superheating – Bean Thinking

coffee and ice in New Cross on a wooden table — Isn’t it a fact that water boils at 100C and freezes at 0C?

Water boils at 100ºC and the ice in your iced latte is at 0ºC. These are facts that we think we know about water: it boils at 100ºC and it melts at 0ºC. A sharp observer may point out that these are pressure dependent and that if we were at the top of a mountain, the water would boil at a slightly lower temperature (I once had a student argue that this was a good reason to only ever drink green tea at high altitude). But if we are at ground level and it is a normal day, we will be fairly certain that the water for our coffees would boil at 100ºC and ice would form at 0ºC.

Yet these ‘facts’ hide some complicated physics and some oddities about our planet. Pure water, that is, water without any impurities in a clean vessel (such as a clean, scratch free glass) does not boil at 100ºC but at temperatures significantly higher than that. Nor does pure water freeze at 0ºC but at temperatures significantly below that. These are phenomena known as superheating and supercooling respectively and, if you are observant, you could see them occasionally in your coffee cup. To see why, and how, we need to think a bit more about how water freezes.

blue tits, mint water, mint infusion, mint leaves in water — If you put pure water into the freezer, you may find that it freezes at a temperature considerably lower than 0C

If you fill an ice cube tray with water and put it in your freezer, you would expect ice cubes to start forming at about 0ºC. We expect the freezing temperature to be the same as the melting temperature, that is the temperature at which the ice cubes would melt. And yet, if you make the water very pure (even distilled water would be a start) and put that in a clean, defect free container (such as a clean glass jar) in the freezer, the freezing process will not begin until much lower temperatures. It’s because the water has to crystallise and change state from a liquid to a solid and to start this process, there needs to be a seed, a surface on which the ice can form. Called a “nucleation site”, this seed could be a piece of dust, a small impurity in the water, a scratch on the surface of the container holding the water, or in fact anything that allows the bonds of ice to start to form. The same is true at the other end of the temperature scale. When the liquid water turns into steam, nucleation sites are needed so that the gas bubbles can start to form at those sites. In the absence of impurities in the water, the water will not boil until temperatures high above 100ºC.

Fortunately in tap water, or in your super-filtered water that you make your coffee with, there are plenty of such nucleation sites so the water boils and freezes at roughly the temperatures you’d expect them to. The same is not true however for clouds in the sky where some (high altitude) clouds have been shown to contain water droplets that are at -35ºC, well below the “freezing temperature”. Exactly why this occurs is still puzzling and a topic of research, but when you stop and think about it, how would you actually measure this temperature? If you supercooled a cup of water and then put a thermometer into it, the thermometer would provide a nucleation site and the water would immediately freeze. How can you measure the water’s temperature without a thermometer?

kettle, V60, spout, pourover, v60 preparation — You are unlikely to see superheating when you boil the water for your coffee in a kettle like this.

Recently a study reported in Physical Review Letters used a laser to measure the diameter of a series of supercooled liquid droplets by determining the energy of a resonance that depended on the droplet’s size. To calculate the temperature of the droplet, the authors then used the principle that as water evaporates, the droplet from which it is evaporating will become colder at the same time that it shrinks in size. Measuring the size of the droplet allowed them to calculate the evaporative loss and therefore the temperature of the drop. They double checked this new technique by measuring (with the same laser) the energy of a particular atomic bond in water that has a known temperature dependence (at higher temperatures). The temperature determined from the drop’s size corresponded with the extrapolation of the energy of this atomic bond and so the team were fairly confident that they had measured liquid water to very cold temperatures indeed. In fact, the authors suggested that it was still possible to have liquid water at 230.6±0.6 K which, in more every-day units corresponds to -42.55ºC, well below the nominal ‘freezing point’.

So pure, liquid, water can get very cold indeed. But could you ever see this in your coffee cup? Although you may like to try some experiments with freezing ultra-pure water, it is easier to see the phenomenon of superheating in your coffee. However, given the possibility of an accident, it may be safer to watch the effect on the video below. The idea is that if you put very pure water in a clean cup into a microwave, it is possible to superheat it well above 100ºC without it boiling, because there are no nucleation sites in the cup or the water on which the steam bubbles could start to form. When you take the cup out and put a nucleation site in (perhaps a spoon or maybe even instant coffee granules), the water will boil suddenly as a result of those new nucleation sites and can even explode. Obviously if you were anywhere near the water when this happened you could get seriously burnt and so it is probably safer to watch the Mythbusters do it with their robotic arm. Enjoy the video, enjoy your coffee, preferably far from superheated:

Coffee as an art at Briki, Exmouth Market

exterior of Briki coffee London — Briki London on the corner of Exmouth Market

Traditionally made coffee always appeals to my sense of coffee history. Coffee made its way out of Ethiopea via Turkey and the method of brewing the finely ground coffee in a ‘cezve’ or ‘briki’ is one that goes back a long way. It’s therefore always interesting when a new cafe arrives on the scene that offers “Greek” or “Turkish” coffee on its menu. Briki, in Exmouth Market, opened in May last year and so it was only going to be a matter of time before I visited to try it out. Aesthetically Briki appealed to me as soon as I walked through the door. Spacious and with the bar along one wall, there are plenty of seats available at which to slowly enjoy your coffee. The cafe itself is almost triangular and the other two walls have windows running all along them. What better way to sit and enjoy the moment (and your coffee) than to gaze out a window? Still, given that I had gone to a cafe called ‘Briki’ and that it advertised “Briki coffee” on the menu behind the bar, it was obvious that I had to try the briki coffee. The coffee was rich, flavoursome and distinctive, well worth the time taken to savour it. There was also an impressive selection of food behind the counter and the dreaded “does it contain nuts” question was met with a friendly check of the ‘allergen’ folder. I was therefore able to also enjoy the lovely (nut free) chocolate cake. Briki definitely gets a tick in the “cafes with good nut knowledge” box on my categories list.

image from British Museum website — Folio 109b from an album of paintings showing Turkish sultans and court officials. Kahveci. A youth who serves coffee. He is holding a cup in each hand, circa 1620.
© The Trustees of the British Museum

However as I realised later, the coffee was not brewed in the traditional way but in a Beko coffee maker – a coffee maker specifically designed for optimising the brewing of Turkish coffee. The idea of the Beko is that it carefully controls and automates the entire brewing process so that you get a perfect coffee each time. But just how do you make a ‘perfect’ Turkish coffee?

A quick duckduckgo (it’s a mystery to me why has this verb failed to catch on while ‘to google’ is used so frequently) revealed two sets of instructions on how to make Turkish coffee. The first set, (including some otherwise very good coffee brewing websites) suggested ‘boiling’ the coffee repeatedly in the pot (cezve/briki). The second set, which seemed to be more specifically interested in Turkish coffee (as opposed to interested in coffee generally), were much more careful, even to the point of writing, in a very unsubtle way, “NEVER LET IT BOIL“. According to this second set of websites, the coffee in the cezve should be heated until it starts to froth, a process that begins at around 70C, far below the 100C that would be needed to boil it. Warming the cezve to 70C produces these bubbles and the lovely rich taste of the traditionally made coffee. Heating it to boiling point on the other hand destroys the aromatics* that form part of the flavour experience of coffee and therefore makes a terrible cup of coffee.

The contrasting instructions however led me to recall a discussion in Hasok Chang’s Inventing Temperature. Perhaps we all remember from school being taught how thermometers need two fixed points to calibrate the temperature scale and that these two fixed points were the boiling point and the freezing point of water. Perhaps this troubled you at the time: Just as with making coffee in a cezve, just how many bubbles do you need in order to say that the coffee (or water) is ‘boiling’? How were you supposed to define boiling? How much did it matter?

Cezve, ibrik, Turkish Coffee Creative Commons license — Cezve, image © http://www.turkishcoffee.us

It turns out that these questions were not trivial. There is a thermometer in the science museum (in London) on which two boiling points of water are marked. The thermometer, designed by the instrument maker George Adams the Elder (1709 – 1773) marked a lower boiling point (where water begins to boil) and an upper boiling point (where the water boils vigorously). The two points differed by approximately 4C. So how is it that we now all ‘know’ that water boils at 100C? And what was wrong with Adams’ thermometer? The Royal Society set up a committee to investigate the variability of the reported boiling point of water in 1776. Careful control of the heating conditions and water containers reduced the temperature difference observed between different amounts of boiling. However, as they experimented with very pure water in very clean containers they found that things just became more complicated. Water could be heated to 120C or even higher without ‘boiling’. They had, unintentionally, started investigating the phenomenon that we now know as ‘superheating‘. Superheating occurs when water is heated to a temperature far above its boiling point without actually boiling. What we recognise as boiling is the escape of gas (which is usually a mix of air and water vapour) from the body of the water to its surface. In order to escape like this, these bubbles have to form somehow. Small bubbles of dissolved air pre-existing in the water or micro-cracks in the walls of the container enable the water to evaporate and form steam. These bubbles of gas can then grow and the water ‘boils’. If you were to try to calibrate a thermometer using very pure water in very clean containers, it is highly likely that the water would superheat before it ‘boiled’, there just aren’t the ‘nucleation’ sites in the water to allow boiling to start. The Royal Society’s committee therefore came up with some recommendations on how to calibrate thermometers in conditions that avoided superheating which meant thermometers were subsequently calibrated more accurately and superheating (and improved calibration points) could be investigated more thoroughly.

Perhaps viewed in this way there are even more parallels between Turkish coffee and physics. It has been written that “making Turkish coffee is an art form“. It is a process of practising, questioning and practising again. The Beko coffee machine automates part of the process of making Turkish coffee. When it’s done well though, Turkish coffee is far more than just the temperature control and the mechanics of heating it. There is the process of assembling the ingredients, the time spent enjoying the coffee and the atmosphere created by the cafe in which you drink it. Coffee as art in Briki is something that I would willingly spend much more time contemplating.

Briki is at 67 Exmouth Market, EC1R 4QL

“Inventing Temperature”, by Hasok Chang, Oxford University Press, 2004

*Although these aromatics are part of what gives coffee such a pleasurable taste, they decay very rapidly even in coffee that is left to stand for a while, it is this loss of the aromatics that is part of the reason that microwaving your coffee is a bad idea. A second reason involves the superheating effect, but perhaps more on that another day.