High temperature calorimetric studies of heat of solution of NiO, CuO, La2O3, TiO2, HfO2 in sodium silicate liquids

Yannick Linard, Martin C. Wilding, Alexandra Navrotsky*

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

7 Citations (SciVal)

Abstract

The enthalpies of solution of La2O3, TiO2, HfO2, NiO and CuO were measured in sodium silicate melts at high temperature. When the heat of fusion was available, we derived the corresponding liquid–liquid enthalpies of mixing. These data, combined with previously published work, provide insight into the speciation reactions in sodium silicate melts. The heat of solution of La2O3 in these silicate solvents is strongly exothermic and varies little with La2O3 concentration. The variation of heat of solution with composition of the liquid reflects the ability of La(III) to perturb the transient silicate framework and compete with other cations for oxygen. The enthalpy of solution of TiO2 is temperature-dependent and indicates that the formation of Na–O–Si species is favored over Na–O–Ti at low temperature. The speciation reactions can be interpreted in terms of recent spectroscopic studies of titanium-bearing melts which identify a dual role of Ti4+ as both a network-former end network-modifier. The heats of solution of oxides of transition elements (Ni and Cu) are endothermic, concentration-dependent and reach a maximum with concentration. These indicate a charge balanced substitution which diminishes the network modifying role of Na+ by addition of Ni2+ or Cu2+. The transition metal is believed to be in tetrahedral coordination, charge balanced by the sodium cation in the melts.
Original languageEnglish
Pages (from-to)590-601
Number of pages12
JournalGeochimica et Cosmochimica Acta
Volume72
Issue number2
Early online date13 Oct 2007
DOIs
Publication statusPublished - 15 Jan 2008

Keywords

  • TITANIUM COORDINATION
  • STRUCTURAL ENVIRONMENT
  • GEOCHEMICAL IMPLICATIONS
  • MODEL
  • COORDINATION CHEMISTRY
  • SPECTRA
  • TRANSITION
  • GLASS MELT SYSTEMS
  • AMBIENT
  • TI(IV)

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