Gasförmige Komplexe zwischen Kobaltchlorid und Indiumchlorid

Abstract

SummaryThe equilibria (1) and (2) :CoClz (s)+InC13 (g) + CoInCls (g) (2)were investigated by optical spectroscopy and by vapour pressure measurements using the transpiration method: dH(1)= 11.0 * 0.3 kcal mol-1, dS(1)= 8.9 5 0.3 e.u. ~l H ( 2 ) =18.6 * 1.3 kcal mol-l, dS(2)= 14.6 1.4 e.u.Together with thermodynamic data from the literature the results obtained allow a complete description of all heterogeneous solid/gas as well as the homogeneous equilibria in the gas phase of the system CoClz/InCl3 in the temperature range 500-800"

Soft Bending Modes of Terminal Chlorides in Gaseous Two- and Three-Coordinate Cu(II)−Cl Species

“…Also interesting in this respect is the discrepancy between the spectroscopic results for CuCl 2 : The Raman 3 and resonance Raman 2 spectra recorded some 20 years ago display intensive bands at ∼130 cm -1 that were attributed to the bending mode, as well as bands at ∼500 cm -1 assigned to either asymmetric stretch 2 or a combination ν 1 + ν 2 . 3 The apparent Raman activity of ν 2 and ν 3 suggests a bent molecule, which also is the conclusion reached by both Dienstbach et al 3 and Papatheodorou. 2 In contrast, Beattie et al 24 recently claimed that CuCl 2 is linear, on the basis of analysis of data obtained with laserinduced fluorescence and laser excitation spectroscopy, although the isotopic shift pattern in fact indicated a slightly bent (173°) structure.…”

“…Inclusion of such corrections would probably bring the latter estimates in good agreement with at least the experimental value from visible spectroscopy. 3 For technical reasons, we were not able to carry out MCPF calculations on Cu 2 Cl 4 .…”

“…The earliest report on gaseous Cu 2 Cl 4 was in an IR study by Leroi et al 1 Later Papatheodorou 2 and Dienstbach et al 3 published results from resonance Raman investigations, which support a trigonal configuration for the copper atom. All of the reports assume the molecule to have a ring structure with D 2h symmetry.…”

“…Agreement between theory and experiment seems to have been reached concerning the ground state and vital parts of the electronic spectrum for this molecule. 24,25 On the other hand, there exist experimental indications of both linear 24 and bent 2,3 CuCl 2 , and the shape of the molecule has yet to be studied explicitly by quantum chemical methods. Quantum chemistry may assist in the interpretation of the electronic and vibrational spectra 25,26 of the transition metal dihalides, as well as afford information about the potential curves of bending, as recently seen for CrCl 2 .…”

Vapor-complex equilibriums in the cobalt(II) chloride-indium(III) chloride system

“…During the course of this investigation,16 work was published by Emmenegger and co-workers regarding the vapor complexes of indium chloride with CoCl2,17 NiCl2,18 and CuCl2. 19 Our thermodynamic values are compared with those of ref 17 and other CoCl2 vapor complexes and discussed in terms of their structure and stability.…”