A Review on the Generation of Superoxide Ion

1. Introduction:
The life gas molecule i.e oxygen molecule on reduction gives superoxide (O•−
2 )
•−
and the superoxide (O2 ) behaves as both redical and also as anion.

O2 + e− → O2•− (1)
The term “Superoxide” was proposed by many scientists and explain their high
reactivity, particularly as a powerful oxidizing agent, and an initiator of the redical
reaction.1,2,3. The reactivity of superoxide is due to their free electron. The
quantitative measurement of free radical is difficult due to their high reactivity and
short half life time.4,5.

The alkali metals formed stable superoxide like NaO 2, KO2, RbO2, CsO2.

(i) Sodium superoxide was first synthesized in 1449 by the oxidation of sodium
peroxide at an oxygen pressure of 289 atmosphere.6,7.
(ii) The most widely used superoxide is potassium superoxide and this superoxide
is formed by several methods.8,9.
(a) Oxidation of potassium metal in the presence of liquid ammonia (Lux,
1959)
(b) Direct oxidation of metallic vapour (Jackson, 1946)
(c) Oxidation of lower oxide (Kohlmuller, 1959)
(d) Oxidation of potassium hydroxide (Kroger, 1945)
(e) Disproportionation of a peroxide-peroxy hydrate. Latter Kazarnovskii
and Neiding (1952), introduced a new method for the synthesis of
potassium superoxide by potassium peroxide dihydroperoxidate (K2O2 .
2H2O). At higher temperature it disproportionate into the superoxide and
water.

K2O2 . 2H2O → 2KO2 + 2H2O (2)

 (iii) Calcium superoxide [Ca(O2)2] was synthesized by disproportionation of
calcium peroxide diperoxyhydrate.11,12.

2[CaO2 . 2H2O2] → Ca(O2)2 + Ca(OH)2 + 3H2O + 1.5O2 (3)

(iv) Rubidium superoxide (RbO2) is synthesized by using solution method
followed by the reaction at cooling condition of −40 0C. This method was
approved by X-Ray diffraction method.

The reactivity of superoxide are checked by the dissolution of superoxide salt

by the dissolution it noted that the NaO2 is less reactive than the KO2 because
its reduced solubility.10.

2. Generation of Superoxide Ion:

There are many number of methods are available for the generation of superoxide,
such as –

(i) Electrochemical reduction method.

(ii) Chemical generation method.

(iii) Photochemical and photocatalytic generation method.

(iv) Superoxide generation at oxide surface.

(V) Different generation medium.

2.1. Electrochemical Reduction Method:-

Superoxides have short half-life and it generated in aprotic media by using
electrochemical reduction of O2.
Robert and Sawyer introduced superoxide reactivity following the discovery
that the electrochemical reduction of O2 in dimethyl sulfoxide (DMSO) yields
superoxide in a stable state. The electrochemical reduction of O₂ in aprotic
solvent typically occurs at E = ± (&1.0) v. versus the standard calomel
electrod in the absence of protic species, where as superoxid species
disproportionates in the H2O forming O2 and hydroperoxide anion (H2 O−)
.13,14,15,16,17.
2O•− −
2 + H2 → O2 + H2 O + OH
−
(4)
 In 1965 Maricle and Hodgson used the electrolytic reduction of O 2 in aprotic
solvents and introduce a method for superoxide generation in which
superoxide is identified by ESR spectroscopy.14.

2.2 Chemical Generation Method:

This method consists of two steps, in the first step superoxide salts is formed
and in the second step superoxide salt dissolved in useful medium to give
superoxide.

2.2.1. Synthesis of superoxide Salt:-

Superoxide salt of alkali metals, such as potassium and sodium and alkali
earth metals such as barium and strontium, reacts with oxygen at
atmospheric pressure to form stable compound of superoxide.1,18,19..

There are several stable salts of superoxide like KO2, RbO2 and CsO2 they
have yellow or orange colours. They show exciting magnetic properties,
such as the multiferroic effect, and spin- orbital coupled phenomina. It is due
to antibonding superoxide complex molecular orbital. that provide new
functional possibilities for the designing and controlling the properties. KO₂
was widely used as a superoxide salt because its stoichiometry differs from
those of the combustion products.20,21.

2.2.2 Dissolution of superoxide Salt:-

If superoxide salt is dissolving in aprotic solvents then superoxide ion can be

generated.22,23,24. However the solubility of superoxide salt is extremely low,
allmost insoluble in the organic solvents, like DMSO. To increase their
solubility adding tetraalkylammonium salts as supporting electrolytes in
electrochemical methods.24. Crown ether is also used in superoxide reaction
with organic molecules.25,26,27,28.

2.3 Photochemical and Photocalalytic Generation Method:

This method has been widely used to investigate. The effect of superoxide in
various disciplines, particularly in aquatic ecosystem and biotherapy.29,30.
superoxide exists in naturally sunlight surface of waters.
It can be photochemically initiated by electron transfer from an excited state
substrate to oxygen.31,32. They can be stored at -196 °C for a long period of
time with a minor consumtion of superoxide ion.

The photolysis of ethanolic solutions containing oxygen have been illustrated

in (eq. 5-10).33,34. In this process first CH3CH2Ȯ radical is formed and its rapidly
converted to CH3Ċ HOH radicals.

CH3CH2OH + ℎ𝜈 → CH3CHȮ + Ḣ (5)

CH3CH2OH + ℎ𝜈 → CH3Ċ HOH + Ḣ (6)

CH3CH2OH + Ḣ → CH3Ċ HOH + H2 (7)

CH3Ċ HOH + O2 → CH3CHOH (8)

|
O2̇
CH3CHOH + OH− → CH3CHO + H2O + O2− (9)
|
O2

Ionizing radiation or VUV photolysis

H2O . O2− (10)
Oxygen, KOH and HCOONa or ethanol

Another photochemical method generated superoxide in aqueous solution of

p-cresol, acetophenone and aromatic amines such as anthranilic acid, anilic and
N-acetylanthranilic acid, as well as amino acid such as Tyrosine, Trytophan
and Kynurenine.35.

The p- cresol was found to be the most efficien superoxide generator. There are
alternative mechanism for superoxide production that are crucial for other
classes of sensitizers. A photochemically excited sensitizer may be reduced to
a radical anion with superoxide formed by the autoxidation of the sensitizer
radical or with the photochemical generated singlet oxygen (1O2) quenched
through complete electron transfer, yielding superoxide (eq. 11). However
further exploration on these proposed mechanism is required.
OH OH

+ 1O 2 + O2− (11)
CH3 CH3

By using laser flash techenique superoxide formation is possible. If the

reaction between 1O2 and NADH is taken. It is observed by Peters and
Rodgers.36.
1
O2 +NADH → O2− + NAD + H+ (12)

In photocatalysis, electrons react with molecular oxygen via the reductive

pathway to generate the Superoxide.37,38. The photocatalytic activity of the
photocatalyst can be improved using different methods such as catalyst loading
foreign element and self element doping and heterojunction structure
formation. However the introduction of foreign impurities may cause
undesirable thermal stability and difficulty in tuning the oxidation and
reduction species during photocatalysis.39,40.

Self doping can be attract attention, to enhance the activity of photocatalyst

because of its ability to tune the electronic structures without introducing
foreign elements.

Superoxide can also be photogenerated by Bi2WO6 under visible light

irradiation with self doping this was verified by using photo current generation
and ESR spectra as well as superoxide detection methods. Bi2WO6 is a
potential semiconductor photocatalyst, Because of its photostability, chemical
inertnese and environmentally friendly feature.

In Bi2+𝑥 WO6 (x = 0, 0.05, 0.1, 0.15 and 0.2), the four Self-doped x showed
significantly higher photocatalytic activities than the pristine Bi2WO6. The
degeneration of the sodiumpentachlorophenate (NaPCP) constant over the
optimal self-doped catalyst Bi2.1WO6 was approximately 12 times higher
compared with Bi2WO6.
2.4 Superoxide Generation of Oxide Surface:-
A stable superoxide can be generated on oxide surfaces by using methods such
as photoinduction electron transfer, direct surface oxygen electron transfer,
surface intermolecular election transfer, and the decomposition of H2O2.41.

The oxidative pathway involving normal zerovalent iron (nZVI), starts with a
two electron oxidation of dissolved O₂ by Fe o to form H2O2, as shown in (eq.
13). This H2O2 may form H2O by accepting two more electrons from Fe o
(eq.14) React with Fe2+ under acidic conditions (eq.15) to produce a potent
oxidant, OH, or react with Fe4+ under neutral to alkaline pH conditions (eq
16). Under neutral pH conditions, Fe2+ may react with O2 directly to produce
O2− (eq.17)43,43.

O2 + Fe0 + 2H+ → Fe2+ + H2O2 (13)

H2O2 + Fe0 + 2H+ → Fe2+ + H2O (14)

H2O2 + Fe2+ → Fe3+ + OH + OH− (acidic PH) (15)

H2O2 + Fe2+ → Fe4+ = O2+ + H2O (PH>5) (16)

Fe2+ + O2 → Fe3+ + O 2− (PH ~7) (17)

The three dimentional Electro-Fenton (3D-EF) system with foam nickel as the
particle electrod was developed for organic pollutant degradation. 44. Molecular
oxygen was adsorbed on the surface of the foam nickel particle electrode and
activated to produce superoxide via a one electron-transfer pathway, as shown
in (eq18), for increasing H2O2 and OH radicals. Concurrently, the dissolved
O2 was also adsorbed on the surface of an active carbon fiber cathode and
subsequently reduced electrochemically to generate H2O2 via a two electron-
transfer pathway (eq 19) as a result, more H2O2 was generated in the 3D-EF
system compared with the tetra dimentional electro-Fenton system. However,
the nickel usage has environmental risks. For example, a low working, PH
would result in a hydrogen evolution on the cathode surface (eq 20) and
therefore affect the H2O2 electrogeneration.

Ni + 2O2 → Ni2+ + 2O 2− (18)

O2 + 2H+ + 2e− → H2O2 (19)

 2H+ + 2e− → H2 (20)

2.5. Different Generation Medium of Superoxide:-

We know that, there are three types of medium are available for the chemical
reaction such as protic, aprotic and ionic solvents. The selection of medium is
depends on the reaction torget and mechenism of the reaction. However, the
purity of these medium plays an important role for the generation of stable
superoxide.

2.5.1 Aprotic Medium:- As compared to protic and aqueous solution, the

lifetime of superoxide is greater in aprotic medium. Therefore superoxide
can be generated and used in aprotic medium for studying its reactions with
different organic and inorganic substrates.

The very useful aprotic solvents like DMF, DMSO, AcN, dichloromethane,
pyridine acetone, diethyl ether ete.

For biochemical studies, the sutable medium for superoxide generation are
AcN and DMSO. In this time ultrahigh purity (99.9%.) solvents are
available but in 1960s to 1970s there was more risk to superoxide reaction
with solvent impurities. In a number of studies superoxide reacts with DMF
and it is unstable.45,46,47,48,49,50,51,52.

However, for alkyl halide DMSO using as an superoxide medium, R − O−

2
reacts with DMSO to yield alcohol and dimethyl sulfone (eq. 21-23)
O•− •
2 + RX → RO2 + X
−
(RX : Alkyl Halide) (21)
RO•2 + O•− −
2 → RO2 + O2 (22)
R − O− −
2 + (CH3 )2 SO → RO + (CH3 )2 SO2
A stable superoxide can be generated in aprotic medium by using two
methods. The first method involves electrochemical reduction of molecular
oxygen,53,54. whereas the second one employs potassium superoxide (KO2)
solubilized through crown ethers.55,56,57. But, since crown ether are expensive
reagents, their use for large scale preparation has yet limited their
applications. In place of KO2/18-crown-6 combination, the use of
tetraethylammonium superoxide (Et4NO2), obtained by the phase transfer
reaction of KO2/Et4NBr is being explored as a useful and inexpensive
alternative58,59,60. in the organic chemistry.
2.5.2. Protic and Aqueous Medium:- Superoxide has a very short lifetime in
aqueous solutions therefore, pulse methods such as pulse radiolysis or flash
photolysis, are widely used to study the mechenism and kinetics of
superoxide reaction.8.

Superoxide is unstable in aqueous medium and it disproportionates with fast

second order rate constants in the range 107 - 1010 m-1s-1. NaOH and KOH
are the most crucial aqueous alkaline electrolytes and have been regarded as
protic solvents for electroreduction of O2,61. because the atomic size of
Na+ and K+ ions are different, their photochemical properties, such as O2
solubility and diffusion coefficient,62,63. viscosity of the solution,64. and
electrode interfacial phenomena65 are different.

The superoxide reactivity was significantly less than OH • reactivity because

the nucleophilicity of superoxide is greater than that of other reactive oxygen
species. (ROS)66

In a strong alkaline solution periodate reacted with the dissolved oxygen to

produce superoxide.67 Superoxide can be generated in H2O by modified
Fonton's reagent. This reagent was modified by using high concentration of
H2O2 and initiators (eg, iron chelates, soluble Fe(III) or mineral) these
initiate progration reactions and thus generate reactive oxygen species
(ROS) including OH • , HO2• , O•− −
2 and HO2 , (eq. 24-27).
Fe3+ + H2 O2 → Fe2+ + H2 O• + H + (24)
OH • + H2 O2 → HO•2 + H2 (25)
HO•2 → O•−
2 + H
+
(26)
Fe2+ + HO2• → Fe3+ + HO−
2 (27)

Superoxide can also be generated through the reaction of xanthine oxidase

(XOD). Which is obtained from Cow's milk with hypoxanthine in the
presence of O2 in a phosphate buffer solution at room temperature. (eq 28)68
XOD
Hypoxanthine + O2 → Uric Acid + O•−
2 + H 2 O2 (28)
2.5.3 Ionic Liquid Medium:- Ionic Liquids have may favorable properties in
comparison to volatile organic solvents. 69,70,71. The physicochemical
properties of ionic liquids can be modified by altering the cation or the
anion.72,73.
Superoxide in ionic liquids as medium were started in 1991 by Carter.74
They use imedazolium chloride aluminum chloride for O2 reduction to generate
superoxide. However, the generated superoxide was unstable. The generated
superoxide is important especially due to their transient nature. The generation
of stable superoxide in ionic liquid is reported in 2001 by using varying the
structure of cation and anions.75
 References

(1) Sawyer, D. T.; Valentine, J. S. How super Is superoxide? Acc. Chem. Res.
1981, 14, 393-400.
(2) Xiao, H.; Hu, H.-S.; Schwarz, W. H. E.; Li, J. Theoretical Investigations of
Geometry, Electronic structure and stability of UO6: Octaheral Uranium
Hexoxide and its Isomers. J. Phys. chem. A 2010, 114, 8837-8844.
(3) Hayyan M.; Mjalli, F. S.; AlNashef, I. M.; Hashim, M. A. Chemical and
Electrochemical Generation of Superoxide Ion in 1-Butyl-1-
Methylpyrrolidinium Bis(trifluromethylsulfonyl) imide. Int. J. Electrochem.
Sci. 2012, 7, 8116-8127.
(4) Mohammad, M.; Khan, A. Y.; Subhani, M. S.; Bibi, N.; Ahmad, S.; Saleemi,
S. Kinetics and Electrochemical studies on superoxide. Res. Chem. Intermed.
2001, 27, 259-267.
(5) Gulcin, I.; Huyut, Z.; Elmastas, M.; Aboul-Enein, H. Y. Radical Scavenging
and Antioxidant Activity of Tannic Acid. Arabian J. Chem. 2010, 3, 43-53.
(6) Hartmann, P.; Bender, C. L.; Vracar, M.; Durr, A. K.; Garsuch, A.; Janek, J.;
Adelhelm, P. A Rechargeable Room-Temperature Sodium Superoxide (NaO2)
Battery. Nat. Mater 2012, 12, 228-232.
(7) Silver, J. A.; Kolb, C. E. Gas-phase Reaction Rate of sodium Superoxide with
Hydrochloric Acid. J. Phys. Chem. 1986, 90, 3267-3269.
(8) Afanas'ev, I. B. Superoxide Ion: Chemistry and Biological Implications; CRC
Press: Boca Raton, FL, 1989; Vol. 1.
(9) Smith, B. A.; Teel, A. L.; Watts, R. J. Mechanism for the Destruction of
Carbon Tetrachloride and Chloroform DNAPLs by Modified Fenton's
Reagent. J. Contam. Hydrol. 2006, 85, 229-246.
(10) Chern, C.-I.; DiCosimo, R.; De Jesus, R.; San Filippo, J. A study of
Superoxide Reactivity. Reaction of Potassium Superoxide with Alkyl Halides
and Tosylates, J. Am. Chem. Soc. 1978, 100, 7317-7327.
(11) Ballou, E. V.; Wood, P. C.; Spitze, L. A.; Wydeven, T. The Preparation of
Calcium Superoxide from Calciums Peroxide Diperoxyhydrate. Ind. Eng.
Chem. Prod. Res. Dev. 1977. 16, 180-186.
(12) Brosset, C.; Vannerberg, N.-G. Formation of Calcium Superoxide. Nature
1956, 177, 238-238.
(13) Sawyer, D. T.; Sobkowiak, A.; Roberts, J. L. Electrochemistry for chemists,
2nd ed.; Wiley: New York, 1995.
(14) Maricle, D. L.; Hodgson, W. G. Reduction of Oxygen to Superoxide Anion in
Aprotic Solvents. Anal. Chem. 1965, 37, 1562 – 1565.
(15) Sawyer, D. T.; Roberts, J. L., Jr. Electrochemisty оf Oxygen and Superoxide
Ion in Dimethylsulfoxide at Platinum, Gold and Mercury Electrodes. J.
Electroanol. Chem. 1966, 12, 90-101.
(16) Chin, D.H.; Chiericato, G., Jr, Nanni, E. J., Jr; Sawyer D. T. Proton-Induced
Disproportionation of Superoxide Ion in Aprotic Media. J. Am. Chem. Soc.
1982, 104, 1296-1299.
(17) AlNashef, I. M.; Leonard, M. L.; Kittle, M. C.; Matthews, M. A.; Weidner, J.
W. Electrochemical Generation of Superoxide in Room Temperature Ionic
Liquids. Electrochem. Solid-State Lett. 2001, 4. D16-D18.
(18) Carter, G. F.; Margrave, J. L.; Templeton, D. H. A high temperature crystal
modification of KO₂. Acta Crystallogr. 1952, 5, 851.
(19) Krawietz, T. R.; Murray, D. K.; How, J. F. Alkali Metal Oxides, Peroxides,
and superoxides: A Multinuclear MAS NMR study. J. Phys. Chem. A 1998,
102, 8779-8785.
(20) Cha, M.; Shin, K.; know, M.; Koh, D.-Y; Sung, B.; Lee, H. Superoxide Ions
Entrapped in water Cages of Ionic Clathrate Hydrates. J. Am. Chem. Soc.
2010, 132, 3694-3696.
(21) Islam, M. M.; Imase. T.; Okajima, T.; Takahashi, M.; Niikura, Y.;
Kawashima, N.; Nakamura, Y.; Ohsaka, T. Stability of Superoxide Ion in
Imidazolium Cation-Based Room-Temperature Ionic Liquids. J. Phys. Chem.
A 2009, 113, 912-916.
(22) Merritt, M. V.; Sawyer, D. T. Electrochemical Studies of the Reactivity of
Superoxide Ion with Several Alkyl Halides in Dimethyl Sulfoxide. J. Org.
Chem. 1970, 35, 2157-2159.
(23) Johnson, R. A.; Nidy, E. G.; Merritt. M. V. Superoxide Chemistry, Reaction
of Superoxide with Alkyl Halides and Alkyl Sulfonate Esters. J. Am. Chem.
Soc. 1978, 100, 7960-7966.
(24) Moorcroft, M. J.; Hahn, C. E. W.; Compton, R. G. Electrochemical studies of
 the Anaesthetic Agent Enflurane (2-chloro-1,1,2- Trifluoroethyl Difluoromethyl
ether) in the presence of Oxygen: Reaction with Electrogenerated Superoxide.
J. Electroanal. Chem. 2003, 541, 117-131.

(25) Johnson, R. A.; Nidy, E. G. Superoxide Chemisty. Convenient Synthesis of

Dialkyl Peroxides. J. Org. Chem. 1975, 40, 1680-1681.
(26) Yim, E. S.; Park, M. K.; Han, B. H. Ultrasound Promoted N- Alkylation of
Pyrrole Using Potassium Superoxide as Base in Crown ether. Ultrason.
Sonochem, 1997, 4,95-98.
(27) McElroy, A. D.; Hashman, J. S. Synthesis of Tetramethyl-ammonium
Superoxide. Inorg. Chem. 1964, 3, 1798-1799.
(28) Peters, J. W.; Foote, C. S. Chemistry of Superoxide Ion. II. Reaction with
Hydroperoxides. J. Am. Chem. Soc. 1976, 98, 873-875.
(29) Petasne, R. G.; Zika, K. G. Fate of Superoxide in Coastal Sea water. Nature
1987, 325, 516-518.
(30) Jones, A. M.; Garg. S.; He, D.; Pham, A. N.; Waite, T. D. Superoxide-
Mediated Formation and Charging of Silver Nanoparticles. Environ. Sci.
Technol. 2011, 45, 1428-1434.
(31) Zhang, D.; Yon, S.; Song, W. Photochemically Induced Formation of
Reactive Oxygen Species (ROS) from Effluent Organic Matter. Environ. Sci.
Technol. 2014, 48, 12645 12653.
(32) Holroyd, R. A.; Bielski, B. H. J. Photochemical Generation of Superoxide
Radicals in Aqueous Solutions. J. Am. Chem. Soc. 1978, 100, 5796 - 5800.
(33) Bielski, B. H. J.; Arudi, R. L. Preparation and Stabilization of Aqueous /
Ethanolic Superoxide Solutions. Anal. Biochem. 1983, 133, 170-178.
(34) Bothe, E.; Schuchmann, M. N.; Schulte-FrohLinde, D.; Sonntag, C. V.
Hydroxyl Radical- Induced Oxydation of Ethanol in Oxygenated Aqueous
Solutions. A pulse Radiolysis and Product Study. Z. Naturforsch., B: J. Chem.
Sci. 1983, 38, 212-219.
(35) Draper, W. M.; Crosby, D. G. Photochemical Generation of Superoxide
Radical Anion in Water. J. Agric. Food Chem. 1983, 31, 734-737.
(36) Peters, G.; Rodgers, M. A. J. Single-Electron Transfer from NADH
Analogues to Singlet Oxygen. Biochim. Biophys. Acta, Bioenerg. 1981, 637,
43-52.
(37) Salthammer, T.; Fuhrmann, F. Photocatalytic Surface Reactions on
IndoorWall paint. Environ. Sci. Technol. 2007, 41, 6573-6578.
(38) Thompson, T.; Yates, J.; Jr. Surface Science Studies of the photoactivation of
TiO2 New photochemical processes. Chem. Rev. 2006, 106, 4428-4453.
(39) Ding, X.; Zhao, K.; Zhang. L. Enhanced Photocatalytic Removel of Sodium
Pentachlorophenate with Self-Doped Bi2WO6 under Visible Light by
Generating more Superoxide Ions. Environ. Sci. Technol. 2014, 48, 5823-
5831.
(40) Zhang, X.; Zhang, L.; Electronic and Band Structure Tuning of Ternary
Semiconductor photocatalysts by Self Doping: The Case of BiOI. J. Phys.
Chem. C 2010, 114, 18198-18206.
(41) Anpo, M.; che. M.; Fubini, B.; Garrone, E.; Giamello, E.; Paganini, M.C.
Generation of superoxide Ions at Oxide surfaces. Top. Catal. 1999, 8, 189-
198.
(42) Yan, W.; Lien, H.-L.; Koel, B. E.; Zhang, W.-x. Iron Nanoparticles for
Environmental Clean-Up: Recent Developments and Future Outlook. Environ.
Sci.: Processes Impacts 2013, 15, 63-77.
(43) Keenan, C. R.; Sedlak, D. L. Factors Affecting the Yield of Oxidants from the
Reaction of Nanoparticulate Zero-Valent Iron and Oxygen. Environ. Sci.
Technol. 2008, 42, 1262-1267.
(44) Liu, W.; Ai, Z.; Zhang, L. Design of a Neutral Three-Dimentional Electro -
Fenton System with Foam Nickel as Particle Electrodes for Wastewater
Treatment. J. Hazard. Mater. 2012, 243, 257-264.
(45) Wadhawan, J. D.; Welford, P. J.; McPeak, H. B.; Hahn, C. E. W.; Compton,
R. G. The Simultaneous Voltammetric Determination and Detection of
oxygen and Carbon Dioxide: A study of Kinetics of the Reaction between
Superoxide and Carbon Dioxide in Non-Aqueous Media Using Membrane-
Free Gold DiscMicroelectrodes. Sens. Actuators, B. 2003, 88, 40- 52.
(46) Peover, M. E.; White, B. S. Electrolytic Reduction of Oxygen in Aprotic
Solvents: The Superoxide Ion. Electrochim. Acta 1966, 11, 1061-1067.
(47) Islam, M. M.; Saha, M. S.; Okajima, T.; Ohsaka, T. Current Oscillatory
Phenomena Based on Electrogenerated Superoxide Ion at the HMDE in
Dimethylsulfoxide. J. Electroanal. Chem, 2005, 577, 145-154.
(48) AlNashef, I. M.; Leonard, M. L.; Matthews, M. A.; Weidner, J. W.
Superoxide Electrochemistry in an Ionic Liquids Ind. Eng. Chem. Res 2002,
41, 4475- 4478.
(49) Solovyev, I; Pchelkina, Z.; Mazurenko, V. Magnetism of Sodium Superoxide.
CrystEngComm 2014, 16, 522-531.
(50) Solovyev, I. Spin-Orbital Superexchange physics Emerging From Interacting
Oxygen molecule in KO₂. New J. Phys. 2008, 10, 013035.
(51) Corey, E. J.; Nicolaou, K. C.; Shibasaki, M.; Machida, Y.; Shiner, C. S.
Superoxide Ion As A synthetically Useful Oxygen Nucleophile. Tetrahedron
Lett. 1975, 16, 3183-3186.
(52) Fee, J. A.; Hildenbrand, P. G. On the Development of a Well-Defined Source
of Superoxide Ion for Studies with Biological Systems. FEBS Lett. 1974, 39,
79-82.
(53) Sawyer D. T. and Gibian M. J., Tetrahedron, 35, 1979, 1471.
(54) Wilshire J. and Sawyer D. T. Acc. Chem. Res, 12, 1979, 105.
(55) Gibian M. J., Sawyer D. T. Ungermann T., Tangpoonphalvivat R. and
Morrision M. M., J. Am. Chem. Soc. 101, 1979, 640.
(56) Valantine J. S. and Curtis A. B. J. Am. Chem. Soc. 97. 1975, 224.
(57) R. S. Raguvanshi, Phosphorus, Sulfur, Silicon, 190, 2015, 133-137.
(58) Foglia T. A. and Silbert L. S. Synthesis, 1992, 545.
(59) Shukla, A. K.; Singh, S.; Singh, K. N. Henery and Knoevenagel Type
Condensation Reactions Initiated by Tetraethylammonium Superoxide in
Aprotic Midium. Indian J. Chem., Sect. B 2001, 40B, 391-393.
(60) R. S. Raghuvanshi, V. P. Yadav and V. K. Singh, Lett. Org. Chem., 13, 2016,
67-70.
(61) Spendelow, J. S.; Wieckowski, A. Electrocatalysis of Oxygen. Reduction and
Small Alcohol Oxidation in Alkaline media. Phys. Chem. 2007, 9, 2654-2675.
(62) Tromans, D. Modeling Oxygen Solubility in Water and Electrolyte Solutions.
Ind. Eng. Chem. Res. 2000, 39, 805-812.
(63) Gubbins, K. E.; Walker, R. D., Jr. The Solubility and Diffusivity of Oxygen in
Electrolytic Solutions. J. Electrochem. Soc. 1965, 112, 469-471.
(64) Sipos, P. M.; Hefter, G.; May, P.M. Viscosities and Densities of Highly
Concentrated Aqueous MOH Solutions [M+ = Na+, K+ Li+, Cs+, (CH3)4N+] at
25.0 °C. J. Chem. Eng. Data 2000, 45, 613-617.
(65) Magnussen, O. M. Ordered Anion Adlayers on Metal Electrode Surfaces,
Chem. Rev. 2002, 102, 679-726.
(66) Song, W.; Xu, T.; Cooper, W. J.; Dionysiou, D. D.; Cruz, A. A. de la; O'Shea,
 K. E. Radiolysis studies on the Destruction of Microcystin-LR in Aqueous
Solution by Hydroxyl Radicals. Environ. Sci. Technol. 2009, 43, 1487-1492.
(67) Lin, J. M.; Yamada, M. Oxidation Reaction between Periodate and
Polyhydroxyl Compounds and Its Application to Chemiluminescence. Anal.
Chem. 1999, 71, 1760-1766.
(68) Chen, J.; Wollenberger, U.; Lisdat, F.; Ge, B.; Scheller, F. W Superoxide
Sensor Based on Hemin Modified Electrode. Sens. Actuators, B 2000, 70,
115- 120.
(69) Earle, M. J.; Seddon, K. R. Ionic Liquids. Green solvents For the Future. Pure
Appl. Chem. 2000, 72, 1391-1398.
(70) Marsh, K. N.; Deev, A.; Wu, A. C. T.; Tran, E, Klamt, A. Room Temperature
Ionic Liquids as Replacement for Conventional Solvents - A Review. Korean
J.Chem. Eng. 2002, 19, 357-362.
(71) Hayyan, M.; Mjalli, F. S.; Hashim, M. A.; AlNashef, I. M. A Novel
Technique for Separating Glycerine from Palm Oil-Based Biodiesel Using
Ionic Liquids. Fuel Process. Technol. 2010, 91, 116-120.
(72) Armstrong, D. W.; He, L.; Liu, Y. S. Examination of Ionic Liquids and Their
Interaction with. Molecules, When Used as Stationary Phases in Gas
Chromatography. Anal. Chem. 1999, 71, 3873-3876.
(73) Liu, J.; Jiang. G.; Chi,, Y.; Cai, Y.; Zhou, Q.; Hu, J. T. Use of Ionic Liquids
for Liquid Phase Microextraction of Polycyclic Aromatic Hydrocarbons.
Anal.Chem. 2003, 75, 5870-5876.
(74) Carter, M. T.; Hussey, C. L.; Strubinger, S. K. D.; Osteryoung, R. A.
Electrochemical Reduction of Dioxygen in Room-Temperature Imidazolium
Chloride - Aluminum Chloride Molten Salts. Inorg. Chem. 1991, 30, 1149-
1151.
(75) Huang, X. J.; Rogers, E. L.; Hardacre, C.; Compton R. G. The Reduction of
Oxygen in Various Room-Temperature Ionic Liquids in the Temperature
Range 293-318 K: Exploring the Applicability of the Stokes-Einstein
Relationship in Room Temperature Ionic Liquids. J. Phys. Chem. B 2009,
113, 8953-8959.