- Maleic acid
-
Not to be confused with Malic acid or malonic acid.
Maleic acid 
Maleic acid
(Z)-Butenedioic acidOther names(Z)-butenedioic acid, cis-butenedioic acid, malenic acid, maleinic acid, toxilic acidIdentifiers CAS number 110-16-7 
ChemSpider 392248 UNII 91XW058U2C EC number 203-742-5 KEGG C01384 ChEBI CHEBI:18300 
ChEMBL CHEMBL539648 RTECS number OM9625000 Jmol-3D images Image 1 - O=C(O)\C=C/C(=O)O
- InChI=1S/C4H4O4/c5-3(6)1-2-4(7)8/h1-2H,(H,5,6)(H,7,8)/b2-1-
Key: VZCYOOQTPOCHFL-UPHRSURJSA-N
InChI=1/C4H4O4/c5-3(6)1-2-4(7)8/h1-2H,(H,5,6)(H,7,8)/b2-1-
Key: VZCYOOQTPOCHFL-UPHRSURJBG
Properties Molecular formula C4H4O4 Molar mass 116.07 g mol−1 Appearance White solid Density 1.59 g/cm³ [1] Melting point 135 °C, 408 K, 275 °F (decomposes[2])
Solubility in water 788 g/L[2] Acidity (pKa) pka1 = 1.9
pka2 = 6.07 [3]Hazards MSDS MSDS from J. T. Baker EU classification Harmful (Xn) R-phrases R22 R36/37/38 S-phrases (S2) S26 S28 S37 NFPA 704 
030Related compounds Related carboxylic acids fumaric acid
succinic acid
crotonic acidRelated compounds maleic anhydride
maleimide
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Except where noted otherwise, data are given for materials in their standard state (at 25 °C, 100 kPa)Infobox references Maleic acid is an organic compound that is a dicarboxylic acid, a molecule with two carboxyl groups. Maleic acid is the cis-isomer of butenedioic acid, whereas fumaric acid is the trans-isomer. It is mainly used as a precursor to fumaric acid, and relative to its parent maleic anhydride, maleic acid has few applications.
Contents
Physical properties
Maleic acid is a less stable molecule than fumaric acid. The difference in heat of combustion is 22.7 kJ·mol−1. The heat of combustion is -1355 kJ/mole.[4] Maleic acid is more soluble in water, than fumaric acid. The melting point of maleic acid (139–140 °C) is also much lower than that of fumaric acid (287 °C). Both properties of maleic acid can be explained on account of the intramolecular hydrogen bonding[5] that takes place in maleic acid at the expense of intermolecular interactions, and that are not possible in fumaric acid for geometric reasons.
Production and industrial applications
In industry, maleic acid is derived by hydrolysis of maleic anhydride, the latter being produced by oxidation of benzene or butane.[6]
Isomerization to fumaric acid
The major industrial use of maleic acid is its conversion to fumaric acid. This conversion, an isomerization, is catalysed by a variety of reagents, such as mineral acids and thiourea. Again, the large difference in water solubility makes fumaric acid purification easy.
The isomerization is a popular topic in schools. Maleic acid and fumaric acid do not spontaneously interconvert because rotation around a carbon carbon double bond is not energetically favourable. However, conversion of the cis isomer into the trans isomer is possible by photolysis in the presence of a small amount of bromine.[7] Light converts elemental bromine into a bromine radical, which attacks the alkene in a radical addition reaction to a bromo-alkane radical; and now single bond rotation is possible. The bromine radicals recombine and fumaric acid is formed. In another method (used as a classroom demonstration), maleic acid is transformed into fumaric acid through the process of heating the maleic acid in 12 M hydrochloric acid solution. Reversible addition (of H+) leads to free rotation about the central C-C bond and formation of the more stable and less soluble fumaric acid.
Maleic acid is an industrial raw material for the production of glyoxylic acid by ozonolysis.[8]
Other reactions
Although not practised commercially, maleic acid can be converted into maleic anhydride by dehydration, to malic acid by hydration, and to succinic acid by hydrogenation (ethanol / palladium on carbon).[9] It reacts with thionyl chloride or phosphorus pentachloride to give the maleic acid chloride (it is not possible to isolate the mono acid chloride). Maleic acid, being electrophilic, participates as a dienophile in many Diels-Alder reactions.
Maleates
The maleate ion is the ionized form of maleic acid. The maleate ion is useful in biochemistry as an inhibitor of transaminase reactions. Maleic acid esters are also called maleates, for instance dimethyl maleate.
References
- ^ Budavari, Susan, ed. (1996), The Merck Index: An Encyclopedia of Chemicals, Drugs, and Biologicals (12th ed.), Merck, ISBN 0911910123
- ^ a b Record in the GESTIS Substance Database from the IFA
- ^ CRC Handbook of Chemistry and Physics, 73rd ed.; CRC Press: Boca Raton, FL., 1993
- ^ Maleic Anhydride, Maleic Acid, and Fumaric Acid, Huntsman Petrochemical Corporation
- ^ M. N. G James, G. J. B Williams (1974). "A Refinement of the Crystal Structure of Maleic Acid". Acta Crystallographica B30 (5) (5): 1249–1275. doi:10.1107/S0567740874004626.
- ^ Kurt Lohbeck, Herbert Haferkorn, Werner Fuhrmann and Norbert Fedtke "Maleic and Fumaric Acids" in Ullmann's Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim, 2000. doi:10.1002/14356007.a16_053
- ^ Light isomerization experiment (from the University of Regensburg, with video)
- ^ DSM glyoxylic acid production
- ^ Kwesi Amoa (2007). "Catalytic Hydrogenation of Maleic Acid at Moderate Pressures A Laboratory Demonstration". Journal of Chemical Education 84 (12): 1948. doi:10.1021/ed084p1948.
External links
- International Chemical Safety Card 1186
- Titration of Fumaric and Maleic Acid (from the University of Regensburg, about pH, solubility and melting point)
- Calculator: Water and solute activities in aqueous maleic acid
Categories:- Dicarboxylic acids
- Alkenes
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