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 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 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 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.

Acids, bases and buffer solutions

2018 ◽  
Author(s):  
Dennis Sherwood ◽  
Paul Dalby
Keyword(s):  
First Principles ◽  
Buffer Capacity ◽  
Unique Feature ◽  
Dissociation Constants ◽  
Equilibrium Composition ◽  
Buffer Solutions ◽  
Acid And Base ◽  
Water Ph ◽  
Acids And Bases ◽  
Conjugate Bases

Many reactions in solution involve acids and bases, and so this chapter examines these important reactions in detail. Topics covered include the ionisation of water, pH, pOH, acids and bases, conjugate acids and conjugate bases, acid and base dissociation constants, the Henderson-Hasselbalch equation, the Henderson-Hasselbalch approximation, buffer solutions and buffer capacity. A unique feature of this chapter is a ‘first principles’ analysis of how a reaction buffered at a particular pH achieves an equilibrium composition different from that of the same reaction taking place in an unbuffered solution. This introduces some concepts which are important in understanding the biochemical standard state, as required for Chapter 23.

THE SULPHURIC ACID SOLVENT SYSTEM: PART VI. THE BASICITIES OF COMPOUNDS CONTAINING SULPHUR–OXYGEN BONDS

1964 ◽  
Vol 42 (5) ◽  
pp. 1113-1122 ◽  
Author(s):  
S. K. Hall ◽  
E. A. Robinson
Keyword(s):  
Nitrogen Atom ◽  
Sulphuric Acid ◽  
Solvent System ◽  
Dimethyl Sulphoxide ◽  
Strong Base ◽  
Weak Bases ◽  
System Part ◽  
Sulphur Trioxide ◽  
Basic Behavior

Cryoscopic and conductimetric studies of a variety of compounds containing S—O bonds have shown that dimethyl sulphoxide behaves as a strong base in sulphuric acid whereas dialkyl sulphones behave as weak bases. In contrast diaryl sulphones and aryl sulphonic acids behave as non-electrolytes.A correlation is established between the basicities of the alkyl sulphones, H2SO4, and the HSO4− ion, and their sulphur–oxygen stretching frequencies. This relation is used to predict the basicities of other compounds containing S—O bonds. In particular it is shown that the basicity of monomeric sulphur trioxide is similar to that of sulphuric acid, and sulphamide is shown to behave as a strong base in sulphuric acid, which implies protonation on a nitrogen atom rather than on oxygen, since the S—O stretching frequencies indicate only weakly basic behavior for O-protonation.

scholarly journals ON GUAIACOL SOLUTIONS

1934 ◽  
Vol 17 (4) ◽  
pp. 549-561 ◽  
Author(s):  
Theodore Shedlovsky ◽  
Herbert H. Uhlig
Keyword(s):  
Electrical Conductivity ◽  
Dissociation Constants ◽  
Dielectric Constants ◽  
Conductivity Measurements ◽  
Ionic Equilibrium ◽  
Weak Electrolytes ◽  
Ionic Mobilities ◽  
Water Saturated ◽  
Limiting Equivalent Conductances ◽  
Sodium And Potassium

1. Measurements on the densities, viscosities, dielectric constants, and specific conductances of pure anhydrous and water-saturated guaiacol at 25°C. are reported. 2. The solubility of water in guaiacol at 25°C., and its effect on the electrical conductivity of a sodium guaiacolate solution is given. 3. Electrical conductivity measurements are reported on solutions of sodium and potassium guaiacolates in water-saturated guaiacol at 25°C. 4. The decrease of electrical conductivity with increasing concentration for these salts is explained on the basis of an ionic equilibrium combined with the interionic attraction theory of Debye and Hückel. 5. The limiting equivalent conductances of sodium and potassium guaiacolates in water-saturated guaiacol at 25°C., the corresponding limiting ionic mobilities, and the dissociation constants are computed from the conductivity measurements. The salts are found to be weak electrolytes with dissociation constants of the order of 5 x 10–6.

Electrical conductivity of low-pressure shock-ionized argon

1963 ◽  
Vol 17 (2) ◽  
pp. 182-192 ◽  
Author(s):  
P. R. Smy ◽  
H. S. Driver
Keyword(s):  
Electrical Conductivity ◽  
Shock Tube ◽  
Plasma Radiation ◽  
Conductivity Measurements ◽  
Flow Conditions ◽  
Velocity Measurements ◽  
Pressure Shock ◽  
Ionized Gas ◽  
Order Of Magnitude ◽  
Good Agreement

The electrical conductivity of shock-ionized argon produced in an electromagnetic shock tube of low attenuation has been measured at shock speeds of March 10–33, with initial pressures of 0·01–2·0 mm Hg. These measurements extend considerably the range of previous measurements performed with pressure-driven shock tubes. With the higher initial pressures or at the highest Mach numbers the measured conductivity is in good agreement with the previous measurements and with the Spitzer–Harm (1953) formula for the conductivity of a fully ionized gas. With the lower initial pressures (which have not previously been investigated) and at the lower March numbers the conductivity falls to less than half of the Spitzer-Harm value. Order-of-magnitude calculations show that diffusion of atoms, and heat conduction by the plasma atoms from the plasma to the shock-tube walls, can cause appreciable plasma cooling (and hence a reduction of the electrical conductivity) with the lowest initial pressures. This mechanism in conjunction with non-attainment of equilibrium ionization appears to explain the observed diminution in conductivity at the lowest pressures, but not the reduced conductivity at the medium pressures.Induced e.m.f. flow-velocity measurements indicate steady-flow conditions in the shock tube while photomultiplier measurements of the plasma radiation indicate that the column of shock-heated gas is 10–20 cm long; this latter figure is supported by the conductivity measurements. The fact that the length of the shock-heated gas column is not drastically shortened at low initial pressures in constrast to the work of Duff (1959), Roshko (1960) and Hooker (1961) is attributed to the fact that in this experiment both driver and driven gases are at high temperature.

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 IV. SULPHATOCOMPOUNDS OF ARSENIC (III)

1963 ◽  
Vol 41 (2) ◽  
pp. 450-459 ◽  
Author(s):  
R. J. Gillespie ◽  
E. A. Robinson
Keyword(s):  
Sulphuric Acid ◽  
Solvent System ◽  
Dilute Solutions ◽  
Polymeric Compound ◽  
Polymeric Species ◽  
System Part ◽  
Hydrogen Sulphate ◽  
Sulphur Trioxide

The cryoscopic and conductimetric behavior of arsenic (III) oxide in 100% sulphuric acid and in dilute oleum have been investigated. It is concluded that in very dilute solutions in 100% sulphuric acid, arsenic (III) oxide forms arsonyl (III) hydrogen sulphate, AsO.HSO4, which is partly ionized to give the AsO+ cation. Both these species probably exist mainly in solvated forms, e.g., As(OH)(SO4H)2, and As(OH)(SO4H)+ respectively. At higher concentrations polymeric species such as HO.As(HSO4)OAs(HSO4)2 are present in increasing amounts and eventually the insoluble polymeric compound [(AsO)2SO4]n separates from solution. In oleum the more sulphated species As(HSO4)3, [(HSO4)2As]2O, and [(HSO4)2As]2SO4 are formed. Related structures are proposed for some previously prepared compounds of arsenic (III) oxide and sulphur trioxide.

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