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Low on battery?

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2001 a space odyssey

It’s 2015. Where’s my spaceship?

The other day I was reminded of something that happened, if my memory serves me correctly, in 2001. It seems like a long time ago doesn’t it? Strange to think that it seemed so futuristic to Arthur C. Clarke in 1968 that he named his classic science fiction novel with that date. Time is funny like that.

Anyway, back in 2001 I went into a mobile phone shop to get a new phone (yes young people, they did exist 14 years ago). I was shown one of the smaller, lighter phones on the market which was still, certainly by today’s standards, a rather blocky piece of kit. The salesman told me that phones just wouldn’t get much thinner than the model he was trying to convince me to sign up for, because that was the thinnest the batteries could be made.

How wrong was he? Perhaps not quite wrong on the scale of Bill Gate’s infamous (and since strenuously denied) “640K ought to be enough for anybody” line, but pretty wrong. Just a couple of years later lithium ion batteries became widely available, and everything changed.

Lithium-Ion-battery

Argh, my battery is down to 5%!

These days the only time most people think about batteries is when they’re cursing them for running down too quickly and scrabbling about looking for a charging cable. They’re part of modern life; something we take for granted. I’m writing this on a laptop that’s running on a battery. Pretty much everyone has a mobile phone with a battery. Lots of other devices in our households have batteries, either as their primary power source or as a backup to mains electricity. Electric cars, like the Nissan Leaf, run on batteries, and scientists are even investigating the possibility of putting large storage batteries into our houses to store any excess power generated from solar panels on our roofs.

And the majority of those batteries are lithium ion. Stop and think about that for a moment. Smartphones, tablets, eReaders and the like have changed our lives hugely over the last few years and yes, of course, they are the sum of lots of different strands of technology, including touch-screens and increasingly tiny processors. But the fact remains they probably just wouldn’t exist without the humble lithium ion battery, which provides a lightweight, thin and long-lasting (it is, really) source of captive electricity.

Lithium really doesn't place nicely with water.

Lithium really doesn’t play nicely with water.

Lithium batteries were first proposed in the 1970s, and the first ones actually contained lithium metal. Now, even if you’ve forgotten everything else you did in your school chemistry classes, you probably do remember your teacher dropping lithium, sodium and potassium metal into water and watching them suddenly burst into red, orange and purple flames respectively. It’s bad enough accidentally dropping your phone in the loo, imagine if didn’t just stop working but actually exploded. That really would spoil your day.

Lithium reacts spectacularly with oxygen too, so although nice in theory it was ruled out pretty much straight away on safety grounds. Researchers quickly started investigating lithium compounds, and lithium cobalt oxide, LiCoO2, was next up. As a general rule, very reactive elements produce much more stable compounds – and lithium cobalt oxide is much easier to handle than lithium metal.

Unfortunately it does still have poor thermal stability. Which means it has a nasty habit of blowing up if it gets too hot. A bit like that beltric acid stuff in Superman III, only without the turning into strawberry jelly and causing supercomputers to go rogue thing. At high temperatures lithium cobalt oxide starts to generate oxygen, and although oxygen itself isn’t flammable (we all knew that, right?) it does make everything else burn really, really well. Like, say, the plastic cover on your phone, or your curtains. So, that was a problem.

nissan leaf

The Nissan Leaf runs on lithium ion batteries. Big ones.

Not to worry: it didn’t take too long before Rachid Yazami found a way to reversibly insert lithium ions into graphite. The fact that the process is reversible is important: as you charge the battery the lithium ions are absorbed into the graphite, forming LiC6, and as you use it they are slowly released. The electrode that he discovered is still one of the most commonly used ones in commercial lithium ion batteries. These batteries are safe and affordable. The graphite does break down over time, in a process called exfoliation (not the facial wash type). There are ways to reduce this but as we all know from experience, while most lithium ion batteries can happily survive a few years worth of charge cycles, they still don’t last forever. It probably comes as no surprise that there are plenty of researchers out there working on new battery technologies. One of the newer types is the lithium vanadium phosphate battery (LVP), which is increasingly being used in electric cars.

Speaking of cars, we all learned at school that crude oil (the source of petrol and diesel) is a non-renewable resource. This is true, but there are alternatives to producing fuels from crude oil. Bioethanol is relatively easy to produce, diesel vehicles can run directly from plant oil fuel, and there are types of algae which can produce fuels. These alternatives also have the advantage of absorbing carbon dioxide as the plants or algae grow, so reducing the total amount of carbon dioxide that ends up being released into the atmosphere. That’s good, because pretty much everyone agrees now that global warming is a Bad Thing (even Republicans).

If you think about it, no metal is renewable. We can’t make metals (well, beyond a few atoms in a supercollider), and often there’s no really good alternative to using a particular type of metal. Having said that, scientists are working on sodium ion batteries, but they’re not commercially viable just yet. So right now, to feed our desire for new laptops, phones and even cars, we need lithium. Lots and lots and lots of it.

lithium triangle Salde Vida Map

The lithium triangle. Where batteries mysteriously disappear (not really).

Because lithium is so reactive it’s never found in its pure state; it has to be extracted from its compounds. Most of the world’s supply comes from a small group of places colloquially known as the ‘lithium triangle’, which includes the Atacama Salt Flat in Chile (generally considered to produce the best quality lithium in the world) and the Hombre Muerto Salt Flat in Argentina. Most of it, some 40-50% of the world’s reserves, is thought to be in Bolivia, where mining only began a few years ago.

It takes 750 tons of brine, and 24 months, to obtain just ton of lithium from these salt flat locations. The energy cost is high, although lithium itself is still relatively cheap (right now). It can of course be recycled: 20 tons of spent batteries can also provide one ton of lithium. So be good and recycle your phone responsibly. And next time you’re cursing your battery, just stop for a second and think of all the time and energy that went into making it. Pretty amazing, really.

The Salar de Arizaro. Beats a wet January in the UK, that's for sure.

The Salar de Arizaro. Beats a wet January in the UK, that’s for sure.

And if you’re a student thinking about career options, spare a thought for chemical engineering. Our demand for metals is only going to increase and someone needs work on more efficient ways of getting at them. You won’t be short of a job, and you might even get to visit some pretty nice locations along the way.

Now funnily enough, and I swear I’m not just saying this for artistic licence, my laptop battery has just hit 7%. Where did I leave my charging cable…?

The Chronicle Flask: 2014 in review

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Happy New Year!

It’s been an exciting year for this blog, with a big increase in readers (thank you everyone!) The WordPress.com stats helper monkeys prepared a 2014 annual report which is really quite interesting….

Here’s an excerpt:

The Louvre Museum has 8.5 million visitors per year. This blog was viewed about 120,000 times in 2014. If it were an exhibit at the Louvre Museum, it would take about 5 days for that many people to see it.

Click here to see the complete report.

Creepy combustion chemistry…

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Halloween pumpkins

We’re burning!

So it’s October and I’m trying to think of a blog post topic. Hmm.

Well, the Nobel prize for Chemistry was announced earlier this month. But it went to some guys who’d developed a microscopy technique for seeing single molecules, specifically molecules involved in cell interactions. All very nice, but that’s biophysics isn’t it? Why did it get the Chemistry Nobel? (Biology famously doesn’t have it’s own Nobel prize, so maybe the committee just had to sneak it in somewhere?)

What else happens in October? Halloween of course! I love Halloween. But I’ve done pumpkins before. And I’ve written about sugar and chocolate, so that’s tick or treating more or less covered… hmmmm… candles, vampires, ghosts, the paranormal…

250px-Human_Torch

Is anyone else hot? (The Human Torch, art by Adi Granov)

Ahah! Inspiration! Spontaneous human combustion. What else?

If there’s any paranormal topic that touches on the edges of chemistry, it has to be this one. If you’ve never heard of it, spontaneous human combustion refers to the idea that humans can (or, er, maybe not – bear with me) suddenly and unexpectedly burst into flame and be reduced to ashes in a matter of moments. There is apparently no external source of this flame – it seems to come from nowhere.

It’s a creepy idea. I remember one of my chemistry professors at university, who had turned up to lecture us in his chemical-stained lab coat, with bushy white hair and too-dark eyebrows sticking out in all directions, pausing on his way out to tell us that we should think carefully when deciding whether chemical reactions would happen spontaneously or not under real world conditions. “After all,” he said cheerfully, “spontaneous human combustion has a negative Gibbs free energy, and you haven’t all burst into flame. Yet.”† And with that he gave us all an ever-so-slightly crazed grin and sauntered out of the room, leaving us looking around uneasily for traces of smoke.

Gibbs free energy change is a measure of how energy changes during a chemical reaction. It’s linked to couple of very important physical laws that pretty much describe how the world works. In short, do a bit of maths and, if you get a negative number, it tells you whether a chemical reaction can occur spontaneously but, and this was my lecturer’s point, not necessarily whether they actually will. It’s a subtle distinction, and one that’s easily forgotten. (Crucially, activation energy needs to be considered as well – if you want to know more about these terms, follow the links.)

Theatrically-minded chemistry lecturers aside for a moment, the idea that people, and things, might unexpectedly start burning is an old one. You can track it right back to the Old Testament, where there was quite a lot of suddenly bursting into flames going on, for example the angel of the Lord appearing to Moses in flames of fire from within a bush. Mind you, that was an angel rather than a human being, and they might be flame retardant of course. But you get the point. Fire has always been important to humans as a source of vital light and heat – indeed many would argue that the ability to control fire was a key turning point in human evolution – but at the same time it can be horrifyingly destructive. It’s hardly surprising that fire has found its way into so much of our history and mythology.

Let’s think about what the combustion part of ‘spontaneous human combustion’ means. The definition of combustion is a chemical reaction between a fuel and an oxidant (commonly oxygen) that gives out heat.

270px-STDevil_inTheDark

This applies to you, unless you’re a silicon-based lifeform.

There is more than one type of fuel, but the most familiar ones (coal, oil, gas, fats, wood and so on) are made of largely of carbon, hydrogen and oxygen. You are made up of the same elements (assuming you’re not some kind of alien life-form who’s stumbled over my blog – in which case, welcome). Of course you do have some other elements thrown in as well, notably nitrogen, calcium and phosphorous, but most of you is carbon, oxygen and hydrogen.

When you burn these kinds of fuels, this happens:

fuel + oxygen –> carbon dioxide + water (+ lots of energy)

Fuels give out lots of energy when they burn, and so, in theory, would you. Particularly if you have plenty of fat, because fats burn really nicely. After all, what were candles made of before paraffin wax? Largely tallow – which is a processed form of animal fat, usually from cows or sheep. And we all know that candles burn really well, that’s sort of the point.

The idea that you can burn a human isn’t surprising, after all people have been using fire to dispose of human remains for thousands of years. But spontaneous human combustion (SHC) is something different. In these cases, the person burns without any (obvious) source of ignition. At this point, you might be imagining a person suddenly bursting into flame right in front of shocked witnesses, but in truth reliable eyewitness accounts are pretty rare. Instead, what generally seems to happen is that a body is discovered, badly burnt but usually with very little damage to the surrounding furniture or even, sometimes, parts of the victim’s clothes. Observers of the scene then draw their own conclusions, some more rational than others, as to how the burning occurred.

Possibly one of the most famous cases like this is that of Henry Thomas. He was a 73 year-old man whose remains were discovered in the living room of his council house in South Wales in 1980. His entire body had been incinerated, leaving only his skull and a section of each leg. Bizarrely, sections of his socks and trousers were relatively unscathed, as was half of the chair he’d been sitting in, and most of the rest of the room except for some smoke damage.

Could ball lightning cause people to catch fire?

Could ball lightning cause people to catch fire?

There are various theories to explain this kind of gruesome discovery, from ball lightening, to flammable intestinal gases (namely methane, which is the same gas in your kitchen cooker), to acetone building up in the body. The most famous, and probably best accepted of the more scientific theories, is ‘the wick effect‘, popularised in a BBC QED documentary in 1998. This idea likens a clothed human body to a candle, but with the wick (clothes) on the outside. The person’s fat is the fuel source, and the theory goes that the person’s fat melts and burns slowly, like a candle, over a period of several hours. The burning is very localised, which explains the lack of damage to the surroundings. Police forensic officers decided that Henry Thomas’s death was most likely an example of the wick effect in action.

It is often the case that apparent SHC victims are elderly, have low mobility due to illness or obesity, and are smokers (in other words, had a source of ignition in the vicinity). The logic goes that they are somehow incapacitated, perhaps a heart attack or stroke, perhaps excessive alcohol consumption, drop their cigarette and burn slowly.

But there are cases where the burning seemed to be a lot more sudden, and even a few where someone else was on the scene. For example, the most recent (suspected) case of spontaneous human combustion in the UK was that of Jeannie Saffin, who died in 1982. She was a 61 year-old woman, but had the mental capacity of a child due to birth defects. She was sitting with her father in the kitchen of their family home. He wasn’t looking directly at her when she caught fire but, according to his account, something caught his eye and he turned to find her suddenly ablaze. He and his son-in-law put out the fire using water, and then called an ambulance. She eventually died in hospital despite treatment. The coroner refused to accept the suggestion of spontaneous human combustion saying there was “no such thing”, and recorded an open verdict.

Jeannie Saffin’s case clearly wasn’t an example of the wick effect; it happened too fast. As far as I can find out, no one has ever really been able to explain why she caught fire so suddenly. She was in a kitchen, and kitchens do typically contain sources of ignition. Perhaps something went unrecorded: matches, alcohol, use of a gas oven. But even if it did, why did she burn so quickly and so violently? Flammable clothing perhaps? The truth is, we will probably never know.

Not too much now.

Not too much now.

Searching around I found other examples, but in every ‘sudden’ case I found the victim was in close proximity to something flammable or something that could, conceivably, provide a source of ignition. Or both. In particular, there are several cases of apparent SHC happening in cars. Usually a fire crew has investigated and found no traces of petrol in the wrong place. But… this seems like too much of a coincidence to me. Petrol is extremely flammable – could a small trace be present, perhaps from filling up the tank? If something were to ignite it, it could cause other things to burn, like synthetic fibres or, an even more likely culprit, hair products like gel or hairspray. Hair coated in product can burn really quickly. It doesn’t entirely explain every detail, but then it’s hard to know what is and isn’t an accurate account in these cases.

The truth is that spontaneous (if that really is an appropriate adjective) human combustion remains a bit of a mystery.

Just be careful around those jack-o-lanterns.

—

† I may be misquoting, it was a long time ago, but I’m sure I’ll be forgiven if I am.

Any old ions?

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The other day, thanks to an expedition to the swimming pool, I found myself drying my hair twice in one day. As I did so it occurred to me that the process was a lot faster at home with my old, battered hair dryer that it had been in the pool changing rooms.

I pondered variables (what can I say, I’m a scientist). I hadn’t washed my hair at the pool, I’d just rinsed it (hence the need to wash it again later) which meant no shampoo and, critically, no conditioner. Does conditioner’s presumably slightly hydrophobic nature help your hair to shrug off extra moisture? This didn’t seem like it ought to make that much difference. It seemed much more likely that the difference was simply due to the hair dryer itself.

hair-dryer

My battered old hair dryer.

And this got me thinking about the nature of my much-loved, rather battered, bright red hair dryer.

I’m going to ‘fess up here. I didn’t buy this hair dryer because I’d carefully researched its specifications and features and decided it was the best model for the job. No, if I’m honest I bought it because it was red and all the others were boring black and silver. Rational eh?

However, I do remember something about this particular hair dryer, and you can just about see a reference to this feature on the photo. Namely, it apparently contains an “ionic generator”. The little dial that you can see in the middle of the photo (set to orange, which if I recall correctly means, ‘maximum ions’) apparently adjusts the ion levels.

At the time I did try to find out exactly what the technology might be. I recall it was difficult – there didn’t seem to be much information out there – and since to be honest I didn’t care that much so long as it dried my hair, and it wasn’t particularly expensive (and it was red, RED!) I bought it anyway.

It only takes a quick glance at Amazon to see that the idea has not gone away. There are lots of ‘ionic’ hair dryers on the market, making claims such as, “Ionic conditioning with 90 per cent more ions“, “Heat-balancing ionic technology for condition and shine and a frizz-free finish“, “stylish dryer with ionic technology–seals in moisture to the hair cuticle for increased shine and silky, glossy hair” and the simple “4X More Ions“.

Hm.

Ok, well first of all what are ions? Whereas most people have a faint idea what atoms and molecules are, far fewer are confident to describe ions – despite the fact that they are firmly a part of the compulsory GCSE Science syllabus and were, of course, also included in  O-level Chemistry before that. Exactly why this should be is tricky to explain. Possibly it’s simply because ‘atoms’ and ‘molecules’ do occasionally crop up in everyday speech, whereas ions are that bit more obscure. Possibly it’s because children learn about atoms in the most basic terms quite early on, and come back to the idea regularly, but ions only turn up relatively briefly (unless, of course, you choose to study A-level Chemistry). There may be an element (hoho) of confusion over the fact that element 26 is called ‘iron’, which in most English accents sounds the same as ‘ion’. And just to really confound everyone, there are such things as iron ions.

But I think the most likely is that ions are a bit tricky to understand.

I’ll have a go.

Ions are charged particles.

There, that was easy, wasn’t it?

What do you mean, what does ‘charged’ mean? It means they have either a positive or negative charge.

What do you mean, ‘what does that mean’?

Oh all right. All right. Back to basics.

helium atom

A helium atom containing a tiny nucleus made up of two protons and two neutrons (red and blue), surrounded by an ‘electron cloud’. 1 fm = 0.0000000000010 millimetres.

First of all we need to understand a bit about atoms. Atoms are made up of two parts. There is the nucleus, which is made up of protons and neutrons (except for hydrogen’s nucleus, which is just a proton) and then, whizzing around that, are electrons. Electrons are quite fiddly things that behave frankly very oddly. In particular, they don’t actually drift around atoms in stately orbits as shown in most diagrams. In fact, they are sort of there and sort of not-there at the same time, and chemists talk about an ‘electron cloud’ as a result. An electron cloud need not contain lots of electrons (this depends on the size of the atom) – it just describes an area where you might find one or more electrons.

Anyway, that’s all a bit complicated and for our purposes it doesn’t really matter – all we need to know is that there’s a nucleus in the middle and electrons around it.

Electrons have a negative charge, protons have a positive charge, and neutrons have no charge. It’s quite difficult to rigorously define what I mean by ‘charge’ without getting into some tricky maths and physics. If you are ok with the idea of negative numbers (who hasn’t had an overdraft at some point or another?) then think of it like this: electrons are -1 and protons are +1 (and neutrons are 0). If you have one proton and one electron, the overall ‘balance’ is zero – their charges cancel each other out. In the case of helium, there are two protons and two electrons. This neat bit of balancing is no accident: it’s the case for all atoms. Carbon has 6 protons and 6 electrons. Oxygen has 8 protons and 8 electrons. Calcium has 20 protons and 20 electrons, and so on.

If the electrons and protons aren’t balanced for some reason (usually as a result of a chemical reaction) then the thing that you were calling an atom a moment ago stops being an atom and becomes, wait for it….

An ion!

Oxygen atoms have 8 protons and 8 electrons, but oxygen ions (properly called oxide ions) have 8 protons and 10 electrons. Which means they have a bit more minus than plus. They are, if you like, a bit overdrawn. If you add it up, you find the number works out as -2. And so we say that oxide ions have a charge of -2, and chemists (who are lazy) write this as O2-. Which is not, we must be careful here, the same thing as O2. That means two oxygen atoms joined together, to make an oxygen molecule. What do you mean it’s confusing?

One more example then. Calcium atoms have 20 protons and 20 electrons, but calcium ions have 20 protons and 18 electrons. Add that up and you get +2. We say that calcium ions have a charge of +2, and write Ca2+(and there’s no such thing as Ca2, so that’s one less thing to worry about).

Where have we got to? Ions are charged particles, and that means that they either have a positive charge or a negative charge. These charges are typically between 1 and 3, positive or negative.

mineral water label

Fizzy mineral water, chock full of lovely ions.

Ions are very important, because they form during chemical reactions and many everyday substances are made up of ions. For example table salt, sodium chloride, is made up of Cl– ions and Na+ ions.

Tap water, and indeed bottled water, are full of ions. Tap water has chloride ions (chlorinated water is a jolly good thing, assuming you don’t want typhoid, and is definitely not harmful regardless of what your nearest quack might try and tell you). It might also have fluoride ions, which are also very good for your general health (again, there’s lots of nonsense spread about this). Both tap and mineral water usually contain some sodium ions and some calcium ions. The ion balance does affect the taste – the more sodium there is the more salty the water tastes, for example – but that’s about it really. The ions don’t give the water any special properties except, perhaps, the ability to conduct electricity (which pure water, as in just H2O, actually does really badly).

Having explained ions, let’s get back to hair dryers for a moment. Ionic hair dryers claim to produce streams of negatively-charged ions. They usually claim to use something like the mineral tourmaline to do this, but despite much searching I struggled to find out much about how this was supposed to work or, most crucially, what the negative ions actually are. Negative ions are not a thing in and of themselves. They must be ions formed from atoms, so which element? Or elements?

After much hunting I eventually came upon an interesting piece written by Andrew Alden, at about.com. He explains that tourmaline has an interesting trick called pyroelectricity, which means that it does become charged when heated. The ancient Greeks even knew about this: in 314 BC Theoprastus noticed that tourmaline (called lyngourion at the time) attracted sawdust and bits of straw when heated.

Ed Trollope, from Things We Don’t Know, helpfully explained this pyroelectric effect as follows: the crystal structure of tourmaline becomes polarised (in other words the charges already in the structure become unevenly distributed) if you change its temperature. This results in a voltage across the crystal, which in turn leads to a small current being generated.

But I’m still unclear what the ions, if they exist, actually are. And the problem is that if you search for this, the first umpteen links are all pure and utter nonsense. Tourmaline is a complicated mineral that contains a whole host of different metal ions as well as oxygen, OH– (hydroxide) and fluorine. Does it produce oxide ions, O2-? These are very reactive and wouldn’t hang around for any useful length of time. And if they did they would surely be harmful. Presumably they would cause the production of ozone (definitely not a good thing). Are the manufacturers using the word ‘ions’ when they actually mean ‘electrons’? They are not the same thing of course, but perhaps ‘ions’ seemed like a friendlier word.

Electrons would reduce static in your hair, but then static is short-lived anyway. Would it speed up drying time? None of the explanations I’ve actually seen for this including, most memorably, “The negative ions break down water molecules to one-fifth of their size” (errrr, what?), provide a really satisfactory, scientific explanation as to why it should. Or why it should ‘seal water into the hair’, whatever that means. It is feasible that the reduction of static could help keep the hair strands separate, which might help, but surely brushing or even running your fingers through your hair would have a much bigger effect. What I’m also not clear on is whether the tourmaline in your hair dryer carries on producing streams of ions/electrons indefinitely, or whether it becomes degraded over time. Which you would expect, if the charged particles are coming from the tourmaline itself. Is my battered old hair dryer really doing anything at all anymore, if it ever did?

It’s all very unsatisfactory. My best guess? Ionic hair dryers do reduce static build-up in hair, which would leave it smoother immediately after drying. Conditioner and styling products will also help with this mind you, and will probably have a more significant effect. The rest, I strongly suspect, is pure woo. And my hair dryer dries my hair faster simply because it runs hotter and with a faster airflow than the cheap, basic models in the swimming pool changing rooms.

But if you know better, I’d genuinely love to hear from you.