The Big Chill

Jeremy gets as far as my office door, then turns back. “Wait, Mr Moire, that was only half my question. OK, I get that when you squeeze on a gas, the outermost molecules pick up kinetic energy from the wall moving in and that heats up the gas because temperature measures average kinetic energy. But what about expansion cooling? Those mist sprayers they set up at the park, they don’t have a moving outer wall but the air around them sure is nice and cool on a hot day.”

“Another classic Jeremy question, so many things packed together — Gas Law, molecular energetics, phase change. One at a time. Gas Law’s not much help, is it?”

“Mmm, guess not. Temperature measures average kinetic energy and the Gas Law equation P·V = n·R·T gives the total kinetic energy for the n amount of gas. Cooling the gas decreases T which should reduce P·V. You can lower the pressure but if the volume expands to compensate you don’t get anywhere. You’ve got to suck energy out of there somehow.”

Illustrations adapted from drawings by Trianna

“The Laws of Thermodynamics say you can’t ‘suck’ heat energy out of anything unless you’ve got a good place to put the heat. The rule is, heat energy travels voluntarily only from warm to cold.”

“But, but, refrigerators and air conditioners do their job! Are they cheating?”

“No, they’re the products of phase change and ingenuity. We need to get down to the molecular level for that. Think back to our helium-filled Mylar balloon, but this time we lower the outside pressure and the plastic moves outward at speed w. Helium atoms hit the membrane at speed v but they’re traveling at only (v-w) when they bounce back into the bulk gas. Each collision reduces the atom’s kinetic energy from ½m·v² down to ½m·(v-w)². Temperature goes down, right?”

“That’s just the backwards of compression heating. The compression energy came from outside, so I suppose the expansion energy goes to the outside?”

“Well done. So there has to be something outside that can accept that heat energy. By the rules of Thermodynamics, that something has to be colder than the balloon.”

“Seriously? Then how do they get those microdegree above absolute zero temperatures in the labs? Do they already have an absolute-zero thingy they can dump the heat to?”

“Nope, they get tricky. Suppose a gas in a researcher’s container has a certain temperature. You can work that back to average molecular speed. Would you expect all the molecules to travel at exactly that speed?”

“No, some of them will go faster and some will go slower.”

“Sure. Now suppose the researcher uses laser technology to remove all the fast-moving molecules but leave the slower ones behind. What happens to the average?”

“Goes down, of course. Oh, I see what they did there. Instead of the membrane transmitting the heat away, ejected molecules carry it away.”

“Yup, and that’s the key to many cooling techniques. Those cooling sprays, for instance, but a question first — which has more kinetic energy, a water droplet or the droplet’s molecules when they’re floating around separately as water vapor?”

“Lessee… the droplet has more mass, wait, the molecules total up to the same mass so that’s not the difference, so it’s droplet velocity squared versus lots of little velocity-squareds … I’ll bet on the droplet.”

“Sorry, trick question. I left out something important — the heat of vaporization. Water molecules hold pretty tight to each other, more tightly in fact than most other molecular substances. You have to give each molecule a kick to get it away from its buddies. That kick comes from other molecules’ kinetic energy, right? Oh, and one more thing — the smaller the droplet, the easier for a molecule to escape.”

“Ah, I see where this is going. The mist sprayer’s teeny droplets evaporate easy. The droplets are at air temperature, so when a molecule breaks free some neighbor’s kinetic energy becomes what you’d expect from air temperature, minus break-free energy. That lowers the average for the nearby air molecules. They slow their neighbors. Everything cools down. So that’s how sprays and refrigerators and such work?”

“That’s the basic principle.”

“Cool.”

~ Rich Olcott

Thanks to Mitch Slevc for the question that led to this post.

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The Hot Squeeze

A young man’s knock, eager yet a bit hesitant.

“C’mon in, Jeremy, the door’s open.”

“Hi, Mr Moire. How’s your Summer so far? I got an ‘A’ on that black hole paper, thanks to your help. Do you have time to answer a question now that Spring term’s over?”

“Hi, Jeremy. Pretty good, congratulations, and a little. What’s your question?”

“I don’t understand about the gas laws. You squeeze a gas, you raise its temperature, but temperature’s the average kinetic energy of the molecules which is mass times velocity squared but mass doesn’t change so how does the velocity know how big the volume is? And if you let a gas expand it cools and how does that happen?”

“A classic Jeremy question. Let’s take it a step at a time, big-picture view first. The Gas Law says pressure times volume is proportional to the amount of gas times the temperature, or P·V = n·R·T where n measures the amount of gas and R takes care of proportionality and unit conversions. Suppose a kid gets on an airplane with a balloon. The plane starts at sea level pressure but at cruising altitude they maintain cabins at 3/4 of that. Everything stays at room temperature, so the balloon expands by a third –“

Kid drawing of an airplane with a red balloon
Adapted from a drawing by Xander

“Wait … oh, pressure down by 3/4, volume up by 4/3 because temperature and n and R don’t change. OK, I’m with you. Now what?”

“Now the plane lands at some warm beach resort. We’re back at sea level but the temp has gone from 68°F back home to a basky 95°F. How big is the balloon? I’ll make it easy for you — 68°F is 20°C is 293K and 95°F is 35°C is 308K.”

“Volume goes up by 308/293. That’s a change of 15 in about 300, 5% bigger than back home.”

“Nice estimating. One more stop on the way to the molecular level. Were you in the crowd at Change-me Charlie’s dark matter debate?”

“Yeah, but I didn’t get close to the table.”

“Always a good tactic. So you heard the part about pressure being a measure of energy per unit of enclosed volume. What does that make each side of the Gas Law equation?”

“Umm, P·V is energy per volume, times volume, so it’s the energy inside the balloon. Oh! That’s equal to n·R·T but R‘s a constant and n measures the number of molecules so T = P·V/n·R makes T proportional to average kinetic energy. But I still don’t see why the molecules speed up when you squeeze on them. That just packs the same molecules into a smaller volume.”

“You’re muddling cause and effect. Let’s try to tease them apart. What forces determine the size of the balloon?”

“I guess the balance between the outside pressure pushing in, versus the inside molecules pushing out by banging against the skin. Increasing their temperature means they have more energy so they must bang harder.”

“And that increases the outward pressure and the balloon expands until things get back into balance. Fine, but think about individual molecules, and let’s pretend that we’ve got a perfect gas and a perfect balloon membrane — no leaks and no sticky collisions. A helium-filled Mylar balloon is pretty close to that. When things are in balance, molecules headed outward approach the membrane with some velocity v and bounce back inward with the same velocity v though in a different direction. Their kinetic energy before hitting the membrane is ½m·v²; after the collision the energy’s also ½m·v² so the temperature is stable.”

“But that’s at equilibrium.”

“Right, so let’s increase the outside pressure to squeeze the balloon. The membrane closes in at some speed w. Out-bound molecules approach the membrane with velocity v just as before but the membrane’s speed boosts the bounce. The ‘before’ kinetic energy is still ½m·v² but the ‘after’ value is bigger: ½m·(v+w)². The total and average kinetic energy go up with each collision. The temperature boost comes from the energy we put into the squeezing.”

“So the heating actually happens out at the edges.”

“Yup, the molecules in the middle don’t know about it until hotter molecules collide with them.”

“The last to learn, eh?.”

“Always the case.”

~~ Rich Olcott

Thanks to Mitch Slevc for the question that led to this post.