Vibrational modes and structure of liquid and gaseous zirconium tetrachloride and of molten ZrCl4–CsCl mixtures ‡

Photiadis, G. M.; Papatheodorou, George

doi:10.1039/a707126d

Cited by 47 publications

(52 citation statements)

References 32 publications

(31 reference statements)

Supporting

Mentioning

Contrasting

Order By: Relevance

“…We have found general agreement with the proposals and the quantitative results presented in the Raman scattering studies of Photiadis and Papatheodorou [2,3]. At a given value of the ionic radius the main factors gov erning the relative stability of different local config urations are the metal-chlorine Coulomb attractions and the screening by counterions.…”

Section: Discussionsupporting

confidence: 77%

“…We discuss in this section the molecular clusters that according to the experiments of Photiadis and Papapheodorou [2,3] seem to be relevant in the liq uid (CsCl)i_x-(MCl4)I mixtures. We briefly recall their main findings.…”

Section: Charged and Cesium-compensated Clustersmentioning

confidence: 99%

“…Photiadis and Papatheodorou [2] attribute modes at about 338 and 148 cm-1 to either ZrCl5 or Zr2Cl to in liquid CsCl-ZrCl4 mixtures. We find that the breathing mode of these charged or Cs-compensated monomers and dimers lies at about 330 cm-1 in all cases.…”

Section: Charged and Cesium-compensated Clustersmentioning

confidence: 99%

“…In comparison with more con ventional molten salts, this behaviour is macroscopically characterised by a relatively low melting point, high fluidity and very low electrical conductivity of the melt. Among tetrahalides, molten ZrCl4 in a Ra man scattering study of Photiadis and Papatheodorou [2] has been proposed to consist of ZrCl4 tetrahedral monomers in equilibrium with a neutral oligomeric species, possibly the Zr2Cl8 dimer. For molten ThCl4, the same authors [3] have emphasized that the higher melting point (771 °C vs. 437 °C), the observed ionic conductivity (0.6 Q -1cm -1 at 810 °C), and the stability of a glassy state indicate an ionic-type binding.…”

Section: Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Structure and Binding of Ionic Clusters in Th and Zr Chloride Melts

Akdeniz

Tosi

2001

Zeitschrift Für Naturforschung A

View full text Add to dashboard Cite

We discuss microscopic ionic models for the structure and the binding of small clusters which may exist as structural units in molten ThCl4 and ZrCl4 and in their mixtures with alkali halides according to Raman scattering studies of Photiadis and Papatheodorou. The models are adjusted to the two isolated tetrahedral molecules. Appreciably higher ionicity is found for ThCl4 than for ZrCl4, and this fact underlies the strikingly different behaviour of the two systems in the dense liquid state -in particular, a molecular-type structure for molten ZrCl4 against a structure including charged oligomers in molten ThCl4.

show abstract

Section: Discussionsupporting

confidence: 77%

Section: Charged and Cesium-compensated Clustersmentioning

confidence: 99%

Section: Charged and Cesium-compensated Clustersmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

See 2 more Smart Citations

Structure and Binding of Ionic Clusters in Th and Zr Chloride Melts

Akdeniz

Tosi

2001

Zeitschrift Für Naturforschung A

View full text Add to dashboard Cite

show abstract

“…(3) and (5) coincided were determined. As before [29,30], the intensities of the resulting envelope components were considered to be proportional to concentrations without introducing corrections for possible differences in the scattering abilities of the corresponding particles.…”

mentioning

confidence: 99%

Phase Equilibria and Ionic Solvation in the Lithium Tetrafluoroborate–Dimethylsulfoxide System

et al. 2015

View full text Add to dashboard Cite

The phase diagram and electrical conductivity isotherms for the lithium tetrafl uoroborate (LiBF 4 )-dimethylsulfoxide (DMSO) system and Raman spectra of DMSO and the LiBF 4 -DMSO solution were studied. Spectroscopic signatures of a H-bond between DMSO and BF 4 -ions were found. The bonds of Li + ions to the solvent were stronger than the bonds in DMSO dimers because formation of the solvate destroyed dimeric DMSO molecules. The τ ω values for DMSO molecules in the Li + -ion solvate shell of the LiBF 4 -DMSO system were similar to those for associated solvent molecules.Introduction. Solvation is a complicated phenomenon that accompanies the dissolution of both electrolytes and nonelectrolytes [1, 2]. It is described by a combination of energetic and structural changes in the dissolved compound-solvent system and forms a solution of a defi nite composition. In order to understand if a lithium salt-solvent system satisfi es the criteria for battery applications, its phase diagram and concentration dependence of the conductivity are of utmost signifi cance. Vibrational spectroscopy plays an important role among methods for studying equilibria in non-aqueous solvents. Thus, the use of spectroscopic methods can with varying degrees of certainty characterize the solvation of cations and anions, identify ion pairs separated by solvent and more complicated aggregates, and estimate the equilibrium between the various particles in the system [3,4].The structure and properties of LiBF 4 in aprotic solvents have become interesting in the last decade because of its use as a salt for lithium batteries. We used DMSO [(CH 3 ) 2 SO] as the solvent. Equilibria in lithium-salt solutions have been characterized rather well by spectroscopic methods [5,6]. Spectra in the region of SO stretching vibrations [ν 7 (A′), ~1050 cm -1 ] [7] led to the conclusion that individual unassociated DMSO molecules, cyclic dimers, and chain-like associates were present [8,9]. The presence of the last was disputed [10]. Furthermore, the ν 7 vibration is known to be subject to a so-called noncoincidence effect and was split into several components in the pure liquid and concentrated solutions [11][12][13]. Therefore, spectra in the region ~1050 cm -1 were diffi cult to interpret unambiguously. Nevertheless, association constants of DMSO were determined only a few times [14][15][16][17]. It was hypothesized that the anions were solvated through H-bonds between DMSO methyls and F atoms in the anion. However, issues regarding the composition of ionic associates in DMSO and other solvents were treated differently [5,6,18]. We investigated previously electrolytes for lithium-ion current sources based on dimethylsulfone [19][20][21]. Because DMSO and dimethylsulfone are close analogs, it seemed interesting to compare the properties of solutions of lithium salts in these solvents.Experimental. DMSO (Aldrich, ≥98%) was stored over molecular sieves and vacuum distilled. The completeness of the purifi cation was monitored using the melting and boiling points. An...

show abstract

Alkali Metals: Inorganic ChemistryBased in part on the article Alkali Metals: Inorganic Chemistry by Francis S. Mair & Ronald Snaith which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Leung

2005

Encyclopedia of Inorganic Chemistry

View full text Add to dashboard Cite

This article is updated to cover the literature in the area of inorganic chemistry of alkali metals since 1993. The advancement in instrumentation and spectroscopic techniques in the past decade has provided the researchers with more powerful tools for structure determination of compounds. In this respect, alkalides containing mixed‐sandwich complexes of alkali metal cations, complexes with dimers or chains of alkali metal anions, electrides with alkali metal ions intercalating in zeolite, and interstitial hydride enclosed by an unusual (Li + ) 8 cubic cage have been found or studied by NMR. With the successful preparation of Na 3 N recently, its correct structure has been revealed. The exact composition of ‘NaB 6 ’ has also been determined. The role of alkali metals in trielide clusters of traditional Zintl polyanions has been demonstrated. Trimetallic Li‐Na‐K amides, alkoxide compounds, and highly aggregated cage structures of lithium‐heavier alkali metal alkoxides have been reported.

show abstract

Vibrational modes and structure of liquid and gaseous zirconium tetrachloride and of molten ZrCl4–CsCl mixtures ‡

Cited by 47 publications

References 32 publications

Structure and Binding of Ionic Clusters in Th and Zr Chloride Melts

Structure and Binding of Ionic Clusters in Th and Zr Chloride Melts

Phase Equilibria and Ionic Solvation in the Lithium Tetrafluoroborate–Dimethylsulfoxide System

Alkali Metals: Inorganic ChemistryBased in part on the article Alkali Metals: Inorganic Chemistry by Francis S. Mair & Ronald Snaith which appeared in theEncyclopedia of Inorganic Chemistry, First Edition.

Contact Info

Product

Resources

About