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Hydrogen peroxide

From Wikipedia, the free encyclopedia

Hydrogen peroxide
Structural formula of hydrogen peroxide
Structural formula of hydrogen peroxide
  Oxygen, O
  Hydrogen, H
Space filling model of the hydrogen peroxide molecule
Space filling model of the hydrogen peroxide molecule
Names
IUPAC name
Hydrogen peroxide
Systematic IUPAC name
Peroxol
Dioxidane
Other names
Oxidanyl
Perhydroxic acid
0-hydroxyol
Oxygenated water
Peroxaan
Identifiers
3D model (JSmol)
ChEBI
ChEMBL
ChemSpider
ECHA InfoCard100.028.878Edit this at Wikidata
EC Number
  • 231-765-0
KEGG
RTECS number
  • MX0900000 (>90% soln.)
    MX0887000 (>30% soln.)
UNII
UN number2015 (>60% soln.)
2014 (20–60% soln.)
2984 (8–20% soln.)
  • InChI=1S/H2O2/c1-2/h1-2H checkY
    Key: MHAJPDPJQMAIIY-UHFFFAOYSA-N checkY
  • InChI=1/H2O2/c1-2/h1-2H
    Key: MHAJPDPJQMAIIY-UHFFFAOYAL
Properties
H2O2
Molar mass34.014 g·mol−1
AppearanceVery light blue liquid
Odorslightly sharp
Density1.11 g/cm3 (20 °C, 30% (w/w) solution)[1]
1.450 g/cm3 (20 °C, pure)
Melting point−0.43 °C (31.23 °F; 272.72 K)
Boiling point150.2 °C (302.4 °F; 423.3 K) (decomposes)
Miscible
Solubilitysoluble inether,alcohol
insoluble in petroleum ether
logP−0.43[2]
Vapor pressure5 mmHg (30 °C)[3]
Acidity (pKa)11.75
−17.7·10−6 cm3/mol
1.4061
Viscosity1.245 cP (20 °C)
2.26 D
Thermochemistry
1.267 J/(g·K) (gas)
2.619 J/(g·K) (liquid)
−187.80 kJ/mol
Pharmacology
A01AB02 (WHO) D08AX01 (WHO),D11AX25 (WHO),S02AA06 (WHO)
Hazards
GHS labelling:
GHS03: OxidizingGHS05: CorrosiveGHS07: Exclamation mark
Danger
H271,H302,H314,H332,H335,H412
P280,P305+P351+P338,P310
NFPA 704 (fire diamond)
Flash pointNon-flammable
Lethal dose or concentration (LD, LC):
1518 mg/kg[citation needed]
2000 mg/kg (oral, mouse)[4]
1418 ppm (rat, 4 hr)[4]
227 ppm (mouse)[4]
NIOSH (US health exposure limits):
PEL (Permissible)
TWA 1 ppm (1.4 mg/m3)[3]
REL (Recommended)
TWA 1 ppm (1.4 mg/m3)[3]
IDLH (Immediate danger)
75 ppm[3]
Safety data sheet (SDS)ICSC 0164 (>60% soln.)
Related compounds
Related compounds
Water
Ozone
Hydrazine
Hydrogen disulfide
Dioxygen difluoride
Except where otherwise noted, data are given for materials in theirstandard state (at 25 °C [77 °F], 100 kPa).
checkY verify (what is checkY☒N ?)
Chemical compound

Hydrogen peroxide is achemical compound with the formulaH2O2. In its pure form, it is a very pale blue[5]liquid; However at lower concentrations, it appears colorless due to the faintness of the blue coloration.[6] The molecule hydrogen peroxide is asymmetrical and highly polarized. Its strong tendency to form hydrogen bond networks results in greaterviscosity compared towater. It is used as anoxidizer,bleaching agent, andantiseptic, usually as a dilute solution (3%–6% by weight) in water for consumer use and in higher concentrations for industrial use. Concentrated hydrogen peroxide, or "high-test peroxide", decomposes explosively when heated and has been used as both amonopropellant and an oxidizer inrocketry.[7]

Hydrogen peroxide is areactive oxygen species and the simplestperoxide, a compound having an oxygen–oxygensingle bond. It decomposes slowly into water and elementaloxygen when exposed to light, and rapidly in the presence of organic or reactive compounds. It is typically stored with astabilizer in a weakly acidic solution in an opaque bottle. Hydrogen peroxide is found in biological systems including the human body. Enzymes that use or decompose hydrogen peroxide are classified asperoxidases.

Properties

[edit]

The boiling point ofH2O2 has been extrapolated as being 150.2 °C (302.4 °F), approximately 50 °C (90 °F) higher than water. In practice, hydrogen peroxide will undergo potentially explosivethermal decomposition if heated to this temperature. It may be safely distilled at lower temperatures under reduced pressure.[8]

Hydrogen peroxide forms stableadducts withurea (hydrogen peroxide–urea), sodium carbonate (sodium percarbonate) and other compounds.[9] An acid-base adduct withtriphenylphosphine oxide is a useful "carrier" forH2O2 in some reactions.

Structure

[edit]
O−O bond length = 147.4 pm O−H bond length = 95.0 pm
Structure and dimensions ofH2O2 in the gas phase
O−O bond length = 145.8 pm O−H bond length = 98.8 pm
Structure and dimensions ofH2O2 in the solid (crystalline) phase

Hydrogen peroxide (H2O2) is a nonplanar molecule with (twisted) C2symmetry; this was first shown byPaul-Antoine Giguère in 1950 usinginfrared spectroscopy.[10][11] Although the O−O bond is asingle bond, the molecule has a relatively highrotational barrier of 386 cm−1 (4.62 kJ/mol) for rotation betweenenantiomers via thetrans configuration, and 2460 cm−1 (29.4 kJ/mol) via thecis configuration.[12] These barriers are proposed to be due torepulsion between thelone pairs of the adjacent oxygen atoms and dipolar effects between the two O–H bonds. For comparison, the rotational barrier forethane is 1040 cm−1 (12.4 kJ/mol).

The approximately 100°dihedral angle between the two O–H bonds makes the moleculechiral. It is the smallest and simplest molecule to exhibitenantiomerism. It has been proposed that theenantiospecific interactions of one rather than the other may have led to amplification of one enantiomeric form ofribonucleic acids and therefore an origin ofhomochirality in anRNA world.[13]

The molecular structures of gaseous andcrystallineH2O2 are significantly different. This difference is attributed to the effects ofhydrogen bonding, which is absent in the gaseous state.[14] Crystals ofH2O2 aretetragonal with thespace groupD4
4
orP41212.[15]

Aqueous solutions

[edit]

Inaqueous solutions, hydrogen peroxide forms aeutectic mixture, exhibitingfreezing-point depression down as low as −56 °C; pure water has a freezing point of 0 °C and pure hydrogen peroxide of −0.43 °C. The boiling point of the same mixtures is also depressed in relation with the mean of both boiling points (125.1 °C). It occurs at 114 °C. This boiling point is 14 °C greater than that of pure water and 36.2 °C less than that of pure hydrogen peroxide.[16]

  • Phase diagram ofH2O2 and water: Area above blue line is liquid. Dotted lines separate solid–liquid phases from solid–solid phases.
  • Density of aqueous solution ofH2O2
    H2O2 (w/w)Density
    (g/cm3)
    Temp.
    (°C)
    3%1.009515
    27%1.1020
    35%1.1320
    50%1.2020
    70%1.2920
    75%1.3320
    96%1.4220
    98%1.4320
    100%1.4520
  • Hydrogen peroxide is most commonly available as a solution in water. For consumers, it is usually available from pharmacies at 3 and 6wt% concentrations. The concentrations are sometimes described in terms of the volume of oxygen gas generated; one milliliter of a 20-volume solution generates twenty milliliters of oxygen gas when completely decomposed. For laboratory use, 30 wt% solutions are most common. Commercial grades from 70% to 98% are also available, but due to the potential of solutions of more than 68% hydrogen peroxide to be converted entirely to steam and oxygen (with the temperature of the steam increasing as the concentration increases above 68%) these grades are potentially far more hazardous and require special care in dedicated storage areas. Buyers must typically allow inspection by commercial manufacturers.

    Comparison with analogues

    [edit]

    Hydrogen peroxide has several structural analogues withHmX−XHn bonding arrangements (water also shown for comparison). It has the highest (theoretical) boiling point of this series (X = O, S, N, P). Its melting point is also fairly high, being comparable to that ofhydrazine and water, with onlyhydroxylamine crystallising significantly more readily, indicative of particularly strong hydrogen bonding.Diphosphane andhydrogen disulfide exhibit only weak hydrogen bonding and have little chemical similarity to hydrogen peroxide. Structurally, the analogues all adopt similar skewed structures, due to repulsion between adjacentlone pairs.

    Properties ofH2O2 and its analogues
    Values marked * are extrapolated
    NameFormulaMolar mass
    (g/mol)
    Melting
    point (°C)
    Boiling
    point (°C)
    WaterHOH18.020.0099.98
    Hydrogen peroxideHOOH34.01−0.43150.2*
    Hydrogen disulfideHSSH66.15−89.670.7
    HydrazineH2NNH232.052114
    HydroxylamineNH2OH33.033358*
    DiphosphaneH2PPH265.98−9963.5*

    Natural occurrence

    [edit]

    Hydrogen peroxide is produced by various biological processes mediated byenzymes.

    Hydrogen peroxide has been detected in surface water, in groundwater, and in theatmosphere. It can also form when water is exposed to UV light.[17] Sea water contains 0.5 to 14 μg/L of hydrogen peroxide, and freshwater contains 1 to 30 μg/L.[18] Concentrations in air are about 0.4 to 4 μg/m3, varying over severalorders of magnitude depending in conditions such as season, altitude, daylight and water vapor content. In rural nighttime air it is less than 0.014 μg/m3, and in moderatephotochemical smog it is 14 to 42 μg/m3.[19]

    The amount of hydrogen peroxide in biological systems can be assayed using afluorometric assay.[20]

    Discovery

    [edit]

    Alexander von Humboldt is sometimes said to have been the first to report the first synthetic peroxide,barium peroxide, in 1799 as a by-product of his attempts to decompose air, although this is disputed due to von Humboldt's ambiguous wording.[21] Nineteen years laterLouis Jacques Thénard recognized that this compound could be used for the preparation of a previously unknown compound, which he described aseau oxygénée ("oxygenated water") — subsequently known as hydrogen peroxide.[22][23][24]

    An improved version of Thénard's process usedhydrochloric acid, followed by addition ofsulfuric acid to precipitate thebarium sulfate byproduct. This process was used from the end of the 19th century until the middle of the 20th century.[25]

    The bleaching effect of peroxides and their salts onnatural dyes had been known since Thénard's experiments in the 1820s, but early attempts of industrial production of peroxides failed. The first plant producing hydrogen peroxide was built in 1873 inBerlin. The discovery of the synthesis of hydrogen peroxide byelectrolysis withsulfuric acid introduced the more efficient electrochemical method. It was first commercialized in 1908 inWeißenstein,Carinthia, Austria. Theanthraquinone process, which is still used, was developed during the 1930s by the German chemical manufacturerIG Farben inLudwigshafen. The increased demand and improvements in the synthesis methods resulted in the rise of the annual production of hydrogen peroxide from 35,000 tonnes in 1950, to over 100,000 tonnes in 1960, to 300,000 tonnes by 1970; by 1998 it reached 2.7 million tonnes.[18]

    Early attempts failed to produce neat hydrogen peroxide. Anhydrous hydrogen peroxide was first obtained byvacuum distillation.[26]

    Determination of the molecular structure of hydrogen peroxide proved to be very difficult. In 1892, the Italian physical chemist Giacomo Carrara (1864–1925) determined its molecular mass byfreezing-point depression, which confirmed that its molecular formula isH2O2.[27]H2O=O seemed to be just as possible as the modern structure, and as late as in the middle of the 20th century at least half a dozen hypothetical isomeric variants of two main options seemed to be consistent with the available evidence.[28] In 1934, the English mathematical physicistWilliam Penney and the Scottish physicistGordon Sutherland proposed a molecular structure for hydrogen peroxide that was very similar to the presently accepted one.[29][30]

    Production

    [edit]
    Catalytic cycle for theanthraquinone process to produce hydrogen peroxide: an anthraquinone (right) is reduced using hydrogen to produce the corresponding anthrahydroquinone (left). This is oxidized using oxygen to produce hydrogen peroxide and recover anthraquinone.

    In 1994, world production ofH2O2 was around 1.9 million tonnes and grew to 2.2 million in 2006,[31] most of which was at a concentration of 70% or less. In that year, bulk 30%H2O2 sold for around 0.54USD/kg, equivalent to US$1.50/kg (US$0.68/lb) on a 100% purity basis.[32]

    Hydrogen peroxide is manufactured almost exclusively by theanthraquinone process, which was originally developed byBASF in 1939. It begins with the reduction of ananthraquinone (such as2-ethylanthraquinone or the 2-amyl derivative) to the corresponding anthrahydroquinone, typically byhydrogenation on apalladiumcatalyst. In the presence ofoxygen, the anthrahydroquinone then undergoesautoxidation: the labile hydrogen atoms of thehydroxy groups transfer to the oxygen molecule, to give hydrogen peroxide and regenerating the anthraquinone. Most commercial processes achieve oxidation by passingcompressed air through a solution of the anthrahydroquinone, with the hydrogen peroxide thenextracted from the solution and the anthraquinone recycled back for successive cycles of hydrogenation and oxidation.[32][33]

    The net reaction for the anthraquinone-catalyzed process is:[32]

    H2 + O2 → H2O2

    The economics of the process depend heavily on effective recycling of the extraction solvents, thehydrogenation catalyst and the expensivequinone.

    ISO tank container for hydrogen peroxide transportation
    A tank car designed for transporting hydrogen peroxide by rail

    Historical methods

    [edit]

    Hydrogen peroxide was once prepared industrially byhydrolysis ofammonium persulfate:

    [NH4]2S2O8 + 2 H2O → 2 [NH4]HSO4 + H2O2

    [NH4]2S2O8 was itself obtained by theelectrolysis of a solution ofammonium bisulfate ([NH4]HSO4) insulfuric acid.[34]

    Other routes

    [edit]

    Small amounts are formed by electrolysis,photochemistry,electric arc, and related methods.[35]

    A commercially viable route for hydrogen peroxide via the reaction of hydrogen with oxygen favours production of water but can be stopped at the peroxide stage.[36][37] One economic obstacle has been that direct processes give a dilute solution uneconomic for transportation. None of these has yet reached a point where it can be used for industrial-scale synthesis.

    The electrochemical reduction of oxygen allows for the generation of hydrogen peroxide from oxygen and water.[38]

    Reactions

    [edit]

    Acid-base

    [edit]

    Hydrogen peroxide is about 1000 times stronger as an acid than water.[39]

    H2O2 ⇌ H+ + HO2 (pK = 11.65)

    Disproportionation

    [edit]

    Hydrogen peroxide disproportionates to form water and oxygen with aΔHo of −2884.5 kJ/kg[40] and a ΔS of 70.5 J/(mol·K):

    2 H2O2 → 2 H2O + O2

    The rate of decomposition increases with rise in temperature, concentration, andpH.H2O2 is unstable under alkaline conditions. Decomposition is catalysed by various redox-active ions or compounds, including mosttransition metals and their compounds (e.g.manganese dioxide (MnO2),silver, andplatinum).[41]

    Oxidation reactions

    [edit]

    Theredox properties of hydrogen peroxide depend on pH. In acidic solutions,H2O2 is a powerfuloxidizer.

    Oxidizing
    reagent
    Reduced
    product
    Oxidation
    potential

    (V)
    F2HF3.0
    O3O22.1
    H2O2H2O1.8
    KMnO4MnO21.7
    ClO2HClO1.5
    Cl2Cl1.4

    Sulfite (SO2−3) is oxidized tosulfate (SO2−4).

    Reduction reactions

    [edit]

    Underalkaline conditions, hydrogen peroxide is a reductant. WhenH2O2 acts as a reducing agent,oxygen gas is also produced. For example, hydrogen peroxide will reducesodium hypochlorite andpotassium permanganate, which is a convenient method for preparingoxygen in the laboratory:

    NaOCl + H2O2 → O2 + NaCl + H2O
    2 KMnO4 + 3 H2O2 → 2 MnO2 + 2 KOH + 2 H2O + 3 O2

    The oxygen produced from hydrogen peroxide and sodiumhypochlorite is inthe singlet state.

    Hydrogen peroxide also reducessilver oxide tosilver:

    Ag2O + H2O2 → 2 Ag + H2O + O2

    Although usually a reductant, alkaline hydrogen peroxide converts Mn(II) to the dioxide:

    H2O2 + Mn2+ + 2 OH → MnO2 + 2 H2O

    In a related reaction,potassium permanganate is reduced toMn2+ byacidicH2O2:[5]

    2 MnO4 + 5 H2O2 + 6 H+ → 2 Mn2+ + 8 H2O + 5 O2

    Organic reactions

    [edit]

    Hydrogen peroxide is frequently used as anoxidizing agent. Illustrative is oxidation ofthioethers to formsulfoxides, such as conversion ofthioanisole tomethyl phenyl sulfoxide:[42][43]

    Ph-S-CH3 + H2O2 → Ph-S(O)-CH3 + H2O

    Alkaline hydrogen peroxide is used forepoxidation of electron-deficient alkenes such asacrylic acid derivatives,[44] and for the oxidation ofalkylboranes toalcohols, the second step ofhydroboration-oxidation. It is also the principal reagent in theDakin oxidation process.

    Precursor to other peroxide compounds

    [edit]

    Hydrogen peroxide is a weak acid, forminghydroperoxide orperoxidesalts with many metals.

    It also converts metal oxides into the corresponding peroxides. For example, upon treatment with hydrogen peroxide,chromic acid (CrO3 andH2SO4) forms a blue peroxideCrO(O2)2.

    Biochemistry

    [edit]
    Ascaridole

    Production

    [edit]

    The aerobic oxidation ofglucose in the presence of the enzymeglucose oxidase produces hydrogen peroxide. The conversion affordsgluconolactone:[45]

    C6H12O6 + O2 → C6H10O6 + H2O2

    Superoxide dismutases (SOD)s areenzymes that promote thedisproportionation ofsuperoxide intooxygen and hydrogen peroxide.[46]

    2 O2 + 2 H+ → O2 + H2O2
    2 H2O2 → O2 + 2 H2O

    Peroxisomes areorganelles found in virtually alleukaryotic cells.[47] They are involved in thecatabolism ofvery long chain fatty acids,branched chain fatty acids,D-amino acids,polyamines, and biosynthesis ofplasmalogens andether phospholipids, which are found in mammalian brains and lungs.[48] They produce hydrogen peroxide in a process catalyzed byflavin adenine dinucleotide (FAD):[49]

    R-CH2-CH2-CO-SCoA + O2FAD{\displaystyle {\ce {->[{\ce {FAD}}]}}}R-CH=CH-CO-SCoA + H2O2

    Hydrogen peroxide arises by the degradation ofadenosine monophosphate, which yieldshypoxanthine. Hypoxanthine is then oxidativelycatabolized first toxanthine and then touric acid, and the reaction is catalyzed by the enzymexanthine oxidase:[50]

    Degradation of hypoxanthine through xanthine to uric acid to form hydrogen peroxide

    The degradation ofguanosine monophosphate yields xanthine as an intermediate product which is then converted in the same way to uric acid with the formation of hydrogen peroxide.[50]

    Consumption

    [edit]

    Catalase, another peroxisomal enzyme, uses thisH2O2 to oxidize other substrates, includingphenols,formic acid,formaldehyde, andalcohol, by means of a peroxidation reaction:

    H2O2 + R'H2 → R' + 2 H2O

    thus eliminating the poisonous hydrogen peroxide in the process.

    This reaction is important in liver and kidney cells, where the peroxisomes neutralize various toxic substances that enter the blood. Some of theethanol humans drink is oxidized toacetaldehyde in this way.[51] In addition, when excessH2O2 accumulates in the cell, catalase converts it toH2O through this reaction:

    H2O2 → 0.5 O2 + H2O

    Glutathione peroxidase, aselenoenzyme, also catalyzes the disproportionation of hydrogen peroxide.

    Fenton reaction

    [edit]

    The reaction ofFe2+ and hydrogen peroxide is the basis of theFenton reaction, which generateshydroxyl radicals, which are of significance in biology:

    Fe(II) + H2O2 → Fe(III)OH + HO·

    The Fenton reaction explains the toxicity of hydrogen peroxides because the hydroxyl radicals rapidly and irreversibly oxidize all organic compounds, includingproteins,membrane lipids, andDNA.[52] Hydrogen peroxide is a significant source ofoxidative DNA damage in living cells. DNA damage includes formation of8-Oxo-2'-deoxyguanosine among many other altered bases, as well as strand breaks, inter-strand crosslinks, and deoxyribose damage.[53] By interacting with Cl, hydrogen peroxide also leads to chlorinated DNA bases.[53] Hydroxyl radicals readily damage vital cellular components, especially those of themitochondria.[54][55][56] The compound is a major factor implicated in thefree-radical theory of aging, based on its ready conversion into ahydroxyl radical.

    Function

    [edit]
    Australianbombardier beetle

    Eggs ofsea urchin, shortly after fertilization by a sperm, produce hydrogen peroxide. It is then converted tohydroxyl radicals (HO•), which initiateradical polymerization, which surrounds the eggs with a protective layer ofpolymer.

    Thebombardier beetle combineshydroquinone and hydrogen peroxide, leading to a violentexothermicchemical reaction to produce boiling, foul-smelling liquid that partially becomes agas (flash evaporation) and is expelled through an outlet valve with a loud popping sound.[57][58][59]

    As a proposedsignaling molecule, hydrogen peroxide may regulate a wide variety of biological processes.[60][61] At least one study has tried to link hydrogen peroxide production to cancer.[62]

    Uses

    [edit]

    Bleaching

    [edit]

    About 60% of the world's production of hydrogen peroxide is used forpulp- and paper-bleaching.[31] The second major industrial application is the manufacture ofsodium percarbonate andsodium perborate, which are used as mild bleaches inlaundrydetergents. A representative conversion is:

    Na2B4O7 + 4 H2O2 + 2 NaOH → 2 Na2B2O4(OH)4 + H2O

    Sodium percarbonate, which is an adduct ofsodium carbonate and hydrogen peroxide, is the active ingredient in such laundry products asOxiClean andTide laundry detergent. When dissolved in water, it releases hydrogen peroxide and sodium carbonate.[25] By themselves these bleaching agents are only effective at wash temperatures of 60 °C (140 °F) or above and so, often are used in conjunction withbleach activators, which facilitate cleaning at lower temperatures.

    Hydrogen peroxide has also been used as aflour bleaching agent and atooth and bone whitening agent.

    Production of organic peroxy compounds

    [edit]

    It is used in the production of variousorganic peroxides withdibenzoyl peroxide being a high volume example.[63]Peroxy acids, such asperacetic acid andmeta-chloroperoxybenzoic acid also are produced using hydrogen peroxide. Hydrogen peroxide has been used for creatingorganic peroxide-based explosives, such asacetone peroxide. It is used as an initiator inpolymerizations. Hydrogen peroxide reacts with certain di-esters, such asphenyl oxalate ester (cyalume), to producechemiluminescence; this application is most commonly encountered in the form ofglow sticks.

    Production of inorganic peroxides

    [edit]

    The reaction withborax leads tosodium perborate, a bleach used in laundry detergents:

    Na2B4O7 + 4 H2O2 + 2 NaOH → 2 Na2B2O4(OH)4 + H2O

    Sewage treatment

    [edit]

    Hydrogen peroxide is used in certain waste-water treatment processes to remove organic impurities. Inadvanced oxidation processing, theFenton reaction[64][65] gives the highly reactivehydroxyl radical (•OH). This degrades organic compounds, including those that are ordinarily robust, such asaromatic orhalogenated compounds.[66] It can also oxidizesulfur-based compounds present in the waste; which is beneficial as it generally reduces their odour.[67]

    Disinfectant

    [edit]

    Hydrogen peroxide may be used for the sterilization of various surfaces,[68] including surgical instruments,[69] and may be deployed as a vapour (VHP) for room sterilization.[70]H2O2 demonstrates broad-spectrum efficacy against viruses, bacteria, yeasts, and bacterial spores.[71][72] In general, greater activity is seen againstGram-positive thanGram-negative bacteria; however, the presence ofcatalase or otherperoxidases in these organisms may increase tolerance in the presence of lower concentrations.[73] Lower levels of concentration (3%) will work against most spores; higher concentrations (7 to 30%) and longer contact times will improve sporicidal activity.[72][74]

    Hydrogen peroxide is seen as an environmentally safe alternative tochlorine-based bleaches, as it degrades to form oxygen and water and it isgenerally recognized as safe as anantimicrobial agent by the U.S.Food and Drug Administration (FDA).[75]

    Propellant

    [edit]
    Further information:High-test peroxide
    Rocket-belt hydrogen peroxide propulsion system used in ajet pack

    High-concentrationH2O2 is referred to as "high-test peroxide" (HTP). It can be used as either amonopropellant (not mixed with fuel) or the oxidizer component of abipropellant rocket. Use as a monopropellant takes advantage of the decomposition of 70–98% concentration hydrogen peroxide into steam and oxygen. The propellant is pumped into a reaction chamber, where a catalyst, usually a silver or platinum screen, triggers decomposition, producing steam at over 600 °C (1,100 °F), which is expelled through anozzle, generatingthrust.H2O2 monopropellant produces a maximalspecific impulse (Isp) of 161 s (1.6kN·s/kg). Peroxide was the first major monopropellant adopted for use in rocket applications.Hydrazine eventually replaced hydrogen peroxide monopropellant thruster applications primarily because of a 25% increase in the vacuum specific impulse.[76] Hydrazine (toxic) and hydrogen peroxide (less toxic [ACGIH TLV 0.01 and 1 ppm respectively]) are the only two monopropellants (other than cold gases) to have been widely adopted and utilized for propulsion and power applications.[citation needed] TheBell Rocket Belt,reaction control systems forX-1,X-15,Centaur,Mercury,Little Joe, as well as the turbo-pump gas generators for X-1, X-15, Jupiter, Redstone and Viking used hydrogen peroxide as a monopropellant.[77] TheRD-107 engines (used from 1957 to present) in theR-7 series of rockets decompose hydrogen peroxide to power the turbopumps.

    In bipropellant applications,H2O2 is decomposed to oxidize a burning fuel. Specific impulses as high as 350 s (3.5 kN·s/kg) can be achieved, depending on the fuel. Peroxide used as an oxidizer gives a somewhat lowerIsp than liquid oxygen but is dense, storable, and non-cryogenic and can be more easily used to drive gas turbines to give high pressures using an efficientclosed cycle. It may also be used for regenerative cooling of rocket engines. Peroxide was used very successfully as an oxidizer in World War II German rocket motors (e.g.,T-Stoff, containing oxyquinoline stabilizer, for both theWalter HWK 109-500StarthilfeRATO externally podded monopropellant booster system and theWalter HWK 109-509 rocket motor series used for theMe 163B), most often used withC-Stoff in a self-ignitinghypergolic combination, and for the low-cost BritishBlack Knight andBlack Arrow launchers. Presently, HTP is used on ILR-33 AMBER[78] and Nucleus[79] suborbital rockets.

    In the 1940s and 1950s, theHellmuth Walter KG–conceivedturbine used hydrogen peroxide for use insubmarines while submerged; it was found to be too noisy and require too much maintenance compared todiesel-electric power systems. Sometorpedoes used hydrogen peroxide as oxidizer or propellant. Operator error in the use of hydrogen peroxide torpedoes was named as possible causes for the sinking ofHMSSidon and theRussian submarineKursk.[80] SAAB Underwater Systems is manufacturing the Torpedo 2000. This torpedo, used by theSwedish Navy, is powered by a piston engine propelled by HTP as an oxidizer andkerosene as a fuel in a bipropellant system.[81][82]

    Household use

    [edit]
    Contact lenses soaking in a 3% hydrogen peroxide-based solution. The case includes a catalytic disc which neutralises the hydrogen peroxide over time.

    Hydrogen peroxide has various domestic uses, primarily as a cleaning and disinfecting agent.

    Hair bleaching and coloring.

    DilutedH2O2 (between 1.9% and 12%) mixed into a solution withaqueous ammonia, aniline (color molecule) and a coupler, has been used to color humanhair. It can also be mixed with powder or cream bleach compounds, most notably potassium chloride. Bleaching hair follicles does not destroy or remove color molecule or melanocytes. Bleaching compounds work to drive wedges between color molecules or melanocyte's allowing more visible light to pass through the hair shaft. The chemical's bleaching property lends its name to the phrase "peroxide blonde".[83]Hydrogen peroxide is also used fortooth whitening. It may be found in most whitening toothpastes. Hydrogen peroxide has shown positive results involving teeth lightness and chroma shade parameters.[84] It works by oxidizing colored pigments onto theenamel where the shade of the tooth may become lighter.[further explanation needed] Hydrogen peroxide may be mixed with baking soda and salt to make a homemade toothpaste.[85]

    Removal of blood stains

    Hydrogen peroxide reacts with blood as a bleaching agent, and so if a blood stain is fresh, or not too old, liberal application of hydrogen peroxide, if necessary in more than single application, will bleach the stain fully out. After about two minutes of the application, the blood should be firmly blotted out.[86][87]

    Acne treatment

    Hydrogen peroxide may be used to treatacne,[88] althoughbenzoyl peroxide is a more common treatment.

    Oral cleaning agent

    The use of dilute hydrogen peroxide as an oral cleansing agent has been reviewed academically to determine its usefulness in treatinggingivitis andplaque. Although there is a positive effect when compared with a placebo, it was concluded thatchlorhexidine is a much more effective treatment.[89]

    Niche uses

    [edit]
    Chemiluminescence ofcyalume, as found in a glow stick
    Horticulture

    Somehorticulturists and users ofhydroponics advocate the use of weak hydrogen peroxide solution in watering solutions. Its spontaneous decomposition releases oxygen that enhances a plant's root development and helps to treatroot rot (cellular root death due to lack of oxygen) and a variety of other pests.[90][91]

    For general watering concentrations, around 0.1% is in use. This can be increased up to one percent for antifungal actions.[92] Tests show that plant foliage can safely tolerate concentrations up to 3%.[93]

    Fishkeeping

    Hydrogen peroxide is used inaquaculture for controllingmortality caused by various microbes. In 2019, the U.S. FDA approved it for control ofSaprolegniasis in all coldwater finfish and all fingerling and adult coolwater and warmwater finfish, for control of externalcolumnaris disease in warm-water finfish, and for control ofGyrodactylus spp. in freshwater-reared salmonids.[94] Laboratory tests conducted by fish culturists have demonstrated that common household hydrogen peroxide may be used safely to provide oxygen for small fish. The hydrogen peroxide releases oxygen by decomposition when it is exposed to catalysts such asmanganese dioxide.

    Removing yellowing from aged plastics

    Hydrogen peroxide may be used in combination with a UV-light source to remove yellowing from white or light greyacrylonitrile butadiene styrene (ABS) plastics to partially or fully restore the original color. In theretrocomputing scene, this process is commonly referred to asretrobright.

    Safety

    [edit]
    Fingertips
    Skin shortly after exposure to 35%H2O2

    Regulations vary, but low concentrations, such as 5%, are widely available. Concentrated solutions ofH2O2 react violently with organic materials.[95]While concentrations up to 35% produce only "white" oxygen bubbles in the skin (and some biting pain) that disappear with the blood within 30–45 minutes, concentrations of 98% dissolve paper. However, concentrations as low as 3% can be dangerous for the eye because ofoxygen evolution within the eye.[96]

    When hydrogen peroxide is used at moderate to high concentrations in organic laboratories, the associated hazards include:

    1. Decomposition and pressure buildup — The confinement or unintended heating of concentrated solutions can result in rapid gas evolution, leading to the risk of vessel rupture.[97]
    2. Incompatibilities and catalysis by transition metals or organics — The presence of trace contaminants, metal ions, or organic reducing agents may accelerate decomposition or trigger radical pathways.[97]
    3. Thermal runaway or self-accelerating decomposition — In the context of peroxide chemistry, it is crucial to consider the self-accelerating decomposition temperature (SADT) and to avoid scaling up reactions without conducting a thorough hazard assessment.[97]
    4. Oxidizer hazards in the presence of organics — Hydrogen peroxide (H₂O₂) acts as an aggressive oxidizer. When in contact with organic substrates, solvents, or flammable materials, the risk of fire or explosion is heightened; therefore, it is essential to ensure that oxidizer storage is kept separate from reducing materials.[97]

    High-concentration hydrogen peroxide streams, typically above 40%, should be considered hazardous due to concentrated hydrogen peroxide's meeting the definition of aDOT oxidizer according to U.S. regulations if released into the environment. TheEPA Reportable Quantity (RQ) for D001 hazardous wastes is 100 pounds (45 kg), or approximately 10 US gallons (38 L), of concentrated hydrogen peroxide.

    A commercial bottle of H2O2

    Hydrogen peroxide should be stored in a cool, dry, well-ventilated area and away from any flammable or combustible substances. It should be stored in a container composed of non-reactive materials such as stainless steel or glass (other materials including some plastics and aluminium alloys may also be suitable).[98] As it breaks down quickly when exposed to light, it should be stored in an opaque container, and pharmaceutical formulations typically come in brown bottles that block light.[99]

    Hydrogen peroxide, either in pure or diluted form, may pose several risks, the main one being that it forms explosive mixtures upon contact with organic compounds.[100]Distillation of hydrogen peroxide at normal pressures is highly dangerous. It is corrosive, especially when concentrated, but even domestic-strength solutions may cause irritation to the eyes,mucous membranes, and skin.[101] Swallowing hydrogen peroxide solutions is particularly dangerous, as decomposition in the stomach releases large quantities of gas (ten times the volume of a 3% solution), leading to internal bloating. Inhaling over 10% can cause severe pulmonary irritation.[102]

    With a significant vapour pressure (1.2 kPa at 50 °C),[103] hydrogen peroxide vapour is potentially hazardous. According to U.S. NIOSH, theimmediately dangerous to life and health (IDLH) limit is only 75 ppm.[104] The U.S.Occupational Safety and Health Administration (OSHA) has established a permissible exposure limit of 1.0 ppm calculated as an 8-hour time-weighted average (29 CFR 1910.1000, Table Z-1).[100] Hydrogen peroxide has been classified by theAmerican Conference of Governmental Industrial Hygienists (ACGIH) as a "known animal carcinogen, with unknown relevance on humans".[105] For workplaces where there is a risk of exposure to the hazardous concentrations of the vapours, continuous monitors for hydrogen peroxide should be used. Information on the hazards of hydrogen peroxide is available from OSHA[100] and from the ATSDR.[106]

    Wound healing

    [edit]

    Historically, hydrogen peroxide was used for disinfecting wounds, partly because of its low cost and prompt availability compared to otherantiseptics.[107]

    There is conflicting evidence on hydrogen peroxide's effect on wound healing. Some research finds benefit, while other research find delays and healing inhibition.[108] Its use for home treatment of wounds is generally not recommended.[109]1.5–3% hydrogen peroxide is used as a disinfectant in dentistry, especially in endodotic treatments together with hypochlorite and chlorhexidine and 1–1.5% is also useful for treatment of inflammation of third molars (wisdom teeth).[110]

    Use in alternative medicine

    [edit]

    Practitioners ofalternative medicine have advocated the use of hydrogen peroxide for various conditions, includingemphysema,influenza,AIDS, and in particularcancer.[111] Medical authorities and regulatory agencies warn that such uses are unsupported by scientific evidence and can be dangerous. Ingesting or injecting hydrogen peroxide, even in so-called “food-grade” concentrations, has led to serious adverse effects and fatalities.[112][113][114][115]

    Both the effectiveness and safety of hydrogen peroxide therapy is scientifically questionable. Hydrogen peroxide is produced by the immune system, but in a carefully controlled manner. Cells calledphagocytes engulf pathogens and then use hydrogen peroxide to destroy them. The peroxide is toxic to both the cell and the pathogen and so is kept within a special compartment, called aphagosome. Free hydrogen peroxide will damage any tissue it encounters viaoxidative stress, a process that also has been proposed as a cause of cancer.[116]Claims that hydrogen peroxide therapy increases cellular levels of oxygen have not been supported. The quantities administered would be expected to provide very little additional oxygen compared to that available from normal respiration. It is also difficult to raise the level of oxygen around cancer cells within a tumour, as the blood supply tends to be poor, a situation known astumor hypoxia.

    Large oral doses of hydrogen peroxide at a 3% concentration may cause irritation and blistering to the mouth, throat, and abdomen as well as abdominal pain, vomiting, and diarrhea.[112] Ingestion of hydrogen peroxide at concentrations of 35% or higher has been implicated as the cause of numerousgas embolism events resulting in hospitalisation. In these cases,hyperbaric oxygen therapy was used to treat the embolisms.[117]

    Intravenous injection of hydrogen peroxide has been linked to several deaths.[118][114][115]TheAmerican Cancer Society states that "there is no scientific evidence that hydrogen peroxide is a safe, effective, or useful cancer treatment."[113] Furthermore, the therapy is not approved by the U.S. FDA.

    Historical incidents

    [edit]
    • On 16 July 1934, inKummersdorf, Germany, a propellant tank containing an experimental monopropellant mixture consisting of hydrogen peroxide andethanol exploded during a test, killing three people.[119]
    • During theSecond World War, doctors inGerman concentration camps experimented with the use of hydrogen peroxide injections in the killing of human subjects.[120]
    • In December 1943, the pilotJosef Pöhs died after being exposed to theT-Stoff of hisMesserschmitt Me 163.
    • In June 1955, Royal Navy submarineHMSSidon sank after leaking high-test peroxide in a torpedo caused it to explode in its tube, killing twelve crew members; a member of the rescue party also succumbed.
    • In April 1992, an explosion occurred at the hydrogen peroxide plant atJarrie in France, due to technical failure of the computerised control system and resulting in one fatality and wide destruction of the plant.[121]
    • Several people received minor injuries after a hydrogen peroxide spill on board aNorthwest Airlines flight fromOrlando, Florida toMemphis, Tennessee on 28 October 1998.[122]
    • The sinking of the Russian submarineK-141Kursk is attributed to the explosion of one of its hydrogen peroxide-fueled torpedoes.[123]
    • On 15 August 2010, a spill of about 30 US gallons (110 L) of cleaning fluid occurred on the 54th floor of 1515 Broadway, inTimes Square,New York City. The spill, which a spokesperson for theNew York City Fire Department said was of hydrogen peroxide, shut down Broadway between West 42nd and West 48th streets as fire engines responded to thehazmat situation. There were no reported injuries.[124]
    • In August 2024, an explosion occurred atEvonik Industries’ chemical facility in Theodore,Alabama, when a railcar containing 70% hydrogen peroxide experienced overpressure. The incident took place around 2:00 PM, but fortunately, no serious injuries were reported; only minor first-aid was provided on-site. Local fire departments promptly responded to control the situation. After the event, Evonik began a phased restart of operations following comprehensive safety inspections and pledged full cooperation with authorities during the investigation. This explosion highlights the risks linked to the handling of concentrated hydrogen peroxide, a strong oxidizer, and emphasizes the importance of following strict safety measures in industrial settings.[125]

    See also

    [edit]

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    Compounds of theperoxide ion
    H2O2He
    Li2O2BeBCNOO2F2
    O4F2
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    Na2O2MgO2AlSiPH2OSClOOCl
    Cl2O5
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    K2O2CaO2ScTiVCrO(O2)2MnFeCoNiCuO2ZnO2GaGeAsSeBrKr
    Rb2O2SrO2YZrNbMoTcRuRhPdAgCdInSnSbTeIXe
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    *LaCePrNdPmSmEuGdTbDyHoErTmYb
    **AcThPaUO4·nH2ONpPuAmCmBkCfEsFmMdNo
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