Maleic acid

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Maleic acid
Skeletal formula of maleic acid
Ball-and-stick model of the maleic acid molecule
Space-filling model of the maleic acid molecule
Sample of maleic acid.jpg
Identifiers
CAS number110-16-7 YesY
ChemSpider392248 YesY
UNII91XW058U2C YesY
EC number203-742-5
KEGGC01384 YesY
ChEBICHEBI:18300 YesY
ChEMBLCHEMBL539648 YesY
RTECS numberOM9625000
Jmol-3D imagesImage 1
Properties
Molecular formulaC4H4O4
Molar mass116.07 g mol−1
AppearanceWhite solid
Density1.59 g/cm³ [1]
Melting point135 °C (275 °F; 408 K) (decomposes)[2]
Solubility in water478.8 g/L at 20 C[2]
Acidity (pKa)pka1 = 1.9
pka2 = 6.07 [3]
Hazards
MSDSMSDS from J. T. Baker
EU classificationHarmful (Xn)
R-phrasesR22 R36/37/38
S-phrases(S2) S26 S28 S37
NFPA 704
Related compounds
Related carboxylic acidsfumaric acid
succinic acid
crotonic acid
Related compoundsmaleic anhydride
maleimide
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
 YesY (verify) (what is: YesY/N?)
Infobox references
 
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Not to be confused with malic acid or malonic acid.
Maleic acid
Skeletal formula of maleic acid
Ball-and-stick model of the maleic acid molecule
Space-filling model of the maleic acid molecule
Sample of maleic acid.jpg
Identifiers
CAS number110-16-7 YesY
ChemSpider392248 YesY
UNII91XW058U2C YesY
EC number203-742-5
KEGGC01384 YesY
ChEBICHEBI:18300 YesY
ChEMBLCHEMBL539648 YesY
RTECS numberOM9625000
Jmol-3D imagesImage 1
Properties
Molecular formulaC4H4O4
Molar mass116.07 g mol−1
AppearanceWhite solid
Density1.59 g/cm³ [1]
Melting point135 °C (275 °F; 408 K) (decomposes)[2]
Solubility in water478.8 g/L at 20 C[2]
Acidity (pKa)pka1 = 1.9
pka2 = 6.07 [3]
Hazards
MSDSMSDS from J. T. Baker
EU classificationHarmful (Xn)
R-phrasesR22 R36/37/38
S-phrases(S2) S26 S28 S37
NFPA 704
Related compounds
Related carboxylic acidsfumaric acid
succinic acid
crotonic acid
Related compoundsmaleic anhydride
maleimide
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
 YesY (verify) (what is: YesY/N?)
Infobox references

Maleic acid or cis-butenedioic acid is an organic compound that is a dicarboxylic acid, a molecule with two carboxyl groups. Its chemical formula is HO2CCHCHCO2H. 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.

Physical properties[edit]

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 (135 °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[edit]

In industry, maleic acid is derived by hydrolysis of maleic anhydride, the latter being produced by oxidation of benzene or butane.[6]

Maleic acid is an industrial raw material for the production of glyoxylic acid by ozonolysis.[7]

Maleic acid may be used to form acid addition salts with drugs to make them more stable, such as indacaterol maleate.

Isomerization to fumaric acid[edit]

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.[8] 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 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.

Other reactions[edit]

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[edit]

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[edit]

  1. ^ Budavari, Susan, ed. (1996), The Merck Index: An Encyclopedia of Chemicals, Drugs, and Biologicals (12th ed.), Merck, ISBN 0911910123 
  2. ^ a b Record in the GESTIS Substance Database from the IFA
  3. ^ CRC Handbook of Chemistry and Physics, 73rd ed.; CRC Press: Boca Raton, FL., 1993
  4. ^ Maleic Anhydride, Maleic Acid, and Fumaric Acid, Huntsman Petrochemical Corporation
  5. ^ 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. 
  6. ^ 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
  7. ^ DSM glyoxylic acid production
  8. ^ Light isomerization experiment (from the University of Regensburg, with video)
  9. ^ 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[edit]