378. Solutions in sulphuric acid. Part XIX. The formation of tetra(hydrogen sulphato)boric acid and its anion in solutions of boric acid and boric oxide

Flowers, R.H.; Gillespie, R. J.; Oubridge, J. V.

doi:10.1039/jr9560001925

Cited by 17 publications

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“…The first borosulfates where synthesized employing H 3 BO 3 and alkali‐metal hydrogen sulfates, alkali‐metal disulfates, or directly in oleum as solvent. The hitherto always found FBU (fundamental building unit) in form of a super‐tetrahedron, which is non‐condensed in K 5 [BS 4 O 16 ], as well as several publications regarding superacids suggest the complex acid H[B(HSO 4 ) 4 ], which is presumably formed in situ. Thus, our new synthetic approach adopts a strategy of initially synthesizing this acid and reacting it subsequently in an open system with anhydrous salts (for example, anhydrous chlorides of the desired metal) to the respective borosulfates and a volatile molecule (for example, HCl).…”

Section: Figurementioning

confidence: 99%

The Borosulfates K₄[BS₄O₁₅(OH)], Ba[B₂S₃O₁₃], and Gd₂[B₂S₆O₂₄]

2016

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K4 [BS4 O15 (OH)], Ba[B2 S3 O13 ], and Gd2 [B2 S6 O24 ] were obtained by a new synthetic approach. The strategy involves initially synthesizing the complex acid H[B(HSO4 )4 ] which is subsequently reacted in an open system with anhydrous chlorides of K, Ba, and Gd to the respective borosulfates and a volatile molecule (HCl). Furthermore, protonated borosulfates should be accessible by appropriate stoichiometry of the starting materials, particularly in closed systems, which inhibit deprotonation of H[B(HSO4 )4 ] via condensation and dehydration. This approach led to the successful synthesis of the first divalent and trivalent metal borosulfates (Ba[B2 S3 O13 ] with band-silicate topology and Gd2 [B2 S6 O24 ] with cyclosilicate topology) and the first hydrogen borosulfate K4 [BS4 O15 (OH)].

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Section: Figurementioning

confidence: 99%

The Borosulfates K₄[BS₄O₁₅(OH)], Ba[B₂S₃O₁₃], and Gd₂[B₂S₆O₂₄]

2016

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“…Die ersten Borosulfate wurden ausgehend von H 3 BO 3 und einem Alkalimetallhydrogensulfat oder Alkalimetalldisulfat oder auch direkt in Oleum hergestellt; die bisher immer aufgefundene FBU (fundamental building unit) des Supertetraeders, das nicht‐kondensiert in K 4 [BS 4 O 15 (OH)] vorliegt, sowie verschiedene Arbeiten zu Supersäuren lassen auf die Bildung der komplexen Säure H[B(HSO 4 ) 4 ] in situ schließen. Unsere neue Strategie besteht daher darin, diese Säure zunächst zu synthetisieren und sie in einem offenen System mit einem wasserfreien Salz, z.…”

Section: Figureunclassified

Die Borosulfate K₄[BS₄O₁₅(OH)], Ba[B₂S₃O₁₃] und Gd₂[B₂S₆O₂₄]

2016

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K 4 [BS 4 O 15 (OH)],B a[B 2 S 3 O 13 ]u nd Gd 2 [B 2 S 6 O 24 ] wurden durche inen neuen Syntheseansatz erhalten. Dabei wurde zunächst die komplexeSäure H[B(HSO 4 ) 4 ]hergestellt; diese wurdea nschließend in einem offenen System mit wasserfreien Chloriden von K, Ba und Gd zu den jeweiligen Borosulfaten und einem flüchtigen Molekül (HCl) umgesetzt. Protonierte Borosulfate sollten ebenfalls zugänglichs ein, indem eine geeignete Stçchiometrie der Startmaterialien eingestellt wird, besonders in geschlossenen Systemen, welchedie Deprotonierung von H[B(HSO 4 ) 4 ]ü ber Kondensation und Dehydratisierung hemmen. Dieser Ansatz führte zur Synthese der ersten Borosulfate zwei-und dreiwertiger Kationen (Ba-[B 2 S 3 O 13 ]und Gd 2 [B 2 S 6 O 24 ]mit Bandsilicat-bzw.Ringsilicat-Topologien) sowied es ersten protonierten Alkalimetallborosulfats (K 4 [BS 4 O 15 (OH)]).

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“…l/(AHap + 3 2 -HA)$^ -HA) = 1/(AHap/2)2 + m22/m~2Kup(AHup)2. (12) Since the left-hand side of eqn. ( 1 1 ) is not particularly sensitive to the precise values of AH,, and HA for the higher values of m2, it has been used to evaluate HA.…”

Section: (% -H a ) / ( A H ~/ ~)mentioning

confidence: 99%

The partial molar heat contents of solutes in sulphuric acid at 25°C. An investigation of the self-dissociation of sulphuric acid

Kirkbride¹,

Wyatt²

1958

Trans. Faraday Soc.

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Measurements are reported of the partial molar heat contents at 25" of potassium, ammonium, and barium hydrogen sulphates, acetic acid, and water, in solution in sulphuric acid in the region of suppression of the solvent self-dissociation. The thermal effects of adding water (hydroxoniurn hydrogen sulphate) to sulphuric acid already containing other hydrogen sulphates have also been investigated, and these measurements confirm the view of Gillespie, Hughes, and Ingold that water suppresses a form of dissociation that is not suppressed by other hydrogen sulphates. Standard free energy, heat, and entropy values have been calculated for the autoprotolytic and ionic dehydration forms of dissociation and have been shown to be consistent with accurate cryoscopic data.

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378. Solutions in sulphuric acid. Part XIX. The formation of tetra(hydrogen sulphato)boric acid and its anion in solutions of boric acid and boric oxide

Abstract: Flowers, Gillespie, avld Ozcbridge. 1925 378. Solutions in Sulphuric Acid. Part XIX." The B'ormtion of Tetra(hydrogen su1phato)boric Acid and its Anion in Solutions of Boric Acid and Boric Oxide.

Cited by 17 publications

References 0 publications

The Borosulfates K₄[BS₄O₁₅(OH)], Ba[B₂S₃O₁₃], and Gd₂[B₂S₆O₂₄]

The Borosulfates K₄[BS₄O₁₅(OH)], Ba[B₂S₃O₁₃], and Gd₂[B₂S₆O₂₄]

Die Borosulfate K₄[BS₄O₁₅(OH)], Ba[B₂S₃O₁₃] und Gd₂[B₂S₆O₂₄]

The partial molar heat contents of solutes in sulphuric acid at 25°C. An investigation of the self-dissociation of sulphuric acid

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378. Solutions in sulphuric acid. Part XIX. The formation of tetra(hydrogen sulphato)boric acid and its anion in solutions of boric acid and boric oxide

Abstract: Flowers, Gillespie, avld Ozcbridge. 1925 378. Solutions in Sulphuric Acid. Part XIX." The B'ormtion of Tetra(hydrogen su1phato)boric Acid and its Anion in Solutions of Boric Acid and Boric Oxide.

Cited by 17 publications

References 0 publications

The Borosulfates K4[BS4O15(OH)], Ba[B2S3O13], and Gd2[B2S6O24]

The Borosulfates K4[BS4O15(OH)], Ba[B2S3O13], and Gd2[B2S6O24]

Die Borosulfate K4[BS4O15(OH)], Ba[B2S3O13] und Gd2[B2S6O24]

The partial molar heat contents of solutes in sulphuric acid at 25°C. An investigation of the self-dissociation of sulphuric acid

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The Borosulfates K₄[BS₄O₁₅(OH)], Ba[B₂S₃O₁₃], and Gd₂[B₂S₆O₂₄]

The Borosulfates K₄[BS₄O₁₅(OH)], Ba[B₂S₃O₁₃], and Gd₂[B₂S₆O₂₄]

Die Borosulfate K₄[BS₄O₁₅(OH)], Ba[B₂S₃O₁₃] und Gd₂[B₂S₆O₂₄]