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.

Never Chuck Muck at A Duck

Mr Richard Feder of Fort Lee NJ is in terrible shape. Barely halfway into our walk around the park’s lake, he flops onto a bench to catch his breath. The geese look on unsympathetically. “<puff, puff> I got another question, Moire. <wheeze> Why is water wet?”

He’s just trying to make conversation while his heart slows down but I take him up on it. “Depends on what you mean by ‘wet‘ — that’s a slippery word, can be a verb or an adjective or a noun. If you wet something, you’ve got a wet something. If there’s wet weather you go out in the wet. If you live in a wet jurisdiction you can buy liquor if you’re old enough. You can even have wet and dry molecules. Which are you asking about?”

That’s gotten him thinking, always a good sign. “Let’s start with the verb thing. Seems like that’s the key to the others.”

“So we’re asking, ‘Does water wet?‘ The answer is, ‘Sometimes,‘ and that’s where things get interesting. That duck over there, diving for something on the bottom, but when it comes back up again the water rolls off it like –“

“Don’t say it — ‘like water off a duck’s back‘ — yeah, I know, but I’m sweating over here and that ain’t rolling off. Why the difference?”

“Blame it on the Herence twins, Co and Addie.”

“Come again?”

“A little joke, has to do with two aspects of stickiness. Adherence is … you know adhesive tape?”

“Adhe — you playin’ word games, Moire?”

“No, really, adhesive and adherence are both about sticking together things that are chemically different, like skin and tape. Coherence is about stickiness between things that are chemically similar, like sweat and skin.”

“What makes things ‘chemically similar’?”

“Polarity. I don’t want to get into the weeds here –“

“Better not, the ground’s squishy over there.”

“– but there are certain pairs of atoms, like oxygen and hydrogen, where one atom pulls a small amount of electron charge away from the other and you wind up with part of a molecule being plus-ish and another part being minus-ish. That makes the molecule polar. Other pairings, like carbon and hydrogen, are more evenly matched. You don’t get charge separation from them and we call that being non-polar. Charge variation in polar molecules forces them to cluster together positive-to-negative. The electrostatic gang crowds out any nearby non-polar molecules.”

“What’s all that got to do with wetting?”

“Water’s all oxygen and hydrogen and quite polar. Water coheres to itself. If it didn’t you’d get rain-smear instead of raindrops. It also adheres to polar materials like skin and hair and bricks, so raindrops wet them. But it doesn’t adhere to non-polar materials like oil and wax. Duck feathers are oily so they shed water.”

“So that’s why the duck doesn’t get wet!”

“Not unless you throw detergent on him, like they have to do with waterfowl after an oil spill. Detergent molecules have a polar end and a non-polar end so they can bridge the electro divide. Rubbing detergent into a dirty bird’s sludgy oil coating lets water sink into the mess and break it up so you can rinse it off. The problem is that the detergent also washes off the good duck oil. If you let a washed-off duck go swimming too soon after his bath the poor thing will sink. You have to give him time to dry off and replenish his natural feather-oil.”

“Hey, you said ‘wet-and-dry molecules.’ How can they be both?”

“Because they’re really big, thousands of atoms if they’re proteins, even bigger for other kinds of polymers. Anything that large can have patches that are polar and other patches that are oily. In fact, patchwise polarity is critical to how proteins get their 3-D structure and do their jobs. A growing protein strand wobbles around like a spring-toy puzzle until positive bits match up with negative bits and oily meets up with oily. Probably water molecules sneak into the polar parts, too. The configuration’s only locked down when everything fits.”

“So water’s wet because water wets water. Hah!”

~~ Rich Olcott

  • Thanks to Museum visitor Jessie for asking this question.

Where would you put it all?

Vinnie’s a big guy but he’s good at fading into the background. I hadn’t even noticed him standing in the back corner of Cathleen’s impromptu seminar room until he spoke up. “That’s a great theory, Professor, but I wanna see numbers for it.”

“Which part of it don’t you like, Vinnie?”

“You made it seem so easy for all those little sea thingies to scrub the carbon dioxide out of Earth’s early atmosphere and just leave the nitrogen and oxygen behind. I mean, that’d be a lot of CO2. Where’d they put it all?”

“That’s a reasonable question, Vinnie. Lenore, could you put your Chemistry background to work on it for us?”

“Oh, this’ll be fun, but I don’t want to do it in my head. Mr Moire, could you fire up Old Reliable for the calculations?”

“No problem. OK, what do you want to calculate?”

“Here’s my plan. Rather than work with the number of tons of carbon in the whole atmosphere, I’ll just look at the sky-high column of air sitting on a square meter of Earth’s surface. We’ll figure out how many moles of CO2 would have been in that column back then and then work on how thick a layer of carbon stuff it would make on the surface. Does that sound like a good attack, Professor?”

“Sure, but I see a couple of puzzled looks in the class. You’d better say something about moles first.”

“Hey, I know about moles. Sy and me talked about ’em when he was on that SI kick. They’re like a super dozen, right, Sy?”

“Right, Vinnie. A mole of anything is 6.02×1023 of that thing. Eggs, atoms, gas molecules, even stars if that’d be useful.”

“Back to my plan. First thing is the CO2 was in that column back when. Maria, your chart showed that Venus’ atmospheric pressure is 100 times ours and Mars’ is 1/100 ours and each of them is nearly pure CO2, right? So I’m going to assume that Earth’s atmosphere was what we have now plus a dose of CO2 that’s the geometric mean of Venus and Mars. OK, Professor?”

“That’d be a good starting point, Lenore.”

“Good. Now we need the mass of that CO2, which we can get from the weight of the column, which we can get from the air pressure, which is what?”

Every car buff in the room, in chorus — “14½ pounds per square inch.”

“I need that in kilograms per square meter.”

“Strictly speaking, pressure’s in newtons per square meter. There’s a difference between weight and force, but for this analysis we can ignore that. Keep going, Lenore.”

“Thanks, Professor. Sy?”

“Old Reliable says 10194 kg/m².”

“So we’ve got like ten-thousand kilograms of CO2 in that really tall meter-square column of ancient air. Now divide that by, um, 44 to get the number of moles of CO2. No, wait, then multiply by 1000 because we’ve got kilograms and it’s 44 grams per mole for CO2.”

“232 thousand moles. Still sounds like a lot.”

“I’m not done. Now we take that carbon and turn it into coal which is solid carbon mostly. One mole of carbon from each mole of CO2. Take the 232 thousand moles, multiply by 12 grams, no make that 0.012 kilogram per mole –“

“2786 kilograms”

“Right. Density of coal is about 2 grams per cc or … 2000 kilograms per cubic meter. So. Divide the kilograms by 2000 to get cubic meters.”

“1.39 meters stacked on that square-meter base.”

“About what I guessed it’d be. Vinnie, if Earth once had a carbon-heavy atmosphere log-halfway between Venus and Mars, and if the sea-plankton reduced all its CO2 down to coal, it’d make a layer all over the planet not quite as tall as I am. If it was chalk it’d be thicker because of the additional calcium and oxygen atoms. A petroleum layer would be thicker, too, with the hydrogens and all, but still.”

Jeremy’s nodding vigorously. “Yeah. We’ve dug up some of the coal and oil and put it back into the atmosphere, but there’s mountains of limestone all over the place.”

Cathleen’s gathering up her papers. “Add in the ocean-bottom carbonate ooze that plate tectonics has conveyor-belted down beneath the continents over the eons. Plenty of room, Vinnie, plenty of room.”

~~ Rich Olcott

The Moon And Chalk

Cathleen’s talking faster near the end of the class. “OK, we’ve seen how Venus, Earth and Mars all formed in the same region of the protosolar disk and have similar overall compositions. We’ve accounted for differences in their trace gasses. So how come Earth’s nitrogen-oxygen atmosphere is so different from the CO2-nitrogen environments on Venus and Mars? Let’s brainstorm — shout out non-atmospheric ways that Earth is unique. I’ll record your list on Al’s whiteboard.”

“Oceans!”

“Plate tectonics!”

“Photosynthesis!”

“Limestone!”

“The Moon!”

“Wombats!” (That suggestion gets a glare from Cathleen. She doesn’t write it down.)

“Goldilocks zone!”

“Magnetic field!”

“People!”

She registers the last one but puts parentheses around it. “This one’s literally a quickie — real-world proof that human activity affects the atmosphere. Since the 1900s gaseous halogen-carbon compounds have seen wide use as refrigerants and solvents. Lab-work shows that these halocarbons catalyze conversion of ozone to molecular oxygen. In the 1970s satellite data showed a steady decrease in the upper-atmosphere ozone that blocks dangerous solar UV light from reaching us on Earth’s surface. A 1987 international pact banned most halocarbon production. Since then we’ve seen upper-level ozone concentrations gradually recovering. That shows that things we do in quantity have an impact.”

“How about carbon dioxide and methane?”

“That’s a whole ‘nother topic we’ll get to some other day. Right now I want to stay on the Mars-Venus-Earth track. Every item on our list has been cited as a possible contributor to Earth’s atmospheric specialness. Which ones link together and how?”

Adopted from image by Immanuel Giel, CC BY-SA 3.0

Astronomer-in-training Jim volunteers. “The Moon has to come first. Moon-rock isotope data strongly implies it condensed from debris thrown out by a huge interplanetary collision that ripped away a lot of what was then Earth’s crust. Among other things that explains why the Moon’s density is in the range for silicates — only 60% of Earth’s density — and maybe even why Earth is more dense than Venus. Such a violent event would have boiled off whatever atmosphere we had at the time, so no surprise the atmosphere we have now doesn’t match our neighbors.”

Astrophysicist-in-training Newt Barnes takes it from there. “That could also account for why only Earth has plate tectonics. I ran the numbers once to see how the Moon’s volume matches up with the 70% of Earth’s surface that’s ocean. Assuming meteor impacts grew the Moon by 10% after it formed, I divided 90% of the Moon’s present volume by 70% of Earth’s surface area and got a depth of 28 miles. That’s nicely within the accepted 20-30 mile range for depth of Earth’s continental crust. It sure looks like our continental plates are what’s left of the Earth’s original crust, floating about on top of the metallic magma that Earth held onto.”

Jeremy gets excited. “And the oceans filled up what the continents couldn’t spread over.”

“That’s the general idea.”

Al’s not letting go. “But why does Earth have so much water and why is it the only one of the three with a substantial magnetic field?”

Cathleen breaks in. “The geologists are still arguing about whether Earth’s surface water was delivered by billions of incoming meteorites or was expelled from deep subterranean sources. Everyone agrees, though, that our water is liquid because we’re in the Goldilocks zone. The water didn’t steam away as it probably did on Venus, or freeze below the surface as it may have on Mars. Why the magnetic field? That’s another ‘we’re still arguing‘ issue, but we do know that magnetic fields protect Earth and only Earth from incoming solar wind.”

“So we’re down to photosynthesis and … limestone?”

“Photosynthesis was critical. Somewhere around two billion years ago, Earth’s sea-borne life-forms developed a metabolic pathway that converted CO2 to oxygen. They’ve been running that engine ever since. If Earth ever did have CO2 like Venus has, green things ate most of it. Some of the oxygen went to oxidizing iron but a lot was left over for animals to breathe.”

“But what happened to the carbon? Wouldn’t life’s molecules just become CO2 again?”

“Life captures carbon and buries it. Chalky limestone, for instance — it’s calcium carbonate formed from plankton shells.”

Jim grins. “We owe it all to the Moon.”

~~ Rich Olcott

Traces of Disparity

Cathleen’s an experienced teacher — she knows when off-topic class discussion is a good thing, and when to get back to the lesson plan. “My challenge question remains — why isn’t Earth’s atmosphere some average of the Mars and Venus ones? Thanks to Jeremy and Newt and Lenore we have reason to expect the planets to resemble each other, but in fact their atmospheres don’t. Maria, tell us what you’ve found about how Earth compares with the others.”

“Yes, Profesora. I found numbers for many of the gasses on each planet and put them into this chart. One thing Earth is right in the middle, most things not.”

“That’s a complicated chart. Read it out to us.”

“Of course. I had to make the vertical scales logarithmic to get the big numbers and small numbers on the same chart. First is the pressure which is the black dotted line. Venus pressure at the surface is nearly 100 times ours but Mars pressure is a bit less than 1/100th of ours. Does that count as Earth being in the middle?”

“That’d be a geometric average. It could be significant, we’ll see. Go on.”

“The gas that is almost the same everywhere is helium, the grey diamonds. That surprised me, because I thought the giant planets got all of that.”

Al’s been listening in. Nothing else going on in his coffee shop, I guess. “I’ll bet most of that helium came from radioactive rocks, not from space. Alpha particles, right, Cathleen?”

Cathleen takes unexpected interruptions in stride. “Bad bet, Al. Uranium and other heavy elements do emit alphas which pick up electrons to become helium atoms. You probably remembered Cleve and Langlet, who first isolated helium from uranium ore. However, the major source of atmospheric alphas is the solar wind. Solar wind interception and atmosphere mass are both proportional to planetary surface area so a constant concentration like this is reasonable. Continue, Maria.”

“The major gasses follow a pattern — about the same fractions on Venus and Mars but much higher or lower than on Earth. Look at carbon dioxide, nitrogen, even oxygen.”

Astronomer-in-training Jim has been doing some mental arithmetic. “Our atmosphere is 100 times denser than on Mars, and Venus is another factor of 100 beyond that. That’s a factor of 104 between them — for every molecule of CO2 on Mars there’s 10,000 on Venus. Oh, but Venus has four times Mars’ surface area so make that 40,000.”

“Good points, both of you. Jim’s approximation leads into something we can learn from Maria’s trace gas numbers. Why do you suppose the concentration of SO2 is about the same for Earth and Mars but 100 times higher on Venus, but the reverse is true for argon? Where do they each come from?”

Jeremy finally has something he can contribute. “Volcanoes! They told us in Geology class that most of our SO2 comes from volcanoes. Before the Industrial Revolution, I mean, when we started burning high-sulfur coal and fuel oils and made things worse. Venus has to be the same. Except for the industry, of course.”

“Probably correct, Jeremy. From radar mapping of Venus we know that it has over 150 large volcanoes. We don’t know how many of them are active, but the Venus Express spacecraft sent back evidence of active vulcanism. In fact, Venus’ SO2 score would probably be even higher if much of its production didn’t oxidize to SO3. That combines with water to form the clouds of sulfuric acid that hide the planet’s surface and reflect sunlight so brightly.”

Maria’s hand is up again. “I don’t understand argon’s purple diamonds, profesora. I know it’s one of the inert gasses so it doesn’t have much chemistry and can’t react into a mineral like CO2 and SO2 can. Shouldn’t argon be about the same on all three planets, like helium?”

“Mm-hm, argon does have a simple chemistry, but its radiochemistry isn’t so simple. Nearly 100% of natural argon is the argon-40 isotope created by radioactive decay of potassium-40. Potassium is tied up in the rocks, so the atmospheric load of argon-40 depends on rocky surface erosion. Not much erosion, not much argon.”

Al’s on tenterhooks. “All this is nice, but you still haven’t said why Earth’s atmosphere is so different.”

~~ Rich Olcott