The density, electrical conductivity, freezing point, and viscosity of mixtures of trifluoromethanesulfonic acid and water

Corkum, Ronald; Milne, J. B.

doi:10.1139/v78-297

Cited by 23 publications

(18 citation statements)

References 3 publications

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“…3.48 x lo-' ohm-' cm-l, is significantly lower than previously reported values (4,5). and thus represents an upper limit for the conductivity of the pure acid.…”

Section: Resultscontrasting

confidence: 61%

Studies on trifluoromethanesulfonic acid. Part 2. Conductivities of solutions of metal trifluoromethanesulfonates and other bases in trifluoromethanesulfonic acid

Russell¹,

Senior²

1980

Can. J. Chem.

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. Can. J . Chem. 58,22(1980) Electrical conductivity measurements are reported for solutions in trifluoromethanesulfonic acid of a number of simple and complex bases. including univalent and divalent metal trifluoromethanesulfonates. The univalent metal salts, water. aniline, and acetic acid behave a s fully dissociated bases, while the alkaline earth metal salts show considerable ion association. The trifluoromethanesulfonate anion appears to have an abnormally high mobility, as compared to the metal cations. and is believed to conduct by a proton-transfer mechanism. Dissociation constants for some n e a k organic bases and association constants for strontium and barium trifluoromethanesulfonates are estimated. Sulfuric acid behaves as a weak electrolyte, while sulfur trioxide is effectively a non-electrolyte. The conductivities of potassium nitrate and potassium dihydrogenphosphate are consistent nith the formation of the nitryl cation and the phosphate acidium ion. respectively. DAVID G. R U S S E L L~~ JOHN B. SENIOR. Can. J . Chem. 58,22(1980). On rapporte les mesures de conductivite electrique d'un certain nombre de bases simples et complexes incluant les trifluoromethane sulfonates de metaux mono et bivalents en solution dans I'acide trifluoromethane sulfonique. I.es sels de metaux monovalents. l'eau, I'aniline et l'acide acetique se comportent comme des bases totalement dissociees alors que les sels de metaux alcalino terreux montrent une tres grande association d'ions. L'anion trifl~~oromethanesulfonique semble avoir une grande mobilite qui est anormale si on la compare B celle des cations metalliques et on pense que cette mobilite est due a un mecanisme de transfert de proton. On evalue les constantes de dissociation de quelques bases organiques faibles et les constantes d'association des trifluoromethanesulfonates de strontium et de barium. L'acide sulfurique se comporte comme un electrolyte faible alors que l'anhydride sulfurique est effectivement un non electrolyte. Les conductivites du nitrate et du phosphate diacide de potassium sont en accord avec la formation du cation nitryle et de I'ion phosphate acidium respectivement.[Traduit par le journal]

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“…3.48 x lo-' ohm-' cm-l, is significantly lower than previously reported values (4,5). and thus represents an upper limit for the conductivity of the pure acid.…”

Section: Resultscontrasting

confidence: 61%

Studies on trifluoromethanesulfonic acid. Part 2. Conductivities of solutions of metal trifluoromethanesulfonates and other bases in trifluoromethanesulfonic acid

Russell¹,

Senior²

1980

Can. J. Chem.

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“…[30] In the course of this work, we detected only the 33 S signal of MeSO 2 NH 2 in aqueous medium (see below).…”

Section: Resultsmentioning

confidence: 94%

“…[1,2] Common acid systems, like H 2 SO 4 or CF 3 SO 3 H (trifluoromethanesulfonic acid; hereafter triflic acid), have moderate or large viscosities both as neat liquids (h 24.2 and 3.3 mPa s, respectively) and when mixed with water. [26,33] Hence, in order to compare relaxation data among different media, the viscosity should be known or kept constant. It was previously found that use of aqueous solutions of tBuOH makes it possible to vary the viscosity in a suitable range while keeping the environment largely aqueous.…”

Section: Resultsmentioning

confidence: 99%

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Site of Protonation of Carboxylic and Non-Carboxylic Amides in the Gas Phase and in Water

et al. 1999

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The site of protonation of several types of amide bases (carboxylic amides and thioamides, sulfenamides, sulfinamides, sulfonamides, nitrosamides, nitramides, cyanamides, and phosphorous and phosphoric acid triamides) has been investigated through a combination of quantum chemical calculations and heteronuclear NMR measurements. Relative energies of tautomeric ions deriving from protonation at the various sites were determined both in the gas phase (by MP2 calculations) and in water (by the IPCM continuum solvation method). Relevant NMR properties of the involved heteronuclei (nuclear shielding and electric field gradient) were calculated at the GIAO-HF level, and compared with chemical shifts and relaxation rates experimentally measured in 14 N, 17 O, and 31 P spectra. It is shown that such a combination of theoretical and experimental tools allows a dependable prediction of spectral parameters and ultimately of the protonation site of amides. The reliability of common assumptions, like the comparison of spectral parameters of polyfunctional bases and monofunctional models, is also scrutinized and tested.

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“…lar in acidic or strongly basic aqueous medium. On the other hand, HSO,CF, is mixable with water and forms well-defined hydrates (18). It should generally be possible to isolate trifluoromethyl sulfates in high yields, where H 2 0 is a by-product of the reaction.…”

Section: Introductionmentioning

confidence: 99%

The solvolysis of metal fluorosulfates in trifluoromethyl sulfuric acid

Mallela¹,

Sams²,

Aubke³

1985

Can. J. Chem.

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The quantitative conversion of fluorosulfates into trifluoromethyl sulfates is systematically investigated. The reaction proceeds initially according to the general equation[Formula: see text]where E is a coordinatively saturated metal or an organometallic moiety. However, the key to a quantitative substitution is the observed degradation of the SO3F group by excess HSO3CF3 and the noted observation of various volatile by-products that do not appear to interfere in the isolation of analytically pure trifluoromethyl sulfates. The fluorosulfates selected are representatives of the most common bond and coordination types—ionic or covalent with coordination through one, two, or three oxygens of the SO3F groups. The selected substrates display a fairly wide range of solubilities in HSO3F. All conversion attempts are successful except for one, that of polymeric Hg(SO3F)2, and a number of new SO3CF3 derivatives of tin, platinum, germanium, and palladium are described. The solvolysis of tin(IV) acetate in HSO3CF3 is reinvestigated and the syntheses of two other trifluoromethyl sulfuric acid derivatives, CsSO3CF3•HSO3CF3 and CH3CO2H•HSO3CF3, are described.

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The density, electrical conductivity, freezing point, and viscosity of mixtures of trifluoromethanesulfonic acid and water

Cited by 23 publications

References 3 publications

Studies on trifluoromethanesulfonic acid. Part 2. Conductivities of solutions of metal trifluoromethanesulfonates and other bases in trifluoromethanesulfonic acid

Studies on trifluoromethanesulfonic acid. Part 2. Conductivities of solutions of metal trifluoromethanesulfonates and other bases in trifluoromethanesulfonic acid

Site of Protonation of Carboxylic and Non-Carboxylic Amides in the Gas Phase and in Water

The solvolysis of metal fluorosulfates in trifluoromethyl sulfuric acid

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