Difference between revisions of "Sulfur trioxide"
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==Structure of solid SO<sub>3</sub>== | ==Structure of solid SO<sub>3</sub>== | ||
[[File:Sulfur-trioxide-trimer-from-xtal-1967-3D-balls-B.png|thumb|right|200px|[[Ball-and-stick model]] of the ''γ''-SO<sub>3</sub> molecule]] | [[File:Sulfur-trioxide-trimer-from-xtal-1967-3D-balls-B.png|thumb|right|200px|[[Ball-and-stick model]] of the ''γ''-SO<sub>3</sub> molecule]] | ||
| − | The nature of solid SO<sub>3</sub> is a surprisingly complex area because of structural changes caused by traces of water.<ref>{{Holleman&Wiberg}}</ref> Upon condensation of the gas, absolutely pure SO<sub>3</sub> condenses into a trimer, which is often called ''γ''-SO<sub>3</sub>. This molecular form is a colorless solid with a melting point of 16.8 °C. It adopts a cyclic structure described as [S(=O)<sub>2</sub>(''μ''-O)]<sub>3</sub>.<ref name="G&E">{{Greenwood&Earnshaw1st|pages=832–33}}.</ref> | + | The nature of solid SO<sub>3</sub> is a surprisingly complex area because of structural changes caused by traces of water.<ref>{{Holleman&Wiberg}}.</ref> Upon condensation of the gas, absolutely pure SO<sub>3</sub> condenses into a trimer, which is often called ''γ''-SO<sub>3</sub>. This molecular form is a colorless solid with a melting point of 16.8 °C. It adopts a cyclic structure described as [S(=O)<sub>2</sub>(''μ''-O)]<sub>3</sub>.<ref name="G&E">{{Greenwood&Earnshaw1st|pages=832–33}}.</ref> |
| − | If SO<sub>3</sub> is condensed above 27 °C, then ''α''-"SO<sub>3</sub>" forms, which has a melting point of 62.3°C. ''α''-SO<sub>3</sub> is fibrous in appearance, like [[asbestos]] (with which it has no chemical relationship). Structurally, it is the [[polymer]] [S(=O)<sub>2</sub>(''μ''-O)]<sub>''n''</sub>. Each end of the polymer is terminated with OH groups (hence ''α''-"SO<sub>3</sub>" is not really a form of SO<sub>3</sub>). ''β''-SO<sub>3</sub>, 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.<ref name="Merck"> | + | If SO<sub>3</sub> is condensed above 27 °C, then ''α''-"SO<sub>3</sub>" forms, which has a melting point of 62.3°C. ''α''-SO<sub>3</sub> is fibrous in appearance, like [[asbestos]] (with which it has no chemical relationship). Structurally, it is the [[polymer]] [S(=O)<sub>2</sub>(''μ''-O)]<sub>''n''</sub>. Each end of the polymer is terminated with OH groups (hence ''α''-"SO<sub>3</sub>" is not really a form of SO<sub>3</sub>). ''β''-SO<sub>3</sub>, 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.<ref name="Merck">{{Merck9th|8775}}.</ref> |
Relative vapor pressures of solid SO<sub>3</sub> are alpha < beta < gamma at identical temperatures, indicative of their relative [[molecular weight]]s. Liquid sulfur trioxide has vapor pressure consistent with the gamma form. Thus heating a crystal of ''α''-SO<sub>3</sub> 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."<ref name="Merck"/> | Relative vapor pressures of solid SO<sub>3</sub> are alpha < beta < gamma at identical temperatures, indicative of their relative [[molecular weight]]s. Liquid sulfur trioxide has vapor pressure consistent with the gamma form. Thus heating a crystal of ''α''-SO<sub>3</sub> 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."<ref name="Merck"/> | ||
Revision as of 17:08, 24 August 2009
| Sulfur trioxide | |
|---|---|
 |
 |
| IUPAC name | Sulfur trioxide |
| Other names | Sulfuric anhydride Sulfan |
| Identifiers | |
| CAS number | [] |
| UN number | 1829 |
| RTECS | WT4830000 |
| Properties | |
| Chemical formula | SO3 |
| Molar mass | 80.06 g/mol |
| Density | 1.92 g/cm3, liquid |
| Melting point |
16.9 °C |
| Boiling point |
45 °C |
| Solubility in water | hydrolyses |
| Thermochemistry | |
| Std enthalpy of formation ΔfH |
−397.77 kJ/mol |
| Standard molar entropy S |
256.77 J K−1 mol−1 |
| Hazards | |
| Material safety data sheet (MSDS) | ICSC 1202 |
| EU index number | 016-019-00-2 |
| EU classification | Corrosive (C) |
| R-phrases | Template:R14, Template:R35, Template:R37 |
| S-phrases | Template:S1/2, Template:S26, Template:S30, Template:S45 |
| NFPA 704 |
 |
| Flash point | Non-flammable |
| Related compounds | |
| Other cations | Selenium trioxide Tellurium trioxide |
| Other sulfur oxides | Sulfur monoxide Sulfur dioxide |
| Other compounds | Sulfuric acid |
| Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa) | |
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.
Contents
Structure and bonding
Gaseous SO3 is a trigonal planar molecule of D3h symmetry, as predicted by VSEPR theory.
In terms of electron-counting formalisms, 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 molecules.
Sulfur trioxide also exhibits hybridization.
Chemical reactions
SO3 is the anhydride of H2SO4. Thus, the following reaction occurs:
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 + SCl2 → SOCl2 + SO2
SO3 is a strong Lewis acid readily forming crystalline complexes with pyridine, dioxane and trimethylamine which can be used as sulfonating agents.[1]
Preparation
Sulfur trioxide can be prepared in the laboratory by the two-stage pyrolysis of sodium bisulfate. Sodium pyrosulfate 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. 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.
Structure of solid SO3
The nature of solid SO3 is a surprisingly complex area because of structural changes caused by traces of water.[2] 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.[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 (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.[4]
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."[4]
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 carbohydrates.[4]
Application
In process plant environment, SO3 gas is mixed into flue gas from combustion to make the ashes charged up before flowing through electrostatic precipitators. The electrostatic precipitators will then trap the ashes, making cleaner process emission possible.
In popular culture
Sulfur trioxide is mentioned in the Emergency! episode "The Old Engine Cram" which aired in the United States on 20 September 1975.
Sources
See also
References
- ↑ Cotton, F. Albert; Wilkinson, Geoffrey; Murillo, Carlos A.; Bochmann, Manfred Advanced Inorganic Chemistry, 6th ed.; Wiley-Interscience: New York, 1999. ISBN 0-471-19957-5
- ↑ Holleman, A. F.; Wiberg, E. Inorganic Chemistry; Academic Press: San Diego, 2001. ISBN 0-12-352651-5.
- ↑ Greenwood, Norman N.; Earnshaw, A. Chemistry of the Elements; Pergamon: Oxford, 1984; pp 832–33. ISBN 0-08-022057-6.
- ↑ 4.0 4.1 4.2 The Merck Index: An Encyclopedia of Chemicals, Drugs, and Biologicals, 9th ed.; Merck, 8775.
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