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1. 强酸性
(1)与碱反应
(2)与碱性氧化物反应(除锈;制硫酸铜等盐)
(3)与弱酸盐反应(制某些弱酸或酸式盐如制磷酸,制过磷酸钙)
(4)与活泼金属反应(制氢气)
2. 浓硫酸的吸水性 (作气体干燥剂、硝酸浓缩时的吸水剂;)
3. 浓硫酸的脱水性 (使木条、硬纸板等炭化;乙醇脱水制乙烯)
4. 浓硫酸的强氧化性
(1)使铁、铝等金属纯化;
(2)与不活泼金属铜反应(加热)
(3)与木炭反应(加热)
(4)制乙烯时使反应混合液变黑
(5)不适宜用于实验室制碘化氢或溴化氢,因其能氧化它们
5. 高沸点(不挥发性)(制挥发性酸)
A。制氯化氢气体、氟化氢气体(HCl和HF都易溶,用浓硫酸)
B。制硝酸 (HNO3易溶,用浓硫酸)
C。制硫化氢气体(H2S溶解度不大,且浓硫酸能氧化H2S,故应用稀硫酸)
D。制二氧化硫 (二氧化硫溶解度较大,用较浓的硫酸)
实验室制二氧化碳一般不用硫酸,因另一反应物通常用块状石灰石,反应生成的硫酸钙溶解度小易裹在表面阻碍反应的进一步进行。
6. 有机反应中常用作催化剂
(1)乙醇脱水制乙烯(或制乙醚)(作催化剂兼作脱水剂,用多量浓硫酸)
(2)苯的硝化反应(硫酸作催化剂也起吸水作用,用浓硫酸)
(3)酯化反应(硫酸作催化剂和吸水剂,用浓硫酸)
(4)酯水解(硫酸作催化剂,用稀硫酸)
Manufacture
Main article: Contact process
Sulfuric acid is produced from sulfur, oxygen and water via the contact process.
In the first step, sulfur is burned to produce sulfur dioxide.
(1) S(s) + O2(g) → SO2(g)
This is then oxidised to sulfur trioxide using oxygen in the presence of a vanadium(V) oxide catalyst.
(2) 2 SO2 + O2(g) → 2 SO3(g) (in presence of V2O5)
Finally the sulfur trioxide is treated with water (usually as 97-98% H2SO4 containing 2-3% water) to produce 98-99% sulfuric acid.
(3) SO3(g) + H2O(l) → H2SO4(l)
Note that directly dissolving SO3 in water is impractical due to the highly exothermic nature of the reaction. Mists are formed 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.
(3) H2SO4(l) + SO3 → H2S2O7(l)
Oleum is reacted with water to form concentrated H2SO4.
(4) H2S2O7(l) + H2O(l) → 2 H2SO4(l)
In 1993, American production of sulfuric acid amounted to 36.4 million tonnes. World production in 2001 was 165 million tonnes.
[edit]Physical properties
[edit]Forms of sulfuric acid
Although nearly 100% sulfuric acid can be made, this loses SO3 at the boiling point to produce 98.3% acid. The 98% grade is more stable in storage, and is the usual form of what is described as concentrated sulfuric acid. Other concentrations are used for different purposes. Some common concentrations are
10%, dilute sulfuric acid for laboratory use,
33.5%, battery acid (used in lead-acid batteries),
62.18%, chamber or fertilizer acid,
77.67%, tower or Glover acid,
98%, concentrated acid.
Different purities are also available. Technical grade H2SO4 is impure and often colored, but is suitable for making fertilizer. Pure grades such as US 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.
[edit]Polarity and conductivity
Anhydrous H2SO4 is a very polar liquid, having a dielectric constant of around 100. This is because it can dissociate by protonating itself, a process known as autoprotolysis.[2] It occurs to a high degree in sulfuric acid, more than 10 billion times the level seen in water: [citation needed]
2 H2SO4⇌ H3SO4+ + HSO4−
This allows protons to be highly mobile in H2SO4. It also makes sulfuric acid an excellent solvent for many reactions. In fact, the equilibrium is more complex than shown above. 100% H2SO4 contains the following species at equilibrium (figures shown as mol per kg solvent): HSO4− (15.0), H3SO4+ (11.3), H3O+ (8.0), HS2O7− (4.4), H2S2O7 (3.6), H2O (0.1).
[edit]Chemical properties
[edit]Reaction with water
The hydration reaction of sulfuric acid is highly exothermic. If water is added to the concentrated sulfuric acid, it can boil and spit dangerously. One should always add the acid to the water rather than the water to the acid. This can be remembered through mnemonics such as: "Always do things as you oughta, add the acid to the water. If you think your life's too placid, add the water to the acid", "A.A.: Add Acid", or "Drop acid, not water", or "Acid to water, like A&W Root Beer" or "Put the king into the water, not the water into the king" . The necessity for this safety precaution is due to the relative densities of these two liquids. Water is less dense than sulfuric acid, meaning water will tend to float on top of this acid. The reaction is best thought of as forming hydronium ions, by
H2SO4 + H2O → H3O+ + HSO4-,
and then
HSO4- + H2O → H3O+ + SO42-.
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 starch 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.
[edit]Other reactions of sulfuric acid
As an acid, sulfuric acid reacts with most bases to give the corresponding sulfate. For example, copper(II) sulfate. This blue salt of copper, commonly used for electroplating and as a fungicide, is prepared by the reaction of copper(II) oxide with sulfuric acid:
CuO + H2SO4 → CuSO4 + H2O
Sulfuric acid can also be used to displace weaker acids from their salts. Reaction with sodium acetate, for example, displaces acetic acid:
H2SO4 + CH3COONa → NaHSO4 + CH3COOH
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.
Fe(s) + H2SO4(aq) → H2(g) + FeSO4(aq)
Sn(s) + 2 H2SO4(aq) → SnSO4(aq) + 2 H2O(l) + SO2(g)
[edit]Environmental aspects
Sulfuric acid is a constituent of acid rain, which is formed by atmospheric oxidation of sulfur dioxide in the presence of water - i.e. oxidation of sulfurous acid. Sulfur dioxide is the main byproduct produced when sulfur-containing fuels such as coal or oil are burned.
Sulfuric acid is formed naturally by the oxidation of sulphide minerals, such as iron sulfide. The resulting water can be highly acidic and is called Acid Rock Drainage (ARD). 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+:
FeS2 + 7/2 O2 + H2O → Fe2+ + 2 SO42- + 2 H+.
The Fe2+ can be further oxidized to Fe3+, according to:
Fe2+ + 1/4 O2 + H+ → Fe3+ + 1/2 H2O,
and the Fe3+ produced can be precipitated as the hydroxide or hydrous oxide. The equation for the formation of the hydroxide is
Fe3+ + 3 H2O → Fe(OH)3 + 3 H+.
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.
[edit]Extraterrestrial sulfuric acid
Sulfuric acid is produced in the upper atmosphere of Venus by the sun's photochemical action on carbon dioxide, sulfur dioxide, and water vapor. Ultraviolet photons of wavelengths less than 169 nm can photodissociate carbon dioxide into carbon monoxide and atomic oxygen. Atomic oxygen is highly reactive. When it reacts with sulfur dioxide, a trace component of the Venerian atmosphere, the result is sulfur trioxide, which can combine with water vapor, another trace component of Venus' atmosphere, to yield sulfuric acid.
CO2 → CO + O
SO2 + O → SO3
SO3 + H2O → H2SO4
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.
[edit]History of sulfuric acid
John Dalton's 1808 sulfuric acid molecule shown a central sulfur atom bonded to three oxygen atoms.The discovery of sulfuric acid is credited to 8th century alchemist Jabir ibn Hayyan. The acid was later studied by 9th century physician and alchemist Ibn Zakariya al-Razi (Rhases), who obtained the substance by dry distillation of minerals including iron(II) sulfate heptahydrate, FeSO4 • 7H2O, and copper(II) sulfate pentahydrate, CuSO4 • 5H2O. When heated, these compounds decompose to iron(II) oxide and copper(II) oxide, respectively, giving off water and sulfur trioxide, which combine to produce a dilute solution of sulfuric acid. This method was popularized in Europe through translations of Arabic and Persian treatises, as well as books by European alchemists, such as the 13th-century German Albertus Magnus.
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.
[edit]Uses
Sulphuric acid production in 2000Sulfuric acid is a very important commodity chemical, and indeed, a nation's sulfuric acid production is a good indicator of its industrial strength.[3] 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:
Ca5F(PO4)3 + 5 H2SO4 + 10 H2O → 5 CaSO4•2 H2O + HF + 3 H3PO4.
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:
Al2O3 + 3 H2SO4 → Al2(SO4)3 + 3 H2O.
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.
[edit]Sulfur-iodine cycle
The sulfur-iodine cycle is a series of thermo-chemical processes used to obtain hydrogen. It consists of three chemical reactions whose net reactant is water and whose net products are hydrogen and oxygen.
2 H2SO4 → 2 SO2 + 2 H2O + O2 (830°C)
I2 + SO2 + 2 H2O → 2 HI + H2SO4 (120°C)
2 HI → I2 + H2 (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 has been proposed as a way to supply hydrogen for a hydrogen-based economy. It does not require hydrocarbons like current methods of steam reforming.
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.
英文部分来自Wikipedia
sulphuric acid is one of the most important industrial chemicals.A bout 140million tonnes are manufactured in the world every year.It is used in the most industies ranging from agriculture fertilisers to paints,soap and the cleaning of rust.The main use of sulphuric acid is producing fertilisers,particularly superphosphate and ammoniumsulphate