Sulfamic acid
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| Names | |||
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| IUPAC name
Sulfamic acid | |||
| Identifiers | |||
5329-14-6  | |||
| ChEBI | CHEBI:9330 | ||
| ChEMBL | ChEMBL68253 | ||
| ChemSpider | 5767 | ||
| EC Number | 226-218-8 | ||
| Jmol 3D model | Interactive image | ||
| PubChem | 5987 | ||
| RTECS number | WO5950000 | ||
| UN number | 2967 | ||
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| Properties | |||
| H3NSO3 | |||
| Molar mass | 97.10 g/mol | ||
| Appearance | white crystals | ||
| Density | 2.15 g/cm3 | ||
| Melting point | 205 °C (401 °F; 478 K) decomposes | ||
| Moderate, with slow hydrolysis | |||
| Solubility | Moderately soluble in DMF, Slightly soluble in MeOH, Insoluble in hydrocarbons | ||
| Acidity (pKa) | 1.0[1] | ||
| Hazards | |||
| Safety data sheet | ICSC 0328 | ||
| EU classification (DSD) |
Irritant (Xi) | ||
| R-phrases | R36/38 R52/53 | ||
| S-phrases | (S2) S26 S28 S61 | ||
| Related compounds | |||
| Other cations |
Ammonium sulfamate | ||
| Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa). | |||
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| Infobox references | |||
Sulfamic acid, also known as amidosulfonic acid, amidosulfuric acid, aminosulfonic acid, and sulfamidic acid, is a molecular compound with the formula H3NSO3. This colorless, water-soluble compound finds many applications. Sulfamic acid melts at 205 °C before decomposing at higher temperatures to H2O, SO3, SO2, and N2.[2]
Sulfamic acid (H3NSO3) may be considered an intermediate compound between sulfuric acid (H2SO4), and sulfamide (H4N2SO2), effectively – though see below – replacing an –OH group with an –NH2 group at each step. This pattern can extend no further in either direction without breaking down the –SO2 group. Sulfamates are derivatives of sulfamic acid.
Production
Sulfamic acid is produced industrially by treating urea with a mixture of sulfur trioxide and sulfuric acid (or oleum). The conversion is conducted in two stages:
- OC(NH2)2 + SO3 → OC(NH2)(NHSO3H)
- OC(NH2)(NHSO3H) + H2SO4 → CO2 + 2 H3NSO3
In this way, approximately 96,000 tons were produced in 1995.[3]
Structure and reactivity
The compound is well described by the formula H3NSO3, not the tautomer H2NSO2(OH). The relevant bond distances are S=O, 1.44 and S–N 1.77 Å. The greater length of the S–N distance is consistent with a single bond.[4] Furthermore, a neutron diffraction study located the hydrogen atoms, all three of which are 1.03 Å distant from nitrogen.[5] In the solid state, the molecule of sulfamic acid is well described by a zwitterionic form :
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| acid zwitterion in the crystal[5] |
Water solutions are unstable and slowly hydrolyze to ammonium bisulfate, but the crystalline solid is indefinitely stable under ordinary storage conditions. Its behavior resembles that of urea, (H2N)2CO. Both feature amino groups linked to electron-withdrawing centers that can participate in delocalized bonding. Both liberate ammonia upon heating in water.
Acid-base reactions
Sulfamic acid is a moderately strong acid, Ka = 1.01 x 10−1. Because the solid is non-hygroscopic, it is used as a standard in acidimetry (quantitative assays of acid content).
- H3NSO3 + NaOH → NaH2NSO3 + H2O
Double deprotonation can be effected in NH3 solution to give HNSO2−
3.[6]
- H3NSO3 + 2 NH3 → HNSO2−
3 + 2 NH+
4
Reaction with nitric and nitrous acids
With HNO2, sulfamic acid reacts to give N2, while with HNO3, it affords N2O.
- HNO2 + H3NSO3 → H2SO4 + N2 + H2O
- HNO3 + H3NSO3 → H2SO4 + N2O + H2O
Reaction with hypochlorite
The reaction of excess hypochlorite with sulfamic acid or a sulfamate salt gives rise reversibly to both N-chlorosulfamate and N,N-dichlorosulfamate.[7][8][9]
- HClO + H2NSO3H → ClNHSO3H + H2O
- HClO + ClNHSO3H ⇌ Cl2NSO3H + H2O
Consequently sulfamic acid is used as hypochlorite scavenger in the oxidation of aldehydes with chlorite such as the Pinnick oxidation.
Reaction with alcohol
Upon heating sulfamic acid will react with alcohols to form the corresponding organosulfates. It is more expensive than other reagents for doing this, such as chlorosulfonic acid or oleum, but is also significantly milder and will not sulfonate aromatic rings. Products are produced as their ammonium salts.
- ROH + H2NSO3H → ROS(O)
2O−
+ NH+
4
Applications
Sulfamic acid is mainly a precursor to sweet-tasting compounds. Reaction with cyclohexylamine followed by addition of NaOH gives C6H11NHSO3Na, sodium cyclamate. Related compounds are also sweeteners, see acesulfame potassium.
Sulfamates have been used in the design of many types of therapeutic agents such as antibiotics, nucleoside/nucleotide human immunodeficiency virus (HIV) reverse transcriptase inhibitors, HIV protease inhibitors (PIs), anti-cancer drugs (steroid sulfatase and carbonic anhydrase inhibitors), anti-epileptic drugs, and weight loss drugs.[10]
Cleaning agent
Sulfamic acid is used as an acidic cleaning agent, sometimes pure or as a component of proprietary mixtures, typically for metals and ceramics. It is frequently used for removing rust and limescale, replacing the more volatile and irritating hydrochloric acid, which is however cheaper. It is often a component of household descaling agents, for example, Lime-A-Way Thick Gel contains up to 8% sulfamic acid and pH 2–2.2,[11] or detergents used for removal of limescale. When compared to most of the common strong mineral acids, sulfamic acid has desirable water descaling properties, low volatility, low toxicity. It forms water-soluble salts of calcium and ferric iron.
Importantly, sulfamic acid is preferable to use in household in comparison to hydrochloric acid for its intrinsic safety. If erroneously mixed with hypochlorite based products such as bleach, it does not form chlorine gas, where the most common acids would; the reaction (neutralization) with NH3, produces a salt as depicted in the section above.
It also finds applications in the industrial cleaning of dairy and brew-house equipment. Although it is considered less corrosive than hydrochloric acid, corrosion inhibitors are often added to commercial cleansers of which it is a component. Some of its domestic use, e.g. Easy-Off, for descaling include home coffee and espresso equipment and in denture cleaners.
Other uses
- Catalyst for esterification process
- Dye and pigment manufacturing
- Herbicide
- Coagulator for urea-formaldehyde resins
- Ingredient in fire extinguishing media. Sulfamic acid is the main raw material for ammonium sulfamate which is a widely used herbicide and fire retardant material for household product.
- Pulp and paper industry as a chloride stabilizer
- Synthesis of nitrous oxide by reaction with nitric acid
- The deprotonated form (sulfamate) is a common counterion for nickel(II) in electroplating.
Silver polishing
According to the label on the consumer product, the liquid silver cleaning product TarnX contains thiourea, a detergent, and sulfamic acid.
References
- ↑ Candlin, J. P.; Wilkins, R. G. (1960). "828. Sulphur?nitrogen compounds. Part I. The hydrolysis of sulphamate ion in perchloric acid". Journal of the Chemical Society (Resumed): 4236. doi:10.1039/JR9600004236.
- ↑ Yoshikubo, K.; Suzuki, M. (2000). "Sulfamic Acid and Sulfamates". Kirk-Othmer Encyclopedia of Chemical Technology. doi:10.1002/0471238961.1921120625151908.a01. ISBN 0471238961.
- ↑ A. Metzger "Sulfamic Acid" in Ullmann's Encyclopedia of Industrial Chemistry, 2012, Wily-VCH, Weinheim. doi:10.1002/14356007.a25_439
- ↑ Bats, J. W.; Coppens, P.; Koetzle, T. F. (1977). "The experimental charge density in sulfur-containing molecules. A study of the deformation electron density in sulfamic acid at 78 K by X-ray and neutron diffraction". Acta Crystallographica Section B Structural Crystallography and Crystal Chemistry 33: 37. doi:10.1107/S0567740877002568.
- 1 2 Sass, R. L. (1960). "A neutron diffraction study on the crystal structure of sulfamic acid". Acta Crystallographica 13 (4): 320–324. doi:10.1107/S0365110X60000789.
- ↑ Clapp, L. B. (1943). "Sulfamic acid and its uses". Journal of Chemical Education 20 (4): 189–346. doi:10.1021/ed020p189.
- ↑ US 3328294
- ↑ FR 2087248
- ↑ Benson, G. A.; Spillane, W. J. (1980). "Sulfamic acid and its N-substituted derivatives". Chemical Reviews 80 (2): 151. doi:10.1021/cr60324a002.
- ↑ Winum, J. Y.; Scozzafava, A.; Montero, J. L.; Supuran, C. T. (2005). "Sulfamates and their therapeutic potential". Medicinal Research Reviews 25 (2): 186–228. doi:10.1002/med.20021. PMID 15478125.
- ↑ Benckiser, Reckitt. "Material Safety Data Sheet - Lime-A-Way Lime, Calcium and Rust Cleaner (Trigger Spray)" (PDF). hardwarestore.com. Retrieved 17 November 2011.
External links
- "Chemical Sampling Information - Sulfamic Acid". Occupational Health & Safety Administration. 6 May 1997. Retrieved 17 November 2011.
- Cremlyn, R.J. (1996). An Introduction to Organosulfur Chemistry. Chichester: John Wiley and Sons. ISBN 978-0-471-95512-2.
- Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 0-08-037941-9.
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