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Freezing Point of Water

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klimatos
#1
Nov30-13, 02:52 PM
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Why do we define the freezing point of pure water as 0C when most pure water does not freeze at that temperature?

Instead, it can and does remain in the liquid phase down to temperatures as low as -48C [Molinaro & Moore, 2011].

Cold-weather clouds throughout the Earths atmosphere consist primarily of water droplets at temperatures tens of degrees below 0C. These droplets of liquid water are quite stable. They condense, collide, agglomerate, fragment, and vaporizeall without freezing. Most cumulonimbi (thunderheads) do not form their icy anvil until updraft ambient air temperatures approach -42C.

I am well aware that the abundance of exotic (non-water) icing nuclei on the Earths surface brings about surface freezing in the vicinity of 0C, but such water is hardly pure. Water uncontaminated by such nuclei does not freeze at 0C.

Why then should the generally accepted scientific definition of waters freezing point be 0C?
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phinds
#2
Nov30-13, 03:00 PM
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I think it's because that's the highest temperature at which it will freeze. Everything thing you say is true as far as I know but which of those various temperatures at which water CAN freeze would you pick as being the temperature to say that it is where water DOES freeze? You really can't pick any particular temperature in the range of 0 degrees to something like minus 50 degrees. SO ... if you don't like zero, what would you recommend?
Yanick
#3
Nov30-13, 05:33 PM
P: 380
PURE water at the surface of the earth does freeze at zero Celsius. Although I can't explain what goes on in the clouds because I don't know enough about those systems, I can assure you that zero Celsius is not a mistake.

With that said there are plenty of factors which can change the physical properties of water like solutes for example, which will lower the chemical potential of liquid water thereby lowering the freezing point. I would not expect water droplets in the atmosphere to be pure, there's gotta be some 'stuff' in them.

There is also the phenomenon of supercooled water which is a metastable state in which water can exist as a liquid below its freezing point.

Not trying to completely solve the dilemma here. Just trying to say that the freezing point of pure water is not a mistake. In fact water has been measured so thoroughly that temperature scales were built around things like the freezing/boiling/triple point of water for a long time.

I also don't understand what you mean by 'icing nuclei' and would like an example of such.

phinds
#4
Nov30-13, 05:40 PM
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Freezing Point of Water

Quote Quote by Yanick View Post
PURE water at the surface of the earth does freeze at zero Celsius.
Hm ... I though it was possible to cool water below zero if it is kept very still. I've seen videos of so called "supercooled" water that freezes instantly if agitated. Perhaps that was not pure water and had suspended particles.
Yanick
#5
Nov30-13, 06:02 PM
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Quote Quote by phinds View Post
Hm ... I though it was possible to cool water below zero if it is kept very still. I've seen videos of so called "supercooled" water that freezes instantly if agitated. Perhaps that was not pure water and had suspended particles.
Yes you are correct, I mentioned supercooled water in the third paragraph of my reply. Supercooled water can exist at temperatures below the freezing point provided that the container is very clean and, I believe, the water has minimal contaminants. Supercooled liquids will freeze when a site of nucleation is provided, such as a crystal of the already frozen compound. In undergraduate chemistry labs students are instructed to gently scrape the beaker containing the liquid to provide nucleation sites for freezing of supercooled fluids. Supposedly it is the tiny chunk(s) of glass that are scraped off which do this in the latter case.

Metastability is analogous to a ball teetering on the edge of a cliff or top of a hill. Thermodynamically disfavored yet kinetically slow to reach equilibrium.
AlephZero
#6
Nov30-13, 08:45 PM
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Quote Quote by phinds View Post
Hm ... I though it was possible to cool water below zero if it is kept very still. I've seen videos of so called "supercooled" water that freezes instantly if agitated. Perhaps that was not pure water and had suspended particles.
Yup, I accidentally did the experiment once. It was an unopened bottle of distilled water, bought for topping up car batteries (which is showing my age!), left on a shelf in the garage at sub-zero temperatures. it was definitely still liquid until I took it off the shelf and tried to open it, and the expansion of the suddenly-freezing ice cracked the bottle.

I don't know how pure it was, but it don't expect it contained the amount of gunk that is dissolved and suspended in tap water.
klimatos
#7
Nov30-13, 10:13 PM
P: 412
Quote Quote by phinds View Post
You really can't pick any particular temperature in the range of 0 degrees to something like minus 50 degrees. SO ... if you don't like zero, what would you recommend?
I have no problem with saying that water freezes at a variety of temperatures, depending upon a variety of contributing factors. That's what I used to tell my classes.

By the way, 0C is not the maximum temperature at which water freezes. Plant scientists have long reported icing in plant tissues at air temperatures as high as 4C, and very stable water-ice clathrates (ice mixtures that are neither compounds nor solutions) form under pressure in pipelines at temperatures as high as 18C.

The natural world is not as simple as we might wish.
phinds
#8
Nov30-13, 10:22 PM
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Quote Quote by klimatos View Post
I have no problem with saying that water freezes at a variety of temperatures, depending upon a variety of contributing factors. That's what I used to tell my classes.

By the way, 0C is not the maximum temperature at which water freezes. Plant scientists have long reported icing in plant tissues at air temperatures as high as 4C, and very stable water-ice clathrates (ice mixtures that are neither compounds nor solutions) form under pressure in pipelines at temperatures as high as 18C.

The natural world is not as simple as we might wish.
Very interesting. I didn't know any of that.
russ_watters
#9
Nov30-13, 10:24 PM
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The fact that you can sub cool water below 0C does NOT mean it doesn't still freeze at zero: when the sub cooling breaks, the temperature almost instantly rises to 0C and remains there while it freezes.
klimatos
#10
Nov30-13, 10:33 PM
P: 412
Quote Quote by Yanick View Post
PURE water at the surface of the earth does freeze at zero Celsius. Although I can't explain what goes on in the clouds because I don't know enough about those systems, I can assure you that zero Celsius is not a mistake.
How do you define "pure" water. All naturally-occurring water is contaminated to some degree, with various substances in solution and others in suspension. As a general rule, cloud droplets are much "purer" than surface water (the overwhelming bulk of which is saline).

With that said there are plenty of factors which can change the physical properties of water like solutes for example, which will lower the chemical potential of liquid water thereby lowering the freezing point. I would not expect water droplets in the atmosphere to be pure, there's gotta be some 'stuff' in them.
There is--as mentioned above. However, Most of this "stuff" does not depress the freezing point significantly.

[QUOTE]There is also the phenomenon of supercooled water which is a metastable state in which water can exist as a liquid below its freezing point. [QUOTE]

Cold air cloud droplets are supercooled by definition. However, they are not metastable. They are quite stable--as I described in my original question.

Not trying to completely solve the dilemma here. Just trying to say that the freezing point of pure water is not a mistake. In fact water has been measured so thoroughly that temperature scales were built around things like the freezing/boiling/triple point of water for a long time.
Yes. And many of them (including the short-lived centigrade scale) were erroneous.

I also don't understand what you mean by 'icing nuclei' and would like an example of such.
Icing nuclei are exotic substances, often hygroscopic, that mimic real ice crystals to some degree. This enables them to initiate ice crystal formation and tesselation. Examples are some dust particles, some pollen, and even some bacteria. At 0C, water without such contaminants generally does not freeze spontaneously.

Pure water can freeze spontaneously, of course, if "icing ions" are present. For example, the hydronium ion (H3O+) combines with six ordinary water molecules to form the icing ion H15O7+. This ion is electrostatically unsaturated and readily bonds and tessalates throughout a mass of cooling water to form ice.
klimatos
#11
Nov30-13, 10:56 PM
P: 412
Quote Quote by russ_watters View Post
The fact that you can sub cool water below 0C does NOT mean it doesn't still freeze at zero: when the sub cooling breaks, the temperature almost instantly rises to 0C and remains there while it freezes.
I did not read about any such warming in the study by Molinaro & Moore; nor have I read about any such warming in cold air clouds. There is a good deal of literature on the "icing point" in thunderheads that refers to freezing occurring at or near the -40C level. I must admit that I do not know of any researcher brave (or foolish) enough to personally measure the temperature of these freezing cloud droplets in cumulonimbi. I suspect that it was done by remote sensing.

I have no doubt but what you say is true under controlled laboratory conditions. I just wonder how well these conditions apply to the free and often violent atmosphere.
russ_watters
#12
Nov30-13, 10:57 PM
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Quote Quote by klimatos View Post
I have no problem with saying that water freezes at a variety of temperatures, depending upon a variety of contributing factors. That's what I used to tell my classes.
I'm sorry, but you taught them wrong.
By the way, 0C is not the maximum temperature at which water freezes. Plant scientists have long reported icing in plant tissues at air temperatures as high as 4C,
That's wrong too. The air might be at 4C but the water is not. Through evaporation, it cools.
russ_watters
#13
Nov30-13, 11:02 PM
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Quote Quote by klimatos View Post
and very stable water-ice clathrates (ice mixtures that are neither compounds nor solutions) form under pressure in pipelines at temperatures as high as 18C.
0C is for atmospheric pressure. Which also applies to clouds: you'll have to check the freezing point at altitude based on the pressure.
The natural world is not as simple as we might wish.
But simpler than you are making it.
klimatos
#14
Dec1-13, 12:03 AM
P: 412
Quote Quote by russ_watters View Post
I'm sorry, but you taught them wrong.

That's wrong too. The air might be at 4C but the water is not. Through evaporation, it cools.
The studies clearly state that the plant tissues are at the same temperature as the air. The water that freezes is in the cells of the plant tissues. It is not exposed to the air and does not evaporate.

As for the clathrates, I was given to understand that increased pressure depresses the freezing point, not elevates it. You have not given an explanation of water ice forming clathrates in pipelines at temperatures well in excess of 0C.
russ_watters
#15
Dec1-13, 08:51 AM
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Quote Quote by klimatos View Post
I was given to understand that increased pressure depresses the freezing point, not elevates it. You have not given an explanation of water ice forming clathrates in pipelines at temperatures well in excess of 0C.
It should - I was wrong about that. I don't know what is going on there. But:
The studies clearly state....
Without seeing such studies, I decline to speculate further. In any case, this is off track from the OP which was about normal water at atmospheric pressure.

You should read the wikis on freezing point and supercooling:
http://en.wikipedia.org/wiki/Freezing
http://en.wikipedia.org/wiki/Supercooling
Yanick
#16
Dec1-13, 10:35 AM
P: 380
Quote Quote by klimatos View Post
How do you define "pure" water. All naturally-occurring water is contaminated to some degree, with various substances in solution and others in suspension. As a general rule, cloud droplets are much "purer" than surface water (the overwhelming bulk of which is saline).
I should have been more careful with my phrasing. By "the surface" I simply meant under the conditions of a laboratory, at the surface of the Earth. As opposed to the clouds. By pure water, I mean water that has been run through some sort of purification protocol.

Quote Quote by klimatos View Post
There is--as mentioned above. However, Most of this "stuff" does not depress the freezing point significantly.
I never claimed that colligative properties are the sole factor responsible for such behavior. I'm just offering some phenomena up to show you that the freezing point of water can change and that those changes can be accounted for by known factors, instead of "Oh the freezing point of water is just wrong."

Quote Quote by klimatos View Post
Cold air cloud droplets are supercooled by definition. However, they are not metastable. They are quite stable--as I described in my original question.
Then they are, by definition, thermodynamically unstable. Think diamond/graphite, same kind of thing. Graphite is the stable form yet you need not fear that your diamonds will disappear any time soon as the conversion is kinetically disfavored.

Quote Quote by klimatos View Post
Yes. And many of them (including the short-lived centigrade scale) were erroneous.
Please elaborate. Numerically the temperature scales were either identical or had very minor corrections. Certainly not anywhere near the error you are suggesting in your post. Regardless of all that, you do realize that the triple point of water is still used to set up the thermodynamic temperature scale?

Quote Quote by klimatos View Post
Icing nuclei are exotic substances, often hygroscopic, that mimic real ice crystals to some degree. This enables them to initiate ice crystal formation and tesselation. Examples are some dust particles, some pollen, and even some bacteria. At 0C, water without such contaminants generally does not freeze spontaneously.
Yes it does, unless the fluid supercools but, once again, this is a metastable state which is not favored thermodynamically. Hence supplying a site of nucleation will help the kinetics side of it, but the freezing point of pure water is still O C.

Quote Quote by klimatos View Post
Pure water can freeze spontaneously, of course, if "icing ions" are present. For example, the hydronium ion (H3O+) combines with six ordinary water molecules to form the icing ion H15O7+. This ion is electrostatically unsaturated and readily bonds and tessalates throughout a mass of cooling water to form ice.
There is always some amount of auto-ionization in water which is described by the value Kw. I don't know what you mean by electrostatically unsaturated.

Have you ever learned thermodynamics? I think learning some of the core principles will help you greatly. I wish I knew more about atmospheric chemistry so I can help you out with your dilemma but I don't. I only want to get it through to you that the freezing point of pure water is not wrong and isn't a lie or whatever. There are plenty of factors which can explain liquids existing below their freezing points without resorting to such beliefs as all of the measurements were simply wrong.
256bits
#17
Dec1-13, 10:43 AM
P: 1,468
Quote Quote by klimatos View Post
The studies clearly state that the plant tissues are at the same temperature as the air. The water that freezes is in the cells of the plant tissues. It is not exposed to the air and does not evaporate.

As for the clathrates, I was given to understand that increased pressure depresses the freezing point, not elevates it. You have not given an explanation of water ice forming clathrates in pipelines at temperatures well in excess of 0C.
Plant tissue - Are we talking about why you have to bring your tomatoes indoors on a calm clear night where the air temperature can fall to somewhere in the vicinity of 4C. The plants radiate out to space and the air temperature is too low to supply enough heat via conduction to prevent freezing.

Clathrates - that is a different ice structure from that of what we consider where the melting point of normal ice at 0C. Apparantly clathrate formation is thermodynamically favourable above certain pressures and below certain temperatures. Clathrate is actually classified as a hydrate since the ratio of water molecules to the interstial molecule is variable. The water will form around the methane molecule, for example, with hydrogen bonds caging the methane molecule inside. No methane ( or other stabilizing molecule that can fit within the space - no cathrate. )

As you know liquid water molecules are always forming and unforming hydrogen bonds with related neighbors, and I suppose the methane molecule provides a location whereupon which the kinetic energy of other liquid molecules does not interupt the already hydrogen bond formation and thus other low kinetic energy water molecules can attach themselves into favourable locations to form the structure.
fluidistic
#18
Dec1-13, 11:24 AM
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I agree with russ watters when he says that the water, despite freezing at lower than 0C temperatures, will reach a temperature of 0C almost instantly after freezing.
I've played a lot in the lab with small drops of distilled water over a Pelletier cooler which was itself inside a refrigerator.
The smaller the drops were, the lower the temperature would be before freezing. I could measure temperatures as low as -18C, but as soon as they froze (which was instantly for the human eye), they'd reach a temperature of 0.0C instantly.
Water can reach temperatures below 0C without freezing because it isn't an equilibrium state (it's metastable equilibrium). Some people say that with a minor "bump" of energy the water would freeze, but this is not what I've experienced with small drops of distilled water.


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