RSC - Advancing the Chemical Sciences


Chemistry World

 

October


Chemistry World Podcast -October 2011

 

1:05 -Microscopy reveals why ketchup squirts

 

5:07- Toyota create first magnesium-sulphur rechargeable battery

 

7:20-Paul Shearing explains why you might want to swap your home boiler for a fuel cell

 

14:30-Two for one - cleaning water and generating energy

 

17:52-Bacteria responsible for missing 'atmospheric brooms' that sweep the sky clean

 

20:19-How clean is your car's engine? John Bennett reveals what additives are in your fuel to keep your car running smoothly

 

27:21-High-throughput catalyst screening for the masses

 

30:46-Limestone is efficient energy distributor

 

34:00-Trivia - What's the fastest thing in the universe?

 

36:20 - It's our birthday! The Chemistry World podcast is 5 years old this month

 

(Promo)

 

Brought to you by the Royal Society of Chemistry, this is the Chemistry World Podcast.

 

(End Promo)

 

Interviewer - Chris Smith

This month's episode has a lot of sauce (sound of sauce squirting). If you do not shake the bottle, none comes out and then allegedly a lot will. So what I've got here is some ketchup, now we understand a bit more scientifically about what's going on. 

 

Interviewer - Chris Smith

That's the chemistry of ketchup being served up for you very shortly. Hello I'm Chris Smith. Welcome to the October 2011 edition of the Chemistry World podcast. With me this month are Phillip Broadwith, Laura Howes and Patrick Walter and also in this show, why homes in the future will have a fuel cell rather than a boiler and why limestone could become the energy currency of tomorrow. 

 

(Promo)

 

The Chemistry World Podcast is brought to you by the Royal Society of Chemistry. Look us up online at chemistryworld dot org.

 

(End Promo)

 

(1:05 - Microscopy reveals why ketchup squirts)

 

Interviewer - Chris Smith

Ok, Patrick (sound of sauce squirting) if you do not shape the bottle, none comes out and then allegedly a lot will. So what I've got here is some ketchup, coming out quite well. So, now we understand a bit more scientifically about what's going on.

 

Interviewee - Patrick Walter 

Yes so, when you pour ketchup out, it sits on your plate, it's quite solid, but then when you squeeze the ketchup bottle, it comes out quite fast like a liquid.

 

Interviewer - Chris Smith 

Accompanied by the, sort of, farting you know, but I have got something which is a blob in the dish, which is not flowing like a liquid, now it's gone into the dish.

 

Interviewee - Patrick Walter 

Yeah it's become almost solid, hasn't it?

 

Interviewer - Chris Smith

Indeed so why?

 

Interviewee - Patrick Walter 

Right, well this is a behaviour they call, non-Newtonian liquid like. So in this case, the fluid is shear thinning, so as you apply more pressure to it, moves from a solid to a liquid state.

 

Interviewer - Chris Smith

So it's solid in the bottle. I gave it a shake and apply pressure, it became more like a liquid which is why it flowed up, then it settles in the bowl, there's no pressure on it now and it turns back to being a thick fluid again.

 

Interviewee - Patrick Walter 

Exactly and people are also quite familiar I think with the shear thickening process, so perhaps you've seen in the Brainiac episode where they fill the swimming pool with custard and then John Tickle just ran across it, as he applied pressure to what was a liquid to start, it became solid and it could take his weight. 

 

Interviewer - Chris Smith

What is actually going on, if we were to zoom in on this ketchup with a very powerful microscope and look at the molecules, why is it doing this interesting behaviour?

 

Interviewee - Patrick Walter 

Right, it's probably best to start with what's the most popular theory for why this happens, now. So, at the moment they think the behaviour is a bit like a motor way, so the particles in the fluid in there, solid-like fluid are like cars on a motor way, so they move up and down normally. If it's a shear thickening fluid, you'll find that as you apply more and more pressure to it, the cars, it becomes a pile up, they crash, they all lock together and the fluid won't move, whereas in shear thinning behaviour, as you apply more pressure the cars actually just move faster along the lane, so it's like layer sliding across each other. 

 

Interviewer - Chris Smith

I see and know you're saying there's some kind of revision of that theory or that someone's now got some new evidence that's not right.

 

Interviewee - Patrick Walter 

So, Xiang Cheng, at Cornell University  in the US has got an alternative theory. So, he used silica spheres in a water- glycerin mix and they followed what was happening when they applied different pressures to it using a confocal  microscope along with a viscosity meter. So by watching it, they discovered that this kind of layer theory of the building up and the crashing of particles into each other wasn't quite right.

 

Interviewer - Chris Smith

And what do they say is happening instead then?

 

Interviewee - Patrick Walter 

So, they say, for a shear thickening fluid what's happening is you are getting clumps forming together and as these clumps form together they're not lubricated enough to slide across each other and so they're clumping up and then you get this locking. So, like when corn flour, if you hit it too hard, it'll become solid. They're using things like corn flour now in things like body armour, very basic, exactly.

 

Interviewer - Chris Smith

The bullet proof vest. When the bullet hits, all the particles jam together. 

 

Interviewee - Patrick Walter 

Particles jam together.

 

Interviewer - Chris Smith 

The fluid flows out from around them, they form a pseudo solid for a while which spreads the load. 

 

Interviewee - Patrick Walter 

Exactly, it spreads out a lot better than Kevlar does, because.

 

Interviewer - Chris Smith

So what about my ketchup then, what's going on with that? That's a shear thinning

 

Interviewee - Patrick Walter 

So with shear thinning it's slightly different. So perhaps some of the listeners have heard a Brownian motion before. This is idea that.

 

Interviewer - Chris Smith

Brownian sauce motion.

 

Interviewee - Patrick Walter 

(Laughs)With Brownian motion what's happening is the particle is all moving around, it's quite chaotic and they're bumping into each other. Although. It is just the natural movement of the particles. When the pressure is applied what's happening is you're reducing this chaos. You're overcoming the Brownian motion and causing the flow in a single stream, as is the case with the ketchup.

 

Interviewer - Chris Smith

So, flow becomes more streamlined.

 

Interviewee - Patrick Walter 

Exactly and one another possible application of this is in things like industries. So if you're dealing with shear thickening fluids, it could be disastrous if they suddenly clump up. So, the more you understand the easier it would be to prevent such blockages.

 

Interviewer - Chris Smith 

And the whole place now smells of ketchup and it will be for whole of the rest of this recording yummy. 

 

(5:07- Toyota create first magnesium-sulphur rechargeable battery)

 

Interviewer - Chris Smith 

Laura let's distract ourselves from the ketchup and talk about another way of getting energy. Let's talk about batteries.

 

Interviewee - Laura Howes

So, people will probably be aware of various metal ion batteries, lithium ion batteries being the most common example that's what is in your laptop and is also used to power cars. If you're in an electric car, then that's usually powered by lithium ion battery. 

 

Interviewer - Chris Smith

Sure.

 

Interviewee - Laura Howes

But the energy density is not great, if you're in a car, then you've got to have loads and loads of them. It makes the car heavier.

 

Interviewer - Chris Smith

So most of the car is battery. 

 

Interviewee - Laura Howes

Exactly, most of the car is battery.

 

Interviewer - Chris Smith

Not much for people.

 

Interviewee - Laura Howes

It doesn't.

 

Interviewer - Chris Smith

It does just to get the amount of energy you need to make a car practical, you need huge batteries, with the present electrode and electrolyte combos we've got.

 

Interviewee - Laura Howes

Precisely, so people are trying to make batteries smaller, more energy dense, you don't need quite as much and that's what some people at Toyota have come up with. They're actually, instead of using lithium ion they're actually looking at a magnesium-sulphur rechargeable battery. 

 

Interviewer - Chris Smith

It's an unusual combination. Why are they going for that? 

 

Interviewee - Laura Howes

The two electrodes, they match up in a really nice way with their energy levels, it means that they, you can get quite a lot of power out of them

 

Interviewer - Chris Smith

And presumably make them very small. 

 

Interviewee - Laura Howes

And make them much smaller.

 

Interviewer - Chris Smith

And I sense an if coming now or a but.

 

Interviewee - Laura Howes

An if or a but the problem everyone's been like ah! This is theoretically a really good way of doing it, but to make a electrolyte which will work with the magnesium; it ends up degrading the sulphur electrode.

 

Interviewer - Chris Smith

And vice versa.

 

Interviewee - Laura Howes

Yeah. So it's a really good idea in theory but up until now, the electrolyte.

 

Interviewer - Chris Smith

They are not in practice

 

Interviewee - Laura Howes

The electrolyte has been the stumbling block.

 

Interviewer - Chris Smith

Have they solved it?

 

Interviewee - Laura Howes

They have solved it, but the problem is that at the moment, the electrolyte is nucleophilic and that's why it ends up attacking the sulphur. So take a non-nucleophilic organomagnesium halide, which involves magnesium and they also take a Lewis acid, combine them and it crystallizes and then they dissolve it back over and they get this large cobbled structure, that actually isn't nucleophilic, but allows the ions to transport across between the two electrodes. 

 

Interviewer - Chris Smith

Is it practical though, will it work?

 

Interviewee - Laura Howes

I think it will, obviously Toyota think it will. Otherwise, they wouldn't be pursuing it. They don't quite know how long it's going to take to get it into a car, but they certainly think this is worth pursuing further. 

 

(7:20- Paul Shearing explains why you might want to swap your home boiler for a fuel cell)

 

Interviewer - Chris Smith

Laura Howes. Now if you're thinking of replacing your domestic boiler, like I need to, why not consider installing a fuel cell instead you get heat, but then you also get to make your own electricity essentially for free.

 

Interviewee - Paul Shearing

I'm Paul Shearing. I'm an electrical and chemical engineering at University College, London and a Royal Academy of Engineering Research Fellow. There are a number of different fuel cells, but they basically all operate on broadly the same principles, which is what we call a redox reaction. So hydrogen oxidation reaction coupled to the oxygen reduction reaction can create a useful electronic current flow. And so we have catalysts, at the anode and the cathode side that catalyze these two reactions and also generates electricity in an efficient and also a very clean way. We're basically recombining hydrogen and oxygen creating this electronic current and the only emission from the fuel cell is water if we use a clean hydrogen fuel.

 

Interviewer - Chris Smith

Which is obviously a massive bonus because we're very worried about the environment and putting pollutants into it, but what are the big problems that people are struggling with? I mean, I remember, reading a bit of Jules Verne, where he talks about foreseeing the use of hydrogen and oxygen in fuel cells in the future and that was over a hundred years ago. What's holding the field up?

 

Interviewee - Paul Shearing

Sure, so I think William Gray was the first person to demonstrate the fuel cell principle in 1839. This has been hampered by a number of different things, although if you're going to Germany and California, you can find people using fuel cell cars, is that day to day run around in this country, especially, there isn't a huge fuel cell car markets and indeed the cars are unavailable. And I think one of the primary reasons of this isn't the technology behind the fuel cells, because we have this chicken and egg scenario regarding the hydrogen supply infrastructure. The companies who will provide the hydrogen refilling infrastructure are reluctant to implement this, if there's no market. There are no people driving the fuel cell cars to buy the hydrogen. Equally, there's no one that's going to buy the fuel cell cars unless there is the hydrogen infrastructure, so they can refill them. Here in the UK, we do have a number of privately owned filling stations, the first publicly accessible hydrogen filling station opened within the last couple of weeks and I hope they will see the demonstration programs that have been successful in California translates the UK market in the near future.

 

Interviewer - Chris Smith

Cars rob us a huge proportion of our hydrocarbon consumption in Britain, something about half of the fossil fuel burn in Britain is transport, but that means there's still a sizeable chunk of the pie, which isn't cars. So what else could fuel cells be used for to push down our carbon footprint and improve our environmental impact in Britain?

 

Interviewee - Paul Shearing

There are a number of different flavours of fuel cells that find applications in different areas. When we're looking at transport applications, we're normally looking at typically low temperature, we call it PEM fuel cells, that stands for Polymer Electrolyte Membrane fuel cells and these operate at temperatures 60 degrees Centigrade or so. They can be switched on and off very, very quickly and are ideal for these possible applications, but they do use a platinum catalyst, which is obviously very expensive. The other end of the temperature scale, we find fuel cells called solid oxide fuel cells and these are completely solid state devices, using ceramics and non-precious metal catalysts and because they operate in a much higher temperature regime, they can effectively catalyse the hydrogen oxidation and oxygen reduction reactions, using a much cheaper catalysis route.  So, for example by replacing the platinum that you find in a PEM fuel cell with nickel in a solid oxide fuel cell; so, a much cheaper way around. However, because they operate at higher temperatures they have associated problems. They typically take a long time to start up in short time with a ceramic device, thermal cycling is often quite problematic and therefore they lend themselves naturally to stationary applications rather than transport applications. With the solid oxide fuel cell operating at say 800 degrees Centigrade; it may take a number of hours to start that fuel cell up from cold. Obviously this means that they're not so useful for transport applications, but they can be fantastic at generating high-efficiency low carbon energy for stationary applications and there's lots of industrial research and research in universities in UK and around the world in developing solid oxide fuel cells technology for stationary power generation , combined heat power generation as well in homes and on larger scale as well. 

 

Interviewer - Chris Smith

What sort of efficiency can they achieve?

 

Interviewee - Paul Shearing

So, solid oxide fuel cells have fantastic electrical efficiency, but also they generate heat, which can also be usefully used in a home for example for hot water heating and so forth. So, on the top of this the idea is combined heat and power, so the combined efficiency of a solid oxide fuel cell would normally be, if we had a one to one heat power ratio, so for every kilowatt of electricity we generate, we generate a kilowatt of heat, we can typically expect efficiencies a ballpark figure of sort of 70% plus.

 

Interviewer - Chris Smith

Now we traditionally put big power stations and things away from settlements because they're big, they're noisy, they're smelly and they put enormous amounts of pollution up. Are you saying, based on the idea that this could be used for CHP combined heat and power that we're going to see a sort of return to microgeneration. We're going to see more little stations near settlements because they're much cleaner and they're going to be much quieter. 

 

Interviewee - Paul Shearing

Absolutely. So, there are a number of companies developing combined heat and power units for the domestic market and the idea is that you would replace your conventional water boiler in your home with a solid oxide fuel cell, combined heat and power unit. So this would not only provide you with your hot water, but also with some of your electricity. This might not meet the full electricity demand for your entire household, but it means that you can dramatically reduce your energy costs and hopefully reduce your carbon footprint at the same time. 

 

Interviewer - Chris Smith

I need to replace my old boiler right now because it's just blown up; sounds too good to be true. Why is this not being more widely embraced?

 

Interviewee - Paul Shearing

It is being widely embraced and there are a number of companies that are very actively developing this. There are a few who at the position where they're brining their product to market at the moment.

 

Interviewer - Chris Smith

And let me finish by asking you, how do you heat your home?

 

Interviewee - Paul Shearing

I'm afraid I'm still using a condensing boiler to heat my home. Condensing boilers are fantastically efficient technology for providing hot water and heating but one thing they can't do is provide electricity and with the solid oxide fuel cell combined heat and power system, you're in a position where you can take gas from the gas main in your house, which you would pay perhaps 3 pence per kilowatt hour and generate your own electricity which you perhaps pay 11 or 12 pence per kilowatt hour. So for that 3ps spent on gas, you got 12p of electricity. So there's a significant economic incentive as well as an environmental incentive. I would like to be one of the first to sign up to have the CHP system in my house when they're available. 

 

(14:30- Two for one - cleaning water and generating energy)

 

Interviewer - Chris Smith

Paul Shearing from the University College, London and on the subject of two for the price for one, Phil's been looking at the clean water equivalent.

 

Interviewee - Phillip Broadwith 

Okay well, this is kind of interesting. We're talking about solving two problems with one piece of equipment. We have contamination in waste water with various organic molecules that we don't really want to be in there, certainly want to process out before we can use the water again and then the other problem we've got an energy crisis coming. We need new sources of energy. So what Yanbiao Liu from Shanghai Jiao Tong University and his team have done is make a fuel cell that will solve both of those problems. It takes a little bit of sunlight, organic compounds from waste water and turns them into energy.

 

Interviewer - Chris Smith

So, the organic compounds are actually the energy supply? The sunlight effectively helps to unleash the energy in them. 

 

Interviewee - Phillip Broadwith 

Exactly right. So, just like you could burn these compounds to make energy, then you can feed them through a fuel cell to break them down, take some of the energy from the chemical bonds and convert them into safer by-products.

 

Interviewer - Chris Smith

In other words, the amount of energy that comes out is greater than you would get from solar alone.

 

Interviewee - Phillip Broadwith 

Yeah absolutely. I mean, may be it's not. I don't know how it compares to direct photovoltaic generation, but it's not only generating energy. 

 

Interviewer - Chris Smith

Because you're getting the water too.

 

Interviewee - Phillip Broadwith 

Yeah you're getting the clean water as well.

 

Interviewer - Chris Smith

So how does it work?

 

Interviewee - Phillip Broadwith 

What we have is a titanium oxide-nanotube-array. Titanium oxide is very good at taking in sunlight and that's coupled to a semiconductor electrode on the other side of the fuel cell. When the light hits the titanium oxide, it frees up electrons which go around the circuit and are injected into the side of the fuel cell. Those electrons then oxidize the organic compounds in the water, which breaks them down.

 

Interviewer - Chris Smith

Did they say which sorts of organic compounds they've tested because organic compounds are quite a broad term? We all know that some are more persistent than others.

 

Interviewee - Phillip Broadwith 

Yes Chris. Well the ones that they mention in the paper are things like, sort of aromatic compounds, azo dyes, pharmaceuticals like, so if you take a paracetamol then a certain amount of that is going to come out into the water supply, personal care products.

 

Interviewer - Chris Smith

I'll think of oral contraceptive pills and HRTS as well, which we know has onward health effects and people are very worried about this because there's nothing in nature that breaks down these molecules because they're artificial and as a result, they tend to loiter for much longer.

 

Interviewee - Phillip Broadwith 

Yeah, absolutely. I mean, I'm not entire sure, but those kinds of oestrogen compounds would be very susceptible to oxidation by this kind of direct electron injection.

 

Interviewer - Chris Smith

So, where do they see this working then? This is what a third world technology for countries where they can't afford to clean up water or are you saying that this could be deployed anywhere?

 

Interviewee - Phillip Broadwith 

Well, I don't see any reason why it shouldn't be deployed anywhere. I mean, at the moment, waste water treatment is a relatively energy intensive process. If we can reverse that and turn it into an energy generation process, not only do we decrease our energy demand, but we're actually, you know, reversing that and supplying energy. So it's a double winning sometimes.

 

Interviewer - Chris Smith

Given the thing, as you said, it uses sunlight, which here at Britain, as we know, we cannot rely on this?

 

Interviewee - Phillip Broadwith 

At the moment, this, as we say, this is a lab scale kind of project. It depends how far you get in terms of scaling up, as to how intense light works, but in the UK we do have solar photovoltaics that work perfectly well to generate electricity. So, it depends how much intense sunlight you need, but in principle there's no reason why you can't use it.

 

(17:52- Bacteria responsible for missing 'atmospheric brooms' that sweep the sky clean)

 

Interviewer - Chris Smith

We're talking of cleaning things up, well Patrick you've got something on the bacteria, which help us to keep the atmosphere clean.

 

Interviewee - Patrick Walter 

Exactly. Hydroxyl radicals are what help to keep our atmosphere clean, . They react with lots of things like smoke and they clean it out of the atmosphere, break it down and just allow it to get washed down and cleaned up. So, atmospheric chemists have a bit of a puzzle. They know a third of the hydroxyl radicals come from nitrous acid, but they don't know where hardly any of this nitrous acid comes from. So, what it turns out now is they shouldn't have been looking in the skies above, but they should have been looking in so beneath our feet. So, beneath our feet, bacteria are making nitrite ions and these nitrite ions in the presence of water can change into nitrous acid and this nitrous acid can then partition and can turn into a gas that can then break down into these hydroxyl radicals in the presence of sunlight.

 

Interviewer - Chris Smith

How did they make that discovery?

 

Interviewee - Patrick Walter 

Right. So what Yafang Cheng from Peking University in China and Hang Su at the Max Planck's Institute in Germany did was they took some soil samples, they put it in a Teflon coated chamber and they flooded it with synthetic air. They knew exactly what was in there and then they checked what was coming out the other side of the chamber and they're able to see that nitrous acid was actually coming out. 

 

Interviewer - Chris Smith

And that was then all you need in order to get that to partition to become the air-borne form that then gives rise to the hydroxyl radicals then.

 

Interviewee - Patrick Walter 

Exactly. Yes. I mean, we're quite familiar with the idea that plants need nitrite and many people think that some plants are actually able to produce these nitrogen compounds, but it's not actually the plants, they are things like clover, often referred to as nitrogen fixing but it is actually nodules within the clover's roots that contain these bacteria that produce these nitrogen compounds.

 

Interviewer - Chris Smith

So, what's the solution? We have to encourage more of these bacteria to grow in this soil?

 

Interviewee - Patrick Walter 

So it's a big balancing act. This is another piece of the puzzle, so people can understand what's happening more. We need to know it's there so we can try to control what is going on.

 

Interviewer - Chris Smith

Patrick Walter.

 

Jingle

 

Interviewer - Chris Smith

You're listening to the Chemistry World podcast with me Chris Smith. Still to come, a quick and dirty but very cheap way to discover new catalysts and new chemical reactions. When you need to fill up your car, should you buy the supermarket cheap stuff or pay a bit more for one of the big name brands, after all petrol is petrol, right? Well not necessarily because high grade fuels also contain agents to keep engines running smoothly into their old age. 

 

(20:19- How clean is your car's engine? John Bennett reveals what additives are in your fuel to keep your car running smoothly)

 

Interviewee - John Bennett

My name is John Bennett. I'm the technical manager of fuel additives at Afton Chemical in Bracknell in the UK. The problems we're basically looking at are ensuring that the vehicles and their engines maintain the best possible efficiency and are kept in the best possible conditions, certainly as far as the fuel system is concerned. Our primary focus is on maintaining cleanliness. We specialize on the production of detergents which will help to either prevent the deposition or help with the removal of deposits that may in time reduce the efficiency and general ability of an engine to perform as it was designed by the original vehicle manufacturer.

 

Interviewer - Chris Smith

How long have people been putting detergents and other cleansants into fuels, John? When did this first come in?

 

Interviewee - John Bennett

Detergents have been around since the 1950s, they were originally introduced to help keep carburettors clean. Obviously, they've evolved over the years, but as the deposits are moved into the engine, into different parts of the engine, the basic detergents also had to evolve. A lot of this has been tracking the temperature of the location of the deposits. Thus being that case with gasoline, diesel detergents only started being used in the late 1980s, early 1990s. With the diesel detergent, you won't have extremely good performance in the latest generations of engines. Ironically, for older engines because they were made and appeared when detergents didn't really exist, you don't want to have such extremely good performance. This will sound strange, but the older engines were actually optimized to have some deposits present in the engine.

 

Interviewer - Chris Smith

How do you actually prevent that happening with the modern materials that are added to the fuels and what do these chemicals do?

 

Interviewee - John Bennett

They are detergents, dispersants. It's actually they're molecule in its basic form. It's got a pole ahead and a long chain hydrocarbon tail. You're basically looking to something that will attach itself to a deposit or deposit precursor and will then be soluble the fuel that's passing through the engine. 

 

Interviewer - Chris Smith

Actually in the combustion chamber as well.

 

Interviewee - John Bennett

That's harder. I mean, the first thing to recognize with the additive in a fuel, is that it works in a liquid environment. If you have a part of the engine that doesn't actually see any liquid fuel under any circumstances, then the additive is unlikely to be able to have any impact. Having said that, most places will at some stage have some wetting occurring. It's very rare to find partial combustive system where there's some over spray or some other mechanism where a bit of fuel containing additive will actually reach a surface.

 

Interviewer - Chris Smith

So when you go to the petrol station and I won't pick any particular brand, but there's always a higher grade fuel and then a lower grade one and they're usually more expensive than a super market one, at least they were about 10 years ago. Lots of people, the purists said, well that stuff from the high grade known garage that's much better than the supermarket stuff. They don't have as good additives, is that true?

 

Interviewee - John Bennett

Within region, yes it is. The branded fuels have always traditionally wanted to protect their position as having the best quality products and not surprisingly, they will therefore use a level of additive that gives a good level of cleanliness and a good level of performance. The supermarkets in general, will tend to provide the lowest reasonable level that will provide a basic level of protection. As to whether or not they would change in the future, that's another question. 

 

Interviewer - Chris Smith

So if I were to open up an engine, that had been running a fuel with high grade additives and detergents in there, would I see a clear structural difference, would I see that the cylinders were beautifully cleaned, the piston head had none of these coke on it that we all used to have to scrape off with a trowel when we had old lawn mowers and things a long time ago, or is it not as visible that?

 

Interviewee - John Bennett

It's not as visible as that. On gasoline engines, in particular the port fuel injection engines, which is still 75% of all new gasoline cars or so , you would look for intake valve deposits. And the difference between a fuel that contains a good quality detergent and a fuel that has no detergent or a low amount of detergent would be quite visible and that would show up in time with the way the vehicle drove. The introduction of high performance detergents to keep intake valves clean was driven by a problem called drivability where essentially the deposits that formed on the valves stopped the fuel vaporizing properly, vaporizing in the rate that engine management unit was expecting to happen and when that happened you then found that when you try and accelerate the vehicle, the amount of fuel that is actually reaching the combustion chamber was less than predicted and the engine would tend to stumble but run a bit late

 

Interviewer - Chris Smith

So, there is clear evidence that if you run with diesel fuel, your engine is going to last longer and run better.

 

Interviewee - John Bennett

It will be clean, it will be more efficient. It will last longer. Yeah.

 

Interviewer - Chris Smith

So, if we could just finish off by looking at the chemistry in this. How do you work out what to put into the fuel and what you can get away with it, so that it doesn't compromise the function of the fuel and the power delivered by the fuel but does nonetheless return highly drivable engine.

 

Interviewee - John Bennett

Well, the starting point that will determine the performance of an additive is typically been the standard engines that are used by the industry. So there are a series of engines that are used for demonstration of performance of fuel cleanliness. Generally, that's been very successful. There is one small fly in the ointment. The latest generation engine that's used for demonstration of performance is a Direct Injection Common Rail engine, but they used a zinc compound to encourage the formation of deposits. As in chemicals we have some concerns about that. This use of zinc to form these deposits, we believe therefore makes a deposit that's not representative of what we see in the marketplace. That means, you could in theory, and we suspect in practice end up making detergents that are very good at handling the atypical deposits that are being formed in this particular engine tests that use the zinc  dopant and don't actually address the deposits that are used in engines that you see in the real world, which means that potentially, the consumer instead of getting the benefit of clean injectors in their higher mileage vehicles, have the performance benefits I guess, they would instead be buying fuel that contain detergents that was very good at addressing a particular engine test that the engine used that didn't correlate to real life performance. But generally fuel tend to develop detergents to get good performance in the standard industry engine test. 

 

Interviewer - Chris Smith

Aftonchemicals' John Bennett. A now a way to find catalysts quickly and cheaply, Phil.

 

(27:21- High-throughput catalyst screening for the masses)

 

Interviewee - Phillip Broadwith 

Well, one of the things about organic synthesis is that we don't really understand how it works. We have all of these reactions that we know how to do, how to put molecules together in certain ways but there is a massive world of chemistry out there that we don't know how to do this. There are lots of molecules that we don't know how to fix together. So what a lot of organic chemists spend a lot of time doing is looking for new reactions and that's one of the things that John Hartwig of University of California in Berkeley has been spending some time thinking about how to do.

 

Interviewer - Chris Smith

Okay, so what's their technique?

 

Interviewee - Phillip Broadwith 

The beauty of this technique is that it uses very standard equipment. We're talking about sort of 96 well plates, which are very common in especially in biological chemistry and screening chemistry and gas chromatography mass spectrometry and what they've done is take one of these 96 well plates, in each well, they put a mixture of 17 different fairly standard chemicals, sort of with a variety of different functional groups and so there are alkanes, amines, that kind of thing. 

 

Interviewer - Chris Smith

All mixed together.

 

Interviewee - Phillip Broadwith 

All mixed together. So there's lot of different ways that they could possibly combine. Then in each row of the plate, so there are eight different rows, you put a different metal and then in each column, there are12 columns, you put a different ligand, so you have 96 different metal ligand combinations to mix with those 17 different reactants. 

 

Interviewer - Chris Smith

To mix with those different reactions?

 

Interviewee - Phillip Broadwith 

Yeah, so you've got all the different reactions mixed up, you put the whole thing heated up for a few hours, and then you put it all through the mass spectrometer and see what's reacted. Reagents are chosen so that they all have a fairly similar molecular weight so that you can see if two of them have combined, you've got a compound with a much higher molecular weight.

 

Interviewer - Chris Smith

How on earth you unpick it afterwards?

 

Interviewee - Phillip Broadwith 

Exactly. So that's part of the clever design of deciding which molecules to do. You get a new molecule that sticks out on the mass spectrometer. It's significantly heavier. 

 

Interviewer - Chris Smith

Got it, and you're choosing various unknowns that will enable if they do react to start asking questions about new chemistry. 

 

Interviewee - Phillip Broadwith 

Exactly. That's, you know, people do catalysts screens in lots of different ways but it's generally done in a very sort of systematic way. The idea of this is that you're changing lots of different things all at the same time and you screen it using a very standard technique which is very sensitive to low concentration.

 

Interviewer - Chris Smith

But it's also really simple, isn't it?

 

Interviewee - Phillip Broadwith 

That's it. The really beauty of this is that it works on very simple equipment. 

 

Interviewer - Chris Smith

Exactly. So, what have they done beyond just proof of concept? What have they done now to show this can work; this can yield viable results or the valid?

 

Interviewee - Phillip Broadwith 

Okay so this first run through, they chose particular combinations of reagents and metals and ligands that would give certain reactions that are already known. So that's kind of saying, do we find what we expect to find and yes, they did find exactly the reactions that they expected to find and as a bonus, few extra new ones. There are some unexpected ones too.

 

Interviewer - Chris Smith

So that validates it, it works. What are they now looking at?

 

Interviewee - Phillip Broadwith 

Well, in principle, there's no reason why you couldn't use this to screen all sorts of different types of reactions, not just metal catalysts, you could look at organic molecule catalysts or acids and bases and oxidizing agents or whatever, anything like, any kind of reaction. You could start probing new chemicals basically, use different reagent combinations, and all sorts of things.

 

 

(30:46- Limestone is efficient energy distributor)

 

Interviewer - Chris Smith

Ingenious. Now talking of things that are very efficient, who would have thought of limestone, you know, who would have thought that could be a way of distributing energy, shipping limestone or components related there too around the planet, Laura

 

Interviewee - Laura Howes

Yeah. So earlier in this podcast, I was talking about magnesium sulphur batteries, which was in a way surprising but this is limestone batteries, this is literally using the calcium carbonate limestone that we're all familiar with. 

 

Interviewer - Chris Smith

Limestone blackboards with. 

 

Interviewee - Laura Howes

Exactly

 

Interviewer - Chris Smith

  To shells at the seaside from??

 

Interviewee - Laura Howes

So, tried to actually use this material to transport and store energy.

 

Interviewer - Chris Smith

How?

 

Interviewee - Laura Howes

People are looking at these large, sort of, solar arrays in deserts. Deserts are large empty spaces and they get a lot of sunlight and a lot of people are thinking, well if we can concentrate this sunlight down, we can get energy. One of the problems that they have is they can get the energy, but then how do you get it from the desert to where you actually want to use this energy.

 

Interviewer - Chris Smith

So what's the technology here then? How are they talking about using chalk?

 

Interviewee - Laura Howes

So, yeah they're talking about using chalk effectively. They're talking about something which is actually not so much of a new idea. Something that people are calling Calcium Looping, sort of separating out limestone into two constituents being calcium oxide and carbon dioxide. You can separate these two with heat, so the idea would be you would concentrate the sunlight down, heat up your limestone.

 

Interviewer - Chris Smith

CaCO3 goes to CaCo + Co2.

 

Interviewee - Laura Howes

+ Co2 exactly. Now the Co2, you can.

 

Interviewer - Chris Smith

Is solar capable of the heat necessary to do that?

 

Interviewee - Laura Howes

If you can concentrate it down enough, you can get some pretty hot temperature.

 

Interviewer - Chris Smith

Okay.

 

Interviewee - Laura Howes

So, the carbon dioxide, you would then, sort of, take off and the idea is you could combine it with the hydrogen that you've generated through something to make fuels and feedstock chemicals.

 

Interviewer - Chris Smith

Methane.

 

Interviewee - Laura Howes

Methane, exactly.

 

Interviewer - Chris Smith

Carbon Units. Okay

 

Interviewee - Laura Howes

Yeah, meanwhile you've then got this calcium oxide and this is your solid that you can use as a battery, so just literally using the energy that you've put into this compound, transport this.

 

Interviewer - Chris Smith

So, you've got that lime somewhere.

 

Interviewee - Laura Howes

Yes, so I mean.

 

Interviewer - Chris Smith

And recombine it with Co2 somewhere and that's obviously the energy is in the CaO, the calcium oxide because it wants to react.

 

Interviewee - Laura Howes

It wants to become limestone again, if you then react it and the idea is that you do this in say the African desert, you transport it to Germany where you've got a fossil fuel powered power station. You take the carbon dioxide out of that, you combine the two, you're sequestering your carbon dioxide and you're also getting a lot of energy back out.

 

Interviewer - Chris Smith

Is this actually energetically viable?

 

 

Interviewee - Laura Howes

Potentially at the moment, not necessarily. I don't know whether the whole lifecycle analysis including the transport which presumably would be lorries and boats, whether that's all been done and included into the calculations. There also is a problem with eventually doing this cycling is not actually going to last forever. You'll end with impurities. 

 

Interviewer - Chris Smith

 

Sure

 

 

Interviewee - Laura Howes

 

You end up you won't be able to use the same amount of limestone forever. There is a project at the moment called DESERTEC which was what people started thinking about, it's not going to be ready for that, that's coming on stream in a couple of years, but potentially there are ideas that you could have with this.

 

Interviewer - Chris Smith

What a fascinating idea? Now stay there both of you because it is trivia time.

 

(34:00- Trivia - What's the fastest thing in the universe?)

 

Interviewee - Phillip Broadwith 

Okay, well Chris, the trivia for this month is: what is the fastest thing in the universe?

 

Interviewer - Chris Smith

I know this is going to be a trick question now, but I mean, if you asked Einstein that question, he would have said light? 

 

Interviewee - Phillip Broadwith 

Well, absolutely right Chris, but what the scientists at CERN and Gran Sasso laboratories in Italy are going to say is neutrinos. There's been an announcement about an experiment where they fire beams of neutrinos from the Large Hadron Collider at CERN 730 kilometres through the earth through Gran Sasso in Italy and they arrived 16 nanoseconds before they would have done if they'd been going the speed of light.

 

Interviewer - Chris Smith

What do they say is the reason for the early arrival? They're presumably beating light

 

Interviewee - Phillip Broadwith 

Part of the explanation is that neutrinos are very non interacting particles; it's been muted before that they could possibly travel a little bit faster than the speed of light.

 

Interviewer - Chris Smith

Then they've got mass. So they shouldn't be able to

 

Interviewee - Phillip Broadwith 

Well, according to Einstein's theory of special relativity yes, they absolutely shouldn't and that's why this is such an important announcement. If it turns out to be correct, then physicists are going to have a bit of a serious rethink. 

 

Interviewer - Chris Smith

So, it could be rewriting the all laws of physics around the neutrino. What's special about them is that they can get away with this stunt?

 

Interviewee - Laura Howes

Neutrinos are quite well known for being able to pass, whiz through solids. But some people are thinking that actually rather than travelling through the three dimensional or four dimensional space we know, they actually go whizzing through extra dimension, like.

 

Interviewer - Chris Smith

They take a shortcut.

 

Interviewee - Laura Howes

They take a short cut. So it might be that they're not actually travelling faster than light, it's just that they're not travelling as far as we think they are.

 

Interviewer - Chris Smith

So, it gives the impression they're arriving early. They've actually taken some kind of shortcut. 

 

Interviewee - Laura Howes

Exactly. I mean, there are other explanations. I think one of the nice things about this is that when you look at what the scientists are saying is that they've put their hands up and say, we don't know why this results happened, we've checked all the variables we can find but we really actually just want someone to help us, prove it's right or disprove it. There are a couple of other neutrino experiments in the world and so definitely I think there will be a lot of particle physicists who will be giving this a go. 

 

(36:20 - It's our birthday! The Chemistry World podcast is 5 years old this month)

 

Interviewer - Chris Smith

Well I also think far more important than something beating the speed of light and that is do you know what this episode of Chemistry World podcast is why it's important. Philip

 

Interviewee - Phillip Broadwith 

Well, Chris, by my calculations, this is our five year anniversary.

 

Interviewer - Chris Smith

I was amazed actually, when I looked back on my computer and I saw all these previous five years of episodes of the program. This is our 61st version.

 

Interviewee - Phillip Broadwith 

We have had a few staff changes on the way, but the Chemistry World podcast rolls on. 

 

Interviewer - Chris Smith

And don't forget of course Chemistry in its Elements, which is going to be four next year. In 2012we started that's the weekly look at the exciting intriguing molecules and chemicals of the (37.03) periodic table and world around us.

 

Interviewee - Phillip Broadwith 

Exactly. We're up to well over 50 compounds and the whole 115, 116 elements in the periodic table.

 

Interviewer - Chris Smith

All with their own story to tell.

 

Interviewee - Phillip Broadwith 

Absolutely right Chris. 

 

Interviewer - Chris Smith

And on that note, that is it for this month, thank you to Phillip Broadwith and before him Laura Howes and Patrick Walter. Our guests this month were Paul Shearing and John Bennett. The production was by Meera Senthilingam and I'm Chris Smith from thenakedscientits dot com. Join us for more cutting edge chemistry next month, until then good bye.

 

(Promo)

 

The Chemistry World Podcast is brought to you by the Royal Society of Chemistry. Look us up online at chemistryworld dot org.

 

(End Promo)