Molybdate

In chemistry a molybdate is a compound containing an oxoanion with

molybdenum in its highest oxidation state of 6. Molybdenum can form a very
large range of such oxoanions which can be discrete structures or polymeric
extended structures, although the latter are only found in the solid state.The larger
oxoanions are members of group of compounds termed polyoxometalates, and
because they contain only one type of metal atom are often called
isopolymetalates.[1] The discrete molybdenum oxoanions range in size from the
simplest MoO2− 4 , found in potassium molybdate up to extremely large structures
found in isopoly-molybdenum blues that contain for example 154 Mo atoms. The Structure of molybdate
behaviour of molybdenum is different from the other elements in group 6.
Chromium only forms the chromates, CrO2− 2− 2− 2−
4 , Cr2 O 7 , Cr3 O 10 and Cr4 O 13 ions
which are all based on tetrahedral chromium. Tungsten is similar to molybdenum
and forms many tungstates containing 6 coordinate tungsten.[2]

Contents
Examples of molybdate anions
Structure of molybdate anions 3D model of the
molybdate ion
Equilibria in aqueous solution
Peroxomolybdates
Tetrathiomolybdate
Industrial uses
Catalysis
Corrosion inhibitors
Supercapacitors
Medicine
Other
References

Examples of molybdate anions

Examples of molybdate oxoanions are:

MoO2−
4 , in e.g. Na2MoO4 and the mineral powellite, CaMoO4;
Mo2O2−
7 , as hydrated diammonium dimolybdate. The anhydrous tetrabutylammonium salt of
Mo2O2−
7 is also known;
[3]

Mo3O2−
10 in the ethylenediamine salt;
[4]

Mo4O2−
13 in the potassium salt;
[5]

Mo5O2− +
16 in the anilinium (C 6H 5NH 3 ) salt;
[6]

Mo6O2−
19 (hexa-molybdate) in the tetramethylammonium salt;
[7]
 Mo7O6−
24 in ammonium molybdate, (NH 4)6Mo7O24·4H 2O;
[8]

Mo8O4−
26 in trimethylammonium salt.
[1]

The naming of molybdates generally follows the convention of a prefix to show the number of Mo atoms
present. For example, dimolybdate for 2 molybdenum atoms; trimolybdate for 3 molybdenum atoms, etc..
Sometimes the oxidation state is added as a suffix, such as in pentamolybdate(VI). The heptamolybdate ion,
Mo7 O6−
24 , is often called "paramolybdate".

Structure of molybdate anions

The smaller anions, MoO2− 2− 2−
4 and Mo2 O 7 feature tetrahedral centres. In MoO 4 the four oxygens are
equivalent as in sulfate and chromate, with equal bond lengths and angles. Mo2 O2−
7 can be considered to be
[1]
two tetrahedra sharing a corner, i.e. with a single bridging O atom. In the larger anions molybdenum is
generally, but not exclusively, 6 coordinate with edges or vertices of the MoO6 octahedra being shared. The
octahedra are distorted, typical M-O bond lengths are:

in terminal non bridging M–O approximately 1.7 Å

in bridging M–O–M units approximately 1.9 Å

The Mo8 O4−26 anion contains both octahedral and tetrahedral molybdenum and can be isolated in 2 isomeric
forms, alpha and beta.[2]

The hexamolybdate image below shows the coordination polyhedra. The heptamolybdate image shows the
close packed nature of the oxygen atoms in the structure. The oxide ion has an ionic radius of 1.40 Å,
molybdenum(VI) is much smaller, 0.59 Å.[1] There are strong similarities between the structures of the
molybdates and the molybdenum oxides, (MoO3 , MoO2 and the "crystallographic shear" oxides, Mo9 O26 and
Mo10 O29 ) whose structures all contain close packed oxide ions.[9]

(a) [Mo6O19]2− (b) [Mo7O24]6− Hexamolybdate Heptamolybdate

Equilibria in aqueous solution

When MoO3 , molybdenum trioxide is dissolved in alkali solution the simple MoO2− 4 anion is produced. As the
pH is reduced the first species to be formed is the heptamolybdate rather than any of the smaller anions:

7 MoO2− + 6−
4 + 8 H ⇌ Mo7O24 + 4 H 2O
[2]

As the pH is decreased the octamolybdate is formed further anions with 8 and probably 16–18 Mo atoms are
present:[1]
 Mo7O6− + 4−
24 + 3 H ⇌ Mo8O26 + 2 H 2O
[2]

A further decrease leads to anions with probably 16–18 Mo atoms. However careful manipulation of the pH
and temperature coupled with very long precipitation times can cause compounds with ions that do not appear
to be in solution to be precipitated.[1]

Peroxomolybdates

Many peroxomolybdates are known. They tend to form upon treatment of molybdate salts with hydrogen
peroxide. Notable is the monomer–dimer equilibrium [Mo2 O3 (O2 )2 (H2 O)2 ]2− ⇌ [Mo2 O3 (O2 )4 (H2 O)2 ]2−.
Also known but unstable is [Mo(O2 )4 ]2− (see potassium tetraperoxochromate(V)). Some related compounds
find use as oxidants in organic synthesis.[10]

Tetrathiomolybdate

The red tetrathiomolybdate anion results when molybdate solutions are treated with hydrogen sulfide:

[NH4]2[MoO4] + 4 H2S → [NH4]2[MoS4] + 4 H2O

Like molybdate itself, MoS2−

4 undergoes condensation in the presence of acids, but these condensations are
accompanied by redox processes.

Industrial uses

Catalysis

Molybdates are widely used in catalysis. In terms of scale, the largest consumer of molybdate is as a precursor
to catalysts for hydrodesulfurization, the process by which sulfur is removed from petroleum. Bismuth
molybdates, nominally of the composition Bi9 PMo12 O52 , catalyzes ammoxidation of propylene to
acrylonitrile. Ferric molybdates are used industrially to catalyze the oxidation of methanol to formaldehyde.[11]

Corrosion inhibitors

Sodium molybdate has been used in industrial water treatment as a corrosion inhibitor. It was initially thought
that it would be a good replacement for chromate, when chromate was banned for toxicity. However,
molybdate requires high concentrations when used alone, therefore complementary corrosion inhibitors are
generally added,[12] and is mainly used in high temperature closed-loop cooling circuits.[13]. According to an
experimental study, Molybdate has been reported as an efficient biocide against microbiologically induced
corrosion (MIC), where adding 1.5 mM of Molybdate/day resulted in a 50% decrease in the corrosion rate.[14]

Supercapacitors

Molybdates (especially FeMoO4 , Fe2 (MoO4 )3 , NiMoO4 , CoMoO4 and MnMoO4 ) have been used as anode
or cathode materials in aqueous capacitors.[15][16][17][18] Due to pseudocapacitive charge storage, specific
capacitance up to 1500 F g−1 has been observed.[16]
Medicine

Radioactive molybdenum-99 in the form of molybdate is used as the parent isotope in technetium-99m
generators for nuclear medicine imaging.[19]

Other

Nitrogen fixation requires molybdoenzymes in legumes (e.g., soybeans, acacia, etc.). For this reason, fertilizers
often contain small amounts of molybdate salts. Coverage is typically less than a kilogram per acre.[11]

Molybdate chrome pigments are speciality but commercially available pigments.[11] Molybdate (usually in the
form of potassium molybdate) is also used in the analytical colorimetric testing for the concentration of silica in
solution, called the molybdenum blue method.[20] Additionally, it is used in the colorimetric determination of
phosphate quantity in association with the dye malachite green.

References
1. Greenwood, Norman N.; Earnshaw, Alan (1997). Chemistry of the Elements (2nd ed.).
Butterworth-Heinemann. ISBN 978-0-08-037941-8.
2. Cotton, F. Albert; Wilkinson, Geoffrey; Murillo, Carlos A.; Bochmann, Manfred (1999), Advanced
Inorganic Chemistry (6th ed.), New York: Wiley-Interscience, ISBN 0-471-19957-5
3. V. W. Day; M. F. Fredrich; W. G. Klemperer; W. Shum (1977). "Synthesis and characterization of
2−
the dimolybdate ion, Mo2O7 ". Journal of the American Chemical Society. 99 (18): 6146.
doi:10.1021/ja00460a074 (https://doi.org/10.1021%2Fja00460a074).
4. Guillou N.; Ferey G. (August 1997). "Hydrothermal Synthesis and Crystal Structure of
Anhydrous Ethylenediamine Trimolybdate (C2H10N2)[Mo3O10]". Journal of Solid State
Chemistry. 132 (1): 224–227(4). Bibcode:1997JSSCh.132..224G (https://ui.adsabs.harvard.ed
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97.7502).
5. B. M. Gatehouse; P. Leverett (1971). "Crystal structure of potassium tetramolybdate,
K2Mo4O13, and its relationship to the structures of other univalent metal polymolybdates". J.
Chem. Soc. A: 2107–2112. doi:10.1039/J19710002107 (https://doi.org/10.1039%2FJ19710002
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Diffraction Data. The Solution of the Crystal Structure by Direct Methods Package POWSIM". J.
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021889897003105).
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hexamolybdate(VI)". Cryst. Res. Technol. 38 (913): 913–917. doi:10.1002/crat.200310112 (http
s://doi.org/10.1002%2Fcrat.200310112).
8. Howard T. Evans jr.; Bryan M. Gatehouse; Peter Leverett (1975). "Crystal structure of the
heptamolybdate(VI)(paramolybdate) ion, [Mo7O24]6−, in the ammonium and potassium
tetrahydrate salts". J. Chem. Soc., Dalton Trans. (6): 505–514. doi:10.1039/DT9750000505 (htt
ps://doi.org/10.1039%2FDT9750000505).
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Bruce King, John Wiley and Sons (1994) ISBN 0-471-93620-0
10. Dickman, Michael H.; Pope, Michael T. (1994). "Peroxo and Superoxo Complexes of
Chromium, Molybdenum, and Tungsten". Chem. Rev. 94 (3): 569–584.
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water_systems/ch_31_open.jsp). gewater.com.
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g_water_systems/ch_32_closed.jsp). gewater.com.
14. "Microbiologically Influenced Corrosion in the Upstream Oil and Gas Industry" (http://www.crcpr
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15. Purushothaman, K. K.; Cuba, M.; Muralidharan, G. (2012-11-01). "Supercapacitor behavior of
α-MnMoO4 nanorods on different electrolytes". Materials Research Bulletin. 47 (11): 3348–
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