Big Chemistry: Fuel Ethanol

If legend is to be believed, three disparate social forces in early 20th-century America – the temperance movement, the rise of car culture, and the Scots-Irish culture of the South – collided with unexpected results. The temperance movement managed to get Prohibition written into the Constitution, which rankled the rebellious spirit of the descendants of the Scots-Irish who settled the South. In response, some of them took to the backwoods with stills and sacks of corn, creating moonshine by the barrel for personal use and profit. And to avoid the consequences of this, they used their mechanical ingenuity to modify their Fords, Chevrolets, and Dodges to provide the speed needed to outrun the law.

Though that story may be somewhat apocryphal, at least one of those threads is still woven into the American story. The moonshiner’s hotrod morphed into NASCAR, one of the nation’s most-watched spectator sports, and informed much of the car culture of the 20th century in general. Unfortunately, that led in part to our current fossil fuel predicament and its attendant environmental consequences, which are now being addressed by replacing at least some of the gasoline we burn with the same “white lightning” those old moonshiners made. The cost-benefit analysis of ethanol as a fuel is open to debate, as is the wisdom of using food for motor fuel, but one thing’s for sure: turning corn into ethanol in industrially useful quantities isn’t easy, and it requires some Big Chemistry to get it done.
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Big Chemistry: Cement And Concrete

Not too long ago, I was searching for ideas for the next installment of the “Big Chemistry” series when I found an article that discussed the world’s most-produced chemicals. It was an interesting article, right up my alley, and helpfully contained a top-ten list that I could use as a crib sheet for future articles, at least for the ones I hadn’t covered already, like the Haber-Bosch process for ammonia.

Number one on the list surprised me, though: sulfuric acid. The article stated that it was far and away the most produced chemical in the world, with 36 million tons produced every year in the United States alone, out of something like 265 million tons a year globally. It’s used in a vast number of industrial processes, and pretty much everywhere you need something cleaned or dissolved or oxidized, you’ll find sulfuric acid.

Staggering numbers, to be sure, but is it really the most produced chemical on Earth? I’d argue not by a long shot, when there’s a chemical that we make 4.4 billion tons of every year: Portland cement. It might not seem like a chemical in the traditional sense of the word, but once you get a look at what it takes to make the stuff, how finely tuned it can be for specific uses, and how when mixed with sand, gravel, and water it becomes the stuff that holds our world together, you might agree that cement and concrete fit the bill of “Big Chemistry.”

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Big Chemistry: Glass

Humans have been chemically modifying their world for far longer than you might think. Long before they had the slightest idea of what was happening chemically, they were turning clay into bricks, making cement from limestone, and figuring out how to mix metals in just the right proportions to make useful new alloys like bronze. The chemical principles behind all this could wait; there was a world to build, after all.

Among these early feats of chemical happenstance was the discovery that glass could be made from simple sand. The earliest glass, likely accidentally created by a big fire on a sandy surface, probably wasn’t good for much besides decorations. It wouldn’t have taken long to realize that this stuff was fantastically useful, both as a building material and a tool, and that a pinch of this and a little of that could greatly affect its properties. The chemistry of glass has been finely tuned since those early experiments, and the process has been scaled up to incredible proportions, enough to make glass production one of the largest chemical industries in the world today.

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Big Chemistry: Catalysts

I was fascinated by the idea of jet packs when I was a kid. They were sci-fi magic, and the idea that you could strap into an oversized backpack wrapped in tinfoil and fly around was very enticing. Better still was when I learned that these things weren’t powered by complicated rockets but by plain hydrogen peroxide, which violently decomposes into water and oxygen when it comes in contact with a metal like silver or platinum. Of course I ran right to the medicine cabinet to fetch a bottle of peroxide to drip on a spoon from my mother’s good silverware set. Needless to say, I was sorely disappointed by the results.

My little impromptu experiment went wrong in many ways, not least because the old bottle of peroxide I used probably had little of the reactive compound left in it. Given enough time, the decomposition of peroxide will happen all by itself. To be useful in a jet pack, this reaction has to proceed much, much faster, which was what the silver was for. The silver (or rather, a coating of samarium nitrate on the silver) acted as a catalyst that vastly increased the rate of peroxide decomposition, enough to produce jets of steam and oxygen with enough thrust to propel the wearer into the air. Using 90% pure peroxide would have helped too.

As it is for jet packs, so it is with industrial chemistry. Bulk chemical processes can rarely be left to their own devices, as some reactions proceed so slowly that they’d be commercially infeasible. Catalysts are the key to the chemistry we need to keep the world running, and reactors full of them are a major feature of many of the processes of Big Chemistry.

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Big Chemistry: Hydrofluoric Acid

For all of the semiconductor industry’s legendary reputation for cleanliness, the actual processes that go into making chips use some of the nastiest stuff imaginable. Silicon oxide is comes from nothing but boring old sand, and once it’s turned into ultrapure crystals and sliced into wafers, it still doesn’t do much. Making it into working circuits requires dopants like phosphorous and boron to give the silicon the proper semiconductor properties. But even then, a doped wafer doesn’t do much until an insulating layer of silicon dioxide is added and the unwanted bits are etched away. That’s a tall order, though; silicon dioxide is notoriously tough stuff, largely unreactive and therefore resistant to most chemicals. Only one substance will do the job: hydrofluoric acid, or HFA.

HFA has a bad reputation, and deservedly so, notwithstanding its somewhat overwrought treatment by Hollywood. It’s corrosive to just about everything, it’s extremely toxic, and if enough of it gets on your skin it’ll kill you slowly and leave you in agony the entire time. But it’s also absolutely necessary to make everything from pharmaceuticals to cookware, and it takes some big chemistry to do it safely and cheaply.

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Big Chemistry: Liquefied Natural Gas

The topic of energy has been top-of-mind for us since the first of our ancestors came down out of the trees looking for something to eat that wouldn’t eat them. But in a world where the neverending struggle for energy has been abstracted away to the flick of a finger on a light switch or thermostat, thanks to geopolitical forces many of us are now facing the wrath of winter with a completely different outlook on what it takes to stay warm.

The problem isn’t necessarily that we don’t have enough energy, it’s more that what we have is neither evenly distributed nor easily obtained. Moving energy from where it’s produced to where it’s needed is rarely a simple matter, and often poses significant and interesting engineering challenges. This is especially true for sources of energy that don’t pack a lot of punch into a small space, like natural gas. Getting it across a continent is challenging enough; getting it across an ocean is another thing altogether, and that’s where liquefied natural gas, or LNG, comes into the picture.

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Big Chemistry: Ultrapure Water

My first job out of grad school was with a biotech company in Cambridge, Massachusetts. It was a small outfit, and everyone had a “lab job” in addition to whatever science they were hired to do — a task to maintain the common areas of the lab. My job was to maintain the water purification systems that made sure everyone had an ample supply of pure, deionized water to work with. The job consisted of mainly changing the filter and ion-exchange cartridges of the final polishing units, which cleaned up the tap water enough for science.

When I changed the filter packs, I was always amazed and revolted by the layers of slime and sediment in them. A glimpse out the window at the banks of the river Charles — love that dirty water — was enough to explain what I was seeing, and it was a lesson in just how much other stuff is mixed in with the water you drink and cook with and bathe in.

While we humans can generally do pretty well with water that rates as only reasonably pure, our industrial processes are quite another thing. Everything from power plants to pharmaceutical manufacturing facilities needs water of much, much higher purity, but nothing requires purer water than the specialized, nanometer-scale operations of a semiconductor fab. But how does ordinary tap water get transformed into a chemical of such purity that contaminants are measured in parts per trillion? And how do fabs produce enough of this ultrapure water to meet their needs? With some big chemistry.

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