The Trifluoroacetic Acid Solvent System. Part III. The Acid, HB(OOCCF3)4, and the Solvent Autoprotolysis Constant

1971 ◽  
Vol 49 (22) ◽  
pp. 3612-3616 ◽  
Author(s):  
M. G. Harriss ◽  
J. B. Milne
Keyword(s):  
Trifluoroacetic Acid ◽  
Solvent System ◽  
System Part

The limiting equivalent conductivities, Λ0, of the acids, HB(OOCCF3)4 and HSbF5(OOCCF3), and the salt, CsB(OOCCF3)4, have been measured and found to be 22.34, 18.77, and 48.56 ohm−1 cm2 equiv−1, respectively. Calculation of the solvent autoprotolysis constant gives the value: 4 × 10−14 mol2 l−2. The salt, CsB(OOCCF3)4 is readily prepared but the parent acid, B(OOCCF3)3 could not be isolated.

The trifluoroacetic acid solvent system. Part V. Cryoscopic measurements

1976 ◽  
Vol 54 (19) ◽  
pp. 3031-3037 ◽  
Author(s):  
Michael G. Harriss ◽  
John B. Milne
Keyword(s):  
Trifluoroacetic Acid ◽  
Dissociation Constants ◽  
Freezing Point ◽  
Solvent System ◽  
Ion Pair ◽  
Conductivity Measurements ◽  
Cast Doubt ◽  
System Part ◽  
Triple Ions ◽  
Cryoscopic Constant

Measurement of freezing point depressions for the non-electrolytes, CCl4. CH3SO2F, and (CF3CO)2O permit calculation of the cryoscopic constant for trifluoroacetic acid, HOTFA. Water is shown to give freezing point depressions lower than those for non-electrolytes and this is attributed to association. Freezing point depressions for NaOTFA, KOTFA, and CsOTFA have been measured and accounted for in terms of ion-pair dissociation constants previously determined from electrical conductivity measurements. The results cast doubt on the existence of triple ions in this solvent.

The Trifluoroacetic Acid Solvent System. Part II. Acids

1971 ◽  
Vol 49 (18) ◽  
pp. 2937-2942 ◽  
Author(s):  
M. G. Harriss ◽  
J.B Milne
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Trifluoroacetic Acid ◽  
Solvent System ◽  
Fluoroacetic Acid ◽  
Mixed Anhydrides ◽  
System Part ◽  
Nuclear Magnetic

19F nuclear magnetic resonance (n.m.r.) studies show that SbF5 forms HSbF5(OOCCF3) in tri-fluoroacetic acid. This complex acid does not react with (CF3CO)2O which must be added to carry out conductimetric studies in anhydrous HOOCCF3. However, HClO4, HSO3F, and HNO3 all react with (CF3CO)2O to yield mixed anhydrides CF3COClO4, CF3COSO3F, and NO2OOCCF3. HBF4 reacts with the anhydride to give CF3COF while H2SO4 appears to be simply dehydrated to polysulfuric acids.

The Trifluoroacetic Acid Solvent System. Part IV. Triple Ions

1972 ◽  
Vol 50 (23) ◽  
pp. 3789-3798 ◽  
Author(s):  
M. G. Harriss ◽  
J. B. Milne
Keyword(s):  
Trifluoroacetic Acid ◽  
Dissociation Constants ◽  
Solvent System ◽  
Solute Concentration ◽  
Ion Pair ◽  
Ionic Charge ◽  
System Part ◽  
Triple Ions ◽  
Ion Size ◽  
Triple Ion

Electrolytes studied in 100% trifluoroacetic acid exhibit a minimum in equivalent conductivity with increasing solute concentration. This behavior is accounted for by the formation of triple-ions at higher concentrations. Triple-ion dissociation constants, k, have been evaluated and, in general, they show the opposite trend with changing ion size to that of the ion-pair dissociation constants; that is the triple-ions of smaller ions are more dissociated. The experimentally observed trend is accounted for by using a partial ionic charge instead of unit charge for the ion-pair charges in the theoretical Fuoss expression for k.The excellent extrapolation of the triple-ion data to give a value of Λ0Kd for the ion-pair, which agrees well with that determined from a Fuoss plot, permits an estimate of Λ0 for LiO2CCF3 from the triple-ion data.

The Trifluoroacetic Acid Solvent System. Part I. Bases

1971 ◽  
Vol 49 (11) ◽  
pp. 1888-1894 ◽  
Author(s):  
M. G. Harriss ◽  
J. B. Milne
Keyword(s):  
Electrical Conductivity ◽  
Alkali Metal ◽  
Proton Transfer ◽  
Trifluoroacetic Acid ◽  
Ionic Mobility ◽  
Solvent System ◽  
Association Constants ◽  
Metal Trifluoroacetates ◽  
Cation Radius ◽  
System Part

Electrical conductivity has been used to study the ionic behavior of several simple solutes in 100% trifluoroacetic acid. Fuoss extrapolations have been used to evaluate the limiting equivalent conductivities and association constants of the ammonium and alkali metal trifluoroacetates. The dependence of ionic mobility upon cation radius is different from that in water and other solvents and suggests that solvation is much less important in 100% trifluoroacetic acid. On the basis of these results, a proton transfer mechanism of conductance for the trifluoroacetate ion appears unlikely.

The trifluoroacetic acid solvent system. Part VI. Density measurements

1980 ◽  
Vol 58 (3) ◽  
pp. 283-286 ◽  
Author(s):  
John B. Milne
Keyword(s):  
Trifluoroacetic Acid ◽  
Dissociation Constants ◽  
Ion Pairs ◽  
Solvent System ◽  
Apparent Molar Volumes ◽  
Equivalent Conductivity ◽  
Molar Volumes ◽  
Density Measurements ◽  
System Part ◽  
Triple Ions

The densities of solutions of several 1:1 trifluoroacetate electrolytes have been measured in 100% trifluoroacetic acid (HOTFA) and apparent molar volumes for their ion pairs have been determined. The density measurements coupled with limiting equivalent conductivities and dissociation constants, calculated by means of the Fuoss–Hsia equation, permit a more precise treatment of the conductivities of solutions at concentrations where the equivalent conductivity minimum occurs. The existence of triple ions in this solvent is not required to account for the conductivity minimum.

The trifluoroacetic acid solvent system. Part V. Cryoscopic measurements

1977 ◽  
Vol 55 (9) ◽  
pp. 1592-1592
Author(s):  
Michael G. Harriss ◽  
John B. Milne
Keyword(s):  
Trifluoroacetic Acid ◽  
Solvent System ◽  
System Part

not available

THE SULFURIC ACID SOLVENT SYSTEM: PART VII. SOLUTIONS OF SOME TIN(IV) AND LEAD(IV) COMPOUNDS

1966 ◽  
Vol 44 (10) ◽  
pp. 1197-1202 ◽  
Author(s):  
R. J. Gillespie ◽  
R. Kapoor ◽  
E. A. Robinson
Keyword(s):  
Sulfuric Acid ◽  
Sulfonic Acid ◽  
Solvent System ◽  
Lead Tetraacetate ◽  
Benzene Sulfonic Acid ◽  
Tin Compounds ◽  
Cationic Species ◽  
Stannic Acid ◽  
System Part

Solutions of tetramethyl tin trimethyl tin sulfate, di-n-butyl tin diacetate, tetraphenyl tin, and triphenyl tin hydroxide in. 100% sulfuric acid have been investigated by cryoscopic and conductimetric methods. Tetramethyl tin reacts with sulfuric acid with the evolution of methane and the formation of trimethyl tin hydrogensulfate. Trialkyl tin hydrogensulfates and dialkyl tin dihydrogensulfates behave as strong bases. It is probable that the cationic species formed are protonated hydrogensulfates rather than "stannonium" ions. Phenyl-substituted tin compounds are cleaved in sulfuric acid with the formation of benzene sulfonic acid and the complex hexa(hydrogensulfato) stannic acid, H2Sn(HSO4)6, and its anions. Lead tetraacetate gives yellow solutions containing hexa(hydrogensulfato) plumbic acid, H2PB(HSO4O6, and its anions.

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