Candle, Candle, Burning Bright

<chirp, chirp> “Moire here.”

“Hi, Sy, it’s Susan Kim. I did a little research after our chat. The whale oil story isn’t quite what we’re told.”

“Funny, I’ve been reading up on whales, too. So what’s your chemical discovery?”

“What do we get from a fire, Sy?”

“Light, heat and leftovers.”

“Mm-hm, and back in 18th Century America, there was plenty of wood and coal for heat. Light was the problem. I can’t imagine young Abe Lincoln reading by the flickering light of his fireplace — he must have had excellent eyesight. If you wanted a mostly steady light you burned some kind of fat, either wax candles or oil lamps.”

“Wait, aren’t fat and wax and oil three different things?”

“Not to a chemist. Fat’s the broadest category, covers molecules and mixtures with chains of ‑CH2‑ groups that don’t dissolve in water. Maybe the chains include a few oxygen atoms but the molecules are basically hydrocarbons. Way before we knew about molecules, though, we started classifying fats by whether or not the material is solid at room temperature. Waxes are solid, oils are liquid. You’re thinking about waxy‑looking coconut oil, aren’t you?”

“Well….”

“Coconuts grow where rooms are warm so we call it an oil, OK? I think it’s fun that you can look at a molecular structure and kind of predict whether the stuff will be waxy or oily.”

“How do you do that?”

“Mmm… It helps to know that a long chain of ‑CH2‑ groups tends to be straight‑ish but if there’s an ‑O‑ link in the chain the molecule can bend and even rotate there. Also, you get a kink in the chain wherever there’s a –CH=CH– double bond. We call that a point of unsaturation.”

“Ah, there’s a word I recognize, from foodie conversations. Saturated, unsaturated, polyunsaturated — that’s about double bonds?”

“Yup. So what does your physicist intuition make of all that?”

“I’d say the linear saturated molecules ought to pack together better than the bendy unsaturated ones. Better packing means lower entropy, probably one of those solid waxes. The more unsaturation or more ‑O‑ links, the more likely something’s an oil. How’d I do?”

“Spot on, Sy. Now carry it a step further. Think of a –CH2– chain as a long methane. How do suppose the waxes and oils compare for burning?”

“Ooo, now that’s interesting. O2 has much better access to fuel molecules if they’re in the gas phase so a good burn would be a two‑step process — first vaporization and then oxidation. Oils are already liquid so they’d go gaseous more readily than an orderly solid wax of the same molecular weight. Unless there’s something about the –O– links that ties molecules together…”

“Some kinds have hydrogen-bond bridging but most of them don’t.”

“OK. Then hmm… Are the double-bond kinks more vulnerable to oxygen attack?”

“They are, indeed, which is why going rancid is a major issue with the polyunsaturated kinds.”

“Oxidized hydrocarbon fragments can be stinky, huh? Then I’d guess that oil flames tend to be smellier than wax flames. And molecules we smell aren’t getting completely oxidized so the flame would probably be smokier, too. And sootier. Under the same conditions, of course.”

“Uh-huh. Would you be surprised if I told you that flames from waxes tend to be hotter than the ones from oils?”

“From my experience, not surprised. Beeswax candlelight is brighter and whiter than the yellow‑orange light I saw when the frying oil caught fire. Heat glow changes red to orange to yellow to white as the source gets hotter. Why would the waxes burn hotter?”

“I haven’t seen any studies on it. I like to visualize those straight chains as candles burning from the ends and staying alight longer than short oil fragments can, but that’s a guess. Ironic that a hydrogen flame is just a faint blue, even though it’s a lot hotter than any hydrocarbon flame. Carbon’s the key to flamelight. Anyway, the slaughter started when we learned a mature sperm whale’s head holds 500 gallons of waxy spermaceti that burns even brighter than beeswax.”

~~ Rich Olcott

  • Whale image adapted from a photo by Gabriel Barathieu CC BY SA 2.0

The Venetian Blind Problem

Susan Kim gives me the side‑eye. “Sy, I get real suspicious when someone shows me a graph with no axis markings. I’ve seen that ploy used too often by people pushing a bias — you don’t know what happens offstage either side and you don’t know whether an effect was large or small. Your animated chart was very impressive, how that big methane infrared absorption peak just happens to fill in the space between CO2 and H2O peaks. But how wide is the chart compared to the whole spectrum? Did you cherry‑pick a region that just happens to make your point?”

“Susan, how could you accuse me of such underhanded tactics? But I confess — you’re right, sort of. <more tapping on Old Reliable’s keyboard> The animation only covered the near‑IR wavelengths from 1.0 to 5.0 micrometers. Here’s the whole strip from 0.2 micrometers in the near UV, out to 70 micrometers in the far IR. Among other things, it explains the James Webb Space Telescope, right, Al?”

Spectrum of Earth’s atmosphere. Adapted
under the Creative Commons 3.0 license
from Robert Wohde’s work
with the HITRAN2004 spectroscopic database,

“I know the Webb’s set up for IR astronomy from space, Sy. Wait, does this graph say there’s too much water vapor blocking the galaxy’s IR and that’s why they’re putting the scope like millions of miles away out there?”

“Not quite. The mission designers’ problem was the Sun’s heat, not Earth’s water vapor. The solution was to use Earth itself to shield the device from the Sun’s IR emissions. The plan is to orbit the Webb around the Earth‑Sun L2 point, about a million miles further out along the Sun‑Earth line. Earth’s atmosphere being only 60 miles thick, most of it, the Webb will be quite safe from our water molecules. No, our steamy atmosphere’s only a problem for Earth‑based observatories that have to peer through a Venetian blind with a few missing slats at very specific wavelengths.”

“Don’t forget, guys, the water spectrum is a barrier in both directions. Wavelengths the astronomers want to look at can’t get in, but also Earth’s heat radiation at those wavelengths can’t get out. Our heat balance depends on the right amount of IR energy making it out through where those missing slats are. That’s where Sy’s chart comes in — it identifies the wavelengths under threat by trace gases that aren’t so trace any more.”

“And we’re back to your point, Susan. We have to look at the whole spectrum. I heard one pitch by a fossil fuel defender who based his whole argument on the 2.8‑micrometer CO2 peak. ‘It’s totally buried by water’s absorption,‘ he claimed. ‘Can’t possibly do us any further damage.’ True, so far as it goes, but he carefully ignored CO2‘s other absorption wavelengths. Pseudoscience charlatan, ought to be ashamed of himself. Methane’s not as strong an absorber as CO2, but its peaks are mostly in the right places to do us wrong. Worse, both gas concentrations are going up — CO2 is 1½ times what it was in Newton’s day, and methane is 2½ times higher.”

“Funny how they both go up together. I thought the CO2 thing was about humanity burning fossil fuels but you said methane operations came late to that game.”

“Right on both counts, Al. Researchers are still debating why methane’s risen so bad but I think they’re zeroing in on cow gas — belches and farts. By and large, industry has made the world’s population richer over the past two centuries. People who used to subsist on a grain diet can now afford to buy meat so we’ve expanded our herds. Better off is good, but there’s an environmental cost.”

Al gets a far-away look. “Both those gases have carbon in them, right? How about we burn methane without the carbon in, just straight hydrogen?”

Susan gets excited. “Several groups in our lab are working on exactly that possibility, Al. The 2H2+O2→2H2O reaction yields 30% more energy per oxygen atom than burning methane. We just need to figure out how to use hydrogen economically.”

~~ Rich Olcott

Going from Worse to Bad

Al delivers coffees to our table, then pauses. “Why methane?”

Susan Kim looks up from her mocha latte. “Sorry?”

“Why all the fuss about methane all of a sudden? I thought carbon dioxide was the baddie. Everybody’s switching from coal to natural gas which they say is just methane and now that’s a bad thing, too. I’m confused. You’re a chemist, unconfuse me.”

“You’re right, there’s mixed message out there. Here’s the bottom line. Methane’s bad, but coal’s a worse bad.”

“OK, but why?”

“Pass me a paper napkin so I can write down the chemical reactions. When we look at them in detail there’s all kinds of complicated reaction paths, but the overall processes are pretty simple. The burnable part of coal is carbon. In an efficient coal‑fired process what happens is
  C + O2 → CO2 + energy.
The C is carbon, of course and O2 is an oxygen molecule, two atoms linked together. Carbon atoms weigh 12 and each oxygen atoms weighs 16, so 12 grams of carbon produces 12+(2×16)=44 grams of CO2. Scaling up, 12 tons of carbon produces 44 tons of CO2 and so on. The energy scales up, too. and that’s what heats the boilers that make the steam that spins the turbines that make electricity.”

“I heard a couple of weasel words but go on to methane.”

“You caught them, eh? They’re important weasels and we’ll get to them. OK, methane is CH4 and its overall burn equation is
  CH4 + 2O2 → CO2 + 2H2O + energy.
Oxidizing those hydrogens releases about twice as much energy per carbon as the coal reaction does.”

“Already I see one big advantage for methane — more bang per CO2. So about those weasels…”

“Right. Well, coal isn’t just pure burnable carbon. It’s 350‑million‑year‑old trees and ferns and animal carcasses and swamp muck and mineral sediments, all pressure‑baked together. There’s sulfur and nitrogen in there, mixed in with nasty elements like mercury and arsenic.”

“The extras go up the smokestack along with the CO2, huh? Bad, for sure.”

“The good news is that coal-burning power plants are under the gun to clean up those emissions. The bad news is that effective mitigation technologies themselves cost energy. That lowers the net yield. But the inefficiency gets worse. Think coal trains.”

“Yeah, half the time I get held up on the way home by one of those hundred‑car strings, either full-up heading to the power plant or empties going back for another load.”

“Mm-hm. Transporting coal takes energy, and so does mining it and crushing it and pre‑treating to get rid of dirt and then taking care of the ashes. Even less net energy output per ton of smokestack CO2, even worse inefficiency. See why coal’s on its way out?”

“I guess all that didn’t matter when it was cheap to dig up and there wasn’t much competition.”

“You put your finger on it, Al. Coal got its foot in the door with steam engines 300 years ago when about the only other things you could burn were wood and whale oil. Crude oil got big in the mid‑1800s but it had to be refined and that made it expensive. Cheap natural gas wasn’t really a thing until fracking came along 50 years ago, but that brought a different set of issues.”

“Yeah, I’ve seen videos of people lighting their kitchen sink water on fire. And wasn’t there an earthquake thing in Oklahoma?”

“That was an interesting situation. Oklahoma’s in the middle of the continent, not a place you’d expect earthquakes, but they began experiencing flurries of shallow ones in 2011. The fracking process starts with water pumped at high pressure into gas-bearing strata to loosen things up. People suspected fracking was connected to the earthquakes. It was, but only indirectly. When fracked gas comes out of a well, water does, too. The rig operators pump that expelled water down old oil wells. Among other things, the state’s Corporation Commission is in charge of their hydrocarbon production. When the Commission ordered a 60% cut in the waste‑water down‑pumping, the earthquake rate dropped by 90%. Sometimes regulations are good things, huh?”

~~ Rich Olcott

Elementary History

<chirp, chirp> “Moire here.”

“Hi, Sy, it’s Susan.”

“Well, hello. Good to hear from you. What’s up?”

“I’m out here on my back porch, fooling around on my laptop. It’s too nice to work in the lab today.”

“I agree with you. I’m outside, too, enjoying the Springtime. What’s your fooling around?”

“I found a discovery date list for all the chemical elements. Guess which element was the first that humanity worked with in pure form?”

“Mmm, I’d say carbon, in charcoal.”

“Nope, it’s copper.”

“Copper?”

“Mm-hm. Or maybe gold. They both occur as the raw metal but copper’s more common. There was a Copper Age before the Bronze age. The dates are fuzzy because they depend on what the archaeologists find after site scavengers have been there. I’m sending you the first few rows from the list.

Cumulative
Count
Element
(Symbol)
Atomic
number
Estimated
years ago
1Copper (Cu)2910000
2Lead (Pb)826000
3Carbon (C)65750
4Silver (Ag)475000
5Tin (Sn)505000
6Antimony (Sb)515000
7Gold (Au)794500
8Iron (Fe)264000
9Mercury (Hg)803500
10Sulfur (S)162500

“You can win most of them from the right ore with relatively simple processing. It makes sense they’re the ones we got to first.”

“Susan, I’m surprised it took a thousand years to realize you can get sulfur from cinnabar ore at the same time you’re cooking the mercury out of it. I wouldn’t want to be downwind from that process or most of the rest.”

“Sure not. I’ll bet there just wasn’t much interest in sulfur until the alchemists started playing with it. Anyhow, I dumped the element data into a spreadsheet and got some fun facts when I graphed it. Look at this. Eight thousand years for 10 elements through sulfur, then 1800 years of nothing. Arsenic doesn’t show up until the Thirteenth Century when I guess royalty started using it to poison each other. And phosphorus — have you read Neal Stephenson’s Baroque Cycle trilogy?”

“Yes, and I know the episode you’re thinking of, where the hero routed a gang at night by coating himself with glowing phosphorus and bursting out of a cave pretending to be a demon. Stephenson put a lot of words into describing how factories obtained mercury and phosphorus back then.”

“Stephenson puts a lot of words into most everything nerdy. That’s why I enjoy reading him. Oh-ho, now I know how you knew about cinnabar being the source for mercury.”

“Hey, Susan, I don’t only do Physics, but yeah, that was from another Baroque Cycle episode. … Looking at your graph here — things certainly took off at the start of the Eighteenth Century.”

“Yes, indeed. Seventy-four elements, everything that’s not radioactive plus a couple that are. I get a chuckle from cobalt being the first element in that wave after phosphorus. You know the story?”

“What story is that?”

“Seventeenth Century miners kept digging up nasty rocks that emitted poisonous gas when smelted along with the desirable copper and nickel ores. They called the bad stuff kobald Oren, German for ‘goblin ores.’ When a Swedish chemist finally purified the material he simply re-spelled the adjective and called the metal cobalt. I love the linkage with Stephenson’s fictional phosphorus-covered demon.”

“Cute. Why the break between rhenium and technitium?”

“That second wave after 1935 is all radioactives. Funny how the timing paralleled Seaborg’s research career even though he never got involved with technitium, the first artificially-produced element. Imagine being the discoverer of ten different elements.”

“Seaborg practically invented that funny bottom row of the Periodic Table, didn’t he?”

“Oh, yes. Not only did he discover or co-discover more than half of those elements, he was the one who proposed setting off the entire group as Actinides, in parallel with the Lanthanides above them. Oh, that reminds me, I meant to show you the other display I built. You’ve probably never seen one like this.”

“Whoa, you’ve colored each element block by how long we’ve known about it. That’s not the kind of thing you can do with crayons.”

“No, I had to do some programming to get the right tints.”

“What’s the little star for in the middle of the scale?”

“That’s when Mendeleev first proposed the Table, smack in the logarithmic center of my timeline. Don’t you love it?”

~~ Rich Olcott

Getting over The Hill

“You guys want refills? You look like you’re gonna be here a while.”

“Yes, thanks, Al. Your lattes are sooo good. And can we have some more paper napkins?”

“Sure, but don’t let ’em blow away or nothin’, OK? I hate havin’ to pick up the place.”

“They’ll stay put. Just a half-cup of mud for me, thanks.”

The Spring breeze has picked up a little so we hitch our chairs closer together. Susan reaches for a paper napkin, draws a curve. “Here’s another pattern you haven’t featured yet, Sy. It’s in every chemist’s mind when they think about reactions.”

“OK, I suppose this is molecules A and B on one side of some sort of wall and molecule C on the other.”

“It’ll be clearer if I label the axes. It’s a reaction between A and B to make C. The horizontal axis isn’t a distance, it’s a measure of the reaction’s progress toward completion. Beginning molecules to the left, completed reaction to the right, transition in the middle, see? The vertical axis is energy. We say the reaction is energetically favored because C is lower than A and B separately.”

“Then what’s the wall?”

“We call it the barrier. It’s some additional dollop of energy that allows the reaction happen. Maybe A or B have to be reconfigured before they can form an A~B transition state. That’s common in carbon chemistry, for instance. Carbon usually has four bonds, but you can get five‑bonded transition states. They usually don’t last very long, though.”

“Right, carbon and its neighbors prefer the tetrahedral shape. Five‑bonded carbon distorts the stable electron clouds. Heat energy shoves things into position, I suppose.”

“Often but hardy always. Especially for large molecules, heat’s more likely to jostle things out of position than put them together. That’d what cooking does.”

“The curve reminds me of particle accelerator physics, except it takes way more energy to overcome nuclear forces when you mash sub‑atomic thingies together.”

“Oh, yes, very similar in terms of that general picture — except that the C side could be multiple emitted particles.”

“So your sketch covers a processes everywhere, not just Chemistry. They all have different barrier profiles, then?”

“Of course. My drawing was just to give you the idea. Some barriers are high, some are low, either side may rise or fall exponentially or by some power of the distance, some are lumpy, it all depends. Some are even flat.”

“Flat, like no resistance at all?”

“Oh, yes. Hypergolic rocket fuel pairs ignite spontaneously when they mix. Water and alkali metals make flames — have you seen that video of metallic sodium dumped into a lake and exploding like mad? Awesome!”

“I can imagine, or maybe not. If heat energy doesn’t get molecules over that barrier, what does?”

“Catalysts, mostly. Some do their thing by capturing the reactants in adjacent sites, maybe doing a little geometry jiggling while they’re at it. Some play games with the electron states of one or both reactants. Anyhow, what they accomplish is speeding up a reaction by replacing the original barrier with one or more lower ones.”

“Wait, reaction speed depends on the barrier height? I’d expect either go or no‑go.”

“No, it’s usually more complicated than that. Umm … visualize tossing a Slinky toy into the air. Your toss gives it energy. Part of the energy goes into lifting it against Earth’s gravity, part into spinning motion and part into crazy wiggles and jangling, right? But if you toss just right, maybe half of the energy goes into just stretching it out. Now suppose there’s a weak spot somewhere along the spring. Most of your tosses won’t mess with the spot, but a pure stretch toss might have enough energy to break it apart.”

“Gotcha, the transition barrier might be a probability thing depending on how the energy’s distributed within A and B. Betcha tunneling can play a part, too.”

“Mm? Oh, of course, you’re a Physics guy so you know quantum. Yes, some reactions depend upon electrons or hydrogen atoms tunneling through a barrier, but hardly ever anything larger than that. Whoops, I’m due back at the lab. See ya.”

<inaudible> “Oh, I hope so.”

~~ Rich Olcott

The Edge of Pinkness

Susan Kim takes a sip of her mocha latte. eyes me over the rim. “That’s quite a set of patterns you’ve gathered together, Sy, but you’ve left out a few important ones.”

“Patterns?”

A log-linear plot

“Regularities we’ve discovered in Nature. You’ve written about linear and exponential growth, the Logistic Curve that describes density‑limited growth, sine waves that wobble up and down, maybe a couple of others down‑stack, but Chemistry has a couple I haven’t seen featured in your blog.”

“Such as?”

“Log-linear relationships are a biggie. We techies use them a lot to handle phenomena with a wide range. Rather than write 1,000,000,000 or 109, we sometimes just write 9, the base‑10 logarithm. The pH scale for acid concentration is my favorite example. It goes from one mole per liter down to ten micro‑nanomoles per liter. That’s 100 to 10-14. We just drop the minus sign and use numbers between 0 and 14. Fifteen powers of ten. Does Physics have any measurements that cover a range like that?”

“A handful, maybe, in theory. The limitation is in confirming the theory across a billion-fold range or wider. Atomic clocks that are good down to the nanosecond are our standards for precision, but they aren’t set up to count years. Mmmm … the Stefan‑Boltzmann Law that links an object’s electromagnetic radiation curve to its temperature — our measurements cover maybe six or seven powers of ten and that’s considered pretty good.”

“Pikers.” <but I like the way she grins when she says it>

“I took those Chemistry labs long ago. All I remember was acids were colorless and bases were pink. Or maybe the other way around.”

“You’ve got it right for the classic phenolphthalein indicator, but there are dozens of other indicators that have different colors at different acidities. I’ll tell you a secret — phenolphthalein doesn’t kick over right at pH 7, the neutral point. It doesn’t turn pink until the solution’s about ten times less acidic, near pH 8.”

Adapted from this file by Damitr, CC BY-SA 4.0

“So all my titrations were off by a factor of ten?”

“Oh, no, that’s not how it works. I’m going to use round numbers here, and I’ll skip a couple of things like the distinction between concentration and activity. Student lab exercises generally use acid and base concentrations on the order of one molar. For most organic acids, that’d give a starting pH near 1 or 2, way over on the sour side. In your titration you’d add base, drop by drop, until the indicator flips color. At that point you conclude the amounts of acid and base are equivalent, not by weight but by moles. If you know the base concentration you can calculate the acid.”

“That’s about what I recall, right.”

“Now consider that last drop. One drop is about 50 microliters. With a one‑molar base solution, that drop holds 50 nanomoles. OK?”

<I scribble on a paper napkin> “Mm-hm, that looks right.”

“Suppose there’s about 50 milliliters of solution in the flask. Because we’re considering the last drop, the solution in the flask must have become nearly neutral, say pH 6. That means the un‑neutralized acid concentration was 10-6 moles per liter, or one micromolar. Fifty milliliters at one micromolar concentration is, guess what, 50 nanomoles. Your final drop neutralizes the last of the acid sample.”

“So the acid concentration goes to zero?”

“Water’s not that cooperative. Water molecules themselves act like acids and bases. An H2O molecule can snag a hydrogen from another H2O giving an H3O+ and an OH. Doesn’t happen often, but with 55½ moles of water per liter and 6×1023 molecules per mole there’s always a few of those guys hanging around. Neutral water runs 10-7 moles per liter of each, which is why neutral pH is 7. Better yet, the product of H3O+ and OH concentrations is always 10-14 so if you find one you can calculate the other. Take our titration for example. One additional drop adds 50 nanomoles more base. In 50 milliliters of solution that’s roughly 10-6+10-7 molar OH. Call it 1.1×10-6, which implies 0.9×10-8 molar H3O+. Log of that and drop the minus sign, you’re a bit beyond pH 8 which sends phenolphthalein into the pink side. Your titration’s good.”

I eye her over my mug of black mud. “A gratifying indication.”

~~ Rich Olcott

❄❅❆Snowflakes ❆❅❄

<chirp, chirp> “Moire here.”

“Uncle Sy! Uncle Sy! It’s snowing again!”

“Yes, Teena, I noticed. I’ll be over to help you build a snowman in a little while.”

“Yay! There’s so much snow coming down. I bet there’s a kazillion snowflakes!”

“Maybe even more. And no two of them are exactly alike.”

“Yeah, that’s what Mommy said. I went outside a while ago and caught a bunch on my coat sleeve like you showed me. All different shapes — stars and pencils and almost-round ones and spiky balls. I can’t remember them all. How do we know that they never match? Did someone look at them with a computer camera?”

“Whoa, that’s too big a job for even a really fast computer with a really good camera. No, it goes back to how snowflakes grow up.”

“Ha-ha, that’s funny! Little baby snowflake grows up to be a big Mommy snowflake!”

“Well, in a way that’s what happens. You know clouds are really made of teeny water droplets, right?”

“Yeah, Mommy says it’s a fog, but way up in the air. But the fluffy ones are pretty.”

“Yes they are, but inside some of the not-fluffy clouds it can be very cold and windy.”

“Danger cold?”

“Very danger cold. Cold enough for some of those teeny droplets to freeze and become ice droplets. When an ice droplet touches a water droplet they merge to make a bigger piece of ice. The winds blow the ice up and down between wet places and cold places inside the cloud over and over again. The piece of ice grows and grows until it gets so heavy it falls down out of the cloud.”

“Like a roller coaster! But wouldn’t that just make round ice? That’s not what I caught on my sleeve.”

“Sometimes it does. Remember that hail storm we had last year?”

“Oooo. Yeah, we got inside just in time. Those hailstones went pitter‑patter all over the sidewalk and the windows.”

“Just be very glad they were only pinkie‑nail‑sized. I was in a storm once where the hail was as bigger than your shooter marble. It made dents on my car.”

“WOW! That would hurt!”

“It certainly would. I hope you’re never in one of those ice storms, just stars‑and‑pencils snow like you saw on your sleeve. Stars‑and‑pencils happens when the winds inside the cloud are gentler and give the teeny ice droplets time to grow a different way.”

“Different how?”

“Want to do an experiment?”

“Over the phone?”

“Sure. Get your bag of marbles and a lid from one of your board game boxes. Say when you’re ready.”

“OK … ready!”

“OK, Put the lid on the floor face‑down but prop it up so one corner is lower than the other three.”

“Umm … ready!”

“Now slowly pour your marbles into the lid so they lie together in one layer. Slowly, we don’t want them going all over the floor.”

“That’d make Mommy mad. Ooo, pretty! They make a honeycomb pattern. I see a lot of hexa–, um…”

“Hexagons. Good girl, you did that just right. That pattern is a lot like how water molecules arrange themselves when they freeze. When a new molecule walks up to some ice, it tries to touch as many other molecules as it can. That automatically makes hexagons.”

“Oh! Teeny hexagons grow up to be snow hexagons! Ha-ha!!”

“Mm-hm, and depending on conditions some rows grow fast to make flat plate snowflakes or a different set of rows might grow quickly to make frilly stars.”

“But why don’t they all grow the same?”

“Because of how messy it is inside that cloud. Winds blowing up and down and sideways, wet places and not‑so‑wet places scattered all over everywhere. Two baby snowflakes starting right next to each other can wind up on opposite sides of the cloud with entirely different stories to tell.”

“But then how can different sides of the same snowflake be the same?”

“They’re on the same flake so they’re always close together as the flake grows. They don’t get a chance for different stories. OK, I just finished up. It’s snowman time.”

“Yay!”

Nope, ain’t gonna happen. Not with water, not with anything else.

~~ Rich Olcott

Only a H2 in A Gilded Cage

“OK, Susan, you’ve led us through doing high-pressure experiments with the Diamond Anvil Cell and you’ve talked about superconductivity and supermagnetism. How do they play together?”

“It’s early days yet, Sy, but Dias and a couple of other research groups may have brought us a new kind of superconductivity.”

“Another? You talked like there’s only one.”

“It’s one of those ‘depends on how you look at it‘ things, Al. We’ve got ‘conventional‘ superconductors and then there are the others. The conventional ones — elements like mercury or lead, alloys like vanadium‑silicon — are the model we’ve had for a century. Their critical temperatures are generally below 30 kelvins, really cold. We have a 60‑year‑old Nobel‑winning theory called ‘BCS‘ that’s so good it essentially defines conventional superconductivity. BCS theory is based on quantum‑entangled valence electrons.”

“So I guess the unconventional ones aren’t like that, huh?”

“Actually, there seem to be several groups of unconventionals, none of which quite fit the BCS theory. Most of the groups have critical temperatures way above what BCS says should be the upper limit. There are iron‑based and heavy‑metals‑based groups that use non‑valence electrons. There are a couple of different carbon‑based preparations that are just mystical. There’s a crazy collection of copper oxide ceramics that can contain five or more elements. Researchers have come up with theories for each of them, but the theories aren’t predictive — they don’t give dependable optimization guidelines.”

“Then how do they know how to make one of these?”

“Old motto — ‘Intuition guided by experience.’ There are so many variables in these complex systems — add how much of each ingredient, cook for how long at what temperature and pressure, chill the mix quickly or anneal it slowly, bathe it in an electrical or magnetic field and if so, how strong and at what point in the process… Other chemists refer to the whole enterprise as witch’s‑brew chemistry. But the researchers do find the occasional acorn in the grass.”

“I guess the high‑pressure ploy is just another variable then?”

“It’s a little less random than that, Sy. If you make two samples of a conventional superconductor, using different isotopes of the same element, the sample with the lighter isotope has the higher critical temperature. That’s part of the evidence for BCS theory, which says that electrons get entangled when they interact with vibrations in a superconductor. At a given temperature light atoms vibrate at higher frequency than heavy ones so there’s more opportunity for entanglement to get started . That set some researchers thinking, ‘We’d get the highest‑frequency vibrations from the lightest atom, hydrogen. Let’s pack hydrogens to high density and see what happens.'”

“Sounds like a great idea, Susan.”

“Indeed, Al, but not an easy one to achieve. Solid metallic hydrogen should be the perfect case. Dias and his group reported on a sample of metallic hydrogen a couple of years ago but they couldn’t tell if it was solid or liquid. This was at 5 megabars pressure and their diamonds broke before they could finish working up the sample. Recent work has aimed at using other elements to produce a ‘hydrogen‑rich’ environment. When Dias tested H2S at 1.5 megabar pressure, they found superconductivity at 203 kelvins. Knocked everyone’s socks off.”

“Gold rush! Just squeeze and chill every hydrogen‑rich compound you can get hold of.”

“It’s a little more complicated than that, Sy. Extreme pressures can force weird chemistry. Dias reported that shining a green laser on a pressurized mix of hydrogen gas with powdered sulfur and carbon gave them a clear crystalline material whose critical temperature was 287 kelvins. Wow! A winner, for sure, but who knows what the stuff is? Another example — the H2S that Dias loaded into the DAC became H3S under pressure.”

“Wait, three hydrogens per sulfur? But the valency rules—”

“I know, Sy, the rules say two per sulfur. Under pressure, though, you get one unattached molecule of H2 crammed into the space inside a cage of H2S molecules. It’s called a clathrate or guest‑host structure. The final formula is H2(H2S)2 or H3S. Weird, huh? Really loads in the hydrogen, though.”

“Jupiter has a humungous magnetic field and deep‑down it’s got high‑density hydrogen, probably metallic. Hmmm….”

~~ Rich Olcott

Diamonds in The Tough

“Excuse me, they said there’s a coffee shop over here somewhere. Could you please point me to it?”

“Sure. Al’s place is right around the next corner, behind the Physics building. I’ll walk you over there.”

“Oh, I don’t want to bother you.”

“No bother, it’s my coffee time anyway. Hi, Al, new customer for you.”

“Hi, Sy. What’ll it be, Ms … ?”

“I’m Susan, Susan Kim. A mocha latte, please, Al. And you’re Sy …?”

“Moire. Sy Moire, Consulting Physicist. Who’s the ‘they’ that told you about Al’s?”

“An office staffer in the Chemistry Department. I just joined the research faculty over there.”

Al’s ears perk up. “A chemist, at last! For some reason they don’t show up over here very much.”

“Hah, I bet it’s because they’re used to drinking lab coffee from beakers.”

“As a matter of fact, Sy, I do have a coffee beaker. A glass‑worker friend added a very nice handle to a 500‑milliliter beaker for me. It’s not unpacked yet which is why I was looking for a coffee shop. This latte is very good, Al, better than lab coffee any day.”

“Thanks. So what’s the news in Science, guys?”

“Mmm… On Mars, the Insight mission‘s ‘mole’ thermal probe has finally buried itself completely, on its way down we hope to its targeted 5‑meter depth. And the OSIRIS‑REx mission to Asteroid Bennu successfully collected maybe a little too much asteroid sample. One rock fragment blocked the sampler’s lid like a bit of souvenir sticking out of a tourist’s carry‑on bag. Fortunately the engineers figured out how to stow the stuff more neatly for the two‑year trip back home. How about in the Chemistry world, Susan?”

“Hmm… Ranga Dias and his team at the University of Rochester used a diamond anvil cell to—”

“Wait — a diamond anvil? Like the Village Blacksmith but made of diamond?”

“No, Al, nothing like that. Diamond is the hardest substance we know of, right? A DAC uses a pair of quarter‑carat gem‑quality diamonds pushing against each other to create a small volume of crazy high pressure in the space between them, up into the million‑atmosphere range. Here, I’ve got a gorgeous photo of one on my phone…

Diamond anvil cell, photo by J. Adam Fenster / University of Rochester

“To give you an idea of the scale, that square black gasket between the two diamonds is a piece of rhenium metal foil that’s a quarter of a millimeter thick. The reaction vessel itself is a hole they spark-drilled through the gasket. This is teeny, nanoliter chemistry.”

“OK, they’re small diamonds, but .. DIAMONDS! I bet they crack some of them. That’s got to be ex‑PENsive, our tax dollars going CRUNCH!.”

“Not really. You’re right, some do crack, up around the seven million atmosphere mark. But here’s the fun part — the researchers don’t pay market price for those diamonds. They come from the government’s stock of smuggled goods that Customs agents have confiscated at the border.”

“Why go to all that trouble? What’s wrong with test tubes and beakers?”

“Because not all chemistry takes place at atmospheric pressure, Sy. High pressure crams molecules closer together. They get in each other’s way, maybe deform each other enough to react in ways that they wouldn’t under conditions we’d call ‘normal.’ Even water has something like 17 different forms of ice under different pressure‑temperature conditions. The whole discipline of high‑pressure chemistry got started because the seismologists needed to know how minerals transform, melt, flow and react under stress. The thing about diamond is that it doesn’t transform, melt, flow or react.”

“Oo, oo, you can see through a diamond, sorta. I’ll betcha people pipe laser beams down them, right?”

“Absolutely, Al. Before lasers came along researchers were using regular light and optics to track events in a pressurized DAC. Lasers and fiber optics completely changed the game. Not just for observation — you can use intense light to heat things up, get them even closer to deep‑Earth conditions.”

“I suppose chemists are like physicists — once a new tool becomes available everybody dives in to play.”

“You know it. There’s thousands of papers out there detailing work that used a DAC.”

“So what did Dias report on?”

~~ Rich Olcott

The Sight And Sound of Snow

<ring> “Moire here.”

“Uncle Sy! Uncle Sy! It’s snowing! It’s snowing!”

“Yes, Teena, it started last night after you went to bed. But it’s real early now and I haven’t had breakfast yet. I’ll be over there in a little while and we can do snow stuff.”

“Yaaay! I’ll have breakfast, too. Mommie, can we have oatmeal with raisins?” <click>


<knock, knock> “Uncle Sy! You’re here! I wanna go sledding! Get my sled out, please?”

“G’morning, Sis. G’morning, Teena. Get your snowsuit and boots on, Sweetie. Want to come along, Sis? It’s a cold, dry snow, not much wind.”

“No, I’ll just stay warm and get the hot chocolate ready.”

“Bless you for that, Sis. OK, young’un, ready to go?”

“Ready! Pull me on the sled to the sledding hill, Uncle Sy!”


“Ooo, it’s so quiet. Why’s it always quiet when snow’s falling, Uncle Sy? Is the world holding its breath? And why is snow white? When I hold snow in my hand it melts and then it’s no-color.”

“Always the good questions. Actually, these two are related and they both have to do with the shape of snowflakes. Here, hold out your arm and let’s see if you can catch a few. No, don’t try to chase them, the breeze from your arm will blow them away. Just let them fall onto your arm. That’s right. Now look at them real close.”

“They’re all spiky, not flat and pretty like the ones in my picture book!”

“That’s because they grew fast in a really cold cloud and didn’t have time to develop evenly. You have to work slow to make something that’s really pretty.”

“But if they’re spiky like this they can’t lay down flat together and be cozy!”

“Ah, that’s the key. Fresh spiky snowflakes make fluffy snow, which is why skiers love it. See how the flakes puff into the air when I scuff my boot? Those tiny spikes break off easily and make it easy for a ski to glide over the surface. Your sled, too — you’ve grown so big I’d be hard-put to pull you over wet snow. That fluffiness is why <hushed voice> it’s so quiet now.”

“Shhh … <whispered> yeah … <back to full voice> Wait, how does fluffy make quiet?”

“Because sound waves … Have we talked about sound waves? I guess we haven’t. OK, clap your hands once.”

<CLAP!>

“Good. When your hands came together they pushed away the air molecules that were between them. Those molecules pushed on the next molecules and those pushed on the next ones on and on until they got to your ear and you heard the sound. Make sense?”

“Ye-aa-uh. Is the push-push-push the wave?”

“Exactly. OK, now imagine that a wave hits a wall or some packed-down icy snow. What will happen?”

“It’ll bounce off like my paddle-ball toy!”

“Smart girl. Now imagine that a wave hits fluffy snow.”

“Um … it’ll get all lost bouncing between all the spikes, right?”

“Perfect. That’s exactly what happens. Some of the wave is scattered by falling snowflakes and much of what’s left spreads into the snow on the ground. That doesn’t leave much sound energy for us to hear.”

“You said that snow’s white because of what snow does to sound, but look, it’s so bright I have to squint my eyes!”

“That’s not exactly what I said, I said they’re related. Hmm… ah! You know that ornament your Mommie has hanging in the kitchen window?”

“The fairy holding the glass jewel? Yeah, when the sunlight hits it there’s rainbows all over the room! I love that!”

A beam or white light passing through two prisms.  The first produces a spectrum and the second remixes the colors to white.

“I do, too. White light like sunlight has all colors in it and that jewel splits the colors apart so you can see them. Well, suppose that jewel is surrounded by other jewels that can put the colors together again. Here’s a picture on my cellphone for a clue.”

“White goes to rainbow and back to white again … I’ll bet the snowflakes act like little jewels and bounce all the colors around but the light doesn’t get trapped and it comes out and we see the WHITE again! Right?”

“So right that we’re going home for hot chocolate.”

“Yaaay!”

~~ Rich Olcott

PS – A Deeper Look.