The Raman spectra of metallic nitrates and the structure of concentrated solutions of electrolytes

The Raman spectra of sulphuric acid solutions of tetra(hydrogensulphato)boric acid and its sodium and hydronium salts have been examined. Frequencies are assigned to some of the vibrations of the sulphuric acidium ion, H3SO4+, and are compared with the frequencies of the analogous vibrations of H2SO4 and HSO4−. Evidence is presented that elimination of disulphuric acid occurs between molecules of HB(HSO4)4 to give polymers containing B—O—B linkages.

Download Full-text

IX.—On the Relationship between Concentration and Electrolytic Conductivity in Concentrated Aqueous Solutions

Transactions of the Royal Society of Edinburgh ◽

10.1017/s0080456800011698 ◽

1906 ◽

Vol 45 (1) ◽

pp. 241-259 ◽

Cited By ~ 1

Author(s):

John Gibson

Keyword(s):

Aqueous Solutions ◽

General Relationship ◽

Electrolytic Conductivity ◽

Dilute Solutions ◽

Concentrated Solutions ◽

Concentrated Aqueous Solutions ◽

Solutions Of Electrolytes ◽

Weak Electrolytes ◽

The Relationship

Although great advances have been made during the last thirty years in our knowledge of dilute solutions, there has been no corresponding advance in respect of concentrated solutions. This is primarily due to the fact that hitherto no simple and general relationship has been discovered between the conductivity and the concentration of concentrated solutions of electrolytes. Ostwald's law of dilution holds only for dilute solutions of weak electrolytes, and the formulæ of Rudolphi and Van T'Hoff are applicable only to dilute solutions of good electrolytes. It seems therefore important to inquire whether the difficulty may not be to some extent overcome by an alteration in the mode of representing the facts.

Download Full-text

The Felting of Wool in Concentrated Solutions of Electrolytes

Textile Research Journal ◽

10.1177/004051756003000208 ◽

1960 ◽

Vol 30 (2) ◽

pp. 151-152

Author(s):

D.R. Graham ◽

K.W. Statham

Keyword(s):

Concentrated Solutions ◽

Solutions Of Electrolytes

Download Full-text

Resolution of Raman spectra of aqueous sulfuric acid mixtures using principal factor analysis

Canadian Journal of Chemistry ◽

10.1139/v81-372 ◽

1981 ◽

Vol 59 (17) ◽

pp. 2591-2598 ◽

Cited By ~ 32

Author(s):

Robin A. Cox ◽

Ülo L. Haldna ◽

K. Loralee Idler ◽

Keith Yates

Keyword(s):

Factor Analysis ◽

Sulfuric Acid ◽

Raman Spectra ◽

Ion Pair ◽

Medium Composition ◽

Principal Factor ◽

Water Molecules ◽

Concentrated Solutions ◽

Principal Factor Analysis ◽

Hydrated Ion

Principal factor analysis has been applied to Raman spectra of 26 sulfuric acid/water mixtures covering the 0–100% H2SO4 concentration range. The analysis greatly facilitates the identification of peaks due to different species. The results show that SO42− ions and "free" HSO4− ions do not co-exist with undissociated H2SO4 molecules in solution and that two water molecules rather than one are required for the first ionization of H2SO4. A species with the composition H2SO4•2H2O, assigned a hydrated ion pair structure, reaches maximum concentration at the same medium composition at which SO42−, free HSO4−, and H2SO4 are at concentration minima, about 75% w/w. The only species apparent in the more concentrated solutions are the ion pair and undissociated H2SO4, which could be taken to mean that H2SO4 is a weaker acid than H3O+, but a stronger one than H3O+•H2O (or H5O2+, if this entity has a real existence). Separate peaks due to the postulated H3O+•H2SO4 (or H5SO5+) were not observed.

Download Full-text

Kinetic Study of Oxygen Transfer Reactions from Oxo-Monoperoxo Complexes of Vanadium(V) to Thiolatocobalt(III) Complex in Water and Concentrated Solutions of Electrolytes

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19960574 ◽

1996 ◽

Vol 61 (4) ◽

pp. 574-588 ◽

Cited By ~ 4

Author(s):

Oľga Vollárová ◽

Ján Benko ◽

Michal Sivák

Keyword(s):

Oxygen Atom ◽

Oxygen Transfer ◽

Salt Water ◽

Aqueous Media ◽

Order Rate Constant ◽

Transfer Reactions ◽

Oxygen Atom Transfer ◽

Concentrated Solutions ◽

Solutions Of Electrolytes ◽

Ph Range

[Co(en)2SCH2CH2NH2]2+ ion is oxidized to [Co(en)2SOCH2CH2NH2]2+ by the oxo-monoperoxovanadium(V) complexes in aqueous media. These reactions are accompanied by oxygen atom transfer from the peroxo ligand to the coordinated sulfur atom. The relative reactivities for each substrate stand in the order: [VO(O2)(ada)]- << [VO(O2)nta]2- ~ H2O2 ~ [VO(O2)(H2O)4]+ < [VO(O2)(quin)2]3- << [VO(O2)(H2O)2(pic)], where ada = N-(carbamoylmethyl)iminodiacetato(2-), nta = nitrilotriacetato(3-), quin = 2,3-pyridinedicarboxylato(2-) and pic = 2-pyridinecarboxylato(1-) ligands. The effect of pH on the second order rate constant for oxidation by monoperoxo-nta complex is in the pH range 4.8-6.5 consistent with equation k(298.2 K) = 0.709 + 1.28 . 105 [H+]. Two new oxo-monoperoxo complexes of vanadium(V), NH4[VO(O2)(ada)] . H2O and (NH4)3[VO(O2)(quin)2] . 3 H2O, were synthesized and characterized. The salt effects on the thiolatocobalt(III) oxidation by vanadium(V) oxo-monoperoxo complexes as well as by H2O2 were studied at 298.2 K in different, up to 5 M solutions of electrolytes. The results can be rationalized in terms of the salt-water interactions.

Download Full-text