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 In other bits of historical trivia, the mercuric thiocyanate was originally made by the aptly named Otto Hermes.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 ($).

Molecular Jek-yls and -hydes

Like Jekyll and Hyde, changing a functional group changes 
a molecule's behavior. Image from Library of Congress.

Chains of pure carbon and hydrogen, called hydrocarbons by chemists, are notoriously hard to get a chemical handle on.  One of the major driving forces in chemical reactions is "opposites attract" — in this case opposite charges.  Since carbon and hydrogen have essentially the same desire for electrons (negative charges), there is not much difference in charge around to drive a reaction. Swap out a hydrogen for something else that does have a relative charge —  chlorine, fluorine, oxygen, nitrogen — and suddenly you have something to react with.  Chemists call these riffs on a basic carbon framework "functional groups" - they are often the parts of a molecule's structure that drive its function.

Change up the functional group, and you change the molecule's behavior. Like Jekyl and Hyde.  Ethanol is something to drink on a Friday night, ethanal is found in the coffee you drink for the hangover the next morning (in an ironic twist, it's also produced as your body metabolized the ethanol.)

The first part of a chemical name tells the size of the carbon framework, the ending tells you about its function — or lack thereof.  Names that end in -yl or -ane mean a hydrocarbon chain without any fancy functionality.  Propane, a popular fuel, is a three carbon hydrocarbon chain.  Methyl mercaptan (added to odorless natural gas to make it smell, and make leaks quickly noticeable), has a one carbon long "chain" in it. Change -yl to -ol and you have made an alcohol, a chain with an -OH group on it (Ethanol is CH₃CH₂OH, sometimes written EtOH, a 2 carbon chain with an OH group on it.)

Knowing the functional groups means knowing something about the kinds of things a molecule can do.  Esters smell floral, carboxylic acids can remove a layer of skin, and are found in many lotions.

So to decode:

-ol means an alcohol (functional group = -OH) but not necessarily the kind of alcohol you drink 

-al means an aldehyde (-COH); these often smell sweetish 

-oxy means an ether (an oxygen sandwiched between two carbon chains) 

-oic acid or -ic acid means a carboxylic acid (pronounced "car-box-sill-ick") salicylic acid, often found in face washes 

-oate means an ester (a COO group sandwich between two chains); ethyl nonanoate smells like grape, the functional group is between a 2 carbon chain (ethyl) and nine carbon chain (nona) 

-one means a ketone, a CO group sandwiched in between two chains

Check out Andy Brunning's of Compound Interest's great graphic on functional groups and their names and Practically Science's map of molecules in food and their smells.

A rose by any other name is poison ivy

In 1865 John Maisch published a short paper "On the Active Principle of Rhus Toxicodendron". For the unsensitized, rhus toxicodendron is the botanical name for poison ivy. Maisch isolated a fraction he considered to be the "active principle" responsible for the misery that is poison ivy and dubbed it toxicodendric acid. Are you itchy yet? (I am and Maisch surely was, he and various visitors to his lab suffered with outbreaks of poison ivy.)

By 1897 Franz Pfaff of Harvard had weighed in. Toxicodendric acid extracted from poison ivy turned out to be acetic acid - yes, vinegar, by another name, CH₃COOH. He showed the itch was in the oil.

Protecting Groups

The whole family was at camp last week, living in tents, sleeping on cots, eating in the mess hall. Every camp has them, squirrels and chipmunks that survive on the crumbs of campers' treats (or sometimes the whole banana). We were warned - no food in the tents except in metal boxes.

The boys had the tent next door to ours. I came back from dinner one night to find a very happy squirrel just making off with a chip container from the kids tent. At which point I remembered the dried fruit I'd left in my pack after the morning hike. Whew...it was still there. The rodents had been attracted to the far more tasty snack leavings next door. The boys tent is serving as (a chemist would say) a protecting group.

Chemical protecting groups work similarly. Say you have two sites on a molecule that can react with a reagent, but you only want one to undergo the reaction. If you can put a protecting group on the site you want left unmolested, like a cover, you can run the reaction, change the other site and then take off the protecting group. (See the scheme for an example.)

It works wonderfully for many reactions, and is keeping my pack safe from marauders.

Melting Points

Pain perdu - a delicious part of my New Orleans heritage and better known in most of the US as french toast - has a long history. The earliest extant recipe is in Latin and dates to the 4th or 5th century! Friday brought a snow day for my kids, and come evening, some experimental time for me in my favorite home lab.

After a day spent teaching and shoveling in the sleet, I made pain perdu aux pommes from Simon Hopkinson's Second Helpings of Roast Chicken. Think french toast, vanilla custard, apples and caramel sauce. The first step in making the caramel sauce is to melt sugar over high heat. As I stirred the dry sugar in my heaviest sauce pot, alert for the first sign of melting, I flashed back to my days in an organic chemistry research lab. Melting points were used both to identify products (though even then, spectroscopic methods such as NMR were the gold standard) and to verify purity. Taking an accurate melting point required patience - and being attentive to the appearance of that first glistening drop of liquid in the fine capillary tube. It looked almost as if the crystals were sweating.

How is the purity of a compound related to its melting point? An impure sample will tend to melt over a few degree range, pure samples will melt at a sharp temperature. Impurities in a solid will also depress its melting point, in the same way that applying salt to ice (another application of chemistry appropriate for a snow day) lowers the freezing point. This phenomena also offers a low tech way to confirm the identity of a compound. Make a mixture of the sample to be identified and a known sample of (presumably) the same stuff. If the melting point is sharp and the same as the pure compound, the unknown is certain to be what you think it is. This will work even if the melting points of the two compounds are fortuitously the same.

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A nice film of a melting in a capillary tube can be found at Wellesley's organic chem lab site.

Perils of Summer 2: Mephitis Squared

It's war on my dad's farm: humans versus Mephitis mephitis, night time maneuvers complete with chemical weapons. Currently the skunks hold the high ground.

Last night my brother's dog threatened a skunk, with predictable results. The collateral damage included my shoes and feet. The Reverend's Wife produced a bottle of something guaranteed to elminate the smell and we decontaminated me and the dog on the lawn. I was more cooperative about being hosed down. The odor was overpowering, and even after twice deskunking me, my kids swore I still smelled of skunk.

Skunk musk is a mixture of low molecular weight thiols, sulfur containing compounds that have the basic structure ☐-S-H (where the box represents a functional group, such as methyl or butyl), and related compounds called thioacetates. Most thiols have a characteristic, and awful, odor. (Thioacetates don't smell quite so badly.) The simplest thiol is methane thiol, also known as methyl mercaptan, which is used to spike methane (natural gas) so that leaks can be detected. (Methane is actually odorless.) Humans can detect thiols at very low concentrations, less than 1 ppm, which explains why my kids could still pick up the odor.

Skunk odor can be neutralized by converting the thiols to less odiferous molecules. One way this can be accomplished is by reacting the thiols with hydrogen peroxide, which oxidizes the thiol to a sulfonic acid ( ☐-SO₃H), which has virtually no odor. Bleach (a strong oxidizing agent) will work as well. A similar technology is used to remove thiols from industrial waste water, where the thiols are converted to disulfides ( ☐-S-S- ☐), which are oils that separate easily from the water.

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Mercaptan comes from the Latin mercurium captans, something that seizes or captures mercury. Sulfur reacts very effectively with mercury, and one way to clean up a mercury spill is to sprinkle sulfur on the mercury. Thiol is Greek for sulfur.

If you need a recipe to remove skunk odor, try Humbolt's list. I can personally vouch for the effectiveness of the pet/human version. Note that tomato juice is not particularly effective.

1-para-methen-8-thiol is an uncharacteristically and pleasantly scented thiol more commonly known as grapefruit mercaptan.

More demystified chemical perils of summer...

Indolent Molecules

I heard a colleague talk today at the MidAtlantic Regional Meeting of the ACS about his work with fluoroquinones. These molecules (which despite their name contain no fluorine) fluoresce, that is they "glow" when exposed to light. The process can be short circuited by binding another molecule, a quencher, to fluoroquinone. The research discussed the quenching behavior of tryptophan. Tryptophan is an amino acid, one of the building blocks of proteins. Structurally, it's an indole; an aromatic six-membered ring fused to a five-membered ring containing a nitrogen forms the core.
Tryptophan is thought to induce sleep - and is often blamed for post-Thanksgiving meal naps. Melatonin, which also play a role in sleep regulation, is also an indole.

The indoles of chemistry get their name from the Latin for indigo, the dye from which the basic indole structure was first isolated. The indolence which some indoles induce has a different etymological root, dolorens - grief or pain.