Why was water freezing almost instantaneously when shaking a bottle that spent the night outside during a frosty night?

Question

Due to the forecasted frost last night, I placed yesterday evening, some 1.5l standard PET bottles filled up to 90% with warm tap water(+60°C) close to some vegetables that I wanted to protect in my garden. The temperature dropped to roughly -3 ~ -4°C last night.

This morning I went to see how it went. Of the 10 bottles, one was filled half with water, half with ice. In all the other bottles, the water was still in a liquid state.

So I decided to empty them. Here comes the interesting thing: I uncap the bottles, flip them upside down to empty the water, and give them a shake/twist so that it empties faster, and I noticed that some not well structured ice (it was more looking like melting snow actually) was forming almost instantaneously. Curious, I decided to give a strong shake on the next one while emptying it, and well, this mix of ice forming at that moment reminded me the texture of the icy fruit smoothies one can find during summertime.

How do you explain that the water, when still, was 100% liquid, and that when I shake the bottle, ice was forming in no time? I mean, for me, shaking = adding energy, so it should warm the water, not cool it to the point it will form ice? From this experiment I guess not, and that instead, it more or less 'helps' the remaining energy of the 0°C water to dissipate, forming ice super quickly. Am I right in my reasoning?

I'll redo the experiment the next night, trying to take a photo to add it here.

Edit 1: I've placed the same bottles, with the same warm tap water in them at the same position as yesterday. The upcoming night might even be colder... I'll try to take some photos tomorrow morning.

Edit 2: Okay, so this morning it wasn't as impressive as yesterday but it happened again:

Fig.1 When you start to empty the bottle, only cold, clear water comes out of it.

Shaking a little, then

Fig.2 Ice particles have attached to the inside of the bottle as it is being emptied.

Fig.3 Unstructured ice has accumulated on the ground.

It's a totally "wild" and uncontrolled experiment so it's not as impressive as the videos linked by Philip hereunder.

Here are the videos from which the screenshots were extracted:
https://vimeo.com/534346291
https://vimeo.com/534347556

I also made a tiny additional observation but this is probably entirely due to chance: because I filled the bottles with warm water yesterday, they were a little depressurized this morning, having kind of a global concave shape. I have shaken them all before opening; but the water stayed clear. It's only once I opened them, and emptied them, that ice was formed.

You already have a good answer, so I'll just say that what you saw is the opposite of why you shouldn't try to boil water in a microwave without a stick in it: https://www.youtube.com/watch?v=2SzUrjfvWPU — eps, Apr 07 '21 at 20:06
In addition to just shaking the bottles, try poking a straw or stick into the supercooled water, or dropping in a grain of sand. — A. I. Breveleri, Apr 08 '21 at 04:11
My friend, you landed into Wikipedia Commons and on Wikipedia! https://commons.wikimedia.org/wiki/File:Supercooling_water_bottle_after_shaking.jpg https://commons.wikimedia.org/wiki/File:Supercooling_water_bottle_before_shaking.png https://en.wikipedia.org/wiki/Supercooling — Valerio Bozz, Apr 08 '21 at 11:00

score 93 · Accepted Answer · answered Apr 07 '21 at 09:59

93

Congratulations, it sounds to me like you've just observed supercooled water! There are many videos on YouTube that describe this phenomenon, and explain it much better than I could, see here for a Veritasum video where this is discussed for example.

The basic idea is this: when water freezes it forms ice, which is a nice regular crystalline structure. However, ice-crystals need a nucleation site, which is a point where the crystal can start to form, before they can actually start to form. In normal situations, water usually has some impurities which can serve as such nucleation sites, around which the crystal starts to grow and ice starts to form.

However, if you use very pure water, there are no such "natural" nucleation points and so there is a chance that the water molecules want to form ice, but can't quite get around to it. As a result, the liquids are trapped in a "metastable" state well below their freezing point, but such a state has a precarious stability that can easily be disturbed. Shaking the bottle is one way to disturb this stability, as it gives a couple of the water molecules the chance to align in just to right way to start the crystallisation process, and once it's done, it is energetically favourable for the system to form ice, so all the other water molecules hop on as well. As a result, you would usually see the crystal "growing" in one direction until all the water becomes ice.

Of course, you don't need to shake it, you could just introduce a different type of nucleation point as can be seen in this very pretty video and it would produce the same results, or alternatively, you could very carefully pour the supercooled water on top of an ice cube and form a sort of ice sculpture (see this video from The Action Lab).

It takes more energy to form supercooled water than ice, meaning that when the water transitions to ice, it actually releases some heat, so supercooled water is actually colder than ice. Incidentally, this process is also observed in other materials, notably sodium acetate which is used in making heat packs like this one.

I've never actually managed to see supercooled water myself, though I've tried quite a few times. I'm quite surprised that you were able to get it from tap water, since it usually requires very pure water. I hope you're able to reproduce the experiment!

answered Apr 07 '21 at 09:59

Philip

11,393

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And for you youngsters, this is the premise behind the danger posed by Ice-Nine in a certain book by a certain author. – Carl Witthoft Apr 07 '21 at 14:09
23

The opposite of this is superheated water, which I (unfortunately) observed in my microwave the other day -- when heating water in a microwave it can go above 100c without boiling only to erupt in a giant explosion of water when it hits a certain temp and/or is slightly disturbed (similar to the OP suddenly getting ice when shaking). – eps Apr 07 '21 at 19:58
1

Thanks a lot for your answer and the nice links! That granita smoothie structure you see in one of the videos is exactly what I experienced! And the fact that water releases energy when it freezes is a technique well known to farmers growing fruit here, where you can often see these scenes during spring frosts, where they sprinkle the young buds with water to protect them: https://www.laliberte.ch/media/image/35/zoom/20200326130952445.jpg – s.k Apr 07 '21 at 20:46
I set my refrigerator to just above freezing, and I usually wind up with my water bottles getting (marginally) supercooled. And incidentally, supercooled water tastes absolutely AMAZING. – Dan Henderson Apr 07 '21 at 21:01
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The heat release is called https://en.wikipedia.org/wiki/Recalescence. Back in my days of pulsed laser melting of thin films, we could get supercoolings of 100s of K for, e.g. liquid silicon. Superheating a solid is harder, since the surface will melt before the bulk (fewer bonds), nucleating the liquid more easily than one might think. – Jon Custer Apr 07 '21 at 21:59
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For an assumedly related event, I will leave a PowerAde in the freezer for an hour or so. When I pull it out, it is still liquid. But after a firm shake, it turns into a slush. – Michael Richardson Apr 07 '21 at 22:12
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now that you say it like that, the water molecule seems like a shy person that want to say something but waits if any other gonna do the same, until that little push and then suddenly everyone joins. cute. – encryptoferia Apr 08 '21 at 06:21
@DanHenderson It sounds like so far it hasn't frozen in your throat and caused a blockage... maybe an undetectable murder weapon, like bullets made of ice? – Andrew Morton Apr 08 '21 at 16:57
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It's interesting that you say it works best with pure water, I have observed it a few times myself with alcoholic beverages (c.5% alcohol), put in the freezer to chill faster, then forgotten about. Release the cap and the escaping gas creates the nucleation sites and freezes the contents instantly. In one example, it didn't freeze when the cap was removed but when somebody tried to "steal" the first mouthful from the bottle, tipping it up was the catalyst and their crime failed to pay due to the instant formation of ice. – Lefty Apr 08 '21 at 17:05
Very cool, @Lefty, I didn't know about this. For anyone else interested, here's a cool video of this happening with a bottle of beer. I think what is meant by the "purity" of the water is just the absence of nucleation sites like bits of dust. I don't think dissolved salts or alcohol allow nucleation, so they don't quite count. Beer might actually be better to supercool than tap water; I suspect it's extremely clean since it goes through a filtration process before it's bottled which removes most impurities that could act as nucleation sites. – Philip Apr 09 '21 at 00:01
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@Philip I think you're right that it's somehow easier to recreate using beer, but not sure why. It could be the filtration as you suggest. A great party-trick if you can do it with some consistency. I've only ever done it by accident as I say, maybe 1 to 2 hours freezing time for a 500ml bottle. – Lefty Apr 09 '21 at 08:23
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Here's another neat video link about those reusable handwarmers and the whole phenomena of supercooling and supersaturating: https://youtu.be/Oj0plwm_NMs – Vilx- Apr 10 '21 at 10:37
It is interesting that the asker started from hot tap water (his intention being keeping plants warm, not wanting to supercool a liquid). This reminds me of the schoolboy Mpemba who found that under some circumstances, hot water can freeze sooner than an equal amount of cool water. See Wikipedia: Mpemba effect for a lot more on that. Maybe the asker discovered a trick (i.e. starting from hot water) that for some reason makes it easier to obtain supercooling, making them a "Mpemba 2". – Jeppe Stig Nielsen Apr 10 '21 at 12:13
Other than solid impurities, the amount (and types) of gasses dissolved in the water before the supercooling attempt could be very important. This may be related to why beer works differently than water. Shaking a closed bottle where gasses are dissolved, can change the pressure in the bottle temporarily. Of course, when you open the bottle, the pressure abruptly changes to that of the surrounding environment. In the asker's case, there was a lower pressure in the bottle before opening. However, you can also experiment with supercooling water in an open container (e.g. a glass with no lid). – Jeppe Stig Nielsen Apr 10 '21 at 12:19

score -3 · Answer 2 · answered Apr 08 '21 at 13:54

Perhaps low pressure?

As you empty the bottle, initially it is hard for air to get in (that glug-glug-glug slow thing) and thus the pressure of the air pocket at the top of the bottle drops and when pressure drop, water freezes faster and easier.

Also your water started warm so possibly less oxygen also leading to making it easier to flash freeze in above conditions.

Why was water freezing almost instantaneously when shaking a bottle that spent the night outside during a frosty night?

2 Answers2

Perhaps low pressure?

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