II Peroxydisulfate

Fernando Albericio Steven A. Kates Millipore Corporation, Bedford, MA, USA 

Solubility slightly sol acetic acid increased hy increasing concentration of acetate ions. 

Analysis of Reagent Purity contents of Ag can he assayed conveniently by addition of potassium iodide followed by iodometric titration. 

Preparative Methods oxidation of an aqueous suspension of silver nitrate in the presence of 2 equiv of 2,2 -hipyridyl hy potassium peroxydisulfate.  

Handling, Storage, and Precautions should he protected from light. 

---

Woods, Kolthoff, and Meehan found for the induced oxidation of As(III) by the Fe(II)-peroxydisulfate or Fe(II)-H202 reactions that the induction factor can approach infinity in the presence of Fe(III) or Cu(II). With peroxydisulfate the initiation reaction is given by (15-48) and by... 

Bis-(2,2-dipyridyl)-silver(II) peroxydisulfate, Ag(dipy)2S2 0g. Mol. wt. 684.44. The reagent is prepared in the same way as the corresponding pyridine complex. Oxidative acetoxylation of arenes. This Ag(II) salt oxidizes arenes in acetic acid containing sodium acetate to acetoxyarenes usually in high yield. The... 

Chemiluminescence determination of chlorpheniramine by use of tris(l,10-phenanthroline)-ruthenium(II) peroxydisulfate system and sequential injection analysis Spec determination of the complex after reducing Ru (IV) to Ru(II)... 

Recently, Perumal and coworkers reported aromatization of NAD(P)H model Hantzch 1,4-dihydropyridnes using potassium peroxydisulfate/Co(II) . ... 

Primary and secondary alcohols are quantitatively oxidized by peroxydisulfate to the corresponding aldehydes and ketones. Thus benzyl alcohols give aldehydes, and in the presence of Ni(II) and ammonia they gives nitriles secondary alcohols give the corresponding ketones . Interestingly, isopropylbenzene reacts with acetates in the presence of peroxy disulfate/Fe(II) to give lactones (equation 18). ... 

The first Ag(II) compound to be isolated in the solid state was tetra-kis(pyridine)silver(2 +) peroxydisulfate.13,14 Its stability can be attributed to its insolubility, the coordination of the Ag(II) ion, and the presence of an anion with an element in a high oxidation state. It can be prepared conveniently, rapidly, and in high yield by reaction of a solution containing silver nitrate and pyridine with a solution of potassium peroxydisulfate. The corresponding, but less stable, nitrate can be prepared by the electrolytic oxidation of silver nitrate in concentrated aqueous pyridine.15... 

Anal. A freshly dried sample of product is added to water, aqueous ammonia is added, and the suspension is boiled for 15 min to destroy the complex and to reduce the Ag(II) to Ag(I) and the peroxydisulfate to sulfate. The resulting solution is acidified with dilute hydrochloric acid, and the silver is determined as silver chloride. Peroxydisulfate is determined by precipitation of the sulfate in the filtrate with barium chloride. Calcd. for Ag(C5H5N)4S208 Ag, 17.50 S2Oi-, 31.17. Found Ag, 17.90 S20 ", 31.32. 

Peroxydisulfate oxidations have also been used to prepare a variety of pyridine mono- and di-carboxylic add silver(II) complexes.496 All these compounds were orange-red in colour and sparingly soluble to insoluble in most solvents, including water. 

Mono and bis 2,2 -bipyridyl and 1,10-phenanthroline complexes of silver(II) have been isolated as red-brown crystals by either peroxydisulfate, anodic or ozone oxidation techniques.497,519 No tris-chelated species have been substantiated,497 although it is worth noting that a 2,2, 2"-terpyridyl bis complex has been isolated and claimed to be a six-coordinate... 

The first preparation of a silver(III) biguanide was as a result of attempts to prepare a silver(II) derivative of ethylenebis(biguanide) (91). 566 Oxidation of a silver(I) salt by sodium peroxydisulfate in the presence of the ligand, however, gave the red silver(III) derivative instead. 

Oxidation of cyclohexene by peroxydisulfate in the presence of copper(II) salts results in the formation of cyclopentanecarboxaldehyde as the main product in an aqueous acetonitrile solution (equation 261), and 2-cyclohexenyl acetate in an acetic acid solution (equation 262).588,589 Reaction (261) has been interpreted as the formation of a radical cation (186) by oxidation of cyclohexene with S2Og, followed by hydrolysis of (186) to the /3-hydroxy alkyl radical (187), which is oxidized by copper(II) salts to the rearranged aldehydic product (188 equation 263).589... 

This complex has been widely used in sensing applications since both radical ions of the complex are relatively stable to decomposition reactions. Many systems using this chromophore exist in which ECL is produced at a single electrode via coreactant oxidation or reduction schemes as discussed in the first segment of this section [Eqs. (5) through (9)]. For example, the reduction product of the peroxydisulfate dianion, S2Og, can function as an oxidant in the ECL reaction by annihilation with the electrochemically generated Ru1+ to yield the MLCT excited state of the Ru(II) complex by the mechanism [24] ... 

Concentrated HCI Manganese (II) sulfate + phosphoric acid Chlorine dioxide gas evolved, imparts yellow color to acid Violet coloration due to diphosphatomanganate formation peroxydisulfate nitrates, bromates, iodates, and periodates react similarly... 

Several other processes have been developed, however, to accomplish the oxidative decarboxylation of carboxylic acids oxidation by Pb(OAc)4, by iodosobenzene-diacetate, and by Ag(II) salt generated in situ in a catalytic cycle from a variety of peroxides (benzoyl peroxide, percarbonate, perborate) [2] other than the already mentioned peroxydisulfate. Representative examples are shown in Eqs (9)—(12) of Table 2. 

Silver (II) oxide has been made by the hydrolytic action of boiling water on a substance of the approximate formula Ag708N03, a material which is obtained by the electrolytic oxidation of silver(I) nitrate solutions.1-4 A more rapid and convenient process for the preparation of this oxide involves the oxidation of silver (I) nitrate by means of potassium peroxydisulfate in an alkaline medium.5,6... 

Toluene has been oxidized by the silver ion catalysed reaction with peroxy-disulfate. The reaction produces a mixture of bibenzyl, benzaldehyde and benzoic acids.299 Russian workers have described the conversion of 4-methoxy-toluene to the benzaldehyde by oxidation with peroxydisulfate in the presence of silver or copper ions and oxalic acid.300 The presence of copper salts in iron or copper catalysed peroxydisulfate oxidation is believed to suppress side-reactions.301 Phillips have patented a palladium(II)/tin(IV)/persulfate system for the oxidation of toluene derivatives.302 The reactions are carried out in carboxylic acid solvents (Figure 3.78). 

---