Phosphorous – An Essential Element

Phosphorus (P) is required by every living plant and animal cell.  It is an important component of the cell tissues of plants and animals and is necessary for the structure, growth, and propagation of all living organisms. Some examples of phosphate’s role in living matter include:

  • Giving shape to DNA (deoxyribonucleic acid), which is a blueprint of
    DNA-1

    Sugar phosphate backbone of standard DNA (Ref – U.S. National Library of Medicine)

    genetic information contained in every living cell. A sugar-phosphate backbone forms the helical structure of every DNA molecule.

  • Playing a vital role in the way living matter provides energy for biochemical reactions in cells. The compound adenosine triphosphate (ATP) stores energy living matter gets from food (and sunlight in plants) and releases it when it is required for cellular activity. After the energy, in the form of a high-energy phosphate bond, is released the ATP becomes a lower-energy adenosine diphosphate
    Madeleine Price Ball _DNA_chemical_structure.svg

    DNA Chemical Structure (Ref – Madeleine Ball)

    (ADP) or a still lower-energy adenosine monophosphate (AMP) molecule. These will be replenished to the higher-energy ATP (or ADP) state with the addition of phosphate by various mechanisms in living cells.

  • The forming and strengthening of bones and teeth.

Ref:  Florida Industrial & Phosphate Institute, Bartow, FL

Discovery of Phosphorous – 17th Century

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The Alchemist Discovers Phosphorous – (Painting by Joseph Wright of Derby, England)

  • Hennig Brandt (1630 – 1710) was a merchant and alchemist in Hamburg, Germany who discovered phosphorus around 1669 when he heated residues from boiled-down urine in a furnace until the retort was red hot, where all of a sudden glowing fumes filled it and liquid dripped out, bursting into flames. He could catch the liquid in a jar and cover it, where it solidified and continued to give off a pale-green glow. What he collected was phosphorus, which he named from the Greek for “light-bearing” or “light-bearer.”
  • The chemical reaction Brandt stumbled on was as follows. Urine contains phosphates PO43-, as sodium phosphate (ie. with Na+), and various carbon-based organics. Under high heat, the oxygen from the phosphate reacts with carbon to produce carbon monoxide (CO). The carbon also reduces phosphorous to elemental P2 gas. Phosphorus gas condenses to a liquid below about 280°C and then solidifies (to the white phosphorus allotrope) below about 44°C (depending on purity). This same essential reaction is still used today (but with mined phosphate ores, coke for carbon, and electric furnaces).
  • The phosphorus Brandt’s process yielded was far less than it could have been. The salt part he discarded contained most of the phosphate. He used about 5,500 liters of urine to produce just 120 grams of phosphorus. If he’d ground up the entire residue he could have got 10 times or 100 times more (1 liter of adult human urine contains about 1.4g phosphorus).

 

Discovery of Phosphoric Acid – 18th Century

  • Brandt kept his discovery secret, as alchemists of the time did, and worked with the phosphorus trying to use it to produce gold (unsuccessfully of course). He later sold the secret recipe to Johann Daniel Krafft (1624 – 1697).  Robert Boyle (1627 – 1691) later elicited that the recipe’s critical ingredient was from man, either urine or feces, and went on to develop his own process with help from his assistants. The process was further improved through the use of red lead and charcoal.
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Oven for the Calcination of Bones, about 1870.

  • Phosphorous production was based on urine until 1769 when Carl Wilhelm Scheele (1742 -1786) and Johan Gottlieb Gahn (1745 – 1818) corresponded with each other on the nature of bone.  They tried dissolving bone ash in sulfuric acid so making phosphoric acid. The phosphoric acid was heated with charcoal releasing phosphorous. Scheele later isolated phosphorus from bone ash (1774) and produced phosphoric acid by the action of nitric acid on phosphorus (1777). Here we see the beginning of the modern process for the production of phosphoric acid.  In the late 18th century, France became the center of phosphorous manufacture.
  • Bernard Pelletier (1761 – 1797) began to manufacture phosphorus on large scale (3200 ounces/year) using the process proposed by Gahn and Scheele  for a small market of lights, theatrical uses and flame proofing.

 

Ref:  R. Gilmour – Phosphoric Acid, Purification, Uses, Technology & Economics  (Boca Raton, FL, CRC Press, 2014)

Production of Phosphorous in Europe – 19th Century

  • In 1818, Coignet & Cie, was founded in Lyon, France to manufacture gelatin and glue by treating bone with hydrochloric acid and became a manufacturer of pure phosphorus and a major manufacturer of matches. Later Coignet improved the Pelletier Process of making bone ash, acidifying it with sulfuric acid to make phosphoric acid and then converting it to phosphorous.
  • All over France, kilns were built for the calcination of bones and in the 1840’s export from France to England was 4500 kg.
  • In 1855, Arthur Albright and John Wilson founded Albright and Wilson, Ltd in Oldbury, England. Still using what was basically the Pelletier process, Albright & Wilson produced 1 ton of phosphorous from 10 tons of bone ash – an impressive 80% yield.
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Advertisement with view of plant for manufacturing superphosphate about 1867

  • Bone became increasingly hard to source.  In 1870, Albright and Wilson imported sombrerite, a phosphate rock of guano origin from the West Indies.  Guano is derived from the excrement of seabirds and bats.
  • In 1880, Albright & Wilson production was 450 tons.  The latter half of the 19th century would see a dash to secure guano as a  phosphate source.

 

Ref:  R. Gilmour – Phosphoric Acid, Purification, Uses, Technology & Economics  (Boca Raton, FL, CRC Press, 2014)

Matches  & Phosphorous

  • Prior to the use of matches, fires were obtained using a burning glass (a lens) to focus the sun on tinder, a method that could only work on sunny days, or by igniting tinder with sparks produced by striking flint and steel.
  • The first matches were made in Paris in 1805 and the head of the match consisted of a mixture of potassium chlorate, sulfur, sugar, and rubber. The match was ignited by dipping its tip in a small asbestos bottle filled with sulfuric acid. This kind of chemical match was expensive and its usage was dangerous, and did not become common.
  • Friction matches known as Lucifers were invented in 1831. These matches had a number of problems – an initial violent reaction, an unsteady flame and unpleasant odor and fumes. Lucifers could ignite explosively, sometimes throwing sparks a considerable distance.
  • Lucifers were however quickly replaced after the discovery in 1830 by Frenchman Charles Sauria who substituted the antimony sulfide with white phosphorus. Unfortunately, those involved in the manufacture of the new phosphorus matches were afflicted with phossy jaw and other bone disorders.
  • Two French chemists, Henri Savene and Emile David Cahen, proved in 1898 that the addition of phosphorus sesquisulfide meant that the substance was not poisonous, that it could be used in a “strike-anywhere” match, and that the match heads were not explosive.
  • Albright and Wilson, began to produce phosphorus sesquisulfide matches commercially. The company developed a safe means of making commercial quantities of phosphorus sesquisulfide in 1899 and started selling it to match manufacturers.
  • The  match was one of history’s notable products and it transformed the phosphorous industry at the end of the 19th century.  There was now a substantial market for phosphorous production and so phosphorous production moved up to industrial scale.
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Dipping of Matchsticks in France, about 1870. (The frame holds matches so that one end protrudes at the bottom and is lowered over a pan of molten sulfur. The sulfur covered matches are then dropped into a phosphorous paste.)

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Pan for dipping matchsticks into phosphorous paste, about 1870. (A – matches, B – water bath, C – frame, D – plate, E – phosphorous paste, F – oven)

Ref:  R. Gilmour – Phosphoric Acid, Purification, Uses, Technology & Economics  (Boca Raton, FL, CRC Press, 2014)

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