|Wedges to clarify the spatial structure|
|Molecular formula||H 2 O 2|
colorless, almost odorless liquid
|External identifiers / databases|
|Molar mass||34.02 g mol −1|
−0.43 ° C (pure)
150.2 ° C (pure)
|pK s value||
miscible with water
DFG / Switzerland: 0.5 ml m −3 or 0.71 mg m −3
|ΔH f 0||
−188 kJ mol −1
|As far as possible and customary, SI units are used. Unless otherwise noted, the data given apply to standard conditions .|
Hydrogen peroxide (H 2 O 2 ) is a pale blue, in diluted form colorless, largely stable liquid compound made of hydrogen and oxygen . It is a little more viscous than water , a weak acid and a very strong oxidizing agent compared to most substances , which as such reacts violently with substances such as copper , brass , potassium iodide and thus acts as a strong bleaching and disinfecting agent . In its highly concentrated form, it can be used both as a single and as a component rocket fuel.
In commercial trade, hydrogen peroxide is usually available as a 30 to 35 percent aqueous solution.
Hydrogen peroxide was first produced in 1818 by Louis Jacques Thénard by reacting barium peroxide with nitric acid. The process was improved first through the use of hydrochloric acid and then sulfuric acid . The latter is particularly suitable because the barium sulfate by-product is precipitated. Thénard's method was used from the late 19th century to the middle of the 20th century.
For a long time it was believed that pure hydrogen peroxide was unstable because attempts to separate it from the water produced during production failed. This was due to the fact that traces of solid bodies and heavy metal ions lead to catalytic degradation or even to an explosion. Absolutely pure hydrogen peroxide was first obtained in 1894 by Richard Wolffenstein using vacuum distillation .
Extraction and manufacture
Today, hydrogen peroxide is technically produced using the anthraquinone process . For this purpose, anthrahydroquinone is converted to hydrogen peroxide and anthraquinone with atmospheric oxygen under pressure . In the next step, anthraquinone can again be reduced to anthrahydroquinone using hydrogen .
The gross equation is:
On a laboratory scale, hydrogen peroxide is also produced when peroxides are treated with acids . A historically important reagent is barium peroxide , which reacts in a sulfuric acid solution to form hydrogen peroxide and barium sulfate .
- Δ f H 0 gas : −136.11 kJ / mol
- Δ f H 0 liq : −188 kJ / mol
- Δ f H 0 sol : −200 kJ / mol
The compound is miscible with water in any ratio. Although the melting points of the neat components are relatively similar, significantly lower melting points are observed in mixtures. A dihydrate (H 2 O 2 · 2H 2 O) which melts at a defined temperature of −52.1 ° C is found. Together with the pure substance components, this forms two eutectics with a hydrogen peroxide content of 45.2% by mass with −52.4 ° C and 61.2% with −56.5 ° C. Hydrogen peroxide and water do not form an azeotropic mixture.
The H 2 O 2 - molecule is in terms of the two O-O-H planes angled ( dihedral angle = 90.2 ± 0.6 °). The O – O bond length is 145.3 ± 0.7 pm, the O – H bond length is 99.8 ± 0.5 pm, and the O – H bond angle is 102.7 ± 0.3 °. As with water, hydrogen bonds are formed in the liquid phase . The angled structure and modified hydrogen bridge structure lead to a significantly higher density and slightly higher viscosity compared to water.
|Physical properties of aqueous hydrogen peroxide solutions .|
|H 2 O 2 - mass fraction (w)||0%||10%||20%||35%||50%||70%||90%||100%|
|Melting point (in ° C)||0||−6||−14||−33||−52.2||−40.3||−11.9||−0.43|
|Boiling point (in ° C, 101.3 kPa)||100||101.7||103.6||107.9||113.8||125.5||141.3||150.2|
|Density (in g cm −3 )||0 ° C||0.9998||1.1441||1.2110||1.3071||1.4136||1.4700|
|20 ° C||0.9980||1.03||1.07||1.1312||1.1953||1.2886||1.3920||1.4500|
|25 ° C||0.9971||1.1282||1.1914||1.2839||1.3867||1.4425|
|Vapor pressure (in hPa)||20 ° C||23||17th||8th||1.9|
|30 ° C||42||30.7||14.7||6.67||3.9|
|50 ° C||123||13.2|
|Specific heat capacity (in J · K -1 · g -1 )||25 ° C||4.18||3.96||3.78||3.57||3.35||3.06||2.77||2.62|
|Viscosity (in mPas)||0 ° C||1,792||1.82||1.87||1.93||1.88||1,819|
|20 ° C||1.002||1.11||1.17||1.23||1.26||1.249|
|Refractive index ( )||1.3330||1.3563||1.3672||1.3827||1.3995||1.4084|
Hydrogen peroxide is a very weak acid. The following equilibrium is established in water:
The acid constant is K S = 1.6 · 10 −12 or pK S = 11.8.
Hydrogen peroxide tends to break down into water and oxygen. In particular, in the case of highly concentrated solutions and contact with metal surfaces or the presence of metal salts and oxides, spontaneous decomposition can occur. The decay reaction is strongly exothermic with a heat of reaction of −98.20 kJ mol −1 or −2887 kJ kg −1 . In addition, with 329 l kg −1 hydrogen peroxide, a considerable amount of gas is released:
- Disproportionation of two molecules of hydrogen peroxide to form water and oxygen.
This decomposition reaction is, among other things by heavy metal ions, I - - and OH - catalyzed ions. For this reason, stabilizers (including phosphoric acid ) are added to H 2 O 2 solutions on the market . It is a powerful oxidizer . When the oxidation state is reduced from −I to −II, the only reaction products are water and oxygen. Difficult to separate or disruptive by-products are not produced, which simplifies its use in the laboratory.
Biological properties (physiology)
Hydrogen peroxide is very corrosive , especially as steam . If you get hydrogen peroxide on the skin, you should rinse the area well with water (dilution) or at least remove the hydrogen peroxide from the skin immediately. If it penetrates the skin, it decomposes there quickly, and the resulting oxygen bubbles make the skin appear white.
Hydrogen peroxide is produced in numerous biochemical processes. In the biological cycle it arises from the oxidative metabolism of sugar. The organism protects itself against its toxic effects by means of enzymes - catalases , peroxidases , which decompose it again into non-toxic O 2 and H 2 O.
Hair turns gray with age
German and British researchers announced in a study in March 2009 that the " gray color " (actually white color) of hair with age is the result of less breakdown of hydrogen peroxide in the hair. It has been shown in laboratory tests that hydrogen peroxide hinders the function of the enzyme tyrosinase , which is required for melanin production . This happens through oxidation of the amino acid methionine contained in the tyrosinase .
Highly concentrated solutions of hydrogen peroxide can decompose spontaneously with an explosion , so a maximum of 12 percent solutions in water are freely available in stores. From a concentration of 12%, there is a ban on sales to private end users; it also exists in Germany for suspicious transactions or theft reporting obligation to the responsible state police. Aqueous solutions with concentrations of up to 70% H 2 O 2 are available for industrial use .
Hydrogen peroxide is a bleaching agent . The most common application worldwide is pulp bleaching . Pulp is obtained from wood , and the lignin it contains gives the pulp a yellow tone , which is perceived as a nuisance in the main use of pulp for paper and paper products.
It is used for bleaching as well as dyeing , tinting and intensive tones and for fixing permanent changes ( perm and volume wave ) as well as for fixing permanent straightening of hair . A very light, artificial blonde shade is therefore called "hydrogen blonde". The connection becomes even clearer in the English term peroxide blonde .
Hydrogen peroxide and bleaching agents containing hydrogen peroxide, such as a mixture of peroxyacetic acid and hydrogen peroxide , are also referred to in advertising using the artificial word "active oxygen". In addition to hydrogen peroxide, other peroxides can also be used for bleaching purposes , which disintegrate when exposed to water and release the active atomic oxygen .
When UV rays act on hydrogen peroxide, the hydroxyl radical , a much stronger oxidizing agent than the peroxide itself, is formed. Below is the equation for the formation:
This strong oxidation effect is used in water treatment to break down organic impurities. As an example, the so-called UVOX process ( UV light and OX idation), with which the herbicide atrazine and its degradation product desethylatrazine or other toxic ingredients can be safely removed from drinking water. Through this “wet combustion” of the atrazine, only decomposition products such as water , oxygen , carbon dioxide and nitrogen are formed, and there is no additional salt build-up in the water. In addition, this method replaces the use of activated carbon , which is significantly more expensive.
Disinfection and sterilization
A 3 percent solution of hydrogen peroxide is used for disinfection , also in the household sector. Examples of use are the mouth and throat ( it is diluted to 0.3% for mouth rinsing), dentistry , the disinfection of contact lenses in cleaning agents , the disinfection of packaging materials or the disinfection of hands in cases of illness. Accordingly, it is used in face creams: to cleanse the pores and combat pimples and skin impurities. It is also used to disinfect the water when cleaning industrial wastewater and in swimming pool technology.
The 35 percent solution of hydrogen peroxide is used in the food industry in aseptic filling systems for the sterilization of PET bottles, plastic containers and the typical multilayer cardboard packaging. Numerous foods (beverages, milk , dairy products, sauces, soups) are aseptically packaged today in cardboard boxes, cups, bottles and foils for better shelf life and product quality. The packaging material is disinfected with 35 percent hydrogen peroxide before the respective food is filled.
Another area of application is the use of gaseous H 2 O 2 for clean room decontamination. For this purpose, a usually 35 percent solution is evaporated in a special device and blown into the area to be decontaminated (room, chamber, etc.).
The high bactericidal effect of H 2 O 2 , the environmental compatibility and the good technical feasibility are the reasons for the widespread use of this process.
Another method of room disinfection with hydrogen peroxide is cold nebulization. In this process, hydrogen peroxide is converted into an aerosol and, depending on its concentration (from 3%), is distributed in the room by an aerosol generator according to a specified process cycle. The aerosols have a droplet size of 0.5–40 µm. The droplet size depends on the technology used to generate the aerosols. The aerosols distribute themselves evenly in the room after a short time. A small droplet size has a positive effect on the distribution and the ability of the droplets to float. Depending on the initial climatic conditions of the room, some of the droplets present in the liquid phase are converted into the gas phase. The energy required for this is taken from the room temperature. The process is identical to adiabatic humidification. The medium mixes with the medium air and, when used properly, causes a holotic disinfection. The device (generator) for nebulization and the special procedure must be validated in advance for effectiveness. In addition, this must be checked for effectiveness on the basis of the existing standardization. The system of disinfection product and aerosol generator is tested for its effectiveness in a laboratory.
Hydrogen peroxide can be used in aquariums to supply oxygen. Oxygen is generated in an oxidizer . For this purpose, hydrogen peroxide is split into water and oxygen radicals in a vessel in the aquarium with the help of a catalyst .
Against mold growth
During interior renovation, mold infestation can be combated with hydrogen peroxide. It acts as a disinfectant against both the biologically active fungal cells - as a fungicide - and against the " conidia " called spores of the fungi.
Due to its bleaching effect, it also "optically" removes the residues of the mold from porous substrates. Hydrogen peroxide has some advantages over alcohol or sodium hypochlorite because, unlike alcohol, it is non-flammable, has a bleaching effect and, unlike sodium hypochlorite, does not leave any chlorinated by-products behind.
In dentistry , H 2 O 2 is used as a three percent aqueous solution for the local disinfection of tooth tissue and for hemostasis in minor operations. In medicine and emergency medicine , the substance can be used to disinfect surfaces, instruments, skin and mucous membranes . Hydrogen peroxide is still used sporadically to clean wounds these days, but has lost its traditional importance because it is quickly inactivated when it comes into contact with red blood cells and foams and therefore only develops its effect for a short time.
For some time now, a method for sterilizing certain medical products and surgical instruments has been used in which H 2 O 2 is used as a process chemical (H 2 O 2 plasma method). It has advantages over steam sterilization, especially with thermally unstable products. It can e.g. B. evaporated in vacuo at room temperature and additionally ionized .
In addition, H 2 O 2 is used to disinfect piercings . There it is supposed to disinfect the affected area and allow any bleeding to clot, which is supposed to accelerate the healing process.
In agriculture , hydrogen peroxide is used for disinfection in greenhouses and for oxygen enrichment in nutrient solutions from hydroponics. Hydrogen peroxide is also used to disinfect drinking line systems or stable equipment, for example in pig farming.
For the determination of bacterial cultures , the catalase test is carried out with a three percent hydrogen peroxide solution. Most aerobic and facultative anaerobic bacteria as well as fungi have the enzyme catalase , which is able to break down the H 2 O 2 , which is toxic to the cells .
Hydrogen peroxide has been used in forensics to detect blood . Louis Jacques Thénard discovered in 1818 that hemoglobin breaks down hydrogen peroxide. Christian Friedrich Schönbein developed a test for blood from this in 1863. Today, however, the more sensitive Kastle-Meyer test is used to detect blood.
In microelectronics , a mixture of sulfuric acid and hydrogen peroxide - called " piranha " - is used to clean the surface of wafers and to create a thin, three to four nanometer thick, hydrophilic oxide layer on the wafers. Nowadays the name “SPM” (Sulfuric Peroxide Mixture) is more common. The main application is the removal of photoresist from wafers.
- Elemental copper reacts with copper (II) chloride to form copper (I) chloride . This is a comproportioning .
To regenerate the copper chloride etching baths, hydrogen peroxide is used together with hydrochloric acid:
- The copper (II) chloride is regenerated by reacting the copper (I) chloride with hydrogen peroxide and hydrochloric acid. The copper atom is oxidized in the process .
The addition of hydrogen peroxide and hydrochloric acid is controlled via the redox potential; the photoresists used here are stable to hydrogen peroxide.
Rocket / torpedo engines
As an oxygen supplier, H 2 O 2 is used by decomposition (preferably over manganese dioxide ) in submarines. It was used in concentrated form in rocket drives at Max Valier and the Messerschmitt Me 163 , as well as in submarine drives ( Walter U-Boot ). Hydrogen peroxide, decomposed with the help of potassium permanganate, was used as a propellant for the fuel pumps (370 kW power) of the A4 rocket (also known as the V2 miracle weapon).
In British rockets (e.g. Black Arrow ), undecomposed 85 percent hydrogen peroxide was used as an oxygen carrier that was liquid at normal temperatures and burned with kerosene , with which it reacts hypergolically .
One of the theses about the sinking of the Russian nuclear submarine K-141 Kursk in 2000 stated that hydrogen peroxide leaked from a tank of a torpedo , reacted with iron oxide in the launch tube and ignited. The torpedo exploded, causing a devastating fire.
Such a fuel mixture (85-98% hydrogen peroxide) for missiles and torpedoes is also referred to as HTP (High Test Peroxide) .
Hydrogen peroxide tends to decompose in an uncontrolled manner. Kurt Wahmke and two technicians died on July 16, 1934 in Kummersdorf in the explosion of an engine powered by hydrogen peroxide. Due to the dangerousness in use and handling (corrosive effects, uncontrolled decomposition, explosion in the event of contamination in the tank and pipe system), use today is limited to small rocket engines (record attempts, control engines).
Fire hazard can arise in suitable combination with iron filings and cleaning rags; the accident prevention regulations therefore stipulate precautionary measures for process water treatment in metalworking companies.
Due to the peroxide group, the compound is high in energy and decomposes with the release of oxygen. In the presence of a suitable catalyst, hydrogen peroxide reacts with acetone to form acetone peroxide , which is a triacetone triperoxide and is known as an explosive with TATP . The explosive hexamethylene triperoxide diamine (HMTD) is also produced using hydrogen peroxide .
Classic qualitative and quantitative analysis
These classic methods lose their importance in laboratory practice because of their low detection limits and their complexity.
Evidence as blue chromium peroxide (CrO (O 2 ) 2 )
Chromium trioxide CrO 3 is converted in the strongly acidic range (pH <0) by hydrogen peroxide into deep blue colored and ether soluble chromium (VI) peroxide . To do this, potassium dichromate is acidified in the test tube with dilute sulfuric acid and covered with a little ether. In the presence of H 2 O 2 , the ether phase turns bluish. Because of the use of toxic and carcinogenic chromium (VI) compounds, this test is now only of academic interest.
Evidence as a yellow peroxotitanyl (IV) ion
The detection as titanium yellow (not to be confused with the organic reagent of the same name) is very sensitive. Titanium (IV) ions react with traces of hydrogen peroxide to form intensely orange-yellow colored peroxotitanyl complex ions.
Redox titration with potassium permanganate
The concentration of hydrogen peroxide in aqueous sulfuric acid solution can be determined titrimetrically with potassium permanganate. If hydrochloric acid is present instead, Reinhardt-Zimmermann solution is added. The titration is based on the following reaction:
The color changes from colorless to pale pink, which should persist for one minute. The consumption of 1 ml KMnO 4 solution (0.02 mol / l = 0.1N) corresponds to 1.701 mg H 2 O 2 . In this way it is also possible to titrate compounds which split off H 2 O 2 in a sulfuric acid solution , such as peroxides, perborates or percarbonates.
Evidence with starch iodide paper
Iodide-soaked and starch-containing filter paper shows even small amounts of peroxide by turning blue. The peroxide oxidizes the iodide to iodine, which in turn forms a characteristic blue complex with starch.
Instrumental quantitative analysis
The oxidizing power of H 2 O 2 enables a multitude of (partly enzymatically catalyzed) chromogenic reactions. This enables photometric or reflectometric determinations of H 2 O 2 . One of the most proven oxidation reactions is the “Trinder reaction” of phenol with 4-amino antipyrine to form a purple dye. The absorbance is proportional to the analyte concentration and can be measured at 510 nanometers. Chemical modifications of the reagents also allow measurements at wavelengths of 550 and 750 nanometers. With this method a detection limit of 1 µmol could be achieved.
One of the most important detection methods for hydrogen peroxide is the peroxidase- catalyzed oxidation of Amplex Red by H 2 O 2 to resorufin. Resorufin shows a clear fluorescence at 590 nanometers after excitation at 535 nanometers , while Amplex Red does not fluoresce. The hydrogen peroxide concentration can thus be determined with a detection limit of 5 nmol / l.
Amperometric sensors for detecting hydrogen peroxide have been known for a long time. The measuring principle is based on the fact that hydrogen peroxide is either cathodically reduced or anodically oxidized on a working electrode at a constant potential . The resulting current is proportional to the concentration of the H 2 O 2 . The potential for cathodic reduction is usually between −100 and −200 mV and the potential window for anodic oxidation ranges from 600 to 800 mV in relation to an Ag / AgCl reference electrode .
Another approach is the immobilization of enzymes (such as horseradish peroxidase ) on a composite layer of carbon nanotubes and chitosan. A detection limit of 10.3 µmol / l was achieved with these biosensors. Biomimetic, non-enzymatic sensors based on magnetic iron oxide nanoparticles are playing an increasingly important role. These take over the catalytic function of the peroxidase and enable a detection limit of 3.6 µmol / l. Other probes use so-called Mn-NTA nanowires (manganese-nitrilotriacetate complex), which amperometrically track the electrochemical oxidation of the hydrogen peroxide. A detection limit of 0.2 µmol / l was described.
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