Structure, deformation density and atomic charges in potassium hydrogenperoxomonosulfate monohydrate, KHSO5.H2O

Abstract

Introduetlon. Although potassium hydrogenperoxomonosulfate is sold in an impure form commercially, pure salts of peroxomonosulfate have not been previously available. We have developed a procedure involving hydrolysis of K2S208 that affords highly pure KHSOs.H20. This product yielded crystals suitable for the first determination of the structure of the HSO~-ion. An earlier X-ray study (Kyrki & Lappalainen, 1965) reported an orthorhombic unit cell but did not include a structure determination.Because of the difference in chemistry of oxidation- -(Kirfel & Will, 1980, 1981, and for $2032-(Elerman, Bats & Fuess, 1983).0108-2701/84/I 11781-05501.50Experimental. Concentrated solution of sodium peroxodisulfate was converted to the acid by passage through a column of Dowex 50X8 cation-exchange resin in the hydrogen form. The solution was concentrated in a rotary evaporator and hydrolyzed by heating at 323 K until no peroxodisulfate was detected. The solution was then neutralized to pH 3.5 by addition of KHCO 3 in an ice bath, filtered and freeze-dried. The residue was redissolved in a small quantity of water at room temperature and filtered. The filtrate was chilled in an ice bath and the crystals that formed were filtered, washed with a small quantity of absolute ethanol and dried between sheets of filter paper. Iodometric analysis indicated a bulk composition approximating KHSOs.-H20. Plate-like crystal; ~0.07 x 0.23 x 0.27 mm; Enraf-Nonius CAD-4 diffractometer; T maintained by constant flow of N 2 gas; 24 reflections, 0 = 9-15 °, used for cell dimensions; empirical ~,-scan absorption (range of transmission = 0.

Preparation of Purified KHSO5·H2O and nBu4NHSO5 from Oxone by Simple and Efficient Methods

“…[33] This resulted in one of two reported crystal structures of KHSO 5 ·H 2 O. Interestingly, both reports were published within months of each other. [34,35] The purification of KHSO 5 ·H 2 O was revisited by Connick et al in the early 90's along with a modified method for its preparation. [36] Essentially, a straightforward filtration protocol starting from Oxone, followed by evaporation and crystallization resulted in the isolation of analytically pure KHSO 5 ·H 2 O.…”

ChemInform Abstract: Sulfur Compounds. Part 213. Geometries, Acidities, and Dissociation Reactions of the Gaseous Superacids H2S2O3, H2SO5, HSO3F, and HSO3Cl

“…The OϪO bond length (146.4 pm) and the SϪOϪOϪH torsion angle (104°) have values typical for covalent peroxides. [19,20] The anion is of C 1 symmetry with the connectivity HOϪOϪSO 3 Ϫ . The structure of the monoanion HSO 5 Ϫ is known from two independent X-ray crystal structure determinations of the potassium salt KHSO 5 · H 2 O (Table 4).…”

“…The structure of the monoanion HSO 5 Ϫ is known from two independent X-ray crystal structure determinations of the potassium salt KHSO 5 · H 2 O (Table 4). [20] Again, intermolecular hydrogen bonding is a characteristic feature of the structure. The OϪO distance was determined as 146 pm while the SϪOϪOϪH torsion angle was given as ''ca.…”

“…This can be seen from the close agreement of the three torsion angles given in Table 3. Comparison of calculated and crystallographic structure data for the peroxymonosulfate ion HSO 5 Ϫ (C 1 ) (internuclear distances in pm, bond angles and the torsion angle in°); for numbering of atoms see Figure 1 Parameter [20] structure. Most of the bond lengths and bond angles agree rather closely with the solid-state Table 4.…”

Synthesis and X-Ray Crystal Structure of the First Pure and Air-Stable Salt of Peroxymonosulphuric Acid: (Ph)4PHSO5

“…The first stable derivative of Caro's acid prepared was the water soluble mixed salt (2), which is commercially available under the names of Oxone ® , Caroat ® or Curox ® . The X-ray structure of KHSO 5 in (2) [7] and then in (KHSO 5 )(H 2 O) [8] (1), is a powerful oxidant with a wide range of applications. As an example, triple salt (2) is used for both the oxidation of water-soluble substrates [9] and for oxidations catalyzed by metal porphyrins in two-phase systems [10].…”