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More on Grenfell cladding and fridge design

Dear Reader,

It appears that a polyurethane type material was present in the cladding at Grenfell, one newspaper is claiming that a product named “Celotex RS5000”. When I looked up this material it turned out to be a polyisocyanate type polyurethane which suggests that it is going to be a bit harder to burn than a simple polyurethane.

The daily mail did print the rather dire line “Insulation burns at sufficient temperatures and gives off hydrogen cyanide”, I would comment that we need to be careful about some words.

Flammable (inflammable) liquid means that the fumes of a substance will ignite if a flame is presented to above the liquid which is below a particular temperture. Flammable solids are a little harder to define, one good definition is a solid which is one of the following

  1. A desensitized explosive which has sufficent water, plasicizer or some other additive to prevent detonation.
  2. A self reactive material which can burn without added oxygen or air.
  3. Solids which can ignite through friction (such as matches)
  4. Pyrophoric solids and solids which can selfheat to the point of ignition.

I very much doubt if the cladding will be able to fall into one of these subclasses, what the cladding is more likely to be is “combustible”. Combustible means “possible to burn the substance if it is subject to sufficient heating”. For example a pool of JET-A fuel will not burn if it is exposed to flame, but if you were to soak a rug in the jet fuel or add a wick then it would be quite easy to start the fuel burning.

The emission of toxic fumes during burning is not a rare thing, many fuels will when burning under the “right” conditions form toxic gases such as carbon monoxide and sometimes hydrogen cyanide. I hold the view that all carbon containing fuels can form carbon monoxide when burnt. Also the generation of hydrogen cyanide during burning under air poor conditions is very common, cigarette smoke tends to contain hydrogen cyanide.

The problem is that all smoke is harmful but smoke from some materials is worse than others, for example overheating PVC and CSPE cables emit fumes which include hydrogen chloride (hydrochloric acid gas). This will make a fire which involves these materials worse than a fire which involves cables such as XLPE cables when we consider how corrosive the smoke is to objects and how harmful it is to people. On the other hand it is important to note that the very chlorine rich plastics such as PVC and CSPE are very hard to ignite. The great problem I see is that if we purge the world of things with chlorine in them like PVC then while a fire might emit less hydrogen chloride once it gets underway we might end up having more fires unless we find a decent replacement.

We need to consider both the frequency (how often) and the consequence of fires and other misadventures. If we look at the Grenfell fire, then if the cladding was the absent from the building then the consequence (how bad) of the fire which started in one flat would have been lower. Removal of the cladding will not reduce the frequency of the fridge fires but it will alter the likely consequence. If on the other hand we were to improve the design / construction of household electric equipment and thus reduce number which burst into flames each year then we could also reduce the number of deaths, injuries and monetary cost per year due to fires.

Back in 2015 the London Fire Brigade published a statement on fridges, what they want is the design and construction of fridges to be altered to reduce the consequence of a fire in a defective fridge or freezer. They want the casing of the device to be metal (to slow the development and spread of fire) or something else which will resist fire better. Sadly again I think that they are misusing the term “inflammable”.

I think that they are right for calling for the fire safety of fridges and freezers to be improved, one of the problems was that in common with PCB transformer oil the freon used in fridges was introduced as a safe non-combustable material to reduce fires. Freon was used originally in fridges as as a non toxic and non combustable alternative to the toxic and flammable gases (such as sulfur dioxide, ammonia and other horrors) which were used in the first ever fridges.

Now instead of things like freon-12 (dichlorodifluoromethane) fridges are using things like cyclopentane, propane or other similar flammable hydrocarbons. I have to ask the question of why do we have to use these compounds. I would like to know if some fluoro-iodohydrocarbon could be devised which would be non toxic, non flammable, too unstable in the lower atmosphere to pose a threat to the ozone layer and unable to cause global warming. But right now we are stuck with fridges which are using flammable gases for their working fluid.

I would like to suggest that we should consider the question of could we improve a fridge in terms of fire safety. I would like to accept the idea that we go for a metal layer covering the plastic foam insulation and we would change to a flame retardant plastic. Such as a layer of XLPE over the polystyrene foam. This would reduce the rate at which a fridge burns. But are there things we could do to stop fridges igniting in the first place.

I would like to suggest that we could change the law to reduce the chances of a fridge creating the spark which ignites leaking gas, for example I would suggest changing the thermostat for one which has all spark generating bits either sealed in a stainless steel capsule, potted in plastic or designed out. This would reduce the danger that a fridge poses if the pipes inside the fridge start to leak. I would also suggest changing to a brushless motor on the compressor to stop the fridge motor making sparks. I would also target the lamp in the fridge, I would opt for a LED lamp which would last the life of the fridge and is in a sealed module designed to prevent a spark encountering flammable gas.

Another improvement would be to add two semiconductor flammable gas alarms. One inside the fridge and one outside the fridge. The idea is that if the one inside the fridge is triggered that an alarm should start ringing and the power should be cut to the fridge. While the second should be outside the fridge at floor level as the working fluids in a fridge form gases which are more heavy than air. If this one goes off it is a more important matter. It should make the fridge scream for help and also shut down. It could also offer a warning in the event of a gas leak in the kitchen (particularly if the people use LPG to run the cooker).

One of the problems is that some words which have very precise meanings within science are used sometimes in the media in places where they should not be. For example “volatile” has two meanings within the Cambridge Dictionary. The second one is the one which is the “scientific” meaning of volatile.

  1. likely to change suddenly and unexpectedly or suddenly become violent or angry.
  2. A volatile liquid or solid substance will change easily into a gas.

But it was used when discussing fireworks, in Malta there has been a string of rather horrible firework accidents. One of the problems is that the firework industry there use pyrotechnic mixtures which are not permitted in many parts of Europe. In one newspaper report it was commented that “local firework factories use highly volatile chemical mixtures banned in many other countries“. Unless the firework makers are using some rather odd mixture such as ammonium nitrate / nitromethane or a low molecular weight organic explosive I would very much doubt if the energetic materials in the fireworks emit a large amount of vapor. Instead what they were meaning is that the firework makers in Malta are willing to use mixtures of things like chlorates and fuels which are very sensitive to static electricity, friction and impact.

It would have been better to have written “the local firework factories use excessively sensitive chemical mixtures banned in many other countries” or “the local firework factories use chemical mixtures which are easily triggered under accident conditions, some of these are banned in many other countries”. I will not go into a deep discussion of firework chemistry here but I will comment that many chlorate / fuel mixtures are unsafe. Some of them are quite rightly banned by UK law and by the laws on fireworks in many other parts of the world.

I have to ask the question of how should we choose the materials for a high rise tower block, we have two issues. The first is how easy (or how hard) is it to burn the material. While the second is how toxic can the smoke be before we decide it is too toxic. Sadly I am unable to give easy answers to these questions.

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Eliminations

Dear Reader,

Elimination is an important reaction in organic chemistry which forms alkenes. Here are some of my slides on the subject.

The mechanism of the E2 elimination

The E1 mechanism

This is an important problem why are the green equations not the same

By altering the size of the base the ratio of the SN2 to the E2 reaction can be changed

Some example data for you to study with

Which reaction ? Choose between SN1 SN2 E2 and E1

How to favour the E2 reaction

More on how to favour the E2

Predict which products are formed in these reactions, also note that hydrogen cyanide smells nothing like almonds to me. The only thing which smells like HCN to me is HCN.

Another good training problem

Why and how does Prussian Blue form

Dear Reader,

Welcome back and I have to warn you fine folk that I am still thinking about Prussian blue the wonder substance which helps us to manage the radioactive cesium from the Fukushima accident.

While on a boat crossing the north sea I asked myself the question of why does Prussian blue form and how. I think that I have come up with an answer. It is important for us to start with the unfriendly sounding molecule hydrogen cyanide. It goes backward and forwards. It is refined, very much maligned and misunderstood. Go easy on this fellow, he must never be abused. He gets the metals going and you find him fizzing in the corner in the bleach bin.

Some of you may have spotted the reference to 1980s culture, those of you who have not then do not worry. All will become clear soon. It is important to bear in mind that Prussian blue will not give you cyanide poisoning.

HCN is a very refined fellow, the modern and green way to make the dinitrile required for the production of the 1,6-diaminohexane required for nylon-6.6 production is to use hydrogen cyanide (with a nickel catalyst) rather than using sodium cyanide. So the next time some asks you to name a green reagent you can say “hydrogen cyanide” in a truthful way. While it is a toxic reagent it is more green than sodium cyanide as its use forms less toxic solid waste which is hard to deal with.

For a process to be truly green it must satisfy three things.

1. Be economically sustainable (Eg process for making aspirin at £ 10 per gram will not be OK)

2. Be environmentally sustainable, it must not guzzle resources or spew out vast amounts of waste for a small amount of product (Eg if I have to cut down a square mile of rainforest and kill five rare birds to make you an egg sandwich then this method is not an OK egg production system)

3. Be socially sustainable (Eg if a process requires small children to climb up chimneys then it will not be considered morally acceptable. As a result it will be impossible to sustain the process in today’s Soceity)

Next HCN is a very maligned and misunderstood substance; it is a toxic gas but if we want to base our vilification of gases on purely their toxicity then hydrogen sulphide beats it in the top ten worst ever gases. My own view is that carbon monoxide is more of a fright gas as CO has absolutely no smell and is much more common (check your when your gas appliances were last checked by a service engineer). But as a result of the fact that HCN was the poison gas used at some Nazi extermination camps, in the American gas chamber and in many detective stories hydrogen cyanide has acquired a super nasty reputation. It is interesting to note that carbon monoxide was also used by the Nazi murderers (the gas van), but why then has CO not become viewed with equal horror by the public ?

I would say that as a chemist or an industrial worker it is important to avoid breathing in or otherwise absorbing HCN, it is bad for your health. As well as the dire short term effects which are well known it can have some horrible long term effects which are sometimes seen in parts of Africa where people tend to live on a vegetable known as cassava. If you prepare this food wrongly then you will get a dose of cyanide in every meal, this can lead to chronic cyanide poisoning which causes among other things trouble with the nervous system. So my advice is to “go easy on your body” when working with cyanide. Do not abuse your body by forcing it to endure the stress of having to metabolize cyanide, take that bit of extra care to lower your occupational intake of cyanides.

The cyanide anion is a very strong ligand for many transition metals, indeed it does get the metals going. Sometimes in very much the wrong way, some time ago there was a large spill of cyanide waste in eastern Europe. It ended up in a river where it then killed the fish, one of the problems with cyanide it binds to an iron complex in mitochondria which then stops oxygen binding. As a result the fish could no longer use oxygen, as a result they died. But we need to understand why does cyanide bind to metals so well, the binding of cyanide to metals is much stronger than the binding of most simple monodentate ligands.

Monodentate ligands is a fancy term for a molecule or atom which binds through one atom onto a metal.

A snake which grabs you with its mouth is a monodentate animal

A crab which grabs you with both claws is a bidentate animal

A scorpion which grabs you with both claws and applies the stinger to you is a tridentate animal

The reason is the “backwards and forwards”, hydrogen cyanide when deprotonated forms the cyanide anion which uses a lone pair on the carbon to form a sigma bond to a metal. It also uses its empty pi* orbitals to suck electron density off of metals thus forming pi bonds to the metal.

Now we need to look at the orbitals of the hydrogen cyanide, the orbitals of the cyanide anion are almost identical.

Lets start with the HOMO, this is not a sexual term it means Highest Occupied Molecular Orbital in chemistry. Those of you who were expecting something sexual here, I am sorry but I am going to disappoint you, this blog is not about sexual matters. But feel free to carry on reading as you might find the chemistry interesting.

The HOMO of HCN

Here you should be able to see that on the nitrogen atom (blue atom) a lobe of the orbital pokes out into space away from the CH group, this part of the orbital will form the lone pair which allows the nitrogen to bind to things. Around the hydrogen atom is a big blue lobe. When the HCN loses a proton this will form a cloud of electron density which also pokes out into space. Here is another view which may make it more clear, the lone pair on the nitrogen and the blue blob on the carbon will allow it to form the sigma bonds which go to metal atoms.

Alternative view of HCN's HOMO

Here is a view of the HOMO of the cyanide anion, look at how similar it is to the HOMO of hydrogen cyanide.

Next here are two alternative views of the HOMO of the cyanide anion to allow you to have a better idea of the shapes of the orbitals.

The next thing to look at is the p orbitals of HCN, I have calculated these orbitals for the cyanide anion and they are the same shape so I will only show you one set. Here is one of the them.

One of the pi bonding orbitals of HCN

The hydrogen cyanide molecule has two occupied pi orbitals which look like a pair of sausages arranged parallel with the line between the carbon and the nitrogen. Here is a view of the other one.

A view of the other pi orbital

Next we have the pi* antibonding orbitals.

LUMO of HCN

HCN LUMO +1

I guess they looked the same to you, so here is the end view. Note that they are at ninety degrees to each other.

HCN LUMO

HCN LUMO +1

Now to understand antibonding, I want you to think of a nice person. How about St Francis of Assisi, after a wayward youth he grew up to be a man known for being kind to poor people and taking care of animals.

The anti-St Francis would be a nasty man who steals bread from staving single mothers and homeless men, for fun he throws
animals down the well.

The anti-St Francis is the total opposite of St-Francis, everything good about St-Francis has been turned into something horrible in the anti version. In the same way all the energy lowering effects of the bonding orbitals are turned into energy increasing effects in an antibonding orbital. Typically an antibonding orbital is more antibonding than the bonding orbital is bonding. So if you fill up both orbitals with electrons then overall the sum of the two orbitals is antibonding.

In case you want to see some of the other orbitals of HCN then here they are.

LUMO +3

LUMO +2

 

LUMO +1

LUMO

HOMO

HOMO -1

HOMO -2

HCN HOMO -3

HCN HOMO -4

I hope to bring you some more about our new friend (Prussian Blue) soon.

Why is cyanide so interesting to my readers

Some time ago I wrote about cyanide in fruit, while the C word does excite all manner of “mighty dread” I think that the public think about the C word because of war crimes and literature.

I had a long think about this subject, I have to confess that while cyanide is not exactly a health tonic it has a lot of very interesting chemistry. In modern chemistry people try to avoid using it but sometimes it does get used to make things happen.

One nice reaction is that of p-benzoquinone and cyanide in DMSO, this is the basis of a wounderful test for cyanide. If cyanide is added to a solution of the benzoquinone then an aromatic compound which is fluorescent is formed. This test was described in a paper by George G. Guilbault and David N. Kramer, Analytical Chemistry, 1965, volume 37, issue 11, pages 1395-1399. Below is shown the chemical reaction by which is works.

Reaction of benzoquinone with cyanide

Figure 1. The benzoquinone reaction.

Another nice reaction is the condensation reaction of two molecules of benzaldehyde to form a hydroxyketone, this is a reaction which known as the benzoin condensation. In this reaction a cyanide anion attacks the aldehydes as a nucelophile and then forms a new nucleophile which attacks another molecule of the aldehyde. Then to regenerate the cyanide anion the cyanide is lost as a leaving group thus forming the product. This is a nice example of carbonyl chemistry, I stress “example”. The most important thing which I have learn in organic chemistry is that the same reactions keep coming back again and again but dressed up in slightly different outfits.

The first step is the reaction of the cyanide with the benzaldehyde to form the addition product. This is a single step process which is likely to go via the transition state shown. Now I have been kind to you and drawn in the curved arrow, you will need in the future to use the curved arrow to understand organic chemistry and do you grades the world of good. Always keep this golden rule in mind, the curved arrow moves electrons and NEVER atoms or atomic nuclei. Now here it is.

The first step in the benzoin condensation

Now the second step is a transfer of a proton from the carbon onto the oxygen, the cyanide group helps by withdrawing electron density from the carbon bearing the hydrogen which is to be transferred. The cyanide will pull electron density by means of a resonance effect and a little bit of an inductive pull. The inductive pull is due to a tug of war for electron density in the sigma bonds.

As the reaction is normally run in a protic medium (mixture of water and alcohol) I have drawn a mechanism where a proton from the solvent attaches to the alkoxide oxygen before the carbon is deprotonated.

Second stage, the proton transfer

 The next step is the one which forms the carbon carbon bond, here the carbon centred anion attacks a second molecule of benzaldehyde to form a new intermediate.

 

The step which forms the carbon carbon bond

Now what is needed is a proton transfer step to move the minus charge, this should be an easy one.

A proton transfer step to set up the molecule for the last step

Now the last step is where the cyanide is used as a leaving group. The important thing about this reaction is that the cyanide is both a nucleophile and a leaving group. Now we will see the final step.

Final step of the reaction

 

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