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Sulfuric acid history

Sulphuric acid (American English: Sulfuric), H2SO4, is a strong mineral acid. It can form any concentration in water. The old name for sulphuric acid is oil of vitriol. When high concentrations of SO3 are added when making the acid, a solution of SO3 in H2SO4 results. This is called fuming sulphuric acid or Oleum or Nordhausen acid.
Sulphuric acid has many applications, including in many chemical reactions and production processes. It is the most widely used chemical. Principal uses include fertilizer manufacturing, ore processing, chemical synthesis, wastewater processing and oil refining.
In combination with nitric acid it forms the nitronium ion, which is used in the nitration of compounds. The process of nitration is used to manufacture a great many explosives, including trinitrotoluene, nitroglycerine, and guncotton. It is also the acid used in lead-acid batteries, and so is sometimes known as battery acid.
The energy of the hydration reaction with sulphuric acid is highly exothermic, and if water is added to concentrated sulphuric acid it can boil. Always add the acid to the water rather than the water to the acid. Note that part of this problem is due to the relative densities of the two liquids. Water is less dense than sulfuric acid and will tend to layer above the acid, and not mix well, if added to the acid.
Because the hydration of sulfuric acid is thermodynamically favourable, sulphuric acid is an excellent dehydration agent, and is used to prepare many dried fruits.
They are washed with cooled concentrated acid (from the Glover tower); the nitrogen oxides and unreacted sulfur dioxide dissolve in the acid to form the nitrous vitriol used in the Glover tower. Remaining waste gases are usually discharged into the atmosphere.

History of sulfuric acid

Sulfuric acid was known to medieval alchemists under of variety of names including oil of vitriol and spirit of vitriol. These substances were produced by the dry distillation of minerals including ferrous sulfate heptahydrate, FeSO4, 7H2O, called green vitriol, and cupric sulfate pentahydrate, CuSO4, 5H2O, called blue vitriol. When heated, these compounds decompose to ferrous and cupric oxides, respectively, giving off water and sulfur trioxide, which combine to produce a dilute solution of sulfuric acid. Preparations like these have been ascribed to alchemists including the 12th-century Arab Abou Bekr al-Rhases and the 13th-century German Albertus Magnus.
In the 17th century, the German-Dutch chemist Johann Glauber prepared sulfuric acid by burning sulfur together with saltpeter (potassium nitrate, KNO3), in the presence of steam. As the saltpeter decomposes, it oxidizes the sulfur to SO3, which combines with water to produce sulfuric acid. In 1736, Joshua Ward, a London pharmacist, used this method to begin the first large-scale production of sulfuric acid.
In 1746 in Birmingham, John Roebuck began producing sulfuric acid this way in lead-lined chambers [1], which were stronger, less expensive, and could be made larger than the glass containers which had been used previously. This lead-chamber process allowed the effective industrialization of sulfuric acid production, and with several refinements remained the standard method of production for almost two centuries.
In the lead chamber process hot sulfur dioxide gas enters the bottom of a reactor called a Glover tower where it is washed with nitrous vitriol (sulfuric acid with nitric oxide, NO, and nitrogen dioxide, NO2, dissolved in it) and mixed with nitric oxide and nitrogen dioxide gases; some of the sulfur dioxide is oxidized to sulfur trioxide and dissolved in the acid wash to form tower acid or Glover acid (about 78% H2SO4). From the Glover tower a mixture of gases (including sulfur dioxide and trioxide, nitrogen oxides, nitrogen, oxygen, and steam) is transferred to a lead-lined chamber where it is reacted with more water. The chamber may be a large, boxlike room or an enclosure in the form of a truncated cone. Sulfuric acid is formed by a complex series of reactions; it condenses on the walls and collects on the floor of the chamber. There may be from three to twelve chambers in a series;the gases pass through each in succession. The acid produced in the chambers, often called chamber acid or fertilizer acid, contains 62% to 68% H2SO4. After the gases have passed through the chambers they are passed into a reactor called the Gay-Lussac[2] tower where they are washed with cooled concentrated acid (from the Glover tower); the nitrogen oxides and unreacted sulfur dioxide dissolve in the acid to form the nitrous vitriol used in the Glover tower. Remaining waste gases are usually discharged into the atmosphere.
In 1767, John Holker one of the founder of cotton industry in Rouen, built with Chatel the first sulfuric acid unit in France.
The lead chamber was introduced to the United States when John Harrison, then only 20 years old, set up a plant in Philadelphia in 1793. Harrison had earlier studied chemistry with Joseph Priestley in England. Initially, he made only about 45,000 lb of sulfuric acid a year, but by 1804 his plant was 18 ft high, 18 ft wide, and 50 ft long and could turn out nearly 500,000 lb annually. The company Harrison formed, which also manufactured various salts and paint pigments, remained in business until 1917, when it was sold to DuPont. Other lead-chamber units were put in place in Philadelphia, the New York City area, New England, and Baltimore.
Davison, Kettlewell & Co., "Grinders and Acidulators of Old Bones and Oyster Shells" is founded in Baltimore, Maryland by William T. Davison. They utilize the first sulfuric acid chamber in the United States.
In Cincinnati, OH, German immigrant Eugene Grasselli erected the first lead chamber west of the Alleghenies in 1839.
John Roebuck's sulfuric acid was only about 35-40% sulfuric acid, and later refinements in the lead-chamber process improved this to 78%. However, the manufacture of some dyes and other chemical processes require a more concentrated product, and throughout the 18th century, this could only be made by dry distilling minerals in a technique similar to the original alchemical processes. Pyrite (iron disulfide, FeS2) was heated in air to yield ferrous sulfate, FeSO4, which was oxidizied by further heating in air to form ferric sulfate, Fe2(SO4)3, which when heated to 480°C decomposed to ferric oxide and sulfur trioxide, which could be passed through water to yield sulfuric acid in any concentration. The expense of this process prevented the large-scale use of concentrated sulfuric acid.
In 1831, the British merchant Peregrine Phillips patented a far more economical process for producing sulfur trioxide and concentrated sulfuric acid. In this process sulfur dioxide, SO2, produced by roasting either sulfur or pyrite in air, is combined with additional air and passed over a platinum catalyst at high temperatures, where it combines with oxygen from the air to produce nearly pure SO3. Even so, there was little demand for highly concentrated sulfuric acid at the time, and the first sulfuric acid plant using this contact process was not built until 1875 in Freiburg, Germany.
The development of the less expensive and less easily contaminated vanadium pentoxide (V2O5) catalyst by BASF in Gemany in 1915, combined with increasing demand for concentrated sulfuric acid by the chemical industry, has led to the gradual replacement of the lead-chamber process by the contact process. In 1930, sulfuric acid produced by the contact process accounted for only 25% of sulfuric acid production, while today nearly all sulfuric acid is manufactured in this way.
Sulfuric acid makers in the United States did not immediately switch to the catalytic contact technique. Until the 1880s, in fact, they had not adopted the Glover–Gay-Lussac towersor shifted to pyrites, in part because domestic sources were not available at a reasonable price. After the Civil War, though, consumption of sulfuric acid grew, especially for making superphosphate fertilizers and refining petroleum. Output of the acid expanded from 60,000 tons in 1863 to about 700,000 tons in 1890. The first U.S. contact-process plant was built at Mineral Point, WI, in 1899 and used sulfur dioxide from an adjacent zinc smelter. Other, similar facilities quickly followed. By the start of World War I, the annual U.S.output of sulfuric acid, at 4 million tons, led the world.
With improvements in design and engineering, production from contact-process plants gradually eclipsed that from lead-chamber plants (where the units were no longer necessarily built as boxlike chambers but as towers). In 1910, about 80% of the sulfuric acid made in Europe and North America came from the chamber process. By 1930, it had dropped below 75%. By 1960, chamber-process acid’s share of total output was only about 15%. Probably no new chamber-process plants have been built since the 1950s. Meanwhile, an increasing share of the sulfur dioxide used in contact-process plants has come from the off-gases of smelters, waste (spent) sulfuric acid, and other environmentally harmful wastes. These sources have largely replaced pyrites. But whatever the raw material, sulfuric acid’s world ranking as the volume leader among industrial chemicals remains secure.

Sources:

http://www.wikipedia.org/wiki/Sulfuric_acid
http://www.encyclopedia.com/topic/sulfuric_acid.aspx
http://pubs.acs.org/subscribe/journals/tcaw/10/i09/html/09chemch.html
http://www.mecsglobal.com/sulfuric-acid-plant-processes.aspx