Stoichiometry of technetium hexafluoride reactions is studied. Magnetic properties and infrared spectra of reaction products are studied and compared with those of analogous complexes of the hexafluorides of tungsten, rhenium, and osmium

Holloway, J. H.

Selig, H.

English

NASA Technical Reports Server

April 1970
	
Brief 70-10233 
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Reactions of Technetium Hexafluoride 
with Nitric Acid, Nitrosyl Fluoride, and Nitryl Fluoride 
.
The problem: 
To determine the reactions of technetium hexa-
fluoride with nitric oxide, nitrosyl fluoride, and nitryl 
fluoride. The reactions of various hexafluorides with 
nitrogen oxides and nitrogen oxide fluorides have 
recently been studied increasingly. In particular, the 
reactions of third-transition-series hexafluorides with 
nitric oxide and nitrosyl fluoride have been used for 
assessment of the relative oxidizing powers of these 
hexafluorides. Of the thermodynamically stable metal 
hexafluorides, least is known about technetium hexa-
fluoride, possibly because the radioactivity of tech-
netium has inhibited experimental work. 
The solution: 
Reactions of technetium hexafluoride with nitric 
oxide, nitrosyl fluoride, and nitryl fluoride gave the 
compounds NOTcF 6 , (NO)2TcF 8 , and NO2TcF7. 
The stoichiometry of each reaction was studied. The 
magnetic properties and infrared spectra of these 
compounds were studied and compared with those of 
some analogous complexes of the hexafluorides of 
tungsten, rhenium, and osmium. Attempts to prepare 
NOTcF 7 were unsuccessful. 
How it's done: 
A vacuum manifold of monel and nickel was used 
for all experimental manipulations. Reactions were 
carried out either in thin-walled (1/32 in.) nickel 
weighing cans, fitted with small brass valves, or in 
3/4-in. Kel-F test tubes fitted with Kel-F valves. The 
metal vacuum system and reaction vessels were 
passivated with fluorine and chlorine trifluoride prior 
to use. Stoichiometries of the reactions were followed
by weighing both starting materials and reaction 
products in tared reaction vessels. 
Considerable difficulties were encountered in chemi-
cal. analyses of the samples. In general, fluoride 
analyses were low owing to the exceptional stability 
of the TcF 6 2 ion which is formed upon hydrolysis of 
the solids. Technetium analyses were performed by 
evaporation of aliquots of the solutions on platinum 
plates, and counting of the Tc 99 betas in a calibrated 
PCC-10 proportional counter having an overall 
geometry factor of 0.785. These results are somewhat 
uncertain because of self-absorption of the soft betas 
in the solid sample. However, the reproducibilities of 
reaction stoichiometries, combined with supporting 
evidence of physical properties, leave little doubt as to 
the correctness of the stated compositions. 
The infrared, x-ray-diffraction, and magnetic-sus-
ceptibility samples were prepared in a small, nitro-
gen-filled, dry box under slight positive pressure 
The details of and methods for the specific reactions 
with technetium hexafluoride are available. 
Notes: 
1. This information may interest physical chemists 
doing transition-metal research. 
2. Inquiries concerning this information may be di-
rected to:
Office of Industrial Cooperation 
Argonne National Laboratory 
9700 South Cass Avenue 
Argonne, Illinois 60439 
Reference: B70-10233 
Source: J. H. Holloway and H. Selig

Chemistry Division

(ARG- 10412) 
(continued overleaf) 
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Patent status: 
Inquiries concerning rights for commercial use of 
this information may be made to: 
Mr. George H. Lee, Chief 
Chicago Patent Group 
U.S. Atomic Energy Commission 
Chicago Operations Office 
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Argonne, Illinois 60439 
Brief 70-10233	 Category 04


Reactions of technetium hexafluoride with nitric acid, nitrosyl fluoride, and nitryl fluoride

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