[Physics] How strong is the force of ice expanding when freezing

estimationforcesfreezingthermodynamicswater

Why does water contract on melting whereas gold, lead, etc. expand on melting? reminded me about something I've been wondering myself for some time.

We know that water expands as it freezes. The force is quite formidable – it can cause solid steel pipes to rupture. But nothing is limitless. If we created a huge ball of steel and placed a small amount of water inside it (in a small, closed cavity) and then froze it – I don't think the big ball would rupture.

But what would we get? Compressed ice? Can this even be done? Can you compress ice? Or would the water simply never freeze? Or freeze only partially? What if we kept cooling it, down to absolute zero (or as close as we can get)?

What happens when water should expand, but there is no room for it to do so, and the container is too strong to be deformed?

Best Answer

But what would we get? Compressed ice? Can this even be done? Can you compress ice?

Absolutely; all passive materials can be compressed. The bulk modulus, a material property with units of pressure, couples the applied pressure to a relative reduction in volume. The bulk modulus for ice at 0°C is around 8 GPa, which means that about 8 MPa or 80 bar pressure is required for a -0.1% volumetric change.

What happens when water should expand, but there is no room for it to do so, and the container is too strong to be deformed?

Here, a phase diagram for water is useful. The discussion in Powell-Palm et al.'s "Freezing water at constant volume and under confinement" includes a pressure–volume phase diagram:

From this, we can predict the equilibrium response when heating or cooling water at constant volume (by moving vertically) or compressing or expanding water at constant temperature (by moving horizontally). We find that at constant volume (moving vertically downward from 0°C and 1 g/cc), over 200 MPa and 20°C undercooling is required* to get even a 50% slush of water and ice.

Let's zoom out a little. From Powell-Palm, "On a temperature-volume phase diagram for water and three-phase invariant reactions in pure substances," we find that 209.9 MPa is ultimately required* for complete solidification, into a two-phase region (at equilibrium) of ice-Ih (ordinary ice) and ice-III:

(Note that "0.00611 MPa" should read "0.000611 MPa"—the authors missed a zero.)

We can interpret this as the compact structure of ice-III providing a solution to the problem of ice-Ih being anomalously voluminous. We find from the temperature–pressure phase diagram of water that this ice-III nucleates (at equilibrium) upon cooling to 251 K, or -22°C:

enter image description here

With further cooling, the ice-I–ice-III mixture transforms* to ice-I–ice-II, then to ice-IX–ice-II, and then to ice-XI–ice-IX. (How can this be determined, since the volume–temperature chart doesn't include any of that information? It's from the horizontal line on the temperature–pressure chart and the knowledge that ice-I and ice-XI have specific volumes of >1 g/cc and that ice-II, ice-III, and ice-IX have specific volumes of <1 g/cc; thus, a higher-density and lower-density combination is required to maintain a constant 1 cc/g, and we can't move an iota above or below that two-phase line upon cooling at constant volume.)

Note that no power can be generated under the condition of constant volume, as no displacement occurs. And although there's no thermodynamics prohibition about allowing the system to expand and do useful work, you would have to heat it up again to liquefy it to repeat the process, and this would use up the energy you gained.

*Note that this answer always refers to equilibrium phase predictions. Sufficiently rapid cooling involves kinetic limitations that delay or essentially even preclude phase transitions. For example, liquid water can be cooled fast enough that crystals essentially never form even though the thermodynamic driving force is large. Here, the solid water is said to be in a glassy or amorphous state.

(See also the fun rotatable 3D phase diagram of water here.)