The chlorosulfuric acid solvent system. Part II. The solutes SeCl4 and TeCl4; evidence for the formation of the SeCl3+ and TeCl3+ ions

1968 ◽  
Vol 46 (20) ◽  
pp. 3197-3200 ◽  
Author(s):  
E. A. Robinson ◽  
J. A. Ciruna
Keyword(s):  
Electrical Conductivity ◽  
Raman Spectra ◽  
Vibrational Spectra ◽  
Strong Acid ◽  
Ionic Species ◽  
Solvent System ◽  
Acid Solutions ◽  
Conductivity Measurements ◽  
System Part

From the results of electrical conductivity measurements on solutions in chlorosulfuric acid and the Raman spectra of solutions in chlorosulfuric acid (and fluorosulfuric acid) it is shown that SeCl4 and TeCl4 ionize quantitatively in these strong acid solutions to give the SeCl3+ and TeCl3+ cations.By comparison of the spectra with the vibrational spectra of solid SeCl4 and solid TeCl4, reported by other workers, it is suggested that the solids contain covalent MCl4 molecules rather than the ionic species MCl3+•Cl−, suggested previously.

THE SULPHURIC ACID SOLVENT SYSTEM: PART I. ACID-BASE REACTIONS

1960 ◽  
Vol 38 (8) ◽  
pp. 1363-1370 ◽  
Author(s):  
R. H. Flowers ◽  
R. J. Gillespie ◽  
E. A. Robinson
Keyword(s):  
Electrical Conductivity ◽  
Sulphuric Acid ◽  
Dissociation Constants ◽  
Solvent System ◽  
Conductivity Measurements ◽  
Acid Base ◽  
Acid And Base ◽  
System Part ◽  
Acids And Bases ◽  
Good Agreement

Acid–base reactions in the solvent sulphuric acid are discussed. Such reactions are conveniently studied by electrical conductivity measurements. A relation between the composition at which the conductivity has a minimum value and the strengths of the acid and base is derived. Values of the dissociation constants of acids and bases obtained in this way are shown to be in good agreement with values obtained by other methods.

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 chlorosulfuric acid solvent system. Part I. Electrical conductivity, transport number, and density measurements on solutions of simple bases

1968 ◽  
Vol 46 (10) ◽  
pp. 1719-1725 ◽  
Author(s):  
E. A. Robinson ◽  
J. A. Ciruna
Keyword(s):  
Electrical Conductivity ◽  
Alkali Metal ◽  
Alkaline Earth ◽  
Transport Number ◽  
High Mobility ◽  
Earth Metal ◽  
Solvent System ◽  
Alkaline Earth Metal ◽  
Density Measurements ◽  
System Part

Electrical conductivity, transport number, and density measurements on solutions of some simple bases, including alkali metal and alkaline earth metal chlorosulfates, are reported in the chlorosulfuric acid solvent system. The SO3Cl− ion was found to have a high mobility compared with, for example, the mobilities of the alkali metal and alkaline earth metal cations, and is believed to conduct by an abnormal Grotthus-type chain mechanism. Alkali metal chlorosulfates appear to behave as fully dissociated electrolytes, whereas alkaline earth metal chlorosulfates are incompletely dissociated. Difficulties encountered in preparing pure chlorosulfuric acid are discussed.

THE SULPHURIC ACID SOLVENT SYSTEM: PART III. THE PREPARATION AND STRUCTURES OF SOME COMPLEX SULPHATOBORATES

1962 ◽  
Vol 40 (5) ◽  
pp. 1009-1017 ◽  
Author(s):  
R. J. Gillespie
Keyword(s):  
Boric Acid ◽  
Sulphuric Acid ◽  
Solvent System ◽  
Membered Ring ◽  
Acid Solutions ◽  
Sodium Potassium ◽  
System Part

By neutralizing sulphuric acid solutions of tetra(hydrogensulphato)boric acid with various metal hydrogensulphates, sodium, potassium, ammonium, and strontium salts have been prepared. From the compositions of these salts, and from the results of cryoscopic and conductimetric measurements on their solutions in sulphuric acid, it is concluded that they are best formulated as polysulphatoborates containing the six-membered ring [Formula: see text]It is shown that previously described sulphato compounds of boron can also be satisfactorily formulated on this basis.

THE SULPHURIC ACID SOLVENT SYSTEM: PART II. CONDUCTIVITY MEASUREMENTS ON SOLUTIONS OF SOME ACIDS

1961 ◽  
Vol 39 (6) ◽  
pp. 1266-1273 ◽  
Author(s):  
J. Barr ◽  
R. J. Gillespie ◽  
E. A. Robinson
Keyword(s):  
Dissociation Constant ◽  
Sulphuric Acid ◽  
Dissociation Constants ◽  
Solvent System ◽  
Acid Dissociation ◽  
Acid System ◽  
Conductivity Measurements ◽  
Acid Dissociation Constants ◽  
Strong Base ◽  
System Part

Conductivity measurements have been made on solutions of the following substances in sulphuric acid: HClO4, HSO3F, HSO3Cl, HPO2F2, HAs(HSO4)4, CH3SO3H, and CF3CO2H. Of these substances HSO3F, HSO3Cl, HAs(HSO4)4, and probably HClO4, behave as acids, CF3CO2H is a non-electrolyte, and HPO2F2, and probably CH3SO3H, are bases of the sulphuric acid system. Acid dissociation constants for HSO3F, HSO3Cl, and HAs(HSO4)4 have been determined by comparing the conductivities of their solutions with those of H2S2O7, whose dissociation constant is known from other measurements, and also by conductimetric titration with a strong base, e.g. KHSO4. These acids of the sulphuric acid system decrease in strength in the order HSO3F > HAs(HSO4)4 > HSO3Cl > HClO4.

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.

Total Body Electrical Conductivity Measurements in the Neonate

1991 ◽  
Vol 18 (3) ◽  
pp. 611-627 ◽  
Author(s):  
Marta L. Fiorotto ◽  
William J. Klish
Keyword(s):  
Electrical Conductivity ◽  
Conductivity Measurements ◽  
Total Body
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