Is Water's Volume Expansion Upon Freezing an Intrinsic Property?

[swissgirl1999 Refer]

Agreed — and we should do it ourselves. Your protocol eliminates thermal air contraction as a variable. If the bottle still shrinks with zero headspace at 4°C before freezing, the standard explanation collapses entirely. Let's run it.

 

[256bits]

Here lies a paradox: to the independent researcher it is demanded "infinite controls", nevertheless, when the outcome contradicts the textbooks, the results are dismissed as probable mistakes made by the independent researcher… unless peers start to review by replicating the experiment, the independent researcher cannot scape this loophole — he can't (shouldn't and never will) change the textbooks by himself.
The best that anyone can do by itself is to point to an unexpected outcome — to investigate it further ought to be a burden for the scientific community as a whole.

the answers that you have received are coming from the belief that your experiment is as you say it is and nothing else. There is no bias against the experimental investigation as outlined..

A valid experiment does not rely upon I think it is so, therefor it must be.
A valid experiment relies upon verifiable measurement. One easy measurement that has been proposed is the buoyancy of the water bottle before and after the water has frozen.
A replication of the experiment would then have a quantity for a comparison of test results.

 

[swissgirl1999 Refer]

The water can dissolve a quantity of gas based upon its temperature and the external pressure. If the pressure in the liquid is decreased, some gas will come out of solution as bubbles.

Water turning into Ice is purified by expulsion of dissolved gases. This happens at the boundary of ice crystal formation where tiny bubbles form. Rapid ice crystal growth surpasses the tiny bubbles entrapping them and the ice will look cloudy.

The structure seen is the ice crystal formation and structure outside the bubble. Whether one can call that internal bubble structure is debatable, but what is seen is the surface of the bubble/ice interface rather than anything else.

Is it possible to break a gas -- I am not sure what you mean,

Yes — the mechanism is different, and that is precisely what makes it interesting, not what explains it away. Still water, no added CO₂, cap opened only to equalize pressure — and yet spherical gas bubbles form slowly over 30 minutes, survive ice formation, and show altered internal structure. If the mechanism is different from standard degassing, then what is it? That is the question.

Mineral water with bubbles adhered to the plastic.

You say the structure seen is the ice/bubble interface — not the inside of the bubble. But the microscopy was done using only refracted light, which reveals internal structure, not surface. And the structure changed after freezing. If it were just the outer interface, why would freezing fracture it? Something inside the bubble was altered.

Mineral water showing fractured structures in the bubbles.

Hence the question: "is it possible to break a gas"?
Because or it is possible (which doesn't make sense), or that's not gas.
If it is gas, then, there must be an explanation to why previously dissolved gas molecules arranged themselves into spherical bubbles attached to the plastic, which would be a direct contradiction to the second law of thermodynamics, and there must be an explanation to why these gas bubbles inside water resist to the volume expansion of ice formation, and, at last but not least, there must be an explanation to why gas can have shape and can break.
Or, if it's not gas — what is it?

 

[FactChecker]

Here lies a paradox: to the independent researcher it is demanded "infinite controls", nevertheless, when the outcome contradicts the textbooks, the results are dismissed as probable mistakes made by the independent researcher… unless peers start to review by replicating the experiment, the independent researcher cannot scape this loophole — he can't (shouldn't and never will) change the textbooks by himself.
The best that anyone can do by itself is to point to an unexpected outcome — to investigate it further ought to be a burden for the scientific community as a whole.

I don't expect "infinite controls". I would just encourage you to be reasonably careful about your experiment before you expect good answers from a physics forum. Was the water pure, distilled water? What is in the mineral water, and what are all those gas bubbles? Please use distilled water with no air in the bottle to keep things simple. As others have said, you can verify that nothing has leaked by comparing before and after weights. And you can measure volume changes by submerging the bottle in a bath of water and measuring any change in the bath water level.

 

[256bits]

refracted light

Isn't that where light bends when passing from one medium to the next?

 

[swissgirl1999 Refer]

I don't expect "infinite controls". I would just encourage you to be reasonably careful about your experiment before you expect good answers from a physics forum. Was the water pure, distilled water? What is in the mineral water, and what are all those gas bubbles? Please use distilled water with no air in the bottle to keep things simple. As others have said, you can verify that nothing has leaked by comparing before and after weights. And you can measure volume changes by submerging the bottle in a bath of water and measuring any change in the bath water level.

You didn't get my point, which is: any sophisticated data that I bring that might contradict mainstream thermodynamics won't mean anything if anyone cares to also investigate.
If all the qualitative material I brought for discussion didn't raise curiosity enough for you and for others, it will not be the additional quantitative data that will.

If "gas bubbles" resisting the pressure of ice formation while copper tears apart, and, if internal structures of "gas bubbles" fractured after frozen don't raise enough curiosity, it definitely will not be some unexpected numbers that will...

 

[Ibix]

Ok, it floats, but that doesn't explain why it shrinks.

Indeed - it's a data point suggesting that water expands when it freezes. The density of ice in the bottle is lower than water, and that's why the bottle of water sinks while the bottle of ice floats, as expected.

That's why I think there's a confounding factor in your experiment. Several have been suggested. Directly weighing and measuring the volume of the ice you produce would help to eliminate some.

 

[Roberto Pavani]

Corollary: since ice forms asymmetrically inside the bottle, it also expands asymmetrically. As noted by @Jonathan Scott, when a plastic bottle collapses in one direction, it gets larger in another. The total volume likely did increase, it just looks like it shrank due to non-uniform deformation.

However, a very nice experiment!

 

[Dale]

Here lies a paradox: to the independent researcher it is demanded "infinite controls", nevertheless, when the outcome contradicts the textbooks, the results are dismissed as probable mistakes made by the independent researcher…

This is no paradox, it is standard experimental science. Well-considered and carefully-executed controls are critical to good experiments. Good science is difficult. And challenges to mainstream results are especially difficult, precisely because they already went through that careful effort. We hold all scientists to this high standard.

In the end, this is the difference between the “independent researcher” and the “crackpot”. The “independent researcher” is doing actual science outside of a university or corporate setting, while the “crackpot” is just posturing.

the independent researcher cannot scape this loophole

Indeed, nobody can. Nor should they.

to investigate it further ought to be a burden for the scientific community as a whole

You need to ask yourself if you are an independent researcher or a crackpot. Researchers (independent or not) see their observations/questions as an opportunity for them to do some scientific research and contribute to the body of knowledge. If you see your own research questions as a burden to be placed on others then you are not a researcher.

Assuming that you are an independent researcher, at this point you are at the “observation/question” stage of the scientific method. You have an interesting observation. Now you do your background research and form a question about possible mechanisms that could explain your observation. Then you design an experimentally testable hypothesis. You have received a lot of advice about important controls and measurements, which should inform your experimental design. Then you execute the experiment, analyze the data, and report the results. That is the scientific method, the mark of any researcher

 

[Andy Resnick]

Quite the contrary — this is still water (no added CO₂). The bubbles are not dissolved gas escaping; they are forming where there should be none, surviving ice formation, and showing fractured internal structure under microscopy. That is what needs explaining.

While the images of carbonated mineral water are highly informative, note that even 'still water' can have a lot of dissolved gas (air) present- cloudy ice cubes are proof of that. You can de-gas tap water by first boiling it and then, after it cooled, carefully pouring it into your container of choice and then leaving that container open in a well-ventilated area for 24 hours or so.

Also, the bubbles in ice do not have a 'fractured internal structure'- what you see is the ice-vapor interface.

 

[Andy Resnick]

The container could impose compressive stress on the ice which alters the thermodynamic relationship between ice and water, and can result in volumetric strain.

For sure! I was simply noticing the gas bubbles in the images.

 

[pbuk]

If all the qualitative material I brought for discussion didn't raise curiosity enough for you and for others, it will not be the additional quantitative data that will.

But your qualitative description ("I put some bottles of water in the freezer and it looks like they shrank") has already been addressed (perhaps they actually expanded but the way they deformed made you think that they had shrunk).

You can easily measure the volumes before and after to get some quantitative data: why do you refuse to do that?

 

[pbuk]

Also, the bubbles in ice do not have a 'fractured internal structure'- what you see is the ice-vapor interface.

...which has deformed due to compression of the vapour as the ice expands.

 

[pbuk]

Some of those photos show a LOT of loss of volume.

No, they show a lot of deformation. It is impossible to say without measurement how the volume has changed.

 

[CrysPhys]

If the compressive stress is very high, a new equilibrium between ice and water will be established at the lower temperature, and ice will melt. This is what happens under the blade of an ice skate.

OK, I understand that the ice melts because of the high pressure under the ice skate blade.

This is off-topic, so I won't dwell on it too much. Standard textbooks have often stated that ice skating functions because the pressure of the blade causes the ice to melt. But this turns out not to be true. Even under the worst case of a figure skate (curved rocker so only a small segment of the blade is in contact with the ice at any time; and the skater is skating on only one foot and is skating on only one of the two edges of the blade), a skater cannot exert enough pressure to melt the ice under typical rink conditions. More recent surface studies have concentrated on a quasi-liquid layer on the surface of the ice. But these layers are at most only several atomic (or molecular) layers thick; whereas, a skate blade penetrates much deeper.

Most of the studies are flawed in that they do not take into account the entire complex blade-ice system that is in a non-equilibrium state (to me it's clear that often the researchers are themselves not ice skaters). But some progress is finally being made. There are papers in technical journals, but they are behind paywalls. Here is a brief summary from a scientific magazine: https://www.quantamagazine.org/why-is-ice-slippery-a-new-hypothesis-slides-into-the-chat-20251208/. One freely accessible journal article on the quasi-liquid surface layer is the following: https://pmc.ncbi.nlm.nih.gov/articles/PMC6727213/. [ETA: Here's one study under actual rink conditions: https://www.cambridge.org/core/jour...d-hypothesis/AC9154A588AC121ADE373EAEC3A50BAA]

So after several centuries, we really still don't have a detailed understanding of how ice skating works.

 

[256bits]

f it is gas, then, there must be an explanation to why previously dissolved gas molecules arranged themselves into spherical bubbles attached to the plastic, which would be a direct contradiction to the second law of thermodynamics, and there must be an explanation to why these gas bubbles inside water resist to the volume expansion of ice formation,

Very good questions I must admit, and not without merit. One would tend to think that the 'pressure' of the ice would shrink the bubble size according to PV=nRT, hence the thermodynamic reference.
Consider an arch or dome under external load. The material of the dome becomes stressed and resists the external load. What is under the dome is immaterial in most cases, especially if its compressive strength is much lower than the compressive strength of the dome, and shares little in supporting the load.

Originally, the bubble air pressure in water is that of the external loading due to hydrostatic forces commensurate with their depth in the liquid. Upon initial formation of ice crystals around the bubble, the air pressure would remain at the hydrostatic level. Once the 'dome' formed around the bubble, the internal pressure is set to some degree, and can only increase by the 1. solidification of small water pockets between the dome and the bubble increasing the air pressure within through the process of ice crystal penetration. 2. changing external pressure brought about by bulk container restraints as more water turns to ice, and in turn stressing the dome, and shrinking the size if the external pressure is increasing. 3. migration of air bubbles and merging brought about by ice crystal movement as they attempt to equalize stress and strain due to external bulk container restraints.

somewhat similar to the difficulty in compressing an eggshell due to its curved shape.

You may be interested in bubbles in glacier ice that explode upon melting of the ice, where over time the air pressure within the bubble has reached high values.
https://pof.tnw.utwente.nl/media/files/Studentprojects/PoF_MeltingBubbles.pdf

and core sample expansion due to bubble pressure relaxation
https://www.cambridge.org/core/jour...-glacier-ice/C8CB03F5D01BDA8C9D203B8BEDFC8FC4

 

[Chestermiller]

Here's a focus problem: I have a spherical shell of low density polyethylene of inner radius 10 cm and outer radius 10.1 cm. The shell is completely full of liquid water at 0 C. I lower the temperature of the shell and water to -1 C. Quantitatively, what is the state of stress of the water and what is the state of stress of the shell?

 

[PAllen]

Here's a focus problem: I have a spherical shell of low density polyethylene of inner radius 10 cm and outer radius 10.1 cm. The shell is completely full of liquid water at 0 C. I lower the temperature of the shell and water to -1 C. Quantitatively, what is the state of stress of the water and what is the state of stress of the shell?

My understanding is that it would take a much stronger shell than that to keep the water liquid; so it would beak or stretch.

 

[256bits]

Here's a focus problem: I have a spherical shell of low density polyethylene of inner radius 10 cm and outer radius 10.1 cm. The shell is completely full of liquid water at 0 C. I lower the temperature of the shell and water to -1 C. Quantitatively, what is the state of stress of the water and what is the state of stress of the shell?

One can calculate the radial increase from the volume boost due to the phase change.

For a container of stretchy material that expands willingly, ( such as thin rubber balloon )
A 9% increase in volume translates into a 2.9 mm difference from initial inner radius to final.
The outer radius would increase somewhat less than 2.9mm, but not much less.

V1 = 4/3 π r1³ = 4188.78 where r1= 10 cm
V2 = 4/3 π r2³ = 4565.78 a 9% increase due to phase change
r2 = 10.29 cm

Visually noticeable, maybe??

 

[FactChecker]

One can calculate the radial increase from the volume boost due to the phase change.

For a container of stretchy material that expands willingly, ( such as thin rubber balloon )
A 9% increase in volume translates into a 2.9 mm difference from initial inner radius to final.
The outer radius would increase somewhat less than 2.9mm, but not much less.

V1 = 4/3 π r1³ = 4188.78 where r1= 10 cm
V2 = 4/3 π r2³ = 4565.78 a 9% increase due to phase change
r2 = 10.29 cm

Visually noticeable, maybe??

IMO, 9% should be noticeable. I was actually surprised that it is that large.
CORRECTION: I was thinking about a 9% increase in radius, not volume.

 

[256bits]

Here is a representations of 2 spheres, one 9% larger in volume than the other due to phase change of water from liquid to solid.

 

[erobz]

Here's a focus problem: I have a spherical shell of low density polyethylene of inner radius 10 cm and outer radius 10.1 cm. The shell is completely full of liquid water at 0 C. I lower the temperature of the shell and water to -1 C. Quantitatively, what is the state of stress of the water and what is the state of stress of the shell?

Is this a nasty problem? Qualitatively, the polyethylene will tend to contract and compress the ice somewhat from its freely expanded volume under the temperature change, unless of course the induced stress from the ice expansion dominates and brings the shell to yield?

Is the computation involve $e = \frac{1-2\nu}{E} \left( \sigma_x + \sigma_y \right)$ and perhaps $\sigma_x = \sigma_y = \frac{pr}{2t}$ for a thin walled pressure vessel. The objective to solve for the pressure $p$?

 

[swissgirl1999 Refer]

This is no paradox, it is standard experimental science. Well-considered and carefully-executed controls are critical to good experiments. Good science is difficult. And challenges to mainstream results are especially difficult, precisely because they already went through that careful effort. We hold all scientists to this high standard.

In the end, this is the difference between the “independent researcher” and the “crackpot”. The “independent researcher” is doing actual science outside of a university or corporate setting, while the “crackpot” is just posturing.

Indeed, nobody can. Nor should they.

You need to ask yourself if you are an independent researcher or a crackpot. Researchers (independent or not) see their observations/questions as an opportunity for them to do some scientific research and contribute to the body of knowledge. If you see your own research questions as a burden to be placed on others then you are not a researcher.

Assuming that you are an independent researcher, at this point you are at the “observation/question” stage of the scientific method. You have an interesting observation. Now you do your background research and form a question about possible mechanisms that could explain your observation. Then you design an experimentally testable hypothesis. You have received a lot of advice about important controls and measurements, which should inform your experimental design. Then you execute the experiment, analyze the data, and report the results. That is the scientific method, the mark of any researcher

Yes, I'm an independent researcher with access to a functional kitchen, a bunch of thermometers, and several different types of microscopes.

My “laboratory” is as sophisticated as it can be.

I also do not expect the community to do the work for me.

However, when the observations from an outsider contradict the textbook, even with precise quantitative data, it is not taken seriously by the academic community, because "challenges to mainstream results are especially difficult, precisely because they already went through that careful effort."

Nevertheless, that effort took place inside institutions, with peer review, with labs, with grants and prestige.

I do not have any of those.

That’s why my focus is to present qualitative observations that are robust, cheap, and visible enough, so that it could raise curiosity.

The gas bubbles that form in still water and survive freezing.
The structures that fracture under microscopy.

Or, like this comparison between these two apparently distinct types of vesicles (i.e., bubbles):

One type seems empty, as one would expect from empty voids filled by air; the other presents 5 recurrent patterns.

I couldn’t find official literature about the second one, which is much more frequent, at any magnification from the most type of fluids.

Here, again, however, I refrain myself from presenting any conclusion, because my goal is for others to go look for themselves.

At the end of the day, I’m an independent researcher without theories, but with observations.

 

[A.T.]

when the outcome contradicts the textbooks

If by 'textbooks' you mean school books, which present an extremely simplified version of usually somewhat outdated state of current knowledge, then it's really no surprise that observations often seem at odds with them.

For example, if you pour boiling water into a PET-bottle, it will shrink, not expand.

 

[weirdoguy]

when the observations from an outsider contradict the textbook

I don't even think that what you do with your experiments (with so many complexities and variables) is covered in any textbook. I am worried though that you think you're doing something against 'mainstream", because you don't, so:

it is not taken seriously by the academic community

Because 99,99% of people who think they discovered something contradicting mainstream are wrong. Stop talking that you are doing something that contradicts known science (because you don't) and you will be taken seriously.

 

[Dale]

Yes, I'm an independent researcher with access to a functional kitchen, a bunch of thermometers, and several different types of microscopes.

My “laboratory” is as sophisticated as it can be

Excellent. Most of the suggestions you have received can be done with kitchen equipment.

when the observations from an outsider contradict the textbook, even with precise quantitative data, it is not taken seriously

This is simply not correct. I have been a peer reviewer for well over 100 manuscripts. In all of those, I only knew who I was reviewing once (and that only because they cited themselves in the first person in the text).

The process is double-blind by design, precisely to avoid any decision-making based on the people. All I have access to, as a reviewer, is the manuscript itself, so the decision can only be based on the quality of the work. Even if a peer reviewer wanted to make a biased decision, they simply could not.

Independent researchers do not struggle because the community doesn’t take them seriously or otherwise discriminates against them. They struggle because good science is difficult.

my goal is for others to go look for themselves

That is not independent research.