Month: December 2021

Save The Whales? Burn Turpentine

On By rolcottIn Physics: Money, UncategorizedLeave a comment

“OK, Sy, I’ve told you the oil, wax and spermaceti story from my chemistry viewpoint. What got you reading up on whales?”

“A client asked a question that had me going down a rabbit hole that turned into a wormhole leading to a whole bunch of Biology and some Economics. Good thing I enjoy learning random facts.”

“OK, I’ll bite. What was the question?”

“Alright, Susan, see how you do with this. We need our eyes to be round so they can rotate in their sockets and still focus images on their retinas. They can hold that spherical shape against atmospheric pressure because they’re filled with watery stuff and they have a pump‑and‑drain mechanism inside that maintains a slight positive internal pressure. Whales dive down to where water pressures are a hundred atmospheres or more, enough to squeeze their lungs shut. They must use their vision sense down there because their retinal rod cells, the low‑light receptors, are sensitive to blue light. That’s what you’d need for hunting where the water above you filters out all the longer wavelengths. So why doesn’t the pressure down there crumple their eyeballs?”

“Oh, Sy, that’s easy. Water’s among the least compressible molecular liquids we know of. It takes an immense amount of pressure to reduce its volume even by 1%. Hunting-ground pressure isn’t nearly high enough to sabotage water‑filled eyeballs.”

“D’oh! So simple. And here I am, reading a dissection report on a sperm whale’s eyeball. Which, by the way, is about 22 times heavier than a human’s.”

“That’s where your wormhole led you?”

“No, actually, it led me to a econo-political argument about why kerosene got big in the 1860s.”

“Say what? I thought kerosene came in because sperm whales were getting hard to find.”

“That’s the story Big Oil likes. Apparently free-market enthusiasts have been lauding the petroleum industry as heroes dashing in with kerosene to save the whales and by the way, prospering completely independent of any government actions. Turns out History doesn’t support either claim. Ever hear of Camphine?”

“Nope.”

“Camphine saved the whales but then sank with nary a trace. I got most of the story from a PBS blog but pieced that together with a Wikipedia article and a bunch of old government statistics.. I charted the numbers and came up with some interesting correlations. Are you at your computer so I can email it to you?”

Data from W S Tower, “A History of The American Whale Fishery” (1907)

“Sure.”

“On its way.”

“Ooo, complicated. Care to read it to me?”

“Of course. Fun fact — fats from toothed whales are generally waxier than fat from baleen whales. Sperm whales just happen to be at the far end of that trend. Anyway, I concentrated on the sperm whale data. The red line is the total amount of spermaceti obtained from whales taken by US craft in each year,”

“Five million gallons in 1842? That’s ten thousand whales!”

“Mm-hm. The red line drops sharply after those peak years despite the whalers floating a bigger fleet — that’s the black line. The hunters found diminishing returns because the harvest just wasn’t sustainable. But people still wanted their spermaceti candles — the green line shows the price continued to rise until the mid‑1850s. Not only inside the US — the blue line shows exports rising because foreign whalers couldn’t supply demand from their own markets.”

“Bad prospects. What happened in the yellow part of the chart?”

“Competition from a new product called Camphine, a.k.a. ‘burning oil.’ In the mid‑1830s a guy in Maine and a couple of New Yorkers started making liquid substitutes for spermaceti. The products were mixtures of turpentine, grain alcohol and a little camphor for aroma. You needed a special lamp to burn it but you got a flame that rivaled sperm candles for brightness and color purity. Sold like gang‑busters, up to 200 million gallons per year, but the Civil War killed it off.”

“How?”

“Federal embargoes on Southern pine forest turpentine, Federal taxes on alcohol. Kerosene and the Pennsylvania oil wells in 1859 rode in decades late to save the whales. Camphine was helping but government trade and tax policies cut it off at the pass.”

~~ Rich Olcott

Candle, Candle, Burning Bright

On By rolcottIn Chemistry, Physics: Light and Relativity, UncategorizedLeave a comment

<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

On By rolcottIn Astronomy: Planetary Science, Chemistry, Physics: Light and Relativity, UncategorizedLeave a comment

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.”

Data from EPA Climate Indicators Explorer

“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

It’s A Trap!

On By rolcottIn Astronomy: Planetary Science, Physics: Light and Relativity, UncategorizedLeave a comment

Late morning, no-one else in his coffee shop so Al pulls up a chair. “OK, Susan, so coal’s a mess for ash and air pollution but also each carbon from coal gives us less energy than a carbon from methane. So why the muttering against switching to natural gas?”

“Big-ticket reasons, Al. One, natural gas isn’t pure methane. Mostly methane, sure, but depending on the source you get a whole collection of other things in the mix — heavier hydrocarbons like propane and butane, stinky sulfides and amines, even helium and mercury. Gas from a well has to be purified before you’d want it piped to your house.”

“Piped. Oh, yeah, pipelines. Probably a lot more efficient than coal transport but I see how they get problems, too.”

“Indeed they do. Pipelines break and leak and some idiots even use them for target practice. The worst kind of waste.”

“Yeah, when the oil gets out and ruins the land or someone’s water supply.”

“That’s bad locally, all right, but it’s when methane leaks out that the global damage starts.”

“Global?”

“Mm-hm, because methane’s a gas and mixes in with the rest of the atmosphere. If a pipeline or a truck or anything springs a leak in, say, Chicago, the methane molecules can go anywhere.”

“So?”

“So a couple of things. A decade in the atmosphere oxidizes most methane molecules to, guess what, CO2, the same problematic CO2 we get from burning coal. But before it degrades, methane’s an even bigger heat‑trapper than CO2 is.”

“Whaddaya mean, heat‑trapper?”

“Do you want to take this, Sy? It’s more Physics than Chemistry and besides, my mocha latte’s getting cold.”

“Hmm, there’s a bunch of moving parts in this. Al, you owe Susan a warm-up while I think.”

“Here ya go, Susan.”

“Thanks, Al. I’ll get you guys started. Why did my coffee get cold?”

“Good one, Susan. Al, it’s a universal principle — left to itself, energy spreads out. Heat finds ways to travel from a concentrated, high‑temperature source to low‑temperature absorbers. The exceptions occur when some extra process expends energy to pump heat in the other direction. So, that coffee naturally lost heat to the table by conduction, to the air by convection and to the general environment by radiation. The only thing that can stop those processes is perfect insulation. That’s the thing about the atmosphere.”

“Whoa, that’s a jump or three too fast.”

“OK, let’s follow a sunbeam aimed in the Earth’s direction. Its photons carry a wide range of energies, ultraviolet down to far infrared. On the way in, a UV photon hits an atmospheric ozone molecule and gets absorbed. No more UV photon but now the molecule is in an excited state. It calms down by joggling its neighbor molecules, that’s heat transfer, and maybe emitting a longer wavelength photon or two. Ozone filters out incoming UV and in the process spreads out the photon’s concentrated energy. What’s left in the sunbeam is visible and infrared light that gets down to us. You with me?”

“Makes sense so far.”

“Good. Next stage is that the visible and IR light heat the Earth, which then re-radiates the energy as infrared light mostly at longer wavelengths. The problem is that not all the IR gets out. Water molecules absorb some wavelengths in that range. Every absorption event means more heat distribution into the atmosphere when the molecule relaxes. Ocean evaporation maintains a huge number of IR‑blocking water molecules in the atmosphere.”

“I heard that ‘some‘ weasel‑word. Other wavelengths still make it through, right?”

I unholster Old Reliable, tap a few keys. “Here’s water’s absorption pattern in the mid‑to‑far‑infrared. A high peak means absorption centered at that wavelength. This is scaled per molecule per unit area, so double the molecules gives you double the absorption.”

Spectrum profiles from M. Etminan, et al., doi:10.1002/2016GL071930

“Lots of blank space between the peaks, though.”

“Which is where CO2 and methane get into the game. It’s like putting green and blue filters in front of a red one. With enough of those insulating molecules up there there’s no blank space and lots of imbalance from trapped heat.”

“Methane’s worse.”

“Lots worse.”

~~ Rich Olcott