The Variation of the Properties of Electrolytic Solutions with Degrees of Dissociation.

Young, Thomas M.; Blatz, L. A.

doi:10.1021/cr60137a007

Cited by 56 publications

(46 citation statements)

References 28 publications

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“…In a 1949 review, 8 Young and Blatz mentioned various Raman studies of the acid, but centered their attention on the spectral data of Rao. In a 1949 review, 8 Young and Blatz mentioned various Raman studies of the acid, but centered their attention on the spectral data of Rao.…”

Section: àmentioning

confidence: 99%

Structure and ionization of sulfuric acid in water

Fraenkel

2015

New J. Chem.

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Newly recorded Raman spectra of aqueous sulfuric acid provide scattering shifts of very high sensitivity hence signal-to-noise ratios, at a broad concentration range, up to 17 M. I interpret the spectra as (a) providing no evidence for incomplete H 2 SO 4 ionization at low concentration, (b) reflecting only one dissociation event below B5 M, (c) indicating a gradual ion association at B5-12.5 M, and (d) exhibiting further structural changes of the sulfate above 12.5 M. The analysis of the Raman shifts supports the postulated presence in solution of the para-bisulfate anion HSO 5 3À as a sole sulfate ion up to B5 M, as concluded before (D. Fraenkel, ion association producing para-sulfuric acid, H 4 SO 5 between 5 and 12.5 M, and a dehydration of H 4 SO 5 to H 2 SO 4 above 12.5 M. These conclusions are rationalized and corroborated by (1) a correlation of the Raman spectra with wellknown physicochemical properties of aqueous sulfuric acid, and (2) structural analogies between the proposed para-sulfates and related compounds and anions.

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Section: àmentioning

confidence: 99%

Structure and ionization of sulfuric acid in water

Fraenkel

2015

New J. Chem.

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“…The limited information presently available has been based, for the most part, on observations of the optical absorption or Raman spectra of undissociated molecules and the anions produced in dissociation (1,6,7,9,10,12). The degree of dissociation of a few oxyacids, notably nitric and perchloric acids, seems to be reliably established over a wide concentration range, but these methods are not applicable to binary strong acids.…”

Section: Introductionmentioning

confidence: 99%

HYDRONIUM ION ABSORPTION IN THE REGION 1.7 µ

Biermann¹,

Gilmour²

1959

Can. J. Chem.

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Optical absorption of the hpclroni~~m ion in the region 1.7 p was measured in solutions ol n i t r~c acid arid perchloric acid in the concentration range 0.01 t o 4.0 moles per liter. Above 0.1 molar the absorption did not follow Beer's Law, being smaller than predicted from the low concentration behavior. This e~ihancecl transparency is attributed t o a "negative absorption" band, associated with the change in solvent s t r~~c t~r r e , lound in this spectral region. I N T R O D U C T I O NIn an attempt to establish relationships between the thermochemical properties of aqueous solutions of strong acids and the structures of these solutions, the degree of dissociation of the acid is an indispe~lsable quantity. The limited information presently available has been based, for the most part, on observations of the optical absorption or Raman spectra of undissociated molecules and the anions produced in dissociation (1,6,7,9,10,12). The degree of dissociation of a few oxyacids, notably nitric and perchloric acids, seems to be reliably established over a wide concentration range, but these methods are not applicable to binary strong acids.While casting about for alternate methods of studying the dissociation of strong acids in aqueous solutions, we observed the near infrared absorption spectra of a nunlber of aqueous solutions of strong acids (2). I n all cases, these spectra showed a strong absorption band centered in the region of 1.7 p (5800 cm-I). I t appeared reasonable to classify this as an harmonic of a fundamental vibrational frequency of the hydronium ion. Very shortly thereafter, Gigu&re and Fall; (5) reported broad absorption pealcs for the hydroniuin ion a t 2900 cm-' and 3300 cm-l.A study of this absorption band over a range of concentrations was undertalten, primarily to determine the applicability of Beer's Law. If Beer's Law were obeyed, a useful method mould be available for the determination of the degree of dissociation of acids in water. Nitric acid and perchloric acid solutions were chosen because the hydroniuin ion concentrations of these can be calculated with some degree of confidence from existing data. E X P E R I M E N T A LNitric and perchloric acid solutions were prepared by diluting concentrated reagent grade chemicals with conductivity water. The diluted solutions were analyzed by titration with carbonate-free sodium hydroxide solutions, using bromcresol purple as indicator. The percentages of light transmitted by the diluted solutions were measured on a Beckmann DK-I1 spectrophotometer, using 1.0-cm Corex cells a t room temperature. Conventional procedures were used to insure temperature similarity between the solution and the water-filled reference cell, to correct for inequalities of cell length, and to n~inii~lize the chance of gross error by a suitable schedule of repetition of observations.The experimental results are summarized in Tables I and 11, which give the average absorbancy (loglo Toll) and the wavelength of the maximum of the absorption peak for a range of concen...

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“…The data for H2SO4 was calculated based on the dissociation behavior of H2SO4 and HSO4 in sulfuric acid solutions (Young and Blatz 1949 …”

Section: The Effect Of Ionic Strength On Oxygen Solubility Is Illustrmentioning

confidence: 99%