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Visual fireworks

Dear Reader,

I have found an interesting web site devoted to interesting looking curves. No not curves on people but mathematical curves.

I have started to plot some of the curves with excel, I hope to show you the pretty pictures soon.

Corrosives in the eye accidents

Dear Reader,

I saw something interesting recently on a rather disagreeable subject, the subject is eye injury caused by corrosive substances. Now for about 20 years I have worked surrounded by acids, caustic and a range of other not so eye friendly nasties. One has to ask the question of who is more at risk in a given year of getting an eye injury from a corrosive substance.

  1. A cleaner who uses bleach to clean toliets
  2. A farm worker who has to mix and use pesticides
  3. An analytical worker who dissolves and dilutes everything in acid
  4. A platinum group metal refinery worker who works in a plant where everything is digested in acid before chemical separations
  5. A two year old child

Well think about it for a moment, I can not claim to know the exact eye injury rate for each of the four adult trades, but a study by workers at the Johns Hopkins Bloomberg School of Public Health in Maryland revealed that for each million adults (18 to 64 years old) the rate of chemical burns to the eye is about half as high as it is for 1 and 2 year old children.

Now we should ask ourselves the question of why is this the case, myself and the researchers hold the view that the small children are likely to access the corrosive products in the form of household chemicals (bleach and cleaning materials) in the home and other places where they go.

The problem with this age group is that they can not read a warning sign and that they tend to experiment (play) with everything that they encounter. I suspect that the best way to reduce the rate of these accidents is to further reduce the ability of children to access corrosive liquids.

I would suggest child resistant caps and packages, I would also suggest that people use a locked cupboard to store garden and household chemicals. For example even while Roundup™ is not toxic to humans I normally keep it either in the basement on a high shelf or in a locked shed in the garden. My reasoning is that my three year old son might know how to open a bottle, but he is less likely to be able to find a padlock key, then reason that the key unlocks a big black / grey box in the garden and then to open it and thus gain access to a stock bottle of Roundup™.

I also have to ask is sufficient effort being put in to making things like lighters and poison / corrosive bottles unattractive to children. Looking at my Roundup™ and most cleaning products they do not look much like toys to me. But I was troubled to see in a supermarket a lighter which has a picture of a pretty doll like girl on the side. My worry is that such a lighter is more attractive to a child than a plain one like a Zippo with a polished chrome finish or a dirt cheap bic lighter.

I would also like to suggest that we consider if we need a particular household chemical or not, for example while oil based paints might give you a nice finish you can often get as good a finish with a water based emulsion paint. I hold the view that the water based paints tend to be less toxic and flammable than oil based paints, also you do not need to use white spirit for cleaning brushes after using emulsion paint. As a result of careful choice of paint type you can reduce the amount of flammable and toxic liquid which you need to keep in the shed, basement or house. As well as reducing the amount of harm which your children can do on a Sunday morning as you try to get that layin which you feel that you so royally deserve, it will make a improvement to the fire safety of your home.

This improvement will be to limit the potential for a flammable liquid fire in your home.

Is vapping safe ? Maybe not.

Dear Reader,

It has come to my attention that electronic cigarettes emit a range of nasty chemicals, while the chemicals might be different to those emitted by conventional cigarettes they still have the potential to cause serious diseases such as cancer.

I would like to suggest to my readers that they abstain from both conventional and electronic cigarettes. These electronic gadgets have been found to form epoxides which are alkylation agents which can damage DNA. The epoxides include propylene oxide and glycidol. Below on the left is shown glycidol (oxiran-2-ylmethanol) while on the right is shown propylene oxide (2-methyloxirane).

epoxidesfromecigs

The study which I have seen reviewed reported that nicotine, nicotyrine, formaldehyde, acetaldehyde, glycidol, acrolein, acetol, and diacetyl were all observed in the “smoke” from an e-cigarette. If you want to see the paper then look here.

The core idea in the paper is that the solvents (glycerol and propylene glycol) can decompose to form toxic substances when heated by the electric heater used in the e-cigg. The problem is that while it is safe to drink moderate amounts of glycerol or propylene glycol it is possible by heating to convert these food safe chemicals into toxic products.

Changing newspaper

Dear Reader,

After the disgraceful politics of the Brit exit leave campaign I choose to switch from reading the Daily Mail (Right wing newspaper) to the more left wing and intellectually serious Guardian newspaper. Now after changing I found that the Guardian seemed to write articles which were written in a more intelleigent and in depth way. I was enjoying this new experience and then I saw something about some loathsome herbs from South America which reminds me of the way in which LSD, peyote cactus (mescaline) and mushrooms (psilocin and psilocybin) were being touted by the likes of Timothy Leary. For those of you who are interested here are the chemical structures below.

halocogen

Now those of you who have taken an organic chemistry course should notice that all three drugs are either indoles or have an indole like structure. The new herbal horror mix which the Guardian seem to be praising is a mixture of 7-methoxy-1-methyl-9H-pyrido[3,4-b]indole which is a MAO inhibitor (MAOI) mixed with DMT (2-(1H-indol-3-yl)-N,N-dimethylethan-1-amine). The DMT is a hallucinogen which has a short lifetime in a human, the MAOI increases the lifetime of the drug in the person thus making the ayahuasca a more horrible concoction.

Please understand that while MAOI drugs are serious, the scary thing about the MAOIs is that they can interact with other drugs and even common foods in some very scary and potentially deadly ways. The author Elizabeth Lee Wurtzel, she wrote of how a person on some types of MAOI drugs can fall down dead by eating some types of cheese and wine. On the otherhand I recall that a MAOI can protect the brain from MPTP, MPTP is a neurotoxin which horrifies me. Thankfully it is a substance which is hard to obtain, the reason why it horrifies me is that it has the potential to induce parkinsonism in healthy people.

As a chemist I have to ask why a national newspaper would want to promote drug abuse, my own view is that the physical and mental risks posed by drug abuse to the user are a perfectly good reason to outlaw substances such as LSD and psilocybin. We also need to consider the threat to society, assume that we have 1000 people who are paying tax and in work. If 1 % of them go to prison for drug crimes for five years each and 1 % end up as long term psychiatric patients then it is going to impose a great cost on society.

The drug crimes include things like dealing (supply), possession, property crimes committed to fund a habit and crimes of violence committed either by dealers or users of the drugs.

We are going to ignore for a moment the moral arguments and just consider the money. The cost of putting someone in prison in the first year is £63000 while in the other years it is £ 40000. So each of the 99 % who do not go to prison has to pay out £ 2252 (£ 450) for the cost of five years prison time for the 1 % who go to jail.

The UK average salary is £ 26500 per year, based on the UK tax office rules you can expect to pay tax on this.

The first £ 11000 is tax free, so we will ignore this.

Then on everything between £ 11000 and 43000 you have to pay 20 % on your income. So the average tax payer will have to pay £ 3100 per year.

More than 10 %, in fact 14.5 % of this will have to go on the prison costs for the 1 %. So if drugs result in 1 % of the population being sent to jail for five years then it will impose a very large cost on the general public.

I do not assume that all hospital patients cost the same amount, but one average estimate was that a single person spending one day in hospital costs £ 400. Now if drugs cause 1 % of the population to stay all year in a hospital then this is going to cost per 100 people a total of £ 146000, if we split this between the 99 who do not end in hospital then it is going to be £ 1474 each. This is going to be even more expensive than the prison cost.

Now the 1 % values are pulled out of thin air, but they do show that if we were to allow drug abuse to occur which results in 1 % of the population being jailed and 1 % being laid up in hospital then it is going to hurt society. While people might not like the cost in pounds of jail and hospital being considered, we need to note that for every pound which is spent on cleaning up the mess created by substance abuse it is one less pound for the following

Schools, treatment for cancer, university, treatment / prevention of heart disease, old people’s homes, social care, protecting the environment, protecting our national heritage, arts, culture, road building, investment in new industries and a whole series of other worthy causes.

By the way if you are considering doing drug abuse then please consider the tale of Barry Kidston and some other people who were taking what they thought was heroin. While Barry set out to take an exotic version of pethidine, the others did not. The thing about illegal drugs is that you never know quite what is being sold on the street. For example I have heard of mixtures of heroin and LSD being sold as MDMA. The horrible thing about the drug which Barry made was that it resembles heroin, it is a much stronger version of pethidine. So it can be sold on the street as “heroin”, the biggest problem I see with 1-methyl-4-phenyl-4-propionoxypiperidine (MPPP, or Desmethylprodine) is that the synthesis is a simple short synthesis route which a mediocre chemist could get some yeild of MPPP. But even a skilled synthetic chemist would find it hard to avoid forming some MPTP in the synthesis, the substrate for the final step is set up for a E1 elimination (dehydration) which forms MPTP.

I have heard that in some cases the product from a illicit MPPP synthesis is close to pure MPTP, the thing is that MPTP can punish a person in ways that even the strictest legal systems can not. For instance in the far east some countries offer the death penalty for some drug offenses, the mode of execution varies but I have heard of hanging and shooting being used. The UK and Swedish legal systems offer long sentences in a prison, but MPTP can give what I imagine a “living death”, MPTP can imprison a person inside their own body ! I have heard tales of people being awake and aware but locked into their bodies by MPTP poisoning.

English case law

Dear Reader,

This morning I was reading about the case law on false imprisonment, and I noticed Sayers v Harlow Urban District Council a 1958 case about a woman who was trapped in a toilet by a defective door lock (missing handle). Here the argument is that a deliberate act is required for a person (natural or otherwise) to have committed the tort of false imprisonment . The case reminds me of a stupid song which I recall for my days at primary school

“Oh, dear, what can the matter be?
Seven old ladies were locked in the lavatory”

Thankfully as children we only knew the first two lines of this dire song about ladies being trapped in the toilet. I recall as a child being shown by my father a book of case law on the subject of contract law, this was a yellow book which was a collection of court cases which relate to contract law. My favorite as a boy was Carlill v Carbolic Smoke Ball Co. This was because as a boy I imagined a “smoke ball” to be some outlandish gadget which emits smoke and does strange things. It was nothing to do with the fact that this is the classic english case relates to promises made in adverts and a warrenty.

BritExit and Tony Blair’s lies

Dear Reader,

It has come to my attention that a major report into the way in which the UK parliament decided to go ahead with the second gulf war between Iraq and the US/UK. The Chilcot report is likely to be rather interesting, there is already a discussion regarding the question of “should we put Tony Blair on trial for dishonesty relating to the transition to war ?“.

Now it can be reasoned that consent obtained through fraud is not true consent, so if the UK parliament gave consent for the gulf war after having be lied to then this consent is not true consent. If we look at section 74 of the Sexual Offences Act (2003) it explains how consent obtained by fraud where “the defendant intentionally deceived the complainant as to the nature or purpose of the relevant act” is not true consent. I can also point out that the idea of consent obtained by fraud is not valid consent also appears in US law.

While the laws mentioned in the two sources I mentioned might not apply directly to Tony Blair, we can safely say that the idea that “consent obtained by fraud is not valid consent does exist in UK law”.

This may become more than just an academic question as I know that there talk of impeaching him and starting civil cases against him for “malfeasance in public office”.

Now the second example I want to consider regarding consent obtained by fraud is the referendum for the UK to leave the EU. Now we should be aware that the leave side made a large number of “wild and wonderful” promises to the British public regarding what they would deliver if the UK public were to vote to leave the EU.

Great things like 350 million pounds a week to spend on the NHS, the problem with that one is that it was made by someone who clearly does not have the power to deliver on that promise. Also the facts on which the claim were made are shall we say somewhat iffy. Even the leave side have now withdrawn this claim. I have it on good authority that the leave campaign have closed down their website, maybe this is to try to stop people checking after the vote what the “leave” campaign were promising.

NS rings

Dear Reader,

An event at Chalmers reminded me of a reaction which one of the other PhD students at Loughborough did in the inorganic lab what Tuan Q. Ly did was to heat up a mixture of ammonium chloride and sulfur(I) chloride in a big flask with an air condenser on it. An air condenser is not a think for condensing air it is a condenser cooled by air not water.

What happens is that the ammonium chloride reacts with the sulfur chloride to form SNCl according to the following reaction

NH4Cl + 2S2Cl2 → NSCl + 4HCl + 3S

The NSCl then reacts further to form other things, the vapors of NSCl and S2Clreact to form another product.

2NSCl + S2Cl2 → SCl2  +  N2S3Cl2

The N2S3Cl2 forms a crystals of a solid which appear in the air condensor. Now through the miricle of X-ray crystallography the strucutre of the ions in this solid is known. This solid is an ionic solid which contains chloride anions and N2S3Cl+ cations. Now the cation has the following structure.

N2S3Cl cation

The locations of the double and single bonds in this ion are a little unclear to say the least, based on the bond lengths from the crystallography we can draw the following initial thing.

X2S3Cl cation with double bonds

Now we can add up all the valence electrons which the different atoms give us

Chlorine 7

Three sulfurs (3 x 6 ) = 18

Two nitrogens (2 x 5) = 10

Now to give the chlorine a full octet we need one more electron in the form of the covalent bond to the sulfur. This means we have used up 2 of the valence electrons. We have a total of five more sigma bonds so the sigma bonds will use up 12 valence electrons. Our chlorine will have three lone pairs so we have used up in total 18 electrons.

We started with a total of 35 valence electrons, we now have 17 left.

We subtract one as we have a cation, so we now have 16 to use up.

If we assume that each nitrogen and the sulfur at the top of the ring bears a lone pair pointing out into space away from the centre of the ring then we will have 10 electrons left to use up. Here is the ion with the lone pairs added so far.

S3N2Cl ion with three lone pairs

We next add the lone pair on the bottom right sulfur which points out into space away from the centre of the ring. This will give us a total of 8 electrons left to use. Here is the diagram now.

S3N2Cl ion with four lone pairs

Now we add the second lone pair on the bottom right sulfur to the pi system of the ring and one electron from each of the other atoms in the ring. This gives us two electrons left over. Now this makes the idea of us having a nice aromatic molecule unlikely. Lets try again.

If we have the following bonding where more lone pairs are on the sulfurs that point out into space. To give the following.

S3N2Cl ion lots of lone pairs

Then the lone pairs on the chlorine, nitrogens and sulfurs (10 lone pairs in total) consume 20 electrons. As we have 34 valence electrons after detecting one for the charge, we have a total of 14 left. We have six normal sigma bonds which will use up 12 electrons, the last two will be used either by a long bons (most likely pi) between the nitrogens or by putting two unpaired electrons on the two nitrogens to make the molecule a diradical. Here is the drawing of the diradical version of the cation.

S3N2Cl ion diradical

So it will be hard or impossible to make this molecule aromatic, even while we can draw the single and double bonds to make it look like it is aromatic. I will deal with the N3S3Cl3 molecule later. If you want to see the details of how to make N2S3Cl2 then see W.L. Jolly, K.D. Maguire AND D. Rabixov, Inorganic Chemistry, 1963, 3, 1304-1305. For the crystallography see A. Zalkin, T.E. Hopkins and D.H: Templeton, Inorganic Chemistry, 1966, 5, 1767-1770..

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