Spectrophotometric work on structural determinations with fused-salt solutions is reviewed. Constraints placed on the method, as well as interpretation of the spectra, are discussed with parallels drawn to aqueous spectrophotometric curves of the same materials

Gruen, D. M.

English

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September 1969	 Brief 69-10423 
ICY
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the Clearinghouse for Federal Scientific and Technical Information, Springfield, Virginia 22151, 
Coordination Chemistry in Fused-Salt Solutions 
• Spectrophotometric work on structural determi-
nations with fused-salt solutions is reviewed (1). The 
constraints placed on the method, as well as inter-
pretation of the spectra, are discussed, with parallels 
drawn to aqueous spectrophotometric curves of the 
same materials. 
In attempts to overcome the limitations of water 
as a solvent and to study new chemical reactions, 
many "nonaqueous" solvent systems have been in-
vestigated, among which fused salts constitute a 
particularly extensive and unique class of inorganic 
solvents. The study of chemical reactions in fused 
salts is of scientific interest, primarily because of the 
possibilities offered by these unusual high-tempera- 
ture solvents for exploration of new chemical phe-
nomena. 
For study of the chemistry of fused salts, new 
methods and techniques have been developed, and 
older ones modified, to cope with the special prob-
lems that arise with these materials. Now one can 
study them by a startling variety of techniques includ-
ing electrochemical-potential measurements, polar-
ography, chronopotentiometry, chromatography, 
electromigration, solvent extraction, nuclear mag-
netic resonance, and electron spin resonance. 
Since it is clearly impossible to cover the tremen-
dous amount of research on fused salts during the 
last decade, this review is limited to results by one 
technique—absorption spectrophotometry. Absorp-
tion spectra are especially useful for study of the 
solution chemistry of transition-metal ions; their 
unique features enable one to characterize the oxida-
tion states of the ions, determine their concentrations, 
and establish the identities and stabilities of complex 
ionic species. By means of spectral changes, one can 
follow the courses of chemical reactions and study 
their kinetics and mechanisms.
Although spectral measurements have long been 
used for aqueous solutions, specialized techniques 
for making quantitative spectral measurements of 
fused-salt solutions are only recently deyeloped. One 
problem to be solved,' for measurement of absorption 
spectra of fused salts at high temperatures, entailed 
the elimination of black-body radiation, emitted by 
the sample, sample container, and furnace, from the 
detection system. The solution is use of a source of 
chopped radiation, coupled with phase-sensitive 
amplification, in the following sequence of com-
ponents: light source -. chopper - sample and fur-
nace -. monochromator -. detector - a-c amplifier 
-. recorder. 
Use of instrumentation having these design features 
has made possible measurement of absorption spec-
tra at high temperatures (about 1,000°C) with the 
same accuracy as from conventional aqueous solu-
tions at room temperature. 
Reference: 
L D. M. Gruen, "Coordination chemistry in fused 
salt solutions" (Argonne National Laboratory, June 
1967). 
• Notes: 
I. Metals-producers and coordination chemists may 
be interested. 
2. Inquiries concerning this innovation may be di-
rected to:
Office of Industrial Cooperation 
Argonne National Laboratory 
- 9700 South Cass Avenue 
Argonne, Illinois 60439 
Reference: B69-10423 
Source: D. M. Gruen
Chemistry Division
(ARG- 10469) 
(continued ocerletti) 
This document was prepared under the sponsorship of the Atomic 
Energy Commission and/or the National Aeronautics and Space 
Administration. Neither the United States Government nor any per-
son acting on behalf of the United States Government assumes any
liability resulting from the use of the information contained in this 
document, or warrants that the use of any information, apparatus, 
method, or process disclosed in this document may not infringe pri-
vately owned rights.
https://ntrs.nasa.gov/search.jsp?R=19690000415 2020-03-16T18:02:22+00:00Z
Patent status: 
Enquiries concerning rights for commercial use of 
this innovation may be made to: 
Mr. George H. Lee, Chief 
Chicago Patent Group 
U.S. Atomic Energy Commission 
Chicago Operations Office 
9800 South Cass Avenue 
Argonne, Illinois 60439 
Brief 69-10423	 Category 03


Coordination chemistry in fused-salt solutions

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