When heated, the pure 100% acid loses sulfur trioxide gas, SO3, until a constant-boiling solution, or azeotrope, containing about 98.5% H2SO4 is formed at 337°C;. Concentrated sulfuric acid is a weak acid (see acids and bases) and a poor electrolyte because relatively little of it is dissociated into ions at room temperature. When cold it does not react readily with such common metals as iron or copper. When hot it is an oxidizing agent, the sulfur in it being reduced; sulfur dioxide gas may be released. Hot concentrated sulfuric acid reacts with most metals and with several nonmetals, e.g., sulfur and carbon. Because the concentrated acid has a fairly high boiling point, it can be used to release more volatile acids from their salts, e.g., when sodium chloride (NaCl), or common salt, is heated with concentrated sulfuric acid, hydrogen chloride gas, HCl, is evolved.
Concentrated sulfuric acid has a very strong affinity for water. It is sometimes used as a drying agent and can be used to dehydrate (chemically remove water from) many compounds, e.g., carbohydrates. It reacts with the sugar sucrose, C12H22O11, removing eleven molecules of water, H2O, from each molecule of sucrose and leaving a brittle spongy black mass of carbon and diluted sulfuric acid. The acid reacts similarly with skin, cellulose, and other plant and animal matter.
When the concentrated acid mixes with water, large amounts of heat are released; enough heat can be released at once to boil the water and spatter the acid. To dilute the acid, the acid should be added slowly to cold water with constant stirring to limit the buildup of heat. Sulfuric acid reacts with water to form hydrates with distinct properties.
Dilute sulfuric acid is a strong acid and a good electrolyte; it is highly ionized, much of the heat released in dilution coming from hydration of the hydrogen ions. The dilute acid has most of the properties of common strong acids. It turns blue litmus red. It reacts with many metals (e.g., with zinc), releasing hydrogen gas, H2, and forming the sulfate of the metal. It reacts with most hydroxides and oxides, with some carbonates and sulfides, and with some salts. Since it is dibasic (i.e., it has two replaceable hydrogen atoms in each molecule), it forms both normal sulfates (with both hydrogens replaced, e.g., sodium sulfate, Na2SO4) and acid sulfates, also called bisulfates or hydrogen sulfates (with only one hydrogen replaced, e.g., sodium bisulfate, NaHSO4).
There are two major processes (lead chamber and contact) for production of sulfuric acid, and it is available commercially in a number of grades and concentrations. The lead chamber process, the older of the two processes, is used to produce much of the acid used to make fertilizers; it produces a relatively dilute acid (62%-78% H2SO4). The contact process produces a purer, more concentrated acid but requires purer raw materials and the use of expensive catalysts. In both processes sulfur dioxide is oxidized and dissolved in water. The sulfur dioxide is obtained by burning sulfur, by burning pyrites (iron sulfides), by roasting nonferrous sulfide ores preparatory to smelting, or by burning hydrogen sulfide gas. Some sulfuric acid is also made from ferrous sulfate waste solutions from pickling iron and steel and from waste acid sludge from oil refineries.Lean Chamber Process
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 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.Contact Process
In the contact process, purified sulfur dioxide and air are mixed, heated to about 450°C;, and passed over a catalyst; the sulfur dioxide is oxidized to sulfur trioxide. The catalyst is usually platinum on a silica or asbestos carrier or vanadium pentoxide on a silica carrier. The sulfur trioxide is cooled and passed through two towers. In the first tower it is washed with oleum (fuming sulfuric acid, 100% sulfuric acid with sulfur trioxide dissolved in it). In the second tower it is washed with 97% sulfuric acid; 98% sulfuric acid is usually produced in this tower. Waste gases are usually discharged into the atmosphere. Acid of any desired concentration may be produced by mixing or diluting the products of this process.
Sulfuric acid is one of the most important industrial chemicals. More of it is made each year than is made of any other manufactured chemical; more than 40 million tons of it were produced in the United States in 1990. It has widely varied uses and plays some part in the production of nearly all manufactured goods. The major use of sulfuric acid is in the production of fertilizers, e.g., superphosphate of lime and ammonium sulfate. It is widely used in the manufacture of chemicals, e.g., in making hydrochloric acid, nitric acid, sulfate salts, synthetic detergents, dyes and pigments, explosives, and drugs. It is used in petroleum refining to wash impurities out of gasoline and other refinery products. Sulfuric acid is used in processing metals, e.g., in pickling (cleaning) iron and steel before plating them with tin or zinc. Rayon is made with sulfuric acid. It serves as the electrolyte in the lead-acid storage battery commonly used in motor vehicles (acid for this use, containing about 33% H2SO4 and with specific gravity about 1.25, is often called battery acid).
Although sulfuric acid is now one of the most widely used chemicals, it was probably little known before the 16th cent. It was prepared by Johann Van Helmont (c.1600) by destructive distillation of green vitriol (ferrous sulfate) and by burning sulfur. The first major industrial demand for sulfuric acid was the Leblanc process for making sodium carbonate (developed c.1790). Sulfuric acid was produced at Nordhausen from green vitriol but was expensive. A process for its synthesis by burning sulfur with saltpeter (potassium nitrate) was first used by Johann Glauber in the 17th cent. and developed commercially by Joshua Ward in England c.1740. It was soon superseded by the lead chamber process, invented by John Roebuck in 1746 and since improved by many others. The contact process was originally developed c.1830 by Peregrine Phillips in England; it was little used until a need for concentrated acid arose, particularly for the manufacture of synthetic organic dyes.
Sulfuric acid is formed naturally by the oxidation of sulfide minerals, such as iron sulfide. The resulting water can be highly acidic and is called Acid Mine Drainage (AMD). This acidic water is capable of dissolving metals present in sulfide ores, which results in brightly-colored, toxic streams. The oxidation of iron sulfide pyrite by molecular oxygen produces iron(II), or Fe2+:
The Fe2+ can be further oxidized to Fe3+, according to:
The iron(III) ion ("ferric iron", in casual nomenclature) can also oxidize pyrite. When iron(III) oxidation of pyrite occurs, the process can become rapid. pH values below zero have been measured in ARD produced by this process.
ARD can also produce sulfuric acid at a slower rate, so that the Acid Neutralization Capacity (ANC) of the aquifer can neutralize the produced acid. In such cases, the Total Dissolved solids (TDS) concentration of the water can be increased form the dissolution of minerals from the acid-neutralization reaction with the minerals.
In the upper, cooler portions of Venus's atmosphere, sulfuric acid exists as a liquid, and thick sulfuric acid clouds completely obscure the planet's surface when viewed from above. The main cloud layer extends from 45–70 km above the planet's surface, with thinner hazes extending as low as 30 and as high as 90 km above the surface.
Infrared spectra from NASA's Galileo mission show distinct absorptions on Jupiter's moon Europa that have been attributed to one or more sulfuric acid hydrates. The interpretation of the spectra is somewhat controversial. Some planetary scientists prefer to assign the spectral features to the sulfate ion, perhaps as part of one or more minerals on Europa's surface.
Finally the sulfur trioxide is treated with water (usually as 97-98% H2SO4 containing 2-3% water) to produce 98-99% sulfuric acid.
Note that directly dissolving SO3 in water is not practical due to the highly exothermic nature of the reaction, forming a corrosive mist instead of a liquid. Alternatively, SO3 can be absorbed into H2SO4 to produce oleum (H2S2O7), which may then be mixed with water to form sulfuric acid.
Oleum is reacted with water to form concentrated H2SO4.
Different purities are also available. Technical grade H2SO4 is impure and often colored, but is suitable for making fertilizer. Pure grades such as United States Pharmacopoeia (USP) grade are used for making pharmaceuticals and dyestuffs.
When high concentrations of SO3(g) are added to sulfuric acid, H2S2O7, called pyrosulfuric acid, fuming sulfuric acid or oleum or, less commonly, Nordhausen acid, is formed. Concentrations of oleum are either expressed in terms of% SO3 (called% oleum) or as% H2SO4 (the amount made if H2O were added); common concentrations are 40% oleum (109% H2SO4) and 65% oleum (114.6% H2SO4). Pure H2S2O7 is a solid with melting point 36°C.
Anhydrous H2SO4 is a very polar liquid, having a dielectric constant of around 100. It has a high electrical conductivity, caused by dissociation through protonating itself, a process known as autoprotolysis.
The comparable equilibrium constant for water, Kw is 10−14, a factor of 1010 (10 billion) smaller.
In spite of the viscosity of the acid, the effective conductivities of the H3SO4+ and HSO4− ions are high due to an intra-molecular proton-switch mechanism (analogous to the Grotthuss mechanism in water), making sulfuric acid a good conductor. It is also an excellent solvent for many reactions.
The equilibrium is actually more complex than shown above; 100% H2SO4 contains the following species at equilibrium (figures shown as millimol per kg solvent): HSO4− (15.0), H3SO4+ (11.3), H3O+ (8.0), HS2O7− (4.4), H2S2O7 (3.6), H2O (0.1).
Because the hydration of sulfuric acid is thermodynamically favorable, sulfuric acid is an excellent dehydrating agent, and is used to prepare many dried fruits. The affinity of sulfuric acid for water is sufficiently strong that it will remove hydrogen and oxygen atoms from other compounds; for example, mixing starch (C6H12O6)n and concentrated sulfuric acid will give elemental carbon and water which is absorbed by the sulfuric acid (which becomes slightly diluted): (C6H12O6)n → 6C + 6H2O. The effect of this can be seen when concentrated sulfuric acid is spilled on paper; the cellulose reacts to give a burned appearance, the carbon appears much as soot would in a fire. A more dramatic reaction occurs when sulfuric acid is added to a tablespoon of white sugar; a rigid column of black, porous carbon will quickly emerge. The carbon will smell strongly of caramel.
Similarly, reacting sulfuric acid with potassium nitrate can be used to produce nitric acid and a precipitate of potassium bisulfate. When combined with nitric acid, sulfuric acid acts both as an acid and a dehydrating agent, forming the nitronium ion NO2+, which is important in nitration reactions involving electrophilic aromatic substitution. This type of reaction, where protonation occurs on an oxygen atom, is important in many organic chemistry reactions, such as Fischer esterification and dehydration of alcohols.
Sulfuric acid reacts with most metals via a single displacement reaction to produce hydrogen gas and the metal sulfate. Dilute H2SO4 attacks iron, aluminium, zinc, manganese, magnesium and nickel, but reactions with tin and copper require the acid to be hot and concentrated. Lead and tungsten, however, are resistant to sulfuric acid. The reaction with iron (shown) is typical for most of these metals, but the reaction with tin is unusual in that it produces sulfur dioxide rather than hydrogen.
Sulfuric acid is a very important commodity chemical, and indeed, a nation's sulfuric acid production is a good indicator of its industrial strength. The major use (60% of total production worldwide) for sulfuric acid is in the "wet method" for the production of phosphoric acid, used for manufacture of phosphate fertilizers as well as trisodium phosphate for detergents. In this method, phosphate rock is used, and more than 100 million tonnes are processed annually. This raw material is shown below as fluorapatite, though the exact composition may vary. This is treated with 93% sulfuric acid to produce calcium sulfate, hydrogen fluoride (HF) and phosphoric acid. The HF is removed as hydrofluoric acid. The overall process can be represented as:
Sulfuric acid is used in large quantities by the iron and steelmaking industry to remove oxidation, rust and scale from rolled sheet and billets prior to sale to the automobile and white-goods industry. Used acid is often recycled using a Spent Acid Regeneration (SAR) plant. These plants combust spent acid with natural gas, refinery gas, fuel oil or other fuel sources. This combustion process produces gaseous sulfur dioxide (SO2) and sulfur trioxide (SO3) which are then used to manufacture "new" sulfuric acid. SAR plants are common additions to metal smelting plants, oil refineries, and other industries where sulfuric acid is consumed in bulk, as operating a SAR plant is much cheaper than the recurring costs of spent acid disposal and new acid purchases.
Ammonium sulfate, an important nitrogen fertilizer, is most commonly produced as a byproduct from coking plants supplying the iron and steel making plants. Reacting the ammonia produced in the thermal decomposition of coal with waste sulfuric acid allows the ammonia to be crystallized out as a salt (often brown because of iron contamination) and sold into the agro-chemicals industry.
Another important use for sulfuric acid is for the manufacture of aluminum sulfate, also known as paper maker's alum. This can react with small amounts of soap on paper pulp fibers to give gelatinous aluminum carboxylates, which help to coagulate the pulp fibers into a hard paper surface. It is also used for making aluminum hydroxide, which is used at water treatment plants to filter out impurities, as well as to improve the taste of the water. Aluminum sulfate is made by reacting bauxite with sulfuric acid:
Sulfuric acid is used for a variety of other purposes in the chemical industry. For example, it is the usual acid catalyst for the conversion of cyclohexanoneoxime to caprolactam, used for making nylon. It is used for making hydrochloric acid from salt via the Mannheim process. Much H2SO4 is used in petroleum refining, for example as a catalyst for the reaction of isobutane with isobutylene to give isooctane, a compound that raises the octane rating of gasoline (petrol). Sulfuric acid is also important in the manufacture of dyestuffs solutions and is the "acid" in lead-acid (car) batteries.
Sulfuric acid is also used as a general dehydrating agent in its concentrated form. See Reaction with water.
|2 → 2 + 2 +||(830°C)|
|+ + 2 → 2 +||(120°C)|
|2 → +||(320°C)|
The sulfur and iodine compounds are recovered and reused, hence the consideration of the process as a cycle. This process is endothermic and must occur at high temperatures, so energy in the form of heat has to be supplied.
The sulfur-iodine cycle is currently being researched as a feasible method of obtaining hydrogen, but the concentrated, corrosive acid at high temperatures poses currently insurmountable safety hazards if the process were built on large-scale.
Sulfuric acid was known to medieval European alchemists as oil of vitriol, spirit of vitriol, or simply vitriol, among other names. The word vitriol derives from the Latin vitreus, 'glass', referring to the glassy appearance of the sulfate salts, which also carried the name vitriol. Salts called by this name included copper(II) sulfate (blue vitriol, or rarely Roman vitriol), zinc sulfate (white vitriol), iron(II) sulfate (green vitriol), iron(III) sulfate (vitriol of Mars), and cobalt(II) sulfate (red vitriol).
Vitriol was widely considered the most important alchemical substance, intended to be used as a philosopher's stone. Highly purified vitriol was used as a medium for reacting other substances. This was largely because the acid does not react with gold, production of which was often the final goal of alchemical processes. The importance of vitriol to alchemy is highlighted in the alchemical motto, Visita Interiora Terrae Rectificando Invenies Occultum Lapidem which is a backronym meaning ('Visit the interior of the earth and rectifying (i.e. purifying) you will find the hidden/secret stone'), found in L'Azoth des Philosophes by the 15th Century alchemist Basilius Valentinus, .
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 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 adapted this method to produce sulfuric acid in lead-lined chambers, which were stronger, less expensive, and could be made larger than the previously used glass containers. This lead chamber process allowed the effective industrialization of sulfuric acid production. After several refinements, this method remained the standard for sulfuric acid production for almost two centuries.
Sulfuric acid created by John Roebuck's process only approached a 35–40% concentration. Later refinements to the lead-chamber process by French chemist Joseph-Louis Gay-Lussac and British chemist John Glover improved the yield to 78%. However, the manufacture of some dyes and other chemical processes require a more concentrated product. 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 iron (II) sulfate, FeSO4, which was oxidized by further heating in air to form iron(III) sulfate, Fe2(SO4)3, which, when heated to 480 °C, decomposed to iron(III) oxide and sulfur trioxide, which could be passed through water to yield sulfuric acid in any concentration. However, the expense of this process prevented the large-scale use of concentrated sulfuric acid.
In 1831, British vinegar merchant Peregrine Phillips patented the contact process, which was a far more economical process for producing sulfur trioxide and concentrated sulfuric acid. Today, nearly all of the world's sulfuric acid is produced using this method.
The corrosive properties of sulfuric acid are accentuated by its highly exothermic reaction with water. Hence burns from sulfuric acid are potentially more serious than those of comparable strong acids (e.g. hydrochloric acid), as there is additional tissue damage due to dehydration and particularly due to the heat liberated by the reaction with water; i.e. secondary thermal damage. The danger is obviously greater with more concentrated preparations of sulfuric acid, but it should be remembered that even the normal laboratory "dilute" grade (approx. 1 M, 10%) will char paper by dehydration if left in contact for a sufficient time. Solutions equal to or stronger than 1.5 M should be labeled CORROSIVE, while solutions greater than 0.5 M but less than 1.5 M should be labeled IRRITANT. Fuming sulfuric acid (oleum) is not recommended for use in schools due to it being quite hazardous. The standard first aid treatment for acid spills on the skin is, as for other corrosive agents, irrigation with large quantities of water: Washing should be continued for at least ten to fifteen minutes in order to cool the tissue surrounding the acid burn and to prevent secondary damage. Contaminated clothing must be removed immediately and the underlying skin washed thoroughly.
Preparation of the diluted acid can also be dangerous due to the heat released in the dilution process. It is essential that the concentrated acid is added to water and not the other way round, to take advantage of the relatively high heat capacity of water. Addition of water to concentrated sulfuric acid leads at best to the dispersal of a sulfuric acid aerosol, at worst to an explosion. Preparation of solutions greater than 6 M (35%) in concentration is the most dangerous, as the heat produced can be sufficient to boil the diluted acid: efficient mechanical stirring and external cooling (e.g. an ice bath) are essential.
Sulfuric acid is not considered toxic besides its obvious corrosive hazard, and the main occupational risks are skin contact leading to burns (see above) and the inhalation of aerosols. Exposure to aerosols at high concentrations leads to immediate and severe irritation of the eyes, respiratory tract and mucous membranes: this ceases rapidly after exposure, although there is a risk of subsequent pulmonary edema if tissue damage has been more severe. At lower concentrations, the most commonly reported symptom of chronic exposure to sulfuric acid aerosols is erosion of the teeth, found in virtually all studies: indications of possible chronic damage to the respiratory tract are inconclusive as of 1997. In the United States, the permissible exposure limit (PEL) for sulfuric acid is fixed at 1 mg/m³: limits in other countries are similar. Interestingly there have been reports of sulfuric acid ingestion leading to vitamin B12 deficiency with subacute combined degeneration. The spinal cord is most often affected in such cases, but the optic nerves may show demyelination, loss of axons and gliosis.
In the United States of America, sulfuric acid is included in List II of the list of essential or precursor chemicals established pursuant to the Chemical Diversion and Trafficking Act. Accordingly, transactions of sulfuric acid—such as sales, transfers, exports from and imports to the United States—are subject to regulation and monitoring by the Drug Enforcement Administration.