Chemical Properties
Colorless liquid; pure compound or 90% solution unstable; bitter taste; density 1.463 g/mL; boils at 150.2°C; freezes at –0.43°C; vapor pressure 9.9 torr
at 50°C and 121.5 torr at 100°C; viscosity 1.245 centipoise at 20°C; surface
tension 80.4 dyn/cm at 20°C; miscible with water in all proportions; soluble in
ether; densities of 30%, 70%, and 90% H2O2 solutions are 1.1081, 1.2839 and
1.3867 g/mL, respectively, at 25°C; freezing points at these concentrations are
–25.7°C, –40.3°C and –11.5°C, respectively; and their boiling points are
106.2°C, 125.5°C and 141.3°C, respectively; decomposed by many organic solvents; pKa at 25°C is 11.62.
Definition
ChEBI: An inorganic peroxide consisting of two hydroxy groups joined by a covalent oxygen-oxygen single bond.
General Description
A colorless liquid dissolved in water. Vapors may irritate the eyes and mucous membranes. May violently decompose on contact with most common metals and their compounds. Contact with combustible material may result in spontaneous ignition. Corrosive to tissue. Under exposure to fire or heat containers may violently rupture due to decomposition. Used to bleach textiles and wood pulp, in chemical manufacturing, food processing, and in water purification.
Reactivity Profile
The hazards associated with the use of HYDROGEN PEROXIDE(especially highly concentrated solutions) are well documented. There is a release of enough energy during the catalytic decomposition of 65% peroxide to evaporate all water and ignite nearby combustible materials. Most cellulose materials contain enough catalyst to cause spontaneous ignition with 90% peroxide. Contamination of concentrated peroxide causes the possibility of explosion. Readily oxidizable materials, or alkaline substances containing heavy metals may react violently. Solvents(acetone, ethanol, glycerol) will detonate on mixture with peroxide of over 30% concentration, the violence increasing with concentration. Concentrated peroxide may decompose violently in contact with iron, copper, chromium, and most other metals or their salts, and dust(which frequently contain rust). During concentration under vacuum of aqueous or of aqueous-alcoholic solutions of hydrogen peroxide, violent explosions occurred when the concentration was sufficiently high(>90%), [Bretherick 2nd ed., 1979]. Hydrogen selenide and hydrogen peroxide undergo a very rapid decomposition, [Mellor 1:941(1946-1947)].
Air & Water Reactions
Water soluble.
Health Hazard
TOXIC; inhalation, ingestion or contact (skin, eyes) with vapors, dusts or substance may cause severe injury, burns or death. Fire may produce irritating and/or toxic gases. Toxic fumes or dust may accumulate in confined areas (basement, tanks, hopper/tank cars, etc.). Runoff from fire control or dilution water may cause pollution.
Fire Hazard
May explode from friction, heat or contamination. These substances will accelerate burning when involved in a fire. May ignite combustibles (wood, paper, oil, clothing, etc.). Some will react explosively with hydrocarbons (fuels). Containers may explode when heated. Runoff may create fire or explosion hazard.
Description
Hydrogen peroxide (H2O2) is a strong oxidizing agent that is used
extensively in industry and medicine. It is usually available as
aqueous solutions in concentrations of 3, 30 or 90 percent by
weight. The 3 percent solution is used as a topical antiseptic and
cleansing agent, and as a constituent in mouthwashes, dentifrices
and sanitary lotions; the 30 percent as an effective bleaching agent
and for other industrial uses; and the 90 percent as a vigorous
oxidizer of rocket fuels. The anhydrous form is a colorless, bittertasting liquid with an ozone-like odor. In the absence of stabilizing
agents (e.g., phosphates, tin), hydrogen peroxide solutions are
unstable and decompose upon standing, agitation, exposure to
light, or heating. Hydrogen peroxide reacts vigorously with many
oxidizing as well as reducing agents. Concentrated solutions are
highly caustic to the skin.
In addition to its effectiveness as a bleach, hydrogen peroxide has
proved to be a useful antimicrobial agent. This latter property has
been utilized in some countries as a preservative of milk and whey.
Physical properties
Colorless liquid; pure compound or 90% solution unstable; bitter taste; den-sity 1.463 g/mL; boils at 150.2°C; freezes at -0.43°C; vapor pressure 9.9 torrat 50°C and 121.5 torr at 100°C; viscosity 1.245 centipoise at 20°C; surfacetension 80.4 dyn/cm at 20°C; miscible with water in all proportions; soluble inether; densities of 30%, 70%, and 90% H2O2solutions are 1.1081, 1.2839 and1.3867 g/mL, respectively, at 25°C; freezing points at these concentrations are-25.7°C, -40.3°C and -11.5°C, respectively; and their boiling points are106.2°C, 125.5°C and 141.3°C, respectively; decomposed by many organic sol-vents; pKaat 25°C is 11.62.
Production Methods
From 1920 to 1950, the primary method of production was electrolysis. One process involved passing electric current through sulfuric acid to produce the peroxydisulfate ion (S2O8 2-), which was then hydrolyzed to H2O2: 2H2O + S2O82- (aq) 2H2SO4-(aq) + H2O2(aq).the relatively high cost of electricity of this method encouraged a search for a more economical production process. Hydrogen peroxide is currently produced on a large scale using the anthraquinone autooxidation procedure, which was developed in the 1940s. In this process, an anthraquinone, typically 2-ethyl-anthraquinone, is hydrogenated to a hydroquinone (2-ethyl-anthrahydroquinone) then reoxidized back to the anthraquinone (2-ethyl-anthraquinone) while forming hydrogen peroxide . A metal palladium or nickel catalyst is used to convert the anthraquinone to the hydroquinone, followed by autooxidation in air to generate hydrogen peroxide. The anthraquinone and hydrogen peroxide are separated; the former is recycled to repeat the process while the hydrogen peroxide is purified.
Reactions
Hydrogen peroxide reacts with many compounds, such as borates, carbonates, pyrophosphates, sulfates, silicates, and a variety of organic carboxylic acids, esters, and anhydrides to give peroxy compounds or peroxyhydrates. A number of these compounds are stable solids that hydrolyze readily to give hydrogen peroxide in solution.
Flammability and Explosibility
Hydrogen peroxide is not flammable, but concentrated solutions may undergo
violent decomposition in the presence of trace impurities or upon heating.
Toxicology
Hydrogen peroxide is used as an agent to reduce the number of bacteria in
dairy products or other foodstuffs. In the dairy industry, hydrogen peroxide
also has been used as a substitute for heat pasteurization in the treatment of
milk and as a direct preservative in keeping the quality of the milk. In
Japan, it has been used as a preservative for fish-paste products. Hydrogen
peroxide also has a bleaching effect. The use of highly pure hydrogen peroxide
in manufactured cheese has been approved by the United States Food
and Drug Administration (industrial grade hydrogen peroxide is usually a
3–35% aqueous solution; a commercial home product is a 3% aqueous
solution).
Acute toxicities (LD50) of hydrogen peroxide for rats are 700 mg/kg/b.w.
and 21 mg/kg/b.w. by subcutaneous injection and intravenous injection,
respectively. When large amounts of hydrogen peroxide were injected
directly into the stomachs of rats, weight and blood protein concentrations
were changed slightly. When hydrogen peroxide was mixed with feed, however,
no abnormalities were observed. The use of bactericides has been limited
due to their toxicity to humans, and only hydrogen peroxide currently is
recognized for use.
Potential Exposure
PotentialExposure:CompoundDescription: Drug,Tumorigen,Mutagen, Human Data; Hormone, PrimaryIrritant (90%); Mutagen, Human Data (20%). Hydrogenperoxide is used in the manufacture of acetone, antichlor,antiseptics, benzoyl peroxide, buttons, disinfectants, phar-maceuticals, felt hats, plastic foam, rocket fuel, sponge rub-ber, and pesticides; as a food and feed additive; flavor; as apackaging material; in bleaching bone; feathers, flour, fruit,fur, gelatin, glue, hair, ivory, silk, soap, straw, textiles, wax,and wood pulp; and as an oxygen source in respiratory pr0-tective equipment. Other specific occupations with potentialexposure include liquor and wine agers, dyers, electropla-ters, fat refiners, photographic film developers, wool prin-ters, veterinarians, and water treaters.
First aid
If this chemical gets into the eyes, remove anycontact lenses at once and irrigate immediately for at least15 min, occasionally lifting upper and lower lids. Seek med-ical attention immediately. If this chemical contacts theskin, remove contaminated clothing and wash immediatelywith soap and water. Seek medical attention immediately. Ifthis chemical has been inhaled, remove from ex posure,begin rescue breathing (using universal precautions, includ-ing resuscitation mask) if breathing has stopped and CPR ifheart action has stopped. Transfer promptly to a medicalfacility. When this chemical has been swallowed, get medi-cal attention. If victim is conscious, administer water ormilk. Do not induce vomiting. Medical observation isrecommended for 24- -48 h after breathing overexposure, aspulmonary edema may be delayed. As first aid for pulmo-nary edema, a doctor or authorized paramedic may consideradministering a corticosteroid spray.
Carcinogenicity
Chronic studies in mice found adenomas
and carcinomas of the duodenum after oral
administration. The IARC has determined that
there is limited evidence in experimental
animals for the carcinogenicity of hydrogen
peroxide and inadequate evidence in humans.
storage
Use extreme care when carrying out
reactions with hydrogen peroxide because of the fire and explosion potential
(immediate or delayed). The use of safety shields is advisable, and is essential for
experiments involving concentrated (>50%) solutions of hydrogen peroxide. Sealed
containers of hydrogen peroxide can build up dangerous pressures of oxygen, owing
to slow decomposition.
Shipping
Hydrogen peroxide, stabilized, or hydrogen per-oxide aqueous solutions, stabilized with > 60% hydrogenperoxide,requirea shipping label of “OXIDIZER,CORROSIVE." It falls in Hazard Class 5.1 and PackingGroup I.Hydrogen peroxide, aqueous solutions with > > 40% but not>60% hydrogen peroxide (stabilized as necessary), requiresa shipping label of“OXIDIZER, CORROSIVE." It falls inHazard Class 5.1 and Packing Group II.Hydrogen peroxide, aqueous solutions with not < 20% butnot >40% hydrogen peroxide (stabilized as necessary), requires a shipping label of“OXIDIZER, CORROSIVE."" Itfalls in Hazard Class 5.1 and Packing Group II.Hydrogen peroxide, aqueous solutions with not < <8% but<20% hydrogen peroxide (stabilized as necessary), requiresa shipping label of“OXIDIZER" It falls in Hazard Class5.1 and Packing Group III.
Purification Methods
The 30% material has been steam distilled using distilled water. Gross and Taylor [J Am Chem Soc 72 2075 1950] made 90% H2O2 approximately 0.001M in NaOH and then distilled it under its own vapour pressure, keeping the temperature below 40o, the receiver being cooled with a Dry-ice/isopropyl alcohol slush. The 98% material has been rendered anhydrous by repeated fractional crystallisation in all-quartz vessels. EXPLOSIVE IN CONTACT WITH ORGANIC MATERIAL.
Incompatibilities
Contact with many organic compounds can lead to immediate fires or violent
explosions (consult Bretherick for references and examples). Hydrogen peroxide
reacts with certain organic functional groups (ethers, acetals, etc.) to form peroxides,
which may explode upon concentration. Reaction with acetone generates explosive
cyclic dimeric and trimeric peroxides. Explosions may also occur on exposure of
hydrogen peroxide to metals such as sodium, potassium, magnesium, copper, iron,
and nickel.
Waste Disposal
Excess hydrogen peroxide and waste material containing this substance should be
placed in an appropriate container, clearly labeled, and handled according to your
institution's waste disposal guidelines. For more information on disposal procedures,
see Chapter 7 of this volume.