The Latte Connection

An early taste of Spring’s in the air so Al’s set out tables in front of his coffee shop. I’m enjoying my usual black mud when the Chemistry Department’s Susan Kim passes by carrying her usual mocha latte. “Hi, Sy, mind if I take the socially distant chair at your table?”

“Be my guest, Susan. What’s going on in your world?”

“I’ve been enjoying your hysteresis series. It took me back to Physical Chemistry class. I’m intrigued by how you connected it to entropy.”

“How so?”

“I think of hysteresis as a process, but entropy is a fixed property of matter. If I’m holding twelve grams of carbon at room temperature, I know what its entropy is.”

“Mmm, sorta. Doesn’t it make a difference whether the carbon’s a 60‑carat diamond or just a pile of soot?”

“OK, I’ll give you that, the soot’s a lot more random than the diamond so its entropy is higher. The point remains, I could in principle measure a soot sample’s heat capacity at some convenient temperature and divide that by the temperature. I could repeat that at lower and lower temperatures down to near absolute zero. When I sum all those measurements I’ll have the entropy content of the sample at my starting temperature.”

“A classical definition, just what I’d expect from a chemist. But suppose your soot spills out of its test tube and the breeze spreads it all over the neighborhood. More randomness, higher entropy than what you measured, right?”

“Well, yes. I wouldn’t have a clue how to calculate it, but that goes way beyond Carnot’s and Clausius’ original concept.”

“So entropy has at least a thin linkage with history and hysteresis. To you chemists, though, an element or compound is timeless — lead or water have always been lead or water, and their physical constants are, well, constant.”

“Not quite true, Sy. Not with really big molecules like proteins and DNA and rubber and some plastics. Squirt a huge protein like catalase through a small orifice and its properties change drastically. It might not promote any reaction, much less the one Nature designed it for. Which makes me think — Chemistry is all about reactions and they take time and studying what makes reactions run fast or slow is a big part of the field. So we do pay attention to time.”

“Nice play, Susan! You’re saying small molecules aren’t complex enough to retain memories but big ones are. I’ll bet big molecules probably exhibit hysteresis.”

“Sure they do. Rubber molecules are long-chain polymers. Quickly stretch a rubber band to its limit, hold it there a few seconds then let go. Some of the molecular strands lock into the stretched configuration so the band won’t immediately shrink all the way down to its original size. There’s your molecular memory.”

“And a good example it is — classic linear Physics. How much force you exert, times the distance you applied it through, equals the energy you expended. Energy’s stored in the rubber’s elasticity when you stretch it, and the energy comes back out on release.”

“Mostly right, Sy. You actually have to put in more energy than you get out — Second Law of Thermodynamics, of course — and the relationship’s not linear. <rummaging into purse> Thought I had a good fat rubber band somewhere … ah‑hah! Here, stretch this out while you hold it against your forehead. Feel it heat up briefly? Now keep checking for heat while you relax the band.”

“Hey, it got cold for a second!”

“Yep. The stretched-out configuration is less random so its entropy and heat capacity are lower than the relaxed configuration’s. The stretched band had the same amount of heat energy but with less heat required per degree of temperature, that amount of energy made the band hotter. Relaxing the band let its molecules get less orderly. Heat capacity went back up. temperature went back down.”

“Mmm-HM. My hysteresis diagram’s upward branch is stretch energy input and the downward branch is elastic energy output. The energy difference is the area inside the hysteresis curve, which is what’s lost to entropy in each cycle and there we have your intriguing entropy‑hysteresis connection. Still intrigued?”

“Enough for another latte.”

~~ Rich Olcott

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