Raman spectroscopy

Corona gazing in cafes

interference patterns on coffee

There are many ways in which rainbows of colour are produced as light interacts with our coffee or in a cafe. Looking around yourself now, how many do you see? What physics underlies each?

As the nights grow longer and the days colder, we notice that windows steam up as the water vapour in the café condenses onto the cooler glass. Perhaps we see a similar thing on our glasses while we are drinking tea or on the windows of a bus. Initially we perhaps become frustrated at our inability to see what is going on outside but then we notice the colourful patterns around the lights of passing cars and of street lights. Haloes of coloured light around a central bright spot. What does this tell us and where else can we see it, either in a café or in life generally?

On a window pane, a large number of small droplets of water have condensed into what appears to us as a fog on the glass. As the light shines through from the car headlights, each droplet acts as an obstacle to the light and so bends it. You could see a similar effect with the waves on the sea going around stones or perhaps if you brew a large cup of coffee with the surface waves going around a spoon (let me know if you manage to see this bending in a coffee cup). The amount that the light bends is dependent on the wavelength of the light (look carefully at the waves going around obstacles in ponds to see this) and so different wavelengths (different colours) get bent by different amounts and interfere with each other at different points – a spectrum is produced. It is a phenomenon known as diffraction.

Not all beans are equal! How could you quickly distinguish between arabica and robusta beans?

This phenomenon means that we have a way of separating the frequencies (or wavelengths) of light. And so this means that we have a way of measuring the chemical composition of some substances as different chemicals absorb different frequencies and so have ‘fingerprints’ in the light they scatter. By passing the light scattered from a substance (such as arabica coffee beans compared to robusta) through a diffraction grating (which is an obstacle with a pattern of fixed size), we can separate the frequencies being scattered and see if any of them are ‘missing’ (ie. they have been absorbed by the material we’re studying). It would be  a bit like looking at that rainbow pattern in the café window and not seeing blue, its absence tells you something. This is one of the ways that robusta beans can be quickly found if they have been substituted for arabica beans in coffee trading.

Coffee Corona

Look carefully: Sometimes you can infer the existence of a thin (white) mist over your coffee by the corona pattern around reflected light fittings.

But it is not just its technological aspect that has interest for us surely? When gazing at the moon on a misty evening, the halo around the moon suggests the clouds between us and it. It is something that poets have remarked upon to evoke atmosphere, it is something that we can gaze at as we imagine the giant café window of our atmosphere. But the size, and distinctness of the lunar corona actually give us clues about the droplets making up the cloud. And then we look closer to home and to our own coffee and we see the same diffraction pattern again looking back at us from our coffee’s surface. Occasionally it is possible to see haloes on the coffee surface around the reflection of overhead lights in the café. A coffee corona! This reveals to us the fact that there are droplets of water above the surface of our coffee; an extra layer of hovering droplets. Something that we can sometimes see more directly in the dancing white mists.

Diffraction is a beautiful phenomenon that allows us to gaze and to contemplate how much we are able to deduce and how much we have yet to understand. How atmospheric our coffees and cafés are and the journey of understanding that we have taken to get to this point. Coffee gazing is a hobby that should be taken up by far more of us.

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(Im)perfect reflections on coffee

science in a V60

Have you noticed droplets like these dancing on your drip-brewed coffee?

With the recent coffees from Hundred House and Quarter Horse, there have been many opportunities to observe the coffee brewing in the V60 in the mornings. The steam rising from the filter paper, the different ways different coffees bloom and out-gas, the droplets that skim the surface of the coffee and bounce off the walls of the jug and then, of course, the many different effects with light. Watching the dancing droplets (an explanation of why they may dance is here), it is perhaps not immediately obvious that you could form a connection between these, the light reflections and an insight into something you may have noticed while passing through customs. And yet the connection is definitely there.

The connection is formed through a technique called Raman spectroscopy. Named after Chandrasekhara Venkata Raman (1888-1970) who discovered the Raman effect in 1928. As the ‘spectroscopy’ part of the name suggests, it is a technique that offers a way to identify different chemicals, or components, in a substance. For coffee it has been used both as a non-destructive technique to determine the kahweol content of coffee beans and hence help as a test for identifying rogue robusta in arabica beans and as a way of analysing the brewed coffee. But what is it, how does watching a brewing V60 help to understand it and why would you want to know about Raman spectroscopy while travelling through an airport?

beauty in a coffee, coffee beauty

A collection of bubbles on the side of the coffee. What happens when one of the dancing droplets collides with a group of bubbles?

Generally, it helps to begin with coffee and the link is the way in which the droplets bounce off the side of the jug. Brew a coffee and watch them (if you are a non-coffee drinker, you could try dripping hot water through a filter paper into a jug). When one of these droplets hits the wall of the V60 container, it generally bounces back with a trajectory expected for an elastic collision. Given the relative masses of the droplet and the jug, the speed of the reflected droplet is essentially unchanged (even if its direction is reversed). This is similar to what we would normally expect for light. We are used to considering light as waves but because of the wave-particle duality of quantum mechanics it is equally valid to consider light as a stream of particles called photons. As the photons hit a surface and are reflected off, they recoil with the same energy that they initially had, just like the droplets in the coffee. But now look more closely at the dancing droplets. Normally they hit the walls and not each other but just occasionally, they can hit either another droplet or a group of bubbles that have formed on the coffee surface. In these cases, rather than get reflected as before, the droplets transfer some of their energy to the collection of bubbles causing them to move and to wobble. And when the droplet is reflected back, it has a noticeably slower speed (and so we could say a lower kinetic energy) than when it initially danced into its collision. Where is the analogue with light?

When we think about a coffee bean, we probably think about something that is about 1cm oval, brown and quite solid. But if we zoom in, we find that it is made up of a collection of atoms bound together in molecules or, if we are thinking about a solid like salt, in a crystal structure. These atoms act as if they are balls connected by springs and so they wobble as would any structure of masses connected by springs. This is true whether the crystal is diamond or the molecule is caffeine, kahweol, cocaine or semtex (do you see where the customs part is going to come in yet?). Different crystal structures have different atomic arrangements meaning that they are effectively connected by springs of differing strength. If you build a mental model of masses connected with springs, you can see that changing the spring strength will change the vibration energy of the structure. So if now we think about the photons hitting such a structure, while most will bounce off as we saw with the droplet hitting the V60 wall, some photons will trigger a wobble in the crystal structure and bounce off with lower energy. It is a process analogous to the droplet hitting and bouncing off the collection of bubbles on the coffee surface.

Sun-dog, Sun dog

Sun dogs are caused by a different interaction between light and crystals. Rather than the inelastic scattering of Raman spectroscopy, Sun dogs are caused by the refraction of light by hexagonal platelets of ice crystals.

When a photon of light loses energy, it is equivalent to saying that the frequency of the light has changed (which is very closely related to what Albert Einstein got his Nobel prize for in 1921). So a photon that creates a crystal vibration and is scattered off with lower energy has a lower frequency (or longer wavelength) than it had when it first hit the crystal. Importantly, the energy lost by the photon is identical to the energy gained by the vibrating crystal and so by measuring the frequency change of the scattered light we have a way of determining the energy of the crystal (or molecule) vibration. As this energy depends on the way that the atoms are arranged in the crystal or molecule, measuring the frequency shift offers us a way of identifying the chemical under the laser light: kahweol or cocaine.

It is not an easy technique as you can guess from the V60 analogy. Only around one in a million photons incident on a solid will be Raman scattered. You need some pretty decent optics to detect it. Nonetheless, it is a powerful technique because no two chemical structures are the same and so it can be used to identify tiny amounts of smuggled material completely non-destructively. It becomes easier to understand how this elegant technique has become useful for many areas of our lives from customs, through to pharmaceutical development and even into understanding how fuel cells work.

Although it is stretching the analogy too far to say that you can see Raman scattering by watching the droplets on your V60, it is certainly fair to say that watching them allows you the space to think about what is happening on a more microscopic level as your bag is hand-scanned at customs. What do you see when you look closely at your brewing coffee?