Isotopic tracer experiments and scale-impingement experiments show fluorine to be the migrating species through the nickel fluoride scale formed during the fluorination of nickel. This is in contrast to nickel oxide scales, where nickel is the migrating species

Fischer, J.

Gunther, W.

Jarry, R. L.

English

NASA Technical Reports Server

October 1967
	 Brief 67-10397 
AEC-NASA TECH BRIEF 
1 
AEC-NASA Tech Briefs describe innovations resulting from the research and development program 
of the U.S. AEC or from AEC-NASA interagency efforts. They are issued to encourage commercial 
application. Tech Briefs are published by NASA and may be purchased, at 15 cents each, from 
the Clearinghouse for Federal Scientific and Technical Information, Springfield, Virginia 22151. 
Experiments Shed New Light on Nickel—Fluorine Reactions 
The problem: 
To obtain a better understanding of the mechanism 
and kinetics of the nickel-fluorine reaction. This 
reaction may aid in the development of new fluorine 
chemical processes for industrial products. 
The solution: 
Fluorine was found to be the migrating species 
through the nickel fluoride scale formed during the 
fluorination of nickel. This is in contrast to nickel 
oxide scales, where nickel is the migrating species. 
The reaction rates of the process did not depend upon 
the type of nickel, but were a function of scale 
thickness and pressure. 
How it's done:. 
Marker (isotopic tracer) experiments were con-
ducted in which radioactive nickel-63 was used, as 
well as scale-impingement experiments in which two 
scales formed during the reaction were forced to 
impinge upon each other. These experiments helped 
to determine whether nickel or fluorine migrated 
through the nickel fluoride scale formed during the 
fluorination of nickel. Similar experiments were 
performed with the nickel-oxygen system, a reaction 
of known mechanism, to verify the experimental 
method used in the nickel-fluorine study. 
The radioactive tracer experiments indicated that 
fluorine migrates through the growing fluoride scale. 
The migration of fluorine was evidenced by the lack 
of movement of the radioactive tracer, which was 
located at the nickel fluoride scale-fluorine gas 
interface. 
In the nickel-oxygen experiments, the radioactivity 
was found to be distributed through the oxide scale 
in a manner predicted from the known mechanism,
i.e., that nickel migrates through the nickel oxide 
scale to the nickel oxide-gas interface. 
In the fluoride scale-impingement experiments, the 
existence of an interface between the two scales 
growing from opposing surfaces, indicated that 
fluorine is the migrating species. In the oxide scale-
impingement experiments, a continuous scale was 
formed, thereby indicating that nickel is the migrating 
species. 
Notes: 
I. The kinetics of the nickel-fluorine reaction have 
been studied between 300° and 600°C, using high 
purity and commercial nickel. The parabolic rate 
constants for the reaction with high purity nickel 
were found to be 9.8, 81, 461, and 1860 (g F2/sq 
cm)2 per minute at 3001 , 400°, 500°, and 600°C, 
respectively. No significant difference in reaction 
rates for the two types of nickel was noted except 
in the initial portion (less than 500 mm) of the 
reaction period. The parabolic rate was found 
to be independent of the pressure of fluorine over 
the range of 100 to 700 mm Hg when the thickness 
of the nickel fluoride scale was 10 4 A or less. 
After a scale having thickness of about 10 5 A had 
been deposited, the rate of scale formation was 
found to vary with the one-half power of the 
fluorine pressure. 
2. Additional details are contained in The Mechanism 
and Kinetics of the Reaction between Nickel and 
Fluorine, by R. L. Jarry, W. H. Gunther, and J. 
Fischer, Argonne National Laboratory, Report 
No. ANL-6684, August, 1963. This report is avail-
able from the Clearinghouse for Federal Scientific 
and Technical Information, Springfield, Virginia 
22151; price $3.00; microfiche $0.65.
(continued overleaf) 
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 
TES
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=19670000397 2020-03-11T21:11:26+00:00Z
Inquiries concerning this innovation may be di-
rected to:
Office of Industrial Cooperation 
Argonne National Laboratory 
9700 South Cass Avenue 
Argonne, Illinois 60439 
Reference: B67-10397 
Source: R. L. Jarry, W. Gunther,
and J. Fischer
Chemical Engineering Division 
(ARG- 10008)
Patent status: 
Inquiries about obtaining 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 67-10397	 Category 03


Experiments shed new light on nickel-fluorine reactions

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