How does a shock, such as the snap of the disk in a reusable hand warmer, trigger the re-crystalization of a supersaturated solution?

Question

Reusable handwarmers are made of something dissolved nearly to its saturation point in hot water (Sodium Acetate in the case of HotSnapz) at a high temperature, and then cooled to a temperature at which some would normally be insoluble, but remains dissolved due to a lack of a site to grow a crystal from. When the crystal finally grows, triggered by popping a little disk, the process is exothermic and it releases heat.

What I'm wondering is: how does popping the little metal disk inside the hand warmer allow nucleation to begin?

EDIT: I got a bit more information, but nothing definitive. What I’ve heard is that the metal disk may either be initiating nucleation by releasing tiny metal particles when it snaps or by snapping quickly enough to cause cavitation. The first seems unlikely, because if bits of metal were released and functioned as nucleation sites, the warmer wouldn’t be reusable - the crystals could just reform on those metal bits. Cavitation seems more plausible, though I still don’t understand how that would allow crystallization to begin.

EDIT 2: I did some experimenting, and a whack also starts nucleation, not just the disc snapping. So, any shock can cause the sodium an acetate ions to come out of supersaturated solution. How?

Answer 1

Edit: Contribution of enthalpy and bond formation

Edit 2: Changed the description of entropy

After thinking for sometime, I realized that I neglected to mention three things:

1. The Driving force of precipitation reactions depends on the charge and size of the ions which corresponds directly to the magnitude and order of the hydration shells formed upon dissolution of the salt.

2. The enthalpy as a driving force of the precipitation of the salt. (Remember the Gibbs Free energy equation has two terms, entropy and enthalpy)

3. Additionally, the formation of ionic bonds can be lower in energy (more stable) than the electrostatic interactions present in solution. The release of energy during salt formation is transferred to the surroundings as heat. This would be a negative enthalpy (heat flowing out of the system) and if large enough, would overcome any decreases in entropy stemming from the formation of highly order crystalline structures and drive the precipitation.

In this case it is probably the enthalpy term that is driving the reaction, since you are putting a ton of heat into the system to dissolve the salt, once the solution cools, there is a lot of potential energy that is stored in the position of the atoms in the system. This is then released as heat upon the formation of the crystal structures.

Entropy changes in precipitation reactions:

In order to make a supersaturated solution, you have to add energy to form hydration shells around the ions (entropy in the system is decreasing). The thing to remember is that these hydration shells decrease the dispersal of the ions relative to that in the crystalline structure for some salts. When you heat and mix the solution with excess solute, you are providing sufficient energy to form hydration shells. When the solution cools (Slowly), the hydration shells remain intact, however, the system is unstable and applying enough energy to the solution will disrupt the hydration shells and crystallization of the salt will occur. The large amount of heat that is released is coming from the increase in the micro-states available for the ions (gain in entropy) in removing the hydration shells around the ions. The hydration shells are less dispersed than the crystalline structures of the salt and that is why entropy increases during some crystallization reactions, making this process exothermic.

Here is why the disc snapping is important:

Even though this process is very exothermic, it still requires activation energy. The mechanical force you are referring to (i.e. snapping the disc or whacking the heating pad) is doing just that by simply transferring energy to the molecules, through vibrations, which provides the activation energy for crystallization.

Just as walking can cause energy transfers from the mechanical forces of your legs to the molecules of the floor (i.e. through friction) and increase the temperature of the surface, some of the force applied on the disc transfers to the solution and if it is enough, will overcome the activation energy barrier of the process and crystallization will begin.

Answer 2

The problem with crystallization of a supersaturated solution is that all molecules are equal. No particular molecule is "entitled" to be the first to start the first crystal. An external event is needed to "nominate" the place of the first crystallization. This external event can be an impurity, a sudden shock, an irregularity at the surface of the container. But once the first face of the first microcrystal is created, all other molecules "know" where and how to develop the crystallization process.