Methanesulfonic acid

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Methanesulfonic acid
Structural formula of methanesulfonic acid.svg
Methanesulfonic-acid-3D-balls.png
Names
Preferred IUPAC name
Methanesulfonic acid
Other names
Methylsulfonic acid, MSA; Mesylic acid
Identifiers
3D model (JSmol)
1446024
ChEBI
ChemSpider
ECHA InfoCard 100.000.817 OOjs UI icon edit-ltr-progressive.svg
EC Number
  • 200-898-6
1681
PubChem CID
UNII
UN number 2585
  • InChI=1S/CH4O3S/c1-5(2,3)4/h1H3,(H,2,3,4) Yes check.svgY
    Key: AFVFQIVMOAPDHO-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/CH4O3S/c1-5(2,3)4/h1H3,(H,2,3,4)/f/h2H
  • InChI=1/CH4O3S/c1-5(2,3)4/h1H3,(H,2,3,4)
    Key: AFVFQIVMOAPDHO-UHFFFAOYAS
  • O=S(=O)(O)C
Properties
CH4O3S
Molar mass 96.10 g·mol−1
AppearanceClear, colourless liquid
Density 1.48 g/cm3
Melting point 17 to 19 °C (63 to 66 °F; 290 to 292 K)
Boiling point 167 °C (333 °F; 440 K) at 10 mmHg, 122 °C/1 mmHg
miscible
Solubility Miscible with methanol, diethyl ether.
Immiscible with hexane
log P −2.424 [1]
Acidity (pKa)−1.9 [2]
Hazards
GHS labelling:
GHS-pictogram-acid.svg
Danger
H314
P260, P264, P280, P301+P330+P331, P303+P361+P353, P304+P340, P305+P351+P338, P310, P321, P363, P405, P501
Safety data sheet (SDS) Oxford MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)

Methanesulfonic acid (MsOH) or methanesulphonic acid (in British English) is an organosulfuric, colorless liquid with the molecular formula CH3SO3H and structure H3CS(=O)2OH . It is the simplest of the alkylsulfonic acids (R−S(=O)2−OH). Salts and esters of methanesulfonic acid are known as mesylates (or methanesulfonates, as in ethyl methanesulfonate). It is hygroscopic in its concentrated form. Methanesulfonic acid can dissolve a wide range of metal salts, many of them in significantly higher concentrations than in hydrochloric acid (HCl) or sulfuric acid (H2SO4). [3]

Contents

History and manufacturing

The first commercial production of MSA, developed in the 1940s by Standard Oil of Indiana, was based on oxidation of dimethylsulfide by O
2
from air. Although inexpensive, this process suffered from a poor product quality and explosion hazards.

In 1967, the Pennwalt Corporation (USA) developed a different process for dimethylsulfide (as a water-based emulsion) oxidation using chlorine, followed by extraction-purification. In 2022 this chlorine-oxidation process was used only by Arkema (France) for making high-purity MSA. This process is not popular on a large scale, because it co-produces large quantities of hydrochloric acid.

Between years 1970 and 2000 MSA was used only on a relatively small-scale in niche markets (for example, in the microelectronic and electroplating industries since the 1980s), which was mainly due to its rather high price and limited availability. However, this situation changed around 2003, when BASF launched commercial production of MSA in Ludwigshafen based on a modified version of the aforementioned air oxidation process, oxidising dimethyldisulfide with nitric acid which is then restored using atmospheric oxygen. The former is produced in one step from methanol from syngas, hydrogen and sulfur. [4]

An even better (lower-cost and environmentally friendlier) process of making methanesulfonic acid was developed in 2016 by Grillo-Werke AG (Germany). It is based on a direct reaction between methane and oleum at around 50 °C and 100 bar in the presence of a potassium persulfate initiator. [5] This technology was acquired and commercialized by BASF in 2019. [6]

Applications

Since ca. 2000 methanesulfonic acid has become a popular replacement for other acids in numerous industrial and laboratory applications, because it:

The closely related p-toluenesulfonic acid (PTSA) is solid.

Methanesulfonic acid can be used in the generation of borane (BH3) by reacting methanesulfonic acid with NaBH4 in an aprotic solvent such as THF or DMSO, the complex of BH3 and the solvent is formed. [7]

Electroplating

Solutions of methanesulfonic acid are used for the electroplating of tin and tin-lead solders. It is displacing the use of fluoroboric acid, which releases corrosive and volatile hydrogen fluoride. [8]

Methanesulfonic acid is also a primary ingredient in rust and scale removers. [9] It is used to clean off surface rust from ceramic, tiles and porcelain which are usually susceptible to acid attack.

See also

Related Research Articles

<span class="mw-page-title-main">Ester</span> Compound derived from an acid

In chemistry, an ester is a compound derived from an acid in which the hydrogen atom (H) of at least one acidic hydroxyl group of that acid is replaced by an organyl group. Analogues derived from oxygen replaced by other chalcogens belong to the ester category as well. According to some authors, organyl derivatives of acidic hydrogen of other acids are esters as well, but not according to the IUPAC.

<span class="mw-page-title-main">Nitric acid</span> Highly corrosive mineral acid

Nitric acid is the inorganic compound with the formula HNO3. It is a highly corrosive mineral acid. The compound is colorless, but samples tend to acquire a yellow cast over time due to decomposition into oxides of nitrogen. Most commercially available nitric acid has a concentration of 68% in water. When the solution contains more than 86% HNO3, it is referred to as fuming nitric acid. Depending on the amount of nitrogen dioxide present, fuming nitric acid is further characterized as red fuming nitric acid at concentrations above 86%, or white fuming nitric acid at concentrations above 95%.

<span class="mw-page-title-main">Perchloric acid</span> Chemical compound

Perchloric acid is a mineral acid with the formula HClO4. Usually found as an aqueous solution, this colorless compound is a stronger acid than sulfuric acid, nitric acid and hydrochloric acid. It is a powerful oxidizer when hot, but aqueous solutions up to approximately 70% by weight at room temperature are generally safe, only showing strong acid features and no oxidizing properties. Perchloric acid is useful for preparing perchlorate salts, especially ammonium perchlorate, an important rocket fuel component. Perchloric acid is dangerously corrosive and readily forms potentially explosive mixtures.

Hydroboration–oxidation reaction is a two-step hydration reaction that converts an alkene into an alcohol. The process results in the syn addition of a hydrogen and a hydroxyl group where the double bond had been. Hydroboration–oxidation is an anti-Markovnikov reaction, with the hydroxyl group attaching to the less-substituted carbon. The reaction thus provides a more stereospecific and complementary regiochemical alternative to other hydration reactions such as acid-catalyzed addition and the oxymercuration–reduction process. The reaction was first reported by Herbert C. Brown in the late 1950s and it was recognized in his receiving the Nobel Prize in Chemistry in 1979.

<span class="mw-page-title-main">Cerium(IV) sulfate</span> Chemical compound

Cerium(IV) sulfate, also called ceric sulfate, is an inorganic compound. It exists as the anhydrous salt Ce(SO4)2 as well as a few hydrated forms: Ce(SO4)2(H2O)x, with x equal to 4, 8, or 12. These salts are yellow to yellow/orange solids that are moderately soluble in water and dilute acids. Its neutral solutions slowly decompose, depositing the light yellow oxide CeO2. Solutions of ceric sulfate have a strong yellow color. The tetrahydrate loses water when heated to 180-200 °C.

<span class="mw-page-title-main">Mesylate</span> Salt or ester of methanesulfonic acid (CH₃–SO₂–OH)

In organosulfur chemistry, a mesylate is any salt or ester of methanesulfonic acid. In salts, the mesylate is present as the CH3SO−3 anion. When modifying the international nonproprietary name of a pharmaceutical substance containing the group or anion, the spelling used is sometimes mesilate.

<span class="mw-page-title-main">Sulfonic acid</span> Organic compounds with the structure R−S(=O)2−OH

In organic chemistry, sulfonic acid refers to a member of the class of organosulfur compounds with the general formula R−S(=O)2−OH, where R is an organic alkyl or aryl group and the S(=O)2(OH) group a sulfonyl hydroxide. As a substituent, it is known as a sulfo group. A sulfonic acid can be thought of as sulfuric acid with one hydroxyl group replaced by an organic substituent. The parent compound is the parent sulfonic acid, HS(=O)2(OH), a tautomer of sulfurous acid, S(=O)(OH)2. Salts or esters of sulfonic acids are called sulfonates.

<span class="mw-page-title-main">Sulfamic acid</span> Chemical compound

Sulfamic acid, also known as amidosulfonic acid, amidosulfuric acid, aminosulfonic acid, sulphamic acid and sulfamidic acid, is a molecular compound with the formula H3NSO3. This colourless, water-soluble compound finds many applications. Sulfamic acid melts at 205 °C before decomposing at higher temperatures to water, sulfur trioxide, sulfur dioxide and nitrogen.

<span class="mw-page-title-main">Dimethyl sulfide</span> Chemical compound

Dimethyl sulfide (DMS) or methylthiomethane is an organosulfur compound with the formula (CH3)2S. The simplest thioether, it is a flammable liquid that boils at 37 °C (99 °F) and has a characteristic disagreeable odor. It is a component of the smell produced from cooking of certain vegetables, notably maize, cabbage, beetroot, and seafoods. It is also an indication of bacterial contamination in malt production and brewing. It is a breakdown product of dimethylsulfoniopropionate (DMSP), and is also produced by the bacterial metabolism of methanethiol.

<i>p</i>-Toluenesulfonic acid Chemical compound

p-Toluenesulfonic acid (PTSA, pTSA, or pTsOH) or tosylic acid (TsOH) is an organic compound with the formula CH3C6H4SO3H. It is a white extremely hygroscopic solid that is soluble in water, alcohols, and other polar organic solvents. The CH3C6H4SO2 group is known as the tosyl group and is often abbreviated as Ts or Tos. Most often, TsOH refers to the monohydrate, TsOH.H2O.

<span class="mw-page-title-main">Nitrosyl chloride</span> Chemical compound

Nitrosyl chloride is the chemical compound with the formula NOCl. It is a yellow gas that is commonly encountered as a component of aqua regia, a mixture of 3 parts concentrated hydrochloric acid and 1 part of concentrated nitric acid. It is a strong electrophile and oxidizing agent. It is sometimes called Tilden's reagent, after William A. Tilden, who was the first to produce it as a pure compound.

<span class="mw-page-title-main">Fluoroboric acid</span> Chemical compound

Fluoroboric acid or tetrafluoroboric acid is an inorganic compound with the simplified chemical formula H+[BF4]. Unlike other strong acids like H2SO4 or HClO4, the pure tetrafluoroboric acid does not exist. The term "fluoroboric acid" refers to a range of chemical compounds, depending on the solvent. The H+ in the simplified formula of fluoroboric acid represents the solvated proton. The solvent can be any suitable Lewis base. For instance, if the solvent is water, fluoroboric acid can be represented by the formula [H3O]+[BF4], although more realistically, several water molecules solvate the proton: [H(H2O)n]+[BF4]. The ethyl ether solvate is also commercially available, where the fluoroboric acid can be represented by the formula [H( 2O)n]+[BF4], where n is most likely 2.

Methanesulfonyl chloride is an organosulfur compound with the formula CH3SO2Cl. Using the organic pseudoelement symbol Ms for the methanesulfonyl group CH3SO2–, it is frequently abbreviated MsCl in reaction schemes or equations. It is a colourless liquid that dissolves in polar organic solvents but is reactive toward water, alcohols, and many amines. The simplest organic sulfonyl chloride, it is used to make methanesulfonates and to generate the elusive molecule sulfene.

<span class="mw-page-title-main">Catecholborane</span> Chemical compound

Catecholborane (abbreviated HBcat) is an organoboron compound that is useful in organic synthesis. This colourless liquid is a derivative of catechol and a borane, having the formula C6H4O2BH.

<span class="mw-page-title-main">Chloroauric acid</span> Chemical compound

Chloroauric acid is an inorganic compound with the chemical formula H[AuCl4]. It forms hydrates H[AuCl4nH2O. Both the trihydrate and tetrahydrate are known. Both are orange-yellow solids consisting of the planar [AuCl4] anion. Often chloroauric acid is handled as a solution, such as those obtained by dissolution of gold in aqua regia. These solutions can be converted to other gold complexes or reduced to metallic gold or gold nanoparticles.

<span class="mw-page-title-main">Methanesulfonic anhydride</span> Chemical compound

Methanesulfonic anhydride (Ms2O) is the acid anhydride of methanesulfonic acid. Like methanesulfonyl chloride (MsCl), it may be used to generate mesylates (methanesulfonyl esters).

<span class="mw-page-title-main">Borane dimethylsulfide</span> Chemical compound

Borane dimethylsulfide (BMS) is a chemical compound with the chemical formula BH3·S(CH3)2. It is an adduct between borane molecule and dimethyl sulfide molecule. It is a complexed borane reagent that is used for hydroborations and reductions. The advantages of BMS over other borane reagents, such as borane-tetrahydrofuran, are its increased stability and higher solubility. BMS is commercially available at much higher concentrations than its tetrahydrofuran counterpart and does not require sodium borohydride as a stabilizer, which could result in undesired side reactions. In contrast, BH3·THF requires sodium borohydride to inhibit reduction of THF to tributyl borate. BMS is soluble in most aprotic solvents.

<span class="mw-page-title-main">Zinc–cerium battery</span>

Zinc–cerium batteries are a type of redox flow battery first developed by Plurion Inc. (UK) during the 2000s. In this rechargeable battery, both negative zinc and positive cerium electrolytes are circulated though an electrochemical flow reactor during the operation and stored in two separated reservoirs. Negative and positive electrolyte compartments in the electrochemical reactor are separated by a cation-exchange membrane, usually Nafion (DuPont). The Ce(III)/Ce(IV) and Zn(II)/Zn redox reactions take place at the positive and negative electrodes, respectively. Since zinc is electroplated during charge at the negative electrode this system is classified as a hybrid flow battery. Unlike in zinc–bromine and zinc–chlorine redox flow batteries, no condensation device is needed to dissolve halogen gases. The reagents used in the zinc-cerium system are considerably less expensive than those used in the vanadium flow battery.

<span class="mw-page-title-main">Borane–tetrahydrofuran</span> Chemical compound

Borane–tetrahydrofuran is an adduct derived from borane and tetrahydrofuran (THF). These solutions, which are colorless, are used for reductions and hydroboration, reactions that are useful in synthesis of organic compounds. The use of borane–tetrahydrofuran has been displaced by borane–dimethylsulfide, which has a longer shelf life and effects similar transformations.

Borane, also known as borine, is an unstable and highly reactive molecule with the chemical formula BH
3
. The preparation of borane carbonyl, BH3(CO), played an important role in exploring the chemistry of boranes, as it indicated the likely existence of the borane molecule. However, the molecular species BH3 is a very strong Lewis acid. Consequently, it is highly reactive and can only be observed directly as a continuously produced, transitory, product in a flow system or from the reaction of laser ablated atomic boron with hydrogen. It normally dimerizes to diborane in the absence of other chemicals.

References

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  2. Guthrie, J. Peter (September 1978). "Hydrolysis of esters of oxy acids: pKa values for strong acids; Brønsted relationship for attack of water at methyl; free energies of hydrolysis of esters of oxy acids; and a linear relationship between free energy of hydrolysis and pKa holding over a range of 20 pK units". Canadian Journal of Chemistry. 56 (17): 2342–2354. doi: 10.1139/v78-385 .
  3. Gernon, M. D.; Wu, M.; Buszta, T.; Janney, P. (1999). "Environmental benefits of methanesulfonic acid: comparative properties and advantages". Green Chemistry. 1 (3): 127–140. doi:10.1039/a900157c.
  4. USpatent 6531629B1,Matthias Eiermann, Christian Tragut, Klaus Ebel,"Method of producing alkanesulfonic acid",issued 2003-03-11, assigned to BASF SE
  5. Lobree, Lisa J.; Bell, Alexis T. (2001). "K2S2O8-Initiated Sulfonation of Methane to Methanesulfonic Acid". Ind. Eng. Chem. Res. 40 (3): 736–742. doi:10.1021/ie000725b.
  6. Binnemans, K.; Jones, P. T. (2022). "Methanesulfonic Acid (MSA) in Hydrometallurgy". Journal of Sustainable Metallurgy. 20. doi: 10.1007/s40831-022-00641-6 .
  7. Lobben, Paul C.; Leung, Simon Shun-Wang; Tummala, Srinivas (2004). "Integrated Approach to the Development and Understanding of the Borane Reduction of a Carboxylic Acid". Org. Process Res. Dev. 8 (6): 1072–1075. doi:10.1021/op049910h.
  8. Balaji, R.; Pushpavanam, Malathy (2003). "Methanesulphonic acid in electroplating related metal finishing industries". Transactions of the Imf. 81 (5): 154–158. doi:10.1080/00202967.2003.11871526. S2CID   91584456.
  9. "Archived copy" (PDF). Archived from the original (PDF) on 2016-03-04. Retrieved 2015-12-01.{{cite web}}: CS1 maint: archived copy as title (link)