Sulfur trioxide
Encyclopedia
Sulfur
trioxide (also spelled sulphur trioxide) is the chemical compound with the formula SO3. In the gaseous form, this species is a significant pollutant, being the primary agent in acid rain
. It is prepared on massive scales as a precursor to sulfuric acid
.
molecule of D3h symmetry, as predicted by VSEPR theory
. SO3 belongs to the D3h point group.
In terms of electron-counting formalisms, the three oxygen atoms are in the -2 oxidation state and the sulfur atom has an oxidation state of +6, a formal charge of 0, and is surrounded by 6 electron pairs. From the perspective of molecular orbital theory
, most of these electron pairs are non-bonding in character, as is typical for hypervalent molecule
s.
Sulfur trioxide also exhibits hybridization.
It's a non-polar molecule.
The reaction occurs both rapidly and exothermically, too violently to be used in large-scale manufacturing. At or above 340 °C, sulfuric acid, sulfur trioxide, and water coexist in significant equilibrium concentrations.
Sulfur trioxide also reacts with sulfur dichloride
to yield the useful reagent
, thionyl chloride
.
SO3 is a strong Lewis acid readily forming crystalline complexes with pyridine
, dioxane and trimethylamine
which can be used as sulfonating agents.
of sodium bisulfate
. Sodium pyrosulfate
is an intermediate product:
This method will work for other metal bisulfates, the controlling factor being the stability of the intermediate pyrosulfate salt.
Industrially SO3 is made by the contact process
. Sulfur dioxide
, generally made by the burning of sulfur
or iron pyrite (a sulfide ore of iron), is first purified by electrostatic precipitation. The purified SO2 is then oxidised by atmospheric oxygen
at between 400 and 600 °C over a catalyst consisting of vanadium pentoxide
(V2O5) activated with potassium oxide
K2O on kieselguhr
or silica
support. Platinum
also works very well but is too expensive and is poisoned (rendered ineffective) much more easily by impurities.
The majority of sulphur trioxide made in this way is converted into sulfuric acid
not by the direct addition of water, with which it forms a fine mist, but by absorption in concentrated sulfuric acid and dilution with water of the produced oleum
.
If SO3 is condensed above 27 °C, then α-"SO3" forms, which has a melting point of 62.3°C. α-SO3 is fibrous in appearance, like asbestos
(with which it has no chemical relationship). Structurally, it is the polymer
[S(=O)2(μ-O)]n. Each end of the polymer is terminated with OH groups (hence α-"SO3" is not really a form of SO3). β-SO3, like the alpha form, is fibrous but of different molecular weight, consisting of an hydroxyl-capped polymer, but melts at 32.5 °C. Both the gamma and the beta forms are metastable, eventually converting to the stable alpha form if left standing for sufficient time. This conversion is caused by traces of water.
Relative vapor pressures of solid SO3 are alpha < beta < gamma at identical temperatures, indicative of their relative molecular weights. Liquid sulfur trioxide has vapor pressure consistent with the gamma form. Thus heating a crystal of α-SO3 to its melting point results in a sudden increase in vapor pressure, which can be forceful enough to shatter a glass vessel in which it is heated. This effect is known as the "alpha explosion".
SO3 is aggressively hygroscopic. In fact, the heat of hydration is sufficient that mixtures of SO3 and wood or cotton can ignite. In such cases, SO3 dehydrates these carbohydrate
s.
Sulfur
Sulfur or sulphur is the chemical element with atomic number 16. In the periodic table it is represented by the symbol S. It is an abundant, multivalent non-metal. Under normal conditions, sulfur atoms form cyclic octatomic molecules with chemical formula S8. Elemental sulfur is a bright yellow...
trioxide (also spelled sulphur trioxide) is the chemical compound with the formula SO3. In the gaseous form, this species is a significant pollutant, being the primary agent in acid rain
Acid rain
Acid rain is a rain or any other form of precipitation that is unusually acidic, meaning that it possesses elevated levels of hydrogen ions . It can have harmful effects on plants, aquatic animals, and infrastructure. Acid rain is caused by emissions of carbon dioxide, sulfur dioxide and nitrogen...
. It is prepared on massive scales as a precursor to sulfuric acid
Sulfuric acid
Sulfuric acid is a strong mineral acid with the molecular formula . Its historical name is oil of vitriol. Pure sulfuric acid is a highly corrosive, colorless, viscous liquid. The salts of sulfuric acid are called sulfates...
.
Structure and bonding
Gaseous SO3 is a trigonal planarTrigonal planar
In chemistry, trigonal planar is a molecular geometry model with one atom at the center and three atoms at the corners of a triangle, called peripheral atoms, all in one plane. In an ideal trigonal planar species, all three ligands are identical and all bond angles are 120°. Such species belong to...
molecule of D3h symmetry, as predicted by VSEPR theory
VSEPR theory
Valence shell electron pair repulsion theory is a model in chemistry used to predict the shape of individual molecules based upon the extent of electron-pair electrostatic repulsion. It is also named Gillespie–Nyholm theory after its two main developers...
. SO3 belongs to the D3h point group.
In terms of electron-counting formalisms, the three oxygen atoms are in the -2 oxidation state and the sulfur atom has an oxidation state of +6, a formal charge of 0, and is surrounded by 6 electron pairs. From the perspective of molecular orbital theory
Molecular orbital theory
In chemistry, molecular orbital theory is a method for determining molecular structure in which electrons are not assigned to individual bonds between atoms, but are treated as moving under the influence of the nuclei in the whole molecule...
, most of these electron pairs are non-bonding in character, as is typical for hypervalent molecule
Hypervalent molecule
A hypervalent molecule is a molecule that contains one or more main group elements formally bearing more than eight electrons in their valence shells...
s.
Sulfur trioxide also exhibits hybridization.
It's a non-polar molecule.
Chemical reactions
SO3 is the anhydride of H2SO4. Thus, the following reaction occurs:- SO3 (l) + H2O (l) → H2SO4 (l) (−88 kJ mol−1Mole (unit)The mole is a unit of measurement used in chemistry to express amounts of a chemical substance, defined as an amount of a substance that contains as many elementary entities as there are atoms in 12 grams of pure carbon-12 , the isotope of carbon with atomic weight 12. This corresponds to a value...
)
The reaction occurs both rapidly and exothermically, too violently to be used in large-scale manufacturing. At or above 340 °C, sulfuric acid, sulfur trioxide, and water coexist in significant equilibrium concentrations.
Sulfur trioxide also reacts with sulfur dichloride
Sulfur dichloride
Sulfur dichloride is the chemical compound with the formula SCl2. This cherry-red liquid is the simplest sulfur chloride and one of the most common. It is used as a precursor to organosulfur compounds.-Chlorination of sulfur:...
to yield the useful reagent
Reagent
A reagent is a "substance or compound that is added to a system in order to bring about a chemical reaction, or added to see if a reaction occurs." Although the terms reactant and reagent are often used interchangeably, a reactant is less specifically a "substance that is consumed in the course of...
, thionyl chloride
Thionyl chloride
Thionyl chloride is an inorganic compound with the formula SOCl2. It is a reactive chemical reagent used in chlorination reactions. It is a colorless, distillable liquid at room temperature and pressure that decomposes above 140 °C. Thionyl chloride is sometimes confused with sulfuryl...
.
- SO3 + SCl2 → SOCl2 + SO2
SO3 is a strong Lewis acid readily forming crystalline complexes with pyridine
Sulfur trioxide pyridine complex
Sulfur trioxide pyridine complex is a complex formed where the lone pair on the nitrogen of the pyridine binds to the sulfur of the sulfur trioxide...
, dioxane and trimethylamine
Trimethylamine
Trimethylamine is an organic compound with the formula N3. This colorless, hygroscopic, and flammable tertiary amine has a strong "fishy" odor in low concentrations and an ammonia-like odor at higher concentrations...
which can be used as sulfonating agents.
Preparation
Sulfur trioxide can be prepared in the laboratory by the two-stage pyrolysisPyrolysis
Pyrolysis is a thermochemical decomposition of organic material at elevated temperatures without the participation of oxygen. It involves the simultaneous change of chemical composition and physical phase, and is irreversible...
of sodium bisulfate
Sodium bisulfate
Sodium bisulfate, also known as sodium hydrogen sulfate , is an acid salt. It is a dry granular product that can be safely shipped and stored. The anhydrous form is hygroscopic. Solutions of sodium bisulfate are acidic, with a 1M solution having a pH of Sodium bisulfate, also known as sodium...
. Sodium pyrosulfate
Sodium pyrosulfate
Sodium pyrosulfate is a salt of sodium and pyrosulfate, obtained by the dehydration of sodium bisulfate. This is an intermediate stage in the preparation of sulfur trioxide....
is an intermediate product:
- Dehydration at 315°C:
- 2 NaHSO4 → Na2S2O7 + H2O
- Cracking at 460°C:
- Na2S2O7 → Na2SO4 + SO3
This method will work for other metal bisulfates, the controlling factor being the stability of the intermediate pyrosulfate salt.
Industrially SO3 is made by the contact process
Contact process
The contact process is the current method of producing sulphuric acid in the high concentrations needed for industrial processes. Platinum was formerly employed as a catalyst for the reaction, but as it is susceptible to poisoning by arsenic impurities in the sulfur feedstock, vanadium oxide is...
. Sulfur dioxide
Sulfur dioxide
Sulfur dioxide is the chemical compound with the formula . It is released by volcanoes and in various industrial processes. Since coal and petroleum often contain sulfur compounds, their combustion generates sulfur dioxide unless the sulfur compounds are removed before burning the fuel...
, generally made by the burning of sulfur
Sulfur
Sulfur or sulphur is the chemical element with atomic number 16. In the periodic table it is represented by the symbol S. It is an abundant, multivalent non-metal. Under normal conditions, sulfur atoms form cyclic octatomic molecules with chemical formula S8. Elemental sulfur is a bright yellow...
or iron pyrite (a sulfide ore of iron), is first purified by electrostatic precipitation. The purified SO2 is then oxidised by atmospheric oxygen
Oxygen
Oxygen is the element with atomic number 8 and represented by the symbol O. Its name derives from the Greek roots ὀξύς and -γενής , because at the time of naming, it was mistakenly thought that all acids required oxygen in their composition...
at between 400 and 600 °C over a catalyst consisting of vanadium pentoxide
Vanadium(V) oxide
Vanadium oxide is the chemical compound with the formula V2O5. Commonly known as vanadium pentoxide, this brown/yellow solid is the most stable and common compound of vanadium. Upon heating it reversibly loses oxygen...
(V2O5) activated with potassium oxide
Potassium oxide
Potassium oxide is an ionic compound of potassium and oxygen. This pale yellow solid, the simplest oxide of potassium, is a rarely encountered, highly reactive compound...
K2O on kieselguhr
Diatomaceous earth
Diatomaceous earth also known as diatomite or kieselgur/kieselguhr, is a naturally occurring, soft, siliceous sedimentary rock that is easily crumbled into a fine white to off-white powder. It has a particle size ranging from less than 1 micrometre to more than 1 millimetre, but typically 10 to...
or silica
Silicon dioxide
The chemical compound silicon dioxide, also known as silica , is an oxide of silicon with the chemical formula '. It has been known for its hardness since antiquity...
support. Platinum
Platinum
Platinum is a chemical element with the chemical symbol Pt and an atomic number of 78. Its name is derived from the Spanish term platina del Pinto, which is literally translated into "little silver of the Pinto River." It is a dense, malleable, ductile, precious, gray-white transition metal...
also works very well but is too expensive and is poisoned (rendered ineffective) much more easily by impurities.
The majority of sulphur trioxide made in this way is converted into sulfuric acid
Sulfuric acid
Sulfuric acid is a strong mineral acid with the molecular formula . Its historical name is oil of vitriol. Pure sulfuric acid is a highly corrosive, colorless, viscous liquid. The salts of sulfuric acid are called sulfates...
not by the direct addition of water, with which it forms a fine mist, but by absorption in concentrated sulfuric acid and dilution with water of the produced oleum
Oleum
Oleum , or fuming sulfuric acid refers to a solution of various compositions of sulfur trioxide in sulfuric acid or sometimes more specifically to disulfuric acid ....
.
Structure of solid SO3
The nature of solid SO3 is a surprisingly complex area because of structural changes caused by traces of water. Upon condensation of the gas, absolutely pure SO3 condenses into a trimer, which is often called γ-SO3. This molecular form is a colorless solid with a melting point of 16.8 °C. It adopts a cyclic structure described as [S(=O)2(μ-O)]3.If SO3 is condensed above 27 °C, then α-"SO3" forms, which has a melting point of 62.3°C. α-SO3 is fibrous in appearance, like asbestos
Asbestos
Asbestos is a set of six naturally occurring silicate minerals used commercially for their desirable physical properties. They all have in common their eponymous, asbestiform habit: long, thin fibrous crystals...
(with which it has no chemical relationship). Structurally, it is the polymer
Polymer
A polymer is a large molecule composed of repeating structural units. These subunits are typically connected by covalent chemical bonds...
[S(=O)2(μ-O)]n. Each end of the polymer is terminated with OH groups (hence α-"SO3" is not really a form of SO3). β-SO3, like the alpha form, is fibrous but of different molecular weight, consisting of an hydroxyl-capped polymer, but melts at 32.5 °C. Both the gamma and the beta forms are metastable, eventually converting to the stable alpha form if left standing for sufficient time. This conversion is caused by traces of water.
Relative vapor pressures of solid SO3 are alpha < beta < gamma at identical temperatures, indicative of their relative molecular weights. Liquid sulfur trioxide has vapor pressure consistent with the gamma form. Thus heating a crystal of α-SO3 to its melting point results in a sudden increase in vapor pressure, which can be forceful enough to shatter a glass vessel in which it is heated. This effect is known as the "alpha explosion".
SO3 is aggressively hygroscopic. In fact, the heat of hydration is sufficient that mixtures of SO3 and wood or cotton can ignite. In such cases, SO3 dehydrates these carbohydrate
Carbohydrate
A carbohydrate is an organic compound with the empirical formula ; that is, consists only of carbon, hydrogen, and oxygen, with a hydrogen:oxygen atom ratio of 2:1 . However, there are exceptions to this. One common example would be deoxyribose, a component of DNA, which has the empirical...
s.