Hydrogen peroxide-sulfur reaction

L. Kinetics of the hydrogen peroxide-sulfur(lV) reaction in rainwater collected at a northeastern U.S. site. J. Geophys. Res. 1986, 9JL, 13264-13274. 

Spontaneous reaction of hydrogen peroxide/sulfuric acid/water/organic mixtures. These reactions can accelerate rapidly and terminate violently, and can be outside the predicted explosive area. 

Lee, T. J. and A. P. Rendell (1993) Ab initio characterization of peroxyhypochlorous acid implications for atmospheric chemistry. Journal of Physical Chemistry 97, 6999-7002 Lee, Y- N., J. Shen, P. J. Klotz, S. E. Schwartz and L. Newman (1986) Kinetics of hydrogen peroxide - sulfur(IV) to sulfur(VI) reaction in rainwater collected at a northwestern US. site. Journal of Geophysical Research 91, 13264-13274... 

Theory of Operation. The sulfuric acid/hydrogen peroxide etching reaction is Cu + H2O2 + H2SO4 — CUSO4 + 2H2O (60.1)... 

Beside sulfur compounds, ferric traces are to be considered as particularly critical (Wu, 2008) highlighted especially trace metal ions of Fe and Cu which can accelerate weakening of the electrolyte membrane by catalyzing the formation of oxygen radicals due to the reaction with hydrogen peroxide (Fenton reaction). 

A second sulfur-based oscillator, the hydrogen peroxide-sulfide reaction recently discovered by ORBAN and EPSTEIN [38] shows, in contrast, an almost classic cross-shaped phase diagram. Fig. 3. The Burger-Field system is the first to oscillate in basic solution, while, as we see in Fig. 4, the H O -S oscillations go from acidic to basic pH, making possible dramatic color effects with acid-base indicators. 

Organic hydroperoxides can be prepared by Hquid-phase oxidation of selected hydrocarbons in relatively high yield. Several cycHc processes for hydrogen peroxide manufacture from hydroperoxides have been patented (84,85), and others (86—88) describe the reaction of tert-huty hydroperoxide with sulfuric acid to obtain hydrogen peroxide and coproduct tert-huty alcohol or tert-huty peroxide. 

The electrolytic processes for commercial production of hydrogen peroxide are based on (/) the oxidation of sulfuric acid or sulfates to peroxydisulfuric acid [13445-49-3] (peroxydisulfates) with the formation of hydrogen and (2) the double hydrolysis of the peroxydisulfuric acid (peroxydisulfates) to Caro s acid and then hydrogen peroxide. To avoid electrolysis of water, smooth platinum electrodes are used because of the high oxygen overvoltage. The overall reaction is... 

Toxic or malodorous pollutants can be removed from industrial gas streams by reaction with hydrogen peroxide (174,175). Many Hquid-phase methods have been patented for the removal of NO gases (138,142,174,176—178), sulfur dioxide, reduced sulfur compounds, amines (154,171,172), and phenols (169). Other effluent treatments include the reduction of biological oxygen demand (BOD) and COD, color, odor (142,179,180), and chlorine concentration. 

The synthesis of 2,4-dihydroxyacetophenone [89-84-9] (21) by acylation reactions of resorcinol has been extensively studied. The reaction is performed using acetic anhydride (104), acetyl chloride (105), or acetic acid (106). The esterification of resorcinol by acetic anhydride followed by the isomerization of the diacetate intermediate has also been described in the presence of zinc chloride (107). Alkylation of resorcinol can be carried out using ethers (108), olefins (109), or alcohols (110). The catalysts which are generally used include sulfuric acid, phosphoric and polyphosphoric acids, acidic resins, or aluminum and iron derivatives. 2-Chlororesorcinol [6201-65-1] (22) is obtained by a sulfonation—chloration—desulfonation technique (111). 1,2,4-Trihydroxybenzene [533-73-3] (23) is obtained by hydroxylation of resorcinol using hydrogen peroxide (112) or peracids (113). 

Make acid yields coumaUc acid when treated with fuming sulfuric acid (19). Similar treatment of malic acid in the presence of phenol and substituted phenols is a facile method of synthesi2ing coumarins that are substituted in the aromatic nucleus (20,21) (see Coumarin). Similar reactions take place with thiophenol and substituted thiophenols, yielding, among other compounds, a red dye (22) (see Dyes and dye intermediates). Oxidation of an aqueous solution of malic acid with hydrogen peroxide (qv) cataly2ed by ferrous ions yields oxalacetic acid (23). If this oxidation is performed in the presence of chromium, ferric, or titanium ions, or mixtures of these, the product is tartaric acid (24). Chlorals react with malic acid in the presence of sulfuric acid or other acidic catalysts to produce 4-ketodioxolones (25,26). 

The anhydride can be made by the Hquid-phase oxidation of acenaphthene [83-32-9] with chromic acid in aqueous sulfuric acid or acetic acid (93). A postoxidation of the cmde oxidation product with hydrogen peroxide or an alkaU hypochlorite is advantageous (94). An alternative Hquid-phase oxidation process involves the reaction of acenaphthene, molten or in alkanoic acid solvent, with oxygen or acid at ca 70—200°C in the presence of Mn resinate or stearate or Co or Mn salts and a bromide. Addition of an aHphatic anhydride accelerates the oxidation (95). 

Ca.ro s Acid. Caro s acid is named after Heinrich Caro (1834—1910), who first described its preparation and oxidi2ing properties ia 1898. Hereia Caro s acid is used to designate the equiUbrium mixtures that result from mixing hydrogen peroxide and sulfuric acid. These Hquids mix iastantly, generating a considerable amount of heat. The equiUbrium constant for this reaction is 0.1 (62). 

In a typical isothermal process, 70% hydrogen peroxide is added to 98% sulfuric acid, and subjected to rapid stirring and efficient cooling, so that the temperature does not rise to above 15°C. If equimolar quantities of reactants are used, the product contains 42% H2SO and 10% H2O2. Although the reaction may seem simple, many of its features are critically important and it should only be attempted foUowiag advice from speciaUsts. 

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