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Enthalpies of Formation of Chromium Fluorides. II. Higher Fluorides CrF4, CrF5, and CrF6

Authors
  • Nikitin, M. I.1
  • Malkerova, I. P.1
  • Kayumova, D. B.1
  • Alikhanyan, A. S.1
  • 1 Kurnakov Institute of General and Inorganic Chemistry, Russian Academy of Sciences, Moscow, 119991, Russia , Moscow (Russia)
Type
Published Article
Journal
Russian Journal of Inorganic Chemistry
Publisher
Pleiades Publishing
Publication Date
Oct 01, 2021
Volume
66
Issue
10
Pages
1519–1526
Identifiers
DOI: 10.1134/S0036023621100119
Source
Springer Nature
Keywords
Disciplines
  • Physical Methods of Investigation
License
Yellow

Abstract

AbstractThe paper presents critical analysis of experimental data, including the most recent published data on the gas-phase and heterogeneous equilibria of reactions involving higher chromium fluorides. The results of the analysis are presented as the enthalpies of formation (kJ/mol) of chromium fluorides in the condensed and gas phases: ΔfH°(CrF4, cr, 298.15 K) = –1202.5 ± 12.8; ΔfH°(CrF4, a, 298.15 K) = –1193.5 ± 13.1; ΔfH°(CrF4, g, 0) = –1098.9 ± 12.1; ΔfH°(CrF5, cr, 298.15 K) = –1243.8 ± 12.4; ΔfH°(CrF5, g, 0) = –1150.5 ± 12.1. The standard enthalpy of formation of chromium hexafluoride in the gas phase was determined to be ΔfH°(CrF6, g, 0) = –1077 kJ/mol. The possibility of existence of the mixed crystalline fluoride CrIVCrVF9 was demonstrated and its enthalpy and entropy of formation from crystalline CrF4 and CrF5 were estimated to be ∆rH°(298.15 K) = –12.6 kJ/mol, ∆rS°(298.15 K) = –1.5 J/(mol K). The recommended values provide explanation for the thermal behavior of higher chromium fluorides and the possibility of conducting some procedures with them in the processes that are qualitatively described in available literature.

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