From the portals of hell to built-in fire protection: intumescents

A friend posted the link to this demonstration, wondering if it was safe. (Do listen to the children in the background - their cries of "kraken" at 1:02 are worth it.  Science is great fun!)

The caption that came with it noted that it was a mixture of ammonium dichromate ((NH₄)₂Cr₂O₇ )and HgSCN (mercurous thiocyanate).¹ Mercury and chromium, probably not something you want to eat I told my friend. The whole thing made me curious, just what were those tentacles come out of the burning pile? And what chemical reactions were driving it?

It's a coupled set of decomposition reactions. The volcano comes from the decomposition of ammonium dichromate

(NH₄)₂Cr₂O₇(s) → Cr₂O₃(s)+ N₂(g)+ 4H₂O(g)

The reaction produces a lot of heat, which makes the particles being thrown off by the rapid expansion of the two gases (nitrogen and water vapor) glow.

The heat then triggers the decomposition of the mercury compound:

2 Hg(SCN)₂(s) → 2HgS + 4CS₂ + carbon nitrides

The erupting tentacles are an example of intumescence², a property of mercury thiocyanates noted long ago by the venerable Friedrich Wöhler³. It's a well known demonstration, often called Pharaoh's Serpents. Many material intumesce when heated, and thus produce their own insulation.  Some passive fire protection systems rely on this property of polymers, by which they essentially rapidly produce their own insulating layer upon heating, or by swelling up to block air ducts to prevent smoke and other gases from spreading too quickly through a ventilation system.

It works with mercuric thiocynate as well (Hg(SCN)₂) — by some accounts even better — and better yet if you toss a bit of potassium nitrate and a bit of fuel in the form of sugars. In other bits of historical trivia, the mercuric thiocyanate was originally made by the aptly named Otto Hermes. The sale of mercuric Pharaoh's Eggs ceased after some kids ate them with deleterious (fatal) effects.

If you just want to see the snakes minus chromium salts or mercury - try this demonstration based on calcium gluconate instead or check out pyrotechnic expert Tenney Davis suggestions in the Journal of Chemical Education.

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1.  From the Latin verb "to swell" — related to thumb and tuber (as in root vegetables like potatoes)

2.  The chemist who showed in 1828 that compounds made by nature do not have some "vital essence" that distinguishes them from the same structure crafted by a chemist from inorganic (never living) materials.  Something the Food Babe and hawkers of 'bioidentical' hormones do not get.

Read more:

Brian Clegg at Chemistry World.  A paper on the demonstration from Journal of Chemical Education in 1940, by Tenney Davis of MIT who taught courses in explosives way back when ($).