Is phosphorus the alumina of the ancient world?
Keith S. Taber
What do you need to build a skyscraper?
I was listening to a podcast from the Royal Institution (where Humphrey Davy and Michael Faraday were based). I must confess I had downloaded the 'Recipe for a Skyscraper' episode some time ago but it had been passed over for other titles.
Royal Institution podcast: Recipe for a Skyscraper – with Roma Agrawal
My mistake. In this talk "structural engineer Roma Agrawal delves into the history of the materials that enable immense construction and the developments that have made our structures what they are today. All while noting the accomplishments of key visionary engineers of the past". This proved to be an engaging and fascinating talk.
A 'mega badass engineer'
On her website, Roma Agrawal , "a structural engineer, author and broadcaster, with a physics degree" describes herself as a "mega badass engineer". She is not above being a little mischievous.
The crumbly ages
For example, she has her own take on what historians used to call the 'dark ages', 1
"So, oddly enough, once the Roman empire fell, the use of concrete basically ended for nearly a thousand years, so that we call it the dark ages, or the crumbly ages as I like to call it, because they went back to using slightly older [construction materials], you know, mud and brick and things like that."
Roma Agrawal talking at the Royal Institution
But while the Romans may have championed the use of concrete, the Indians were outperforming them in the production of high quality iron: "The Romans actually used to import Indian steel at the time and they never knew how to make it because that secret was closely guarded…"
Iron is too reactive to be found 'native' but has to be produced by roasting its ores (that contain compounds of iron) with materials that will reduce the iron compounds to iron, and produce, as a by-product, slag – a complex mixtures of substances. The iron produced will contain some slag mixed into the metal unless this is carefully removed. 2
The Delhi column
As an example of the Indian expertise, Roma Agrawal referred to an old iron column near Delhi which "had not rusted" despite having been erected 1500 years ago.3 The column had originally been a stand for a statue of Garuda, the divine winged creature/demigod who acted as the vehicle for Vishnu. Garuda seems to have flown, but the iron column remains.
The (not quite 4) 'rustless wonder' (Srinivasan & Ranganathan, 2013): the Qtub Iron Pillar
(Photograph taken by Mark A. Wilson, available at https://en.wikipedia.org/wiki/Iron_pillar_of_Delhi#/media/File:QtubIronPillar.JPG)
Lord Vishnu on his mount Garuda (wood carving). It is thought the iron pillar near Delhi once supported a statue of Garuda.
(Image by waradet from Pixabay)
Iron is the main constituent of alloys known as steels, and by mixing other elements (principally, but not only, carbon) with iron it is possible to create steels with various properties, including corrosion resistance. 2 But iron itself readily rusts. The rust formed when iron corrodes is permeable and crumbly, exposing the unreacted metal beneath, which in turn forms rust that again fails to protect the iron beneath it. So, over time, a piece of iron can simply 'rust away' as the reacted material will simply fall off, or be eroded by weather.
Yet this iron column, erected around the time of the final collapse of the Roman Empire, seems to have survived throughout 'the crumbly ages' and through to the present day. Although, it is not that it never started rusting 4, but rather,
"it did initially rust, but then because of the climate in Delhi, the phosphorus, a very thin layer of phosphorus formed, between the rust and the fresh metal and basically stopped it from rusting any more…"
Roma Agrawal talking at the Royal Institution
Corrosion (as with tarnishing) is a generic term. Corrosion leads to structural damage to metal objects (whereas tarnishing is a surface effect).
Rusting is specific to iron as it refers to the material produced when iron corrodes – i.e., rust.
Unreactive phosphorus?: An alternative conception
Roma Agrawal's claim seems incredible to a chemist or science teacher because phsophorus is a very reactive element, and a very reactive element does not seem a good choice of material to protect iron from reacting! Even if the phosphorus did not itself react with the iron and so corrode it, it would soon react with air. In the laboratory, some forms of phosphorus can burst into flames spontaneously, suggesting it is very unlikely to remain intact very long exposed to the elements in India. Certainly not many centuries.
Sacrificial elements
Now, sometimes a more valuable metal is protected by connecting it physically to a more reactive but less valuable metal which preferentially corrodes. As the metals are in electrical contact, the one that loses electrons and releases cations more readily reacts first. The metal allowed to corrode is called a 'sacrificial' metal. For example, bars of sacrificial metal may be dangled from piers or oil rigs to protect the structural metal. The sacrificial metal will slowly 'dissolve' away into the sea 5 – but not that slowly that it would not need replacing for over a millennium. In any case, phosphorus is a non-metal, where the sacrificial element of the pair needs to be the more electropositive. So, there is no helpful explanation there.
Alumina – when tarnishing prevents corrosion
Aluminium is a more reactive metal than iron, yet does not readily undergo substantive corrosion. This is because the surface of an aluminium object readily reacts with oxygen from the air to form a layer of aluminium oxide (alumina). This then protects the aluminium because the alumina formed is a fairly inert substance (unlike the highly reactive phosphorus), and it forms an impermeable layer (preventing oxygen from the air reaching the metal beneath).
Any layer that were to form on iron protect it from rusting also needs to be impermeable and relatively inert. Unlike reactive phosphorus.
Phosphorus would not protect iron
Phosphorus is a fire hazard that burns to produce toxic fumes. In the laboratory, the direct reaction of iron and phosphorus usually requires heating to initiate reaction. Without active heating, the rate of reaction would be too low for a useful laboratory process. However, a very low rate of reaction would not prevent reaction over the centuries since the iron column was erected.
Even if phosphorus was able to form a layer that coated over the iron, using it as a means to prevent corrosion would be like fireproofing a wooden building by coating it with petroleum jelly (e.g., Vaseline). [A correspondent to the British Dental Journal (Brewer, 2017) warned of "the death of a bedbound patient who smoked following application of E45 cream…a paraffin-based product, the residue of which can act as an accelerant when ignited". Smoking kills. And even more rapidly if you smother yourself in flammable oil products prior to lighting up.]
So, it seems we have a mystery.
Or, Roma Agrawal simply got it wrong.
Or, perhaps, more likely, when Roma Agrawal refers to a 'layer of phosphorus' she is using the term loosely, and is actually referring to something else. That is, the protective layer may contain one or more phosphorus compounds, but not phosphorus – just as a layer of the unreactive aluminium compound alumina stops corrosion, although aluminium itself is reactive. Is this distinction just being pedantic? Not to a science educator.
An elementary misconception
The claim that a layer of phosphorus could protect iron from corrosion is therefore not credible to the scientifically literate, but might seem perfectly reasonable to a person with limited science background. One of the great challenges of learning chemistry is making sense of the set of ideas that:
- the compound of an element is a completely different substance to the element itself
- the properties of compounds are often quite different (sometimes contrastingly so) to those of the elements the compound was formed from
- although the compound does not behave like the elements, and does not 'contain' the elements in any straightforward way, there is a sense in which something of the elements persists in (and so the element may be recovered from) the compound.
So, sodium is a reactive metal that burns in air, and chlorine is a green, toxic, choking gas; and both should be avoided unless taking very careful precautions; yet they react, very energetically, to give the relatively unreactive compound sodium chloride – which people readily use in cooking, and to season their food, and to dissolve in water to gargle with, or to soak tired feet. Chlorine would destroy the lining of your throat. Yet sodium chloride solution (despite its chlorine 'constituent') will help ease a sore throat! Still, the sodium chloride has the potential to be 'separated' into the elements with their dangerous properties intact.
Although the distinction between elements and compounds is a lot easier to understand once students learn about molecules and atoms (at least, if avoiding the alternative conception that compounds comprise of molecules and elements comprise of atoms!) this topic is fraught with complications and hang-overs from historical ideas about atoms (Taber, 2003).
If not a layer of phosphorus?
The chemist or science teacher hearing about a protective 'layer of phosphorus' preventing rusting will immediately thinks this is not viable…but a compound of phosphorus might well have the necessary properties. Indeed, generally, the more reactive the elements, the more stable the compounds they form when reacting.
It seems that the layer that formed on the iron column contains the phosphorus compound iron hydrogen phosphate hydrate (FePO4·H3PO4·4H2O),
"Several theories have been postulated regarding corrosion resistance of the Delhi iron pillar. Some of those refer to the inherent nature of the construction material, such as the selection of pure iron, presence of slag particles and slag coatings, surface finishing using mechanical operation, phosphate film formation, or the Delhi's climate…
Earlier studies have delineated the formation of crystalline iron hydrogen phosphate hydrate (FePO4·H3PO4·4H2O), 𝛼-, 𝛾-, 𝛿-FeOOH and magnetite in the case of Delhi iron pillar"
Dwivedi, Mata, Salvemini, Rowles, Becker & Lepková, 2021
Yet this critical, and somewhat counter-intuitive, distinction between elements qua elements and elements as in some sense 'components' (or 'ingredients') of compounds needs to be acquired. Novices have to learn this. A common alternative conception is to assume that the properties of elements are carried over into their compounds.
So, if students hear that
- phosphorus is essential in our diet, and that
- phosphorus is important for healthy bones and teeth,
they can draw the obvious and reasonable conclusion – that phosphorus must be a pretty innocuous substance as it is part of our bodies and we eat it quite safely in our food. Actually, we need compounds of phosphorus in our food to allow our metabolisms to build and repair tissues that contain phosphorus compounds – and anyone misguided enough to try to eat any actual (elemental) phosphorus risks a nasty burn.
In conclusion, as a science graduate, Roma Agrawal presumably appreciates the key distinction between (i) elements as substances and (ii) elements as chemically combined components of other substances, and, as a structural engineer knowledgeable about different material properties, is using 'layer of phosphorus' as a shorthand for a layer of material that includes one or more phosphorus compounds.
That is fine as long as those hearing her talk appreciate that. Another scientist would likely automatically hear 'phosphorus layer' as meaning 'phosphorus compound containing layer'. A science teacher, however, might suspect that the reference to how "a very thin layer of phosphorus formed, between the rust and the fresh metal and basically stopped it from rusting" is likely to be misunderstood, and indeed to mislead, some listening to the podcast.
Minding your Ps…
One of the sources referred to reported how:
"P is found present in slag whereas the presence of P in iron was not detected within the limit of the analytical techniques used in this study. On the basis of this result, we speculate application of lime and other basic compounds during the iron making process which would have led to the transfer P to slag."
Dwivedi, Mata, Salvemini, Rowles, Becker & Lepková, 2021
P is the symbol for phosphorus, the element. However, someone with a sufficient scientific background appreciates from the context that references to
- P found in slag
- P in iron
- transfer [of] P to slag
cannot refer to P as phosphorus the element, but rather some compound or compounds of phosphorus. As a reactive element, phosphorus is not found native and so would not be present (as an element) in the raw materials and, in any case, could certainly not survive (as an element) the high temperature conditions of the processes of iron smelting. Therefore the relevant 'context' for reinterpreting 'P' as not standing for the element itself would be any set of circumstances other than the special conditions where phosphorus can be safely stored without risk of reaction.
This is the prerequisite background knowledge that prevents an audience member misinterpreting what must be meant by a "thin layer of phosphorus [sic]" protecting an exposed iron column – as it cannot possibly refer to a thin layer of [actual, elemental] phosphorus.
Sources cited
- Anantharaman, T. R. (1997). The iron pillar at Delhi. In S. Ranganathan (Ed.), Iron and Steel Heritage of India (pp. 1-28). Indian Institute of Metals and Tata Steel.
- Brewer, E. Patient safety: Paraffin-based products. British Dental Journal 223, 620 (2017). https://doi.org/10.1038/sj.bdj.2017.936
- Dwivedi, D., Mata, J. P., Salvemini, F., Rowles, M. R., Becker, T., & Lepková, K. (2021). Uncovering the superior corrosion resistance of iron made via ancient Indian iron-making practice. Scientific Reports, 11(1), 4221. doi:10.1038/s41598-021-81918-w
- Falk, S. (2020). The Light Ages. A Medieval journey of discovery. Allen Lane.
- Srinivasan, S., & Ranganathan, S. (2013). Minerals and Metals Heritage of India. Bangalore: National Institute of Advanced Studies.
- Taber, K. S. (2003). The atom in the chemistry curriculum: fundamental concept, teaching model or epistemological obstacle? Foundations of Chemistry, 5(1), 43-84. (The author's manuscript versions is available here.)
Notes:
1 A simplistic view was that advancing civilisation underwent something of a relapse during the middle ages, until the gains of the classical age (the Greeks, the Romans) were rediscovered in the Enlightenment. Thus, the term 'dark ages' applied to the 'middle ages'.
There were no dark ages:
with apologies to Pink Floyd
as a matter of fact, they are all dark
That is clearly a great simplification, and ignores many medieval achievements, as well as being a rather Eurocentric view. Some historians have been seeking to redress this impression: for example, Seb Falk (2020) has renamed this period 'the light ages'.
2 To suggest that steel deliberately contains impurities added to iron could give the impression that iron artefacts are made of purer materials than steel ones. This is misleading. Basic iron smelting produces iron that is impure (sometimes known as 'pig iron') and which can contain quite high levels of impurities. Pig iron typically has a high level of carbon – more than is usually used in steels.
Wrought iron is produced by physical working of pig iron which expels much of the slag content, giving purer iron. Wrought iron has long been widely used in structures, but still does not have a high level of purity.
Alloys are mixtures of different metals, or of metallic elements with other elements. 'Metal' here is ambiguous as it can refer to
- an electropositive element (the usual meaning in chemistry) or
- a material with certain properties (the usual meaning in engineering) – i.e., malleable, ductile, high electrical and thermal conductivities, lustre, sonorous.
Steels are metals in the 'materials' sense, but 'chemically' are mixtures of the metallic element iron with other elements.
As the properties of steels are sensitive to the levels of other elements, making steel requires using high quality iron that has been treated to remove most of the impurities. This is similar to doping a semiconductor such as silicon to produce electronic components. Very pure silicon is needed as a starting point, so that just the right amount of a specific dopant can be added.
The Indian iron manufacture of Roman times tended to produce iron with a significant phosphorus content.
3 The column was made of wrought iron,
"The forging of wrought iron seems to have reached its zenith in India in the first millennium AD. The earliest large forging is the famous iron pillar with a height of over 7 m and weight of about 6 tons at New Delhi ascribed to Chandragupta Vikramaditya 400- 450 CE… the absence of corrosion is linked to the composition, the high purity of the wrought iron and the phosphorus content and the distribution of slag."
Srinivasan & Ranganathan, 2013
4 The lack of rusting may have been exaggerated,
"The first impression in 1961 was that the portion of the Pillar below the earth was "superficially rusted". However, on detailed examination, the buried portion of the Pillar was found covered with thick crusts of rust and, in fact, copious rust scales could be collected, ranging in thickness from a few millimeters (mm) to no less than 15 mm in some portions. Further, the bulbous base of the Pillar was found riddled with numerous cavities and hollows caused by deep corrosion and mineralization of the iron.
Anantharaman, 1997
Even so, the survival of an iron column exposed to weathering for this length of time is still worthy of note.
5 I thought I should put 'dissolve' into 'scare quotes' here. Corrosion is a chemical change, whereas dissolving refers to what is generally considered a physical change. As the sacrificial metal reacts, it releases cations into solution in the sea, in much the same was as, say, dissolving salt releases sodium ions when common salt is added to water. The metal reacts and enters solution – dissolves, if you are comfortable with that word in this context.