Hydrogen Peroxide & Inorganic Peroxy Compounds
Hydrogen peroxide (H2O2) is the simplest peroxide (a compound with an oxygen-oxygen single bond). It is also a strong oxidizer. Hydrogen peroxide is a clear liquid, slightly more viscous than water. In dilute solution, it appears colorless. Reactions
Hydrogen peroxide decomposes exothermically into water and oxygen gas spontaneously: 2 H2O2 → 2 H2O + O2
This process is thermodynamically favorable. It has a ΔHo of −98.2 kJ·mol−1 and a ΔS of 70.5 J·mol−1·K−1. The rate of decomposition is dependent on the temperature (cool environment slows down decomposition, therefore hydrogen peroxide is often stored in refrigerator) and concentration of the peroxide, as well as the pH and the presence of impurities and stabilizers. Hydrogen peroxide is incompatible with many substances that catalyse its decomposition, including most of the transition metals and their compounds. Common catalysts include manganese dioxide, silver, and platinum. The same reaction is catalysed by the enzyme catalase, found in the liver, whose main function in the body is the removal of toxic byproducts ofmetabolism and the reduction of oxidative stress. The decomposition occurs more rapidly in alkali, so acid is often added as a stabilizer. The liberation of oxygen and energy in the decomposition has dangerous side-effects. Spilling high concentrations of hydrogen peroxide on a flammable substance can cause an immediate fire, which is further fueled by the oxygen released by the decomposing hydrogen peroxide. High test peroxide, or HTP (also called high-strength peroxide) must be stored in a suitable, vented container to prevent the buildup of oxygen gas, which would otherwise lead to the eventual rupture of the container. In the presence of certain catalysts, such as Fe2+ or Ti3+, the decomposition may take a different path, with free radicals such as HO· (hydroxyl) and HOO· (hydroperoxyl) being formed. A combination of H2O2 and Fe2+ is known as Fenton's reagent. A common concentration for hydrogen peroxide is 20-volume, which means that, when 1 volume of hydrogen peroxide is decomposed, it produces 20 volumes of oxygen. A 20-volumeconcentration of hydrogen peroxide is equivalent to 1.667 mol/dm3 (Molar solution) or about 6%.
In acidic solutions, H2O2 is one of the most powerful oxidizers known—stronger than chlorine, chlorine dioxide, and potassium permanganate. Also, through catalysis, H2O2 can be converted intohydroxyl radicals (•OH), which are highly reactive. Oxidant/Reduced product
| Oxidation potential, V
Potassium permanganate/Manganese dioxide
In aqueous solutions, hydrogen peroxide can oxidize or reduce a variety of inorganic ions. When it acts as a reducing agent, oxygen gas is also produced. In acidic solutions Fe2+ is oxidized to Fe3+ (hydrogen peroxide acting as an oxidizing agent), 2 Fe2+(aq) + H2O2 + 2 H+(aq) → 2 Fe3+(aq) + 2H2O(l)
and sulfite (SO2−
3) is oxidized to sulfate (SO2−
4). However, potassium permanganate is reduced to Mn2+ by acidic H2O2. Under alkaline conditions, however, some of these reactions reverse; for example, Mn2+ is oxidized to Mn4+ (as MnO2). Other examples of hydrogen peroxide's action as a reducing agent are reaction with sodium hypochlorite or potassium permanganate, which is a convenient method for preparing oxygen in the laboratory. NaOCl + H2O2 → O2 + NaCl + H2O
2 KMnO4 + 3 H2O2 → 2 MnO2 + 2 KOH + 2 H2O + 3 O2
Hydrogen peroxide is frequently used as an oxidizing agent in organic chemistry. One application is for the oxidation of thioethers to sulfoxides. For example, methyl phenyl sulfidecan be readily oxidized in high yield to methyl phenyl sulfoxide: Ph−S−CH3 + H2O2 → Ph−S(O)−CH3 + H2O
Alkaline hydrogen peroxide is used...
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