

They used stibnite in which you can still see the Latin origin of antimony's chemical symbol, Sb. Stibnite gave the blueish black look which is still alluring, though antimony has been removed from reformulated modern eyeliner. The alchemist's symbol for antimony is:

which sort of resembles an upside down version of the female symbol.
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Kean writes at length about Gilbert N. Lewis, as have I. My take on him is here and here.
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Now on to some substantive descriptive chemistry: Page 24, bottom:

As we move horizontally across the periodic table, each element has one more electron than it neighbor to the left. Sodium, element eleven, normally has eleven electrons; magnesium, element 12, has twelve electrons; and so on. As elements swell in size, they not only sort electrons into energy levels, they also store those electrons in different shaped bunks, called shells.

Early German quantum mechanics called this Aufbau or building up. Kean describes how electrons build shells -- s, p, d, and f orbitals -- in a logical way. His descriptions of p-orbitals as a "misshapen lung" and "d-orbitals" as balloon animals is amusing, but I would explain it differently. They more resemble blobs with 0, 1, 2, and 3 nodes as described here.

What Aufbau builds on is how electrons self-organize around an increasingly charged nucleus in moving from hydrogen to higher and higher elements. Start with the simplest atom having one proton and one electron. The very first electron goes into a spherical shaped 1s orbital surrounding the proton. Now if we add another proton to that picture to get to the next element (helium), we must add a second electron. It too goes into the same 1s-orbital and two electrons are happy as clams--perfectly-paired. The pairing of electrons is one of the most sublime aspects of electronic theory and is one which I struggle to understand.

Now move on to element 3, lithium: the third electron cannot occupy the same orbital space as its first two, so it must go into a higher energy orbital, the so-call 2s orbital. The 2s orbital is not exactly just a larger s-orbital; it actually interleaves with the 1s orbital as I drew attention to here:

The fourth electron in element 4, beryllium, perfectly pairs with the third one and fills the 2s orbital. Now, the fifth electron in boron could go into what's called a 3s orbital depicted above, i.e., electrons could just keep building higher and higher energy shells of spherical symmetry, but something else happens. A different type of node appears which breaks the spherical symmetry, creating what's called a p-orbital:

The 2p-orbitals are lower in energy than the 3s orbitals and that's why the next 6 electrons fill those first. There are 6 spaces because the electrons pair and go into 3 different p-orbitals -- one for each Cartesian dimension, x, y, and z.

[more soon]

Newton in a Nutshell

Sir Isaac Newton
Portrait: Godfrey Kneller (1689)

How much of the universe is empty space? Isaac Newton wondered:

Newton's belief in the particulate nature was supported by his optical experiments. His view was that light is a stream of corpuscles, and in order to explain the fact that some material is transparent he assumed that some of the corpuscles pass through matter without encountering the particles of which it is composed. Matter must therefore consist mainly of empty space, and he made estimates of the size of the particles. His conclusion was that the particles must be extremely small that if all the particles in the solar system came together the total volume would be that of a nut. Later Joseph Priestly (1733-1804), in his "Disquisitions Relating to Matter and Spirit" (1777), first used the expression "matter in a nutshell" to describe Newton's ideas.* 

Newton's reasoning lacked a fuller understanding of how light interacts with matter. Light will resonate with matter if it encounters an energy match--but otherwise it passes on through or reflects away. Charged "corpuscles" like an alpha particle are another matter. Ernest Rutherford used them when he proposed atoms to be mostly space--cf. his famous "backscattering experiments." But electrons are not empty space--anyone who has seen electron densities as revealed in X-ray crystallography knows that atoms and molecules fill space quite densely.
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 *Keith J. Laidler, The World Of Physical Chemistry, Oxford University Press: New York, 1993.

There's more on the origin of the expression "in a nutshell" here from Ask Yahoo. Others trace it back to Shakespeare.

Conversations with Henry

Henry:  Did you see that business in the news about negative absolute temperatures?

Me:  You mean this?

Henry:  Yeah, that.  Good thing you know how to manipulate the Internet. I never got the hang of it. You know what that news reminded me of?

Me: No, what Henry?

Henry:  The inverted Marcus region.

Me: Remind me what the inverted Marcus region is.

[Henry moves to the white board, grumbling that people no longer use chalk & blackboards. He sketched three related figures, and then explained them in words]:

Henry: Rudy Marcus laid out three different scenarios for the reaction coordinate of a simple "downhill" reaction using intersecting parabolas to represent reactant and product. Parabolas have a long history in physics (think of pendulums, and they "track" the potential energy in molecules). In the first, notice that the "initial state" reactant parabola is slightly higher in energy than the "final state" product parabola; where they cross represents a moderately uphill barrier given by the distance, ΔG^‡.

In the second (middle) scheme, the initial state (left) parabola is higher in energy while the final state parabola stays the same—follow?  He got there by translating the left hand reactant parabola straight upwards and their intersection slides "down." The barrier to the more downhill reaction is now zero. See that?

Me: Yes!

Henry:  Here is where Marcus was an absolute genius:  if you keep on going as in the third scheme, the initial state parabola gets higher still—this is now a very downhill reaction—but notice that the barrier, ΔG^‡, goes back up because the intersect climbs up the other side!  This is the so-called "Marcus Inverted Region" and is utterly counter intuitive that a more downhill state should require more energy to reach. Boy, he really shook things up with that one!

Me: Fine, but how does that translate to the real world?

Henry: What?  Didn't you read my other stuff?

Me: Here's what I think...I've been saying all along that uphill effort requires more energy than downhill effort, for example here.  But suppose that we have something really severe like the Fiscal Cliff.  Suppose that the fall is so downhill that we will actually face a higher hurdle to get down there than if it weren't so precipitous.

Henry: Hair-brained economics!

Another Quantum of Solstice...

Rutherford and Bohr

[this story continues in part from here.]

Ernest Rutherford discovered the atom's very kernel, the nucleus, but his tiny solar system model of the atom failed. It failed because it had a fatal flaw according to classical electromagnetic theory: Viewed side-on in the plane of the ecliptic, the orbiting electron oscillates charge from side to side and should behave like a miniature transmitter, broadcasting electromagnetic energy like a Marconi transmitter. Giving off energy, bit-by-bit, the electron should spiral into the nucleus. Rutherford never explained that away.

The Importance of Being Near Ernest

Luckily, Rutherford confided his 1909 experiments to young Niels Bohr prior to publishing them. Rutherford had invited Bohr to Manchester to study physics after a brief (and apparently unsuccessful) stint at Cambridge. Inspired,* Bohr spent the summer of 1910 and the subsequent spring (taking time off to marry and to honeymoon), devising his own theory which he published in 1913 (two years after Rutherford finally published his planetary model in 1911).

Bohr got around Rutherford's electron death spiral problem by postulating that it didn't happen! That may sound audacious and even glib, but he overcame "illogical leaps" by solving a bigger mystery which had puzzled generations of scientists: he explained the long-known but little-understood signature hydrogen lines observed in the spectra of stars (recall that stars are mostly hydrogen). According to Bohr, the lines represented quantum leaps in units of energy. He did the math for the hydrogen atom to prove it. The simplistic hope that atoms and the universe were fundamentally similar -- the too small to be seen and the too big to be noticed were whirling masses in motion or "turtles all the way down" -- shone briefly.

According to Bohr's new 1913 theory, electrons encircled a nucleus, but only in stable, fixed-distance orbits (shades of Bode's earlier but discredited planetary law?) but without the continuous death spiral energy radiation. Bohr called his quantized orbits "stationary orbits" (whence my title). A quantum of solstice or standing still.

Electrons in Bohr's stationary orbits still gained or lost energy -- but only by jumping from one orbit to a bigger orbit and vice verse. That was revolutionary. Bohr's math worked out too and depended on Planck's constant which was only 13 years old then.

Planck quantized radiation and Bohr quantized matter--viz, electrons. Scientists struggled in subsequent years with the question of whether electrons were waves or particles and whether light rays were waves or particles. They worried about the meanings of such apparent dichotomies until they gradually realized that they were fighting about language and not about science.
 _______________
*Inspired is an understatement

****

My inspiration for the "Quantum of Solstice" is here at Victoria's old blog, to whom I dedicate this blog post.

Ecce LUMO

Ecce Homo, Caravaggio (1605)

Behold the HOMO (Highest Occupied Molecular Orbital), seeking reception;
Behold the LUMO (Lowest Unoccupied Molecular Orbital), offering reception.

Chemical reactions are electronic transfers. I don't mean electronic transfers like PayPal is (although there are similarities between electricity and money). I mean electronic transfers like oxidations and reductions, substitutions, proton transfers--which all involve electron donors and acceptors.  I still think that BH₃NH₃ best illustrates how chemistry is like sex: link

Presumably, the chemistry of memory has some donor and acceptor aspect at the molecular level. Long term potentiation. Learning is also like transubstantiation--words becoming neuronal flesh and all that. But there is more to learning than replication.  As Plutarch noted, learning is less like bucket filling and more like igniting little fires; Jefferson echoed that same thought: knowledge is contagious.

Here are some mnemonics for today's lesson:

HOMO/LUMO
Donor/Acceptor
Base/Acid
nucleophile/electrophile
Plug/Socket
Hand/Glove
Foot/Shoe

You can guess the rest.

Correcting A Misconception

A recent article in Science dismayed me. The authors wrote one of those "perspectives" articles describing the gist of one of the real peer-reviewed research articles later on in the magazine.

"Getting Moore from Solar Cells" by David J. Norris and Eray S. Aydil, Science 2012, 238, 625.

After describing some new and interesting materials for solar cells, the authors state:

"Although this sounds exotic, these materials are known to behave like semiconductors, allowing them to absorb the sunlight and create electrons"

At the risk of sounding pedantic, electrons are not created--nor are they destroyed. They are there in the dark in the beginning, and they are still there after the lights go out.  The electrons are merely excited by the light.

Photons knock up electrons and then leave the seen.

The Proof Was In The Pudding

[continued in part from here]

After Thomson discovered and defined the negative portion of the atom, his attention turned to the positive portion which was ill-defined. One problem was that there was no simple tool to probe inside atoms. Electrons could be fired at matter, but so what?  They just softly scattered off (it turns out that organized matter diffracts them but that came later).

The alpha particle was Rutherford's baby: he had named it and had shown that is was a helium atom stripped of electrons, i.e., He²⁺.  By 1909, Rutherford and his students were firing alpha particles at everything in sight, looking for any new and unusual effects, but also testing theories about the positive part of Thomson's Plum Pudding Model.

Rutherford had earlier noted the thickness of sheets of materials needed to stop alpha particles. But why did they? There was nothing about JJ Thomson's atom that should get in the way. If the positively charged portion of each atom were a uniformly thin gruel, alpha particles should sail right through.  But they noticed deflection--eppur si muove.

Eventually, they began measuring how much thin sheets of gold foil deflected beams of alpha particles. The experimental set-up involved aiming a beam of alpha particles at a gold foil and putting a detector on the other side to measure deflection angles of the "filtered" particles. In a sense, Rutherford was trying to quantify the density of the positive pudding portion. The more closely they looked, the more deflection they observed. Almost as an aside, Rutherford suggested putting the detector in front of the gold foil. When they did so, and to everyone's utter surprise, a detectable amount of alpha particles appeared to bounce off the gold foil rather than pass through it. It took Rutherford two years to digest, confirm, reconfirm and then to announce what this all meant. In Rutherford's words:

It was quite the most incredible event that has ever happened to me in my life. It was almost as incredible as if you fired a 15-inch shell at a piece of tissue paper and it came back and hit you. On consideration, I realized that this scattering backward must be the result of a single collision, and when I made calculations I saw that it was impossible to get anything of that order of magnitude unless you took a system in which the greater part of the mass of the atom was concentrated in a minute nucleus. It was then that I had the idea of an atom with a minute massive center, carrying a charge.

[Continued in part here]

Plum Pudding

The more important fundamental laws and facts of physical science have all been discovered, and these are now so firmly established that the possibility of their ever being supplanted in consequence of new discoveries is exceedingly remote.... Our future discoveries must be looked for in the sixth place of decimals.
- Albert. A. Michelson, speech at the dedication of Ryerson Physics Lab, U. of Chicago 1894

The following year, Roentgen discovered X-rays; a year later, in 1896, Becquerel discovered radioactivity; and J.J. Thomson electrified physics in 1897 when he announced that cathode "rays" were really beams of electrons or what he called "corpuscles."

Thomson knew as much as anyone about electricity and its conduction--that electricity could flow here and there like invisible water and it could even be tamed and put to use. The electron, named after the Greek word for amber, had even been proposed before but had remained safely ensconced in matter. Thomson disclosed it. Disrobed it. What the electron lost in privacy, it gained in primacy and notoriety. Alone and naked for the first time, the electron succumbed to further scrutiny--first its mass-to-charge ratio was measured by Thomson. Soon after, it was actually weighed by Millikan (ironically at the University of Chicago--see quote above). But the real shocker at the time was that atoms were divisible--they were not a-tomos. This destroyed a comfortable notion of integrity.

JJ Thomson. Note the photograph (second from right) which is an early X-ray of the hand of Frau Roentgen

Knowing that he could strip off little negative bits, but not having a working notion of the countervailing positive portion which was surely left behind, Thomson theorized that electrons were uniformly sprinkled in a positively-charged, amorphous medium. The model was dubbed Plum Pudding. And why not? Thompson went with what he knew.  He would have overreached any data to have proposed anything else. And so, for the interregnum roughly corresponding to the Edwardian era—until Ernest Rutherford undid it—the atomic model looked like this:

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Suggested reading: history of the electron

This story continues here: link

I thought this was profoundly cool:

In quantum mechanics one replaces the word 'orbit' with orbital, a word introduced by R.S. Mulliken who defined it in a simple way by saying that an orbital is as much like an orbit as quantum mechanics permits.

You see, Bohr's planetary model of an electron orbiting the nucleus (the iconic "atomic" symbol) was undone by Heisenberg. There can be no precisely defined position and energy for an electron as there is for a planet. It's a blur. So you can't really say that the electron orbits the nucleus even though you want to think that it does.  That's what Mulliken was trying to convey.

How the past gets Bury'd

I love stories like this one about the man who first noticed and explained what's behind my Rime of the Ancient Elements:

...an alternative proposal was put forth in 1921 by Charles Rugeley Bury (1890-1968), who was a lecturer at the University College of Wales at Aberystwyth. The scheme that he described succinctly in a mere seven pages is essentially the scheme to be found in modern introductory textbooks of chemistry and physics. He deduced from the chemical evidence that the electrons are arranged in successive layers containing 2, 8, 18, and 32 electrons. He gave a clear discussion of the electronic arrangements in the actinides and lanthanides, and even made some predictions (inevitably but not quite correct) for the transuranic elements.
Bury's scheme was reproduced in The Electronic Theory of Valency by Nevil Vincent Sidgwick (1873-1952); this was an important book that first appeared in 1927 and which interpreted the chemical behavior of the elements in terms of their electronic configurations. Sidgwick acknowledged the important contribution of Bury, but almost all subsequent accounts have failed to do so and Bury's name is now almost entirely forgotten.

~Keith J. Laidler, The World Of Physical Chemistry, Oxford University Press: New York, 1993

I can't even find a photo of Bury on the Internet. :(

Let's take a closer look at those copper atoms

How small can we see? Pretty small, it turns out. We can see atoms (see above)--not with light but with electrons (light is too crude of a yardstick and can't "measure-down" to the job). In Scanning Electron Tunneling Microscopy (STM), a tiny metal wand just an atom or two thick approaches a surface. Electrons, dripping from the tip of the sweeping probe, jump to a surface below, feeding signal back and mapping the atomic topography:

original

Successive traces of electronic signals become a "photo" of the surface. The way STM works reminds me of the spark of life implied so long ago here. The technique is more fully explained here.

Suppose we could zoom a microscope down onto a pure copper surface to find out what's really there. I mean really there there. We'd find, even for ultra pure copper--heterogeneity. What looks the same is really different. No matter where we look, about one in three copper atoms has two "extra" neutrons because native copper comes in two isotopic flavors: ⁶³Cu and ⁶⁵Cu.

A while back, Michael Haz mentioned that pure copper native to Upper Michigan was distinguishable from pure copper native to South America. It's true. Copper sources have isotopic signatures. The natural ratio of the two copper isotopes varies slightly from place to place for various reasons. The reason(s) why they vary are complex and altogether unimportant here. The point is that they differ and they do so in a way that can be reliably measured--like fingerprints. A similar isotopic method has been used to trace the influx of South American silver into European coinage: link

Bondage Is A Two-Way Street

The simple "one-way" notion of chemical bonding described back here is part of the "lone pair theory" developed by G.N. Lewis and N.V. Sidgwick. According to that theory, a neutral molecule such as ammonia donates electrons from its lone pair to a metallic Lewis acid.  But things like ethylene, not having any lone pairs, confounded the theory, since they too formed neutral metal complexes very similar to ammonia-metal complexes.

In 1935, Linus Pauling introduced the novel concept of backbonding to explain the shorter than expected Ni-C bonds observed in the electron diffraction structure of Ni(CO)₄.  Like many concepts in chemistry, backbonding is better illustrated than described:

In this simplified scheme above, CO gives electronic juice to the metal's empty and receptive d-orbital (left-hand side). At the same time, the metal gives back electrons to the CO (right-hand side) using a different full d-orbital: the two sketches overlap. They are synergistic.

Pigments of My Imagination

I got sidetracked by vacation and few other things and lost my way regarding the chemical elements. The following inorganic pigments are mostly familiar.

Red is for red and white lead in striped lighthouses and also miniature manuscripts. The red color comes from lead tetroxide and the stark white comes from lead carbonate. Both pigments are impervious to the elements which is precisely why Michael Faraday chose them to coat Britain's lighthouses.
Red is also for Barn Red. Farmers in Europe started this tradition by adding ground up rust to the linseed oil they used to protect their barns and sheds (the iron inhibits mold).

Orange is for terracotta roof tiles: The color comes mainly from iron oxides.

Yellow is for yellow school buses.  Originally the pigment came from lead chromate (the color comes from the chromate, not the lead). It too was impervious to the elements. Lead chromate is no longer used to paint buses, but the traditional color stuck with us.

Green is for emeralds. Beryl and emerald are essentially the same material, viz., Be₃Al₂Si₆O₁₈. The only difference is that emerald also contains about 2% chromium, the source of its green color. Chromium also makes rubies red, and sapphires blue.  How does the same element do that?

Blue is for the Prussian Blue. I wrote about this back here. Gun bluing, a form of metal passivation, is another iron coating in disguise. Blue is also for cobalt blue.  As the saying goes: if it's blue, it's cobalt (II).

Indigo is for itself. Its color is challenged by some as a separate distinct color: link The most vivid indigo colors I ever saw were solvated electrons trapped as either sodium electride or as sodium benzophenone. What do electrons really look like? link

Violet is for purple permanganate, KMnO₄ which is actually pinkish purple but I couldn't think of a better example. Can you?

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.

Argon Idly Watches The Clouds Go By

Argon: From the Greek word αργον, neut. of αργος [argos] "idle," from α- "without" + εργον "work." = lazy, inactive. Link

Argon is not completely inert. Voracious hydrogen fluoride coaxes some electronic juice out of it, but the two stay coupled only when frozen. Moving further down to krypton and especially to xenon, there is an increasing willingness to redistribute electrons among the noble gas atoms, a consequence of their electronic wealth being more remote from their core and thus more easily removed. 
 
Argon makes up nearly 1 percent of the atmosphere, making it almost 25 times more abundant than carbon dioxide, that vile and evil greenhouse gas. So why is lazy and shiftless argon not implicated in global warming?  For that matter, why isn't air itself (N₂ and O₂) blamed? And why is good ol' water vapor given a pass by the warmists? Those questions have both easy and inconvenient answers.

Greenhouse gases are invisible but retain heat. Argon, being just an atom, never quivers internally, which is how gas molecules absorb and trap heat. So argon has no real greenhouse gas capacity. Nitrogen and oxygen also absorb little heat, even though there are trillions and trillions tons more of them up there. Carbon dioxide absorbs infra red radiation (heat), the sine qua non signature of a greenhouse gas. But water vapor is not only a "better" greenhouse gas than carbon dioxide is--there are also many tons more of it in the sky! (methane is even better than water at greenhouse gassing, but there is so little methane in the air that the point is moot).

So water vapor is by far the most important greenhouse gas. But water vapor also makes clouds which reflect sunlight. That makes clouds the white elephant in the room that the warmists don't really like to talk about. Back in the old days, when environmentalism wasn't so fixated on carbon dioxide, things were more fair and balanced:

If large amounts of carbon dioxide enter the air, then it is quite obvious that a rise in worldwide temperature could result, bringing about the the melting of the polar ice caps. However, an increase in temperatures would also lead to an increased rate of evaporation; with more water vapor in the air, cloudiness would increase. This in turn would mean an increase in reflectivity of insolation, so that less of the sun's energy would reach the earth. The lower temperatures that would result could eventually produce another ice age. Thus we are left with the perplexing thought that increased pollution could cause either a glacial invasion or a worldwide rise in sea levels that could inundate millions of miles of dry land presently in use.

Burrus, T.L; Spiegel, H.J. Earth In Crisis: An Introduction To The Earth Sciences: C. V. Mosby Company: St Louis, 1976 

Talk about putting a damper on global warming.

[UPDATE: link]

Electrons Have Consequences

The valence electrons of lithium and beryllium metal are spherically shaped and easily lost. Once lost, the remaining two electrons revert back to being helium-like electrons except that the kernel, being laden with more charge than helium, sucks in the remaining two even closer. This explains the extremely small sizes of both Li⁺ and Be²⁺ and ultimately why lithium is such an effective battery material and why even tinier beryllium is found in many brilliant gemstones.

Things change dramatically when we move on to boron, a favorite element of mine. The electrons actually reach out further and take shapes.

Conversations with Henry: More Nodes for Nerds

[This post is a continuation-in-part of this one: link]


Henry: So after helium comes lithium with three electrons. That third electron must go into a new and different orbital called the 2s orbital.

Me:  The 2s orbital is like the 1s orbital except it's bigger, right?

Henry:  Not exactly. It's not like those Russian matrushka dolls where the next bigger shell simply encompasses the previous one. The 2s orbital interleaves the 1s orbital so that its electrons can stay closer to the core without getting in the way of the others. Likewise the 3s orbital interleaves the 2s and the 1s. Look at these cross-sections:

original

Me:  Why are you even showing me this stuff?  Trooper York says he hates chemistry.

Henry:  I'm just trying to explain why the toy metals like lithium, sodium, and potassium are so boring -- not the whole of chemistry.

Neither a Borrower Nor a Lender of Electrons Be

Neither a borrower nor a lender be;
For loan oft loses both itself and friend,
And borrowing dulls the edge of husbandry.
This above all: to thine own self be true,
And it must follow, as the night the day,
Thou canst not then be false to any man.

~Act I, Scene 3 of William Shakespeare's Hamlet

Polonius was speaking of money or gold, giving advice to his own son Laertes. But what sort of miserable person never borrows nor lends money?  A King? Nobility?

The noble gas helium neither borrows nor lends electrons. The price it pays is lonely chemical stability. Helium is the most noble of the noble gases, grudgingly condensing to liquid only at extremely low temperatures.

Hydrogen is the the most common element in the universe and it freely gives, takes, and shares electrons with others. It is the most promiscuous element, forming compounds with practically all other elements except the noble gases.

Those very first two elements display the full range of chemical reactivity and stability--another reason why they sit atop the Periodic Table at opposite ends, bracketing the whole thing as it were. And it's all done with the simplest spherical orbital -- the lowly 1s orbital. Every other heavier element has those same electrons at their very core too. But they aren't part of chemistry -- they're just there -- an inert core. And they're not mere abstractions either--they're part of me as well.