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Stephenson:Neal:Quicksilver:18:...a specimen of white phosphorus... (Alan Sinder)

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this page is about phosphorus

Stephensonia

The search for phosphorus can be viewed as an alchemical search for the Philosophick Mercury.

Authored entries

Enoch and the Harvard mob

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A ROYAL SEAL
Imagine one on the letter Princess Caroline's letter METAPHORICALLY is likened to White Phosphorus and generated even odder behavior amongst the Harvard elites on the Charlestown Ferry. Enoch Root loses patience with the don and his waggish toadies. He correctly gauges the amount of progress there by their interest in his activities...

Phosphorus

Phosphorus is a chemical element in the periodic table that has the symbol P and atomic number 15. A multivalent, nonmetal of the nitrogen group, phosphorus is commonly found in inorganic phosphate rocks and in all living cells but is never naturally found alone. It is highly reactive, gives-off a faint glow upon uniting with oxygen (hence its name), occurs in several forms and is an essential element for living organisms.The most important use of phosphorus is in the production of fertilizers. It is also widely used in explosives, friction matches, fireworks, pesticides, toothpaste, and detergents.

Notable Characteristics

Common phosphorus forms a waxy white solid that has a characteristic disagreeable smell but when it is pure it is colorless and transparent.This non metal is not soluble in water,but it is soluble in carbon disulfide. Pure phosphorus ignites spontaneously in air and burns to phosphorus pentoxide.

Forms

Phosphorus exists in four or more allotropic forms: white (or yellow), red, and black (or violet). The most common are red and white phosphorus, both of which are tetrahedral groups of four atoms.White phosphorus burns on contact with air and on exposure to heat or light it can transform into red phosphorus. It also exists in two modifications: alpha and beta which are separated by a transition temperature of -3.8 ° C. Red phosphorus is comparatively stable and sublimes at a vapor pressure of 1 atm at 17 °C but burns from impact or frictional heating. A black phosphorus allotrope exists which has a structure similar to graphite - the atoms are arranged in hexagonal sheet layers and will conduct electricity.

Applications

Concentrated phosphoric acids,which can consist of70% to 75% P 2O5are very important to agriculture and farm production in the form of fertilizers.Global demand for fertilizers has led to large increases in phosphate production in the second half of the 20th century.Other uses; Phosphates are utilized in the making of special glasses that are used for sodium lamps. Bone-ash, calcium phosphate,is used in the production of fine china and to make mono-calcium phosphate which is employed in baking powder.

This element is also an important component in steel production, in the making of phosphor bronze,and in many other related products.

Trisodium phosphate is widely used in cleaning agents to soften water and for preventing pipe/boiler tube corrosion.

White phosphorus is used in military incendiaries, smoke pots, smoke bombs and tracer bullets. Miscellaneous uses; used in the making of safety matches, pyrotechnics, pesticides, toothpaste, detergents, etc.

Biological Role

Phosphorus compounds perform vital functions in all known forms of life. Inorganic phosphorus plays a key role in biological molecules such as DNA and RNA where it forms part of those molecules' molecular backbones. Living cells also utilize inorganic phosphorus to store and transport cellular energy via adenosine triphosphate (ATP). Calcium phosphate salts are usedby animals to stiffen bones and phosphorus is also an important element in cell protoplasm and nervous tissue.P%2C15.jpg
PHOSPHORUS
can appear colorless red silvery or white

History

Phosphorus is the first element to be discovered having an historical register. Phosphorus was first isolated in 1669 by a German physician, merchant, and alchemist named Hennig Brand (or Hennig Brandt), who boiled, filtered and precessed as many as 60 buckets of urine, writing a letter to Leibniz reporting its discovery. It is quite probable that, in the 12th century, Arabian alchemists have obtained the element using this process. However, the credit is given to Brand. The name of phosphorus has a Greek origin meaning "it possesses brilliance" due to its property of shining in the darkness when exposed to the air.

Further investigations by Brand's contemporary researchers revealed that the addition of sand or coal to urine helped the freeing of phosphorus. About one century after its original work, Brand discovered that phosphorus is an important constituent of the bones, introducing a new method of industrial production of phosphorus. The reaction of the bones with nitric or sulfuric acid produces phosphoric acid that, when heated up with coal, produces elementary phosphorus. This was the first method of phosphorus commercial production.

Alchemy

“More than 300 years ago, in 1669, Hennig Brand, a Hamburg alchemist, like most chemists of his day, was trying to make gold. He let urine stand for days in a tub until it putrified. Then he boiled it down to a paste, heated this paste to a high temperature, and drew the vapours into water where they could condense - to gold. To his surprise and disappointment, however, he obtained instead a white, waxy substance that glowed in the dark. Brand had discovered phosphorus, the first element isolated other than the metals and non-metals, such as gold, lead and sulphur, that were known to the ancient civilisations. The word phosphorus comes from the Greek and means light bearer.”

Also known as Dr. Teutonicus, Brand evaporated urine and so produced ammonium sodium hydrogenphosphate (microcosmic salt), which on heating produces sodium phosphite. When heated with carbon (charcoal) this decomposed to produce white phosphorus and sodium pyrophosphate.

Early matches used white phosphorus in their composition, which was dangerous due to its toxicity. Murders, suicides and accidental poisonings resulted from its use (An apocryphal tale tells of a woman attempting to murder her husband with white phosphorus in his food, which was detected by the stew giving off luminous steam). In addition, exposure to the vapors gave match workers a necrosis of the bones of the jaw, the infamous " phossy-jaw. " When red phosphorus was discovered, with its far lower flammability and toxicity, it was adopted as a safer alternative for match manufacture.

  1. (NH4)NaHPO4—› NaPO3+ NH3+ H2O

  2. 8NaPO3+ 10C —› 2Na4P2O7+ 10CO + P4

Brand's discovery was an accident but his discovery of phosphorus mirabile would turn out to be more valuable than gold in the future, for this 'cold fire' would enable inventors to produce fire on demand, an unimaginable achievement to Brand's contemporaries. Brand had tried to keep the method secret but he had sold the 'secret' to the German chemist, Krafft, who showed off the new wonder substance around the courts of Europe where Robert Boyle saw it in London. The secret that it was made from urine leaked out and first Johann Kunckel in Sweden (1678) and later Boyle in London (1680) also managed to make phosphorus.wright.jpg
The Alchymist in Search of the Philosophers' Stone
discovers Phosphorus, 1771
by Joseph Wright of Derby

Robert Boyle had seen samples of Brand's phosphorus exhibited in London and he eventually worked out a method to make phosphorus from urine in 1680, improving on Brand's process by using sand.

  1. 4NaPO3 + 2SiO2+ 10C —› 2Na2SiO3 + 10CO + P4

Notice that Boyle's improved method liberates all the phosphorus in the sodium phosphite. One of Boyle's assistants, Ambrose Godfrey Hankewitz, later set up in business making the new, wonder material. He charged 50/- an ounce for this new scientific curiosity. Robert Boyle was the first to use phosphorus to ignite sulphur-tipped wooden splints, forerunners of our modern matches, in 1680.

Boyle called the material “icy noctiluca” (cold light) and examined its properties in a systematic way, which Brand and co-workers had not. To them it was just an interesting and profitable curiosity. Interestingly white phosphorus became known as English or Boyle's phosphorus to distinguish it from other luminescent materials, which were all called phosphorus. These other names have vanished leaving only elemental phosphorus over many years.

At the end of the 19th century, James Readman developed the first process for the production of the element with an electrical furnace. In spite of many design and operation improvements of electrical furnaces, the basics of Readman's method to obtain elementary phosphorus remains in present technology.

Occurrence

Due to its reactivity to air and many other oxygen containing substances, phosphorus is not found free in nature but it is widely distributed in many different minerals.Phosphate rock, which is partially made of apatite (an impure tri-calcium phosphate mineral) is an important commercial source of this element. Large deposits of apatite are in Russia, Morocco, Florida, Idaho, Tennessee, Utah, and elsewhere.

The white allotrope can be produced using several different methods. In one process, tri- calcium phosphate, which is derived from phosphate rock, is heated in an electric or fuel-fired furnace in the presence of carbon and silica. Elemental phosphorus is then liberated as a vapor and can be collected under phosphoric acid.

Precautions

This is a particularly poisonous element with 50 mg being the average fatal dose.

The allotrope white phosphorus should be kept under water at all times due to its hyper reactivity to air and it should only be manipulated with forceps since contact with skin can cause severe burns. Chronic white phosphorus poisoning of unprotected workers leads to necrosis of the jaw called "phossy-jaw." Phosphate esters are nerve poisons but inorganic phosphates are relatively nontoxic. Phosphate pollution occurs where fertilizers or detergents have leached into soils.

When the white form is exposed to sunlight or when it is heated in its own vapor to 250 °C, it is transmuted to the red form, which does not phosphoresce in air. The red allotrope does not spontaneously ignite in air and is not as dangerous as the white form. Nevertheless, it should be handled with care because it does revert to white phosphorus in some temperature ranges and it also emits highly toxic fumes that consist of phosphorus oxides when it is heated.

Spelling

The only correct spelling of the element is phosphorus. There does exist a word phosphorous, but it is the adjectival form for the smaller valency: so, just as sulfur forms sulfurous and sulfuric compounds, so phosphorus forms phosphorous and phosphoric compounds.