The System Lithium Perchlorate—water

Simmons, John P.; Ropp, Clarence D. L.

doi:10.1021/ja01393a019

Cited by 14 publications

(10 citation statements)

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“…Obviously, the rigidity of the hydration columns gives rise to particular thermal stability. Thus, LiIÁ3H 2 O crystallizes from the cryohydratic point at 182 K to the congruent melting point at about 348 K, similar to LiClO 4 Á3H 2 O with a melting point of 368 K (Simmons & Ropp, 1928). The same structure type was reported for the trihydrates of lithium salts with other large anions such as permanganate (Bauchert et al, 2008;Fischer & Hoppe, 1990), pertechnate (Maruk et al, 2011), perbromate (Blackburn et al, 1993), hexafluoroarsenate (Decken et al, 2006) and tetrafluoroborate (Bogdanov & Kondrashev, 1987).…”

Section: Figurementioning

confidence: 52%

Higher hydrates of lithium chloride, lithium bromide and lithium iodide

Sohr

Schmidt

Voigt

2018

Acta Crystallogr C Struct Chem

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For lithium halides, LiX (X = Cl, Br and I), hydrates with a water content of 1, 2, 3 and 5 moles of water per formula unit are known as phases in aqueous solid-liquid equilibria. The crystal structures of the monohydrates of LiCl and LiBr are known, but no crystal structures have been reported so far for the higher hydrates, apart from LiI·3HO. In this study, the crystal structures of the di- and trihydrates of lithium chloride, lithium bromide and lithium iodide, and the pentahydrates of lithium chloride and lithium bromide have been determined. In each hydrate, the lithium cation is coordinated octahedrally. The dihydrates crystallize in the NaCl·2HO or NaI·2HO type structure. Surprisingly, in the tri- and pentahydrates of LiCl and LiBr, one water molecule per Li ion remains uncoordinated. For LiI·3HO, the LiClO·3HO structure type was confirmed and the H-atom positions have been fixed. The hydrogen-bond networks in the various structures are discussed in detail. Contrary to the monohydrates, the structures of the higher hydrates show no disorder.

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Section: Figurementioning

confidence: 52%

Higher hydrates of lithium chloride, lithium bromide and lithium iodide

Sohr

Schmidt

Voigt

2018

Acta Crystallogr C Struct Chem

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“…Although the data summarized above are of somewhat dubious quality (even at 298 K) they have been used by Söhnel and Novotný and by Aseyev and Zaytsev, in their respective compilations of physicochemical data of electrolyte solutions, to derive smoothed values of ρ(LiClO 4 (aq)) under conditions (0 ≤ m /mol·kg –1 ≤ m satd and 273 ≤ T /K ≤ 373) that go far beyond the published experimental matrix. The present experimental situation is summarized in Figure , which plots the apparent molar volumes ( V ϕ ) of LiClO 4 (aq) at 298.15 and 333.15 K, calculated from the available density data. − Clearly, there is considerable uncertainty in the existing volumetric properties, especially at low and intermediate concentrations, even at 298.15 K. It follows that the smoothed values derived from these data by Söhnel and Novotný (which were adopted by Aseyev and Zaytsev, but assigned an extra significant figure! ) must be viewed with caution.…”

Section: Introductionmentioning

confidence: 80%

“…At high concentrations (m > 2 mol•kg −1 ) the present results (filled symbols) are in good agreement with those of Geffcken 8 and the saturated solution value of Simmons and Ropp. 7 The results of Jones 9 and of Mazzuchelli and Rossi 6 are of historic interest only, while, the data of Haase and Ducker 10 are scattered (some values have been omitted for visual clarity: the maximum deviation was 5.48 cm 3 •mol −1 ; see also Figure 1). Interestingly, at this temperature the smoothed values of Aseyev and Zaytsev, 12 which are in essence identical to those of Soḧnel and Novotny, 11 are in good agreement with the present results except perhaps at low concentrations.…”

Section: Table 3 Debye−huckel Limiting Slopes (A V ) and Standard Mol...mentioning

confidence: 99%

“…Early measurements on the densities (ρ) of LiClO 4 (aq) have been summarized by Timmermans. 5 Thus, Mazzuchelli and Rossi 6 reported densities of LiClO 4 (aq) at three concentrations and two temperatures (288 and 298 K), Simmons and Ropp 7 measured densities of (only) saturated LiClO 4 solutions at five temperatures from 273 to 303 K, and Geffcken 8 at six concentrations over the range 2.0 ≤ m/mol•kg −1 ≤ 4.9 at 298 K. Subsequently, Jones 9 represented his measurements of ρ(LiClO 4 (aq)) at concentrations up to ∼0.1 mol•L −1 at 298 K with an equation, and Haase and Ducker 10 listed densities at 0.001 ≤ c/mol•L −1 ≤ 2.8 and nine temperatures from 273 K to 333 K. All of these studies were made by pycnometry (Haase and Ducker did not specify the method used but the large scatter in their data is consistent with this technique) and were of limited precision, with densities cited to 3, 7 4, 9,10 or (at best) 5 6,8 decimal places, with little or no information provided about the purity of the salt employed.…”

Section: ■ Introductionmentioning

confidence: 99%

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Densities and Molar Volumes of Aqueous Solutions of LiClO₄ at Temperatures from 293 K to 343 K

Hnědkovský

et al. 2016

J. Chem. Eng. Data

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Densities of aqueous solutions of purified lithium perchlorate at solute concentrations ranging from approximately 0.05 to 5 mol·kg–1 have been measured by vibrating-tube densimetry at 5 K intervals over the temperature range 293 ≤ T/K ≤ 343 at atmospheric pressure. Apparent molar volumes of LiClO4(aq) derived from these data varied smoothly with solute concentration and temperature and could be fitted with an average precision of ±0.02 cm3·mol–1 using an extended Redlich–Rosenfeld–Meyer equation. The present results show that volumetric data listed in popular literature compilations are inaccurate. The effects of temperature on the partial molar volumes of LiClO4(aq) are nonlinear and indicate that the structure-breaking or -making character of this salt depends on concentration and temperature. Systematic differences observed between the volumes of lithium and sodium salts with a common anion appear to be related to differences in the strength of hydration of the two cations.

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“…The data on crystallisation temperatures were taken from previously published papers. [23][24][25][26] in the solution of the eutectic concentration. This is the region of maximal disorder, as evidenced by X-ray scattering in solutions, 27,28 by the temperature independence of the relative dynamic viscosity of the solutions of a certain concentration corresponding to the eutectic point 22 and by the relative partial molar entropy having a maximum in this area.…”

Section: Introductionmentioning

confidence: 99%

Detection of Hydrate Forms of Lithium and Sodium Perchlorates in Aqueous Solutions Using near Infrared Spectroscopy

Davidian

Kudrev

Myund

et al. 2014

Journal of Near Infrared Spectroscopy

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A new approach to the study of concentrated electrolyte water solutions is proposed. NIR spectra of aqueous solutions of LiClO 4 and NaClO 4 were studied. The pure spectra and concentration profiles of spectral forms in the solutions were found by deconvolution of an experimentally measured data matrix. The chemometric analysis and the generalised phenomenological model of the structure of aqueous electrolyte solutions were used to establish that the variation in spectra of LiClO 4 solutions with concentration is due to antibatic changes in the fractions of water that is unbonded with ions and of water in the structure of the cybotactic group of lithium perchlorate trihydrate. Corresponding changes in NaClO 4 solutions are also associated with interconversion of sodium perchlorate forms of di-and monohydrates. Hydrate forms of lithium and sodium perchlorates in aqueous solutions are described, and a cybotactic group in a saturated solution is found to be equivalent to a solid-phase structure fragment. A strategy for selecting the nature of a background electrolyte is recommended. IntroductionAqueous solutions of alkali metal salts are of interest from the viewpoint of their use as background electrolytes. A number of studied parameters of chemical processes (the constants of complex formation, hydrolysis etc.) depend on the nature and concentration of the background electrolyte. 1 From a chemical viewpoint, the cations of sodium and lithium differ in the nature of their interaction with water, e.g. the free energies of Li + and Na + ion hydration are 114.6 and 89.7 kcal mol -1 , respectively. 2 The energy of the ion-dipole interaction of singly charged ions with water exceeds that of water-structure destruction by a quantity necessary for ion hydration. Therefore, lithium and sodium ions cannot cause strong polarisation of coordinated water molecules in the solution or change the spectral characteristics of such molecules to any considerable degree. 2 This makes the interpretation of spectral data more involved.The perchlorate anion is convenient because of its weak complexing, electron-donor and proton-acceptor properties. 3 NaClO 4 and LiClO 4 aqueous solutions have been studied using several methods: viscometry, 4 cryoscopy, 5 proton relaxation, 6 Raman spectroscopy in the frequency range of totally symmetric stretch vibration, n Cl-O of the ClO 4 -ion, 7 Fouriertransform infrared attenuated total reflection spectroscopy in the frequency range of the fundamental harmonic of stretch vibrations of water in perchlorate solutions up to the salt concentration 3 M 8 and absorption spectroscopy in the near infrared (NIR) region of 2 M sodium perchlorate water solution . 9 The special features of the physical and chemical properties of concentrated solutions are attributed to ion-ion interactions, in particular, the formation of solvent-separated and contact ion pairs. 7The aim of this paper is to detail a study of hydrate forms of lithium and soldium perchlorates in aqueous solutions using NIR spectroscopy. The prese...

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The System Lithium Perchlorate—water

Cited by 14 publications

References 0 publications

Higher hydrates of lithium chloride, lithium bromide and lithium iodide

Higher hydrates of lithium chloride, lithium bromide and lithium iodide

Densities and Molar Volumes of Aqueous Solutions of LiClO₄ at Temperatures from 293 K to 343 K

Detection of Hydrate Forms of Lithium and Sodium Perchlorates in Aqueous Solutions Using near Infrared Spectroscopy

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The System Lithium Perchlorate—water

Cited by 14 publications

References 0 publications

Higher hydrates of lithium chloride, lithium bromide and lithium iodide

Higher hydrates of lithium chloride, lithium bromide and lithium iodide

Densities and Molar Volumes of Aqueous Solutions of LiClO4 at Temperatures from 293 K to 343 K

Detection of Hydrate Forms of Lithium and Sodium Perchlorates in Aqueous Solutions Using near Infrared Spectroscopy

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Densities and Molar Volumes of Aqueous Solutions of LiClO₄ at Temperatures from 293 K to 343 K