Monthly Archives: June 2016

‘Chemophobia’ podcast with Sam Howarth

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Click to listen to the podcast via Soundcloud

In a debut podcast, Sam Howarth discusses with chemophobia research-enthusiast and chemistry teacher, James Kennedy, the evolution of fearing chemicals and the people who are driving it behind the scenes.

Sam Howarth is a self-taught nutrition and fitness enthusiast – a fanatic learned through trial and error over 3 years of research and over 10 years of personal struggles with food and body image.

In the podcast, we talk about chemophobia, its origins and the money that keeps it alive.

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My iOS app is free until the end of June 2016

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Screenshot from my free iOS app

I quietly released a simple iOS app back in March 2016. It’s free to download and works on iPhone and iPads running iOS 7.0 or later.

It’s called VCE Study Tools (Chemistry) and it’s the fastest way to browse this website on a mobile device.

Get it from the App Store here.

I’m removing it from the App Store at the end of June 2016 so I can release something a little better later on. If you want the app, go ahead and download it before it’s gone!

James Kennedy's iOS app called VCE Study Tools (Chemistry) is available on the App Store

‘Chemophobia’ is irrational, harmful – and hard to break

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Kiran Foster/Flickr

We all feel a profound connection with the natural world. E O Wilson called this sensation biophilia: ‘the urge to affiliate with other forms of life’. That sense of connection brings great emotional satisfaction. It can decrease levels of anger, anxiety and pain. It has undoubtedly helped our species to survive, since we are fundamentally dependent on our surrounding environment and ecosystem. But lately, biophilia has spawned an extreme variant: chemophobia, a reflexive rejection of modern synthetic chemicals.

Continue reading this article on AEON IDEAS…

Let’s add nitrogen gas

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‘Nitrogen’ page from Theodore Gray’s amazing book, ‘The Elements’

Initial conditions

Recall from last week that our Periodic Table Smoothie contains the following species:

Substance Amount present (moles)
He(g) 1.00000
Be(s) 0.51435
LiH(s) 0.27670
Li2C2(s) 0.27165
B2H6(g) 0.23300
Be2C(s) 0.17470
H2(g) 0.14267
BeC2(s) 0.13625
CH4(g) 0.00949

Pressure: 718 kPa
Temperature: 350 °C

Reactions of nitrogen in our 10-litre vessel

Our freshly-added 1.00 mol of nitrogen gas, N2(g), reacts with hydrogen gas to make ammonia in the following reversible (equilibrium) reaction. We will assume that the interior metal surface of the vessel is a suitable catalyst for this reaction (e.g. iron). 

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There are three other reactions below that might have occurred at higher temperature, but I’ve chosen not to raise the temperature of the vessel at this point. Rather, we’ll keep it at 350 °C to keep things manageable.*

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*I was tempted at this point to elevate the temperature of our vessel to 500 °C so that the second reaction could take place as well. This would produce copious amounts of smelly ammonia gas, which would allow for larger quantities of interesting organic compounds to be produced later on. To keep our simulation safe and (relatively) simple, I’ve decided to keep the vessel at 350 °C. Interesting compounds organic will still form – only in smaller amounts.

Equilibria

The ammonia reaction above (the first equation) is actually an equilibrium reaction. That means that the reactants are never completely used up, and the yield is not 100%.

Recall from Le Châtelier’s principle that removing product from an equilibrium reaction causes the position of equilibrium to shift to the right, forming more product. This is because:

“If an equilibrium system is subjected to a change, the system will adjust itself to partially oppose the effect of the change.” – Le Châtelier’s principle

There are three reactions that will remove ammonia from our vessel while it’s being produced, and I’ve put all three of these into the simulation. One of these is the reverse of the reaction above (producing hydrogen and nitrogen gases) and the other two are described below. Let’s take a look at those other two reactions.

With what will the ammonia react in our vessel?

Ammonia can undergo the following reactions with the other things in our vessel**

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**The ammonia does react with methane and beryllium as well, but only at temperatures of 1200 °C and 600 °C, respectively.

Two compounds will be formed: lithium amide and borazine.[1] Lithium amide reacts with nothing else in the vessel, so the reaction chain stops there. Borazine, on the other hand, is much more interesting.

We’ve made borazine!

Borazine is a colourless liquid at room at temperature. It boils at 53 °C and has a structure that resembles that of benzene.

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Borazine is isostructural with benzene
Because of the electronegativity difference of about 1.0 between the B and N atoms in the ring, borazine has a mesomer structure:

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Like benzene, there is partial delocalisation of the lone pair of electrons on the nitrogen atoms.

Borazine polymerises into polyborazine!

Fascinatingly, borazine polymerises into polyborazine at temperatures above 70 °C, releasing an equal number of moles of hydrogen gas.[2] Polyborazine isn’t particularly well-understood or well-documented, but one recent paper suggested it might play a role in the creation of potential ceramics such as boron carbonitrides. Borazine can also be used as a precursor to grow boron nitride thin films on surfaces, such as the nanomesh structure which is formed on rhodium.[3]

Like several of the other compounds we’ve created in our Periodic Table Smoothie, polyborazine has also been proposed as a hydrogen storage medium for hydrogen cars, whereby polyborazine utilises a “single pot” process for digestion and reduction to recreate ammonia borane.

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Polyborazine’s chemical structure
The hydrogen released during the polymerisation process will then react further with a little bit of the remaining nitrogen to produce a little more NH3(g) – but not much. Recall from earlier that the ammonia reaction is an equilibrium one, and the yield of NH3(g) at pressures under 30 atmospheres is very low. Pressure in our vessel is still only around 7 atmospheres.

Simulation results

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Once polymerised, this would form about 12 grams of polyborazine:

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As far as I’m aware, no further reactions will take place in the vessel this week.

Conclusion after adding 1.00 mole of nitrogen gas

Substance Amount in mol
He(g) 1.000
Be(s) 0.514
LiH(s) 0.000
Li2C2(s) 0.272
B2H6(g) 0.000
Be2C(s) 0.175
H2(g) 0.007
BeC2(s) 0.136
CH4(g) 0.009
N2(g) 0.552
NH3(g) 0.154
LiNH2(s) 0.277
polyborazine 12.194 grams

Pressure: 891 kPa (higher than before due to the addition of nitrogen gas)
Temperature: 350 °C (vessel is still being maintained at constant temperature)

Next week, we’ll add a mole of oxygen gas to the vessel. Warning: it might explode.

References

  1. Stock, Alfred and Erich Pohland. “Borwasserstoffe, VIII. Zur Kenntnis Des B 2 H 6 Und Des B 5 H 11”. Berichte der deutschen chemischen Gesellschaft (A and B Series) 59.9 (1926): 2210-2215. Web.
  2. Mohammad, Faiz. Specialty Polymers. Tunbridge Wells: Anshan, 2007. Print.
  3. Toury, Berangere and Philippe Miele. “A New Polyborazine-Based Route To Boron Nitride Fibres”. Journal of Materials Chemistry 14.17 (2004): 2609. Web. 4 May 2016.

Let’s add carbon (graphite) powder

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‘Carbon’ page from Theodore Gray’s amazing book: The Elements

Today, we’re going to add 1.00 mole of carbon to our vessel. After adding boron last week, we left our vessel locked at 350 °C and with a pressure of 638 kPa. These reactions are taking place at 350 °C and constant volume (exactly 10 litres). Pressure inside the vessel will therefore change over time.

Allotropes of carbon

Carbon has various allotropes (structural arrangements of an element). Diamond is extremely strong and highly unreactive, while graphite is soft and brittle. The differences are all due to the type of bonding between carbon atoms. In diamond, carbon atoms are bonded by four strong covalent bonds with the surrounding atoms in a strong, hard three-dimensional ‘network lattice’. Graphite owes its softness and brittleness to the fact that its carbon atoms are bonded by only three strong covalent bonds in a two-dimensional ‘layer lattice’. Individual layers are very strong, but the layers can be separated by just the slightest disturbance. Touching graphite lightly onto paper will remove layers of carbon atoms and place them onto the page (such as in a pencil). Using a diamond the same way would likely tear the paper instead.

For this reason, I’m going to put graphite into the vessel instead of diamond. Diamond is so strong and inert that it’s unlikely to do any interesting chemistry in our experiment. Graphite, on the other hand, will.

The following seven chemical reactions will take place after adding carbon (graphite) powder

As soon as the carbon powder enters the vessel, it will begin to react with the following three species as follows:

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The ethyne produced in the third reaction will then react with any lithium and beryllium remaining in the vessel as follows:

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The hydrogen gas produced by the above two reactions will then react with lithium and carbon (if there’s any left) as follows:

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These reactions have the potential to all occur at the same time. Tracking them properly would require calculus and lots of kinetics data including the activation energy of each reaction and the rate constant for each equation. Quick searches on the National Chemical Kinetics Database yields no results for most of these equations, which means we won’t be able to use a computer model to calculate exact quantities of each product. Instead, I’m going to run a computer simulation using Excel that makes the following three assumptions:

  • all these reactions occur at the same rate;
  • all these reactions are first-order with respect to the limiting reagent;
  • all these reactions are zeroth-order with respect to reagents in excess.

The results will be a close approximation of reality – they’ll be as close to reality as we can get with the data that’s available.

Here are the results of the simulation

Here’s a graph of the simulation running for 24 steps. Exactly one mole of carbon powder is added at step 5.

Periodic Table Smoothie - Let's Add Carbon Carbon quickly reacts to form lithium carbide, beryllium carbide and two organic molecules: methane and ethyne
Carbon quickly reacts to form lithium carbide, beryllium carbide and two organic molecules: methane and ethyne

Summary of results

The results are incredible! We’ve made ethyne and methane, both of which have the potential to do some really interesting chemistry later on. I’m hoping that we can make some more complex organic molecules after nitrogen and oxygen are added – maybe even aminoethane – let’s see.

Hydrogen has also re-formed. I’m hoping that this gas lingers for long enough to react with our next element, nitrogen: we might end up making ammonia, NH3(g).

You may have noticed that I removed the “boron-lithium system” from the vessel. The 0.178 moles we created are now stored separately and will not be allowed to react any further. With such little literature about the reactivity of B3Li, it’s impossible to predict what compounds it’ll form later on. B3Li is so rare that doesn’t even have a Wikipedia page.

Pressure in the vessel increases to 718 kPa after carbon is added
Pressure in the vessel increases to 718 kPa after carbon is added
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Mass of sludge in the vessel changes after adding carbon

Here’s what’s present in the vessel after adding carbon

Substance Moles present after 500 ‘steps’
He(g) 1.00000
Be(s) 0.51435
LiH(s) 0.27670
Li2C2(s) 0.27165
B2H6(g) 0.23300
Be2C(s) 0.17470
H2(g) 0.14267
BeC2(s) 0.13625
CH4(g) 0.00949

We also have 0.178 moles of B3Li stored separately in another vessel.

Next week, we’ll add nitrogen and see what happens.