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ORNL-1702.txt
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FIE A v,
A SUMMARY OF DENSITY MEASUREMENTS ON
MOLTEN FLUORIDE MIXTURES AND A
CORRELATION FOR PREDICTING DENSITIES
71
OF FLUORIDE MIXTURES
S. |. Cohen
T. N. Jones
-‘—
Crasgivication Cuanaen To
By AUTHORITY (}r;-.@,.- e
BT:M
=
CENTRAL RESEARCH LIBRARY
DOCUMENT COLLECTION
LIBRARY LOAN COPY
DO NOT TRANSFER TO ANOTHER PERSON
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If you wish someone else to see this document,
send in name with document and the library will
arrange a loan.
T
OPERATED BY i
CARBIDE AND CARBON CHEMICALS COMPANY
A DIVISION OF UNION CARBIDE AMND CARBOMN CORPORATION
(T3
POST OFFICE BOX P
CAK RIDGE. TENNESSEE
OAK RIDGE NATIONAL LABORATORY @
- oRag.-1702
This document consists of 38 pages
Copy y'of 222 copies Series A
Contract No W-T405-eng-26
Reactor Experimental Engineeraing Division
A SUMMARY OF DENSITY MEASUREMENTS ON MOLTEN FLUORIDE MIXTURES
AND A CORREIATION FOR PREDICTING DENSITIES
OF FLUCRIDE MIXTURES
S I Cohen
T N Jones
DATE ISSUED
JUL 19 1954
OAK RIDGE NATIONAL LABORATORY
Operated by
CARBIDE AND CARBON CHEMICALS COMPANY
A Divaision of Union Carbide and Carbon Corporation
Post Office Box P
Oak Ridge, Tennessee
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TABIE OF CONTENTS
PAGE
SUMMARY 5
INTRODUCTION 6
DESCRIPTION OF EXPERIMENTAL PROCEDURE 8
A Dascussion of Method 8
B Description of Equipment 10
EXPTANATION OF THE CORRELATION 15
REFERENCES 26
APPENDIX 27
TABIE 1 Experimental Density-Temperature Data 28
TABLE 2 Constants Used in Calculating Room
Temperature Densities 29
TABLE 3 Calculation of Room Temperature Densities 30
TABLE 4 Comparison of Predicted and Experimental
Density-Temperature Data 37
SUMMARY
This report contains a summary of all the experimental density measure-
ments on molten fluoride mixtures that have been developed for the Aircraft
Nuclear Propulsion Project A correlation of these data 1s presented whaich
can be used to predict liquid densities of fluoride mixtures of known compo-~
sition over wide, elevated temperature ranges
Experimental measurements were made by the buoyancy principle using
a plummet suspended in the molten salts from an analytical balance, the
entire system being enclosed in a dry-box
All the information avallable on compositions, experimental densities,
melting points and cubical coefficients of expansion may be found in this
report, calculated values of liquid and room temperature densities, mo-
lecular weights and molecular volumes of all the mixtures that have been
developed fqor the ANP program are also presented
IRTRODUCTION
Since the outset of the Aircraft Nuclear Propulsion project, interest has
been centered on molten fluoride mixtures as the best potential circulating
fluids for use i1n high temperature reactors of the ARE type Durang the course
of the project, some fifty or more mixtures of fluorides have been suggested
and a number of these aroused sufficient interest to merit measurements off
their physical properties
In the early stages of the density research program the experimental
accuracy was somewhat lower than in the later stages During the former
Period some questions concerning purity of both the molten salts and the
blanketing atmosphere arose Also, the techniques of temperature measurement
and control, and weighing facilities were refined during the latter period
As a result, the more recent determinations afford a somewhat higher degree
of accuracy than the earlier ones
The correlation descraibed in this report i1s based on measurements on
all the mixtures that have been studied In a few instances, notably compo-
sition No 12 (Flinak), 1t has been possible to make a second set of measure-
ments on a mixture for which the properties had been measured very early in
the project, and i1n these instances the data listed below are the revised
values In past reports on several of the compositions, a correction based
. - T- o9
on the volume change of the plummet with temperature was omitted, the error
introduced being well within the accuracy claimed for the data However, this
correction has been applied where necessary in this report and i1t 1s suggested
that i1n subsequent studies involving the densities of fluorides, the data
in this report be used
B 4
DESCRIPTION OF EXPERIMENTAL PROCEDURE
A Discussion of Methed
wme
Density values reported here were determined by the buoyancy principle
involving & plummet suspended in a liquid The density of the liquid, P,
18 defined by
WL,
p:-—_
VL
where,
Wy, weight of liquid displaced by the plummet
Vi, Volume of liquid displaced by the plummet
and WL=WA-WL
Where,
Wy, weight of plummet in air
W1, weight of plummet in liquad
Upon substituting (2) in (1), there results
_ Wy - W
v
p
(1)
(2)
(3)
3 ud
. - 9 -
The volume of liquid displaced by the plummet, vy, 1s also equal to the
volume of the plummet and may be determined by weighing the plummet in a
liquid of known demsity (water was used) At room temperature the volume of
the plummet 1s
Wa - Wgs0
VI, = —_— (L)
pHgO
where,
WHQO’ weight of the plummet in Ho0 at
room temperature
PHS0» densaity of water at room temperature
The volume of the plummet at elevated temperatures is
Wy - W0
V], = VLO [l + BP (T-To)] = -—BE-(-)-e——
F+%(m%fl (5)
2
where,
T, liquid temperature
To, room temperature
BP, cubical expansion coefficient of
the plummet
Upon substituting equation (5) into equation (%), one obtains
(WA = WL) PHo0 (6)
P = (W, - Wgo0) [1 + By (T-To)]
o
i
Was WHQO and the temperature of water were measured before the experiment was
started Values for pHgO and Bp are known, values of WL at the various tempera-
tures were measured
Experimental density data are represented in this report by the equation
o =a - bl (7)
Values of the cubical coefficients of expansion were calculated from the
defining equation
=t
pr = - (%%)P (8)
©
The experimental data are given i1n Table 1 and in Figure 3 where the
temperature range over which measurements were made on each mixture is shown
The experimental data are also tabulated in Teble 4 in the form of equation (7)
A simple analysis indicates that these data are probably not in error by more
than + 5% Experimental values for the coefficients of cubical expansion of
the various liquids may be found in Table 1
B Description of the Equipment
The system (see Figure 1) used for taking these measurements consisted
principally of a stainless steel plummet suspended in the molten salts by a
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Fig. 2. Photograph of Dry Box Containing Density Measurement System.
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fine steel wire from a Voland 'Speedigram" balance (a chainomatic balance on
which weights larger than 100 mg are controlled mechanically by knobs with no
loss 1in accuracy) The plummets were fabricated from 1/4" No 316 stainless
steel rod The containers for the molten salts were fabricated from 1 1/2'
I P S, Schedule 40, No 316 stainless steel pipe The tube furnace was
mounted on a small rolling platform equipped with ball-bearing casters to
facilitate centering of the tube under the balance as well as under the two
systems for determining viscosities which were also housed in the dry-box
(Both density and viscosity measurements were made during the same heat-up
period Viscosity studies will be discussed in a separate report)
The temperature of the melt was measured with the aid of two chromel-
alumel thermocouples and a Brown multipoint recorder, the couples were inserted
in wells made of 1/8’ stainless tubing and supported in the liquid salt so
that one couple was 2-3 inches below the surface and the other 5-6 inches
below the surface The wire supporting the plummet was of such length that
the plummet was suspended at a depth between the two couples Temperature
of the furnace was controlled by a combination of a variac and a
Simplitrol with a chromel-alumel thermocouple The hot Jjunction of thais
couple was 1mbedded 1n the outside surface of a thick-walled copper pipe used
as a thermal diffuser between the heating surfaces of the tube furnace and
the tube containing the melt Since this hot junction "sees' the heating
element face, a very semnsitive temperature control was afforded As the
experiment progressed, the temperature setting was increased by a small
© Yy
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2N
increment and in a short time the temperatures indicated by the two immersed
thermocouples rose to a point slightly below that set on the Simplitrol,
leveled off and approached each other, at this point the two readings were
usually no more than 5 degrees apart After this practically isothermal con-
dition was reached, a weight reading and the average temperature were recorded
Since the fluorides in the molten state are very sensitive to the atmos-
phere, a number of precautions were taken to insure 1ts purity Argon was
circulated through the dry-box and out of & bubbler at a measured rate until
the calculated concentration of argon was above 99 9% These calrulations
have been checked experimentally by measuring the oxygen concentration of the
gas 1n the dry-box with a Burrell Gas Analyzer Effort was made to remove
the final traces of oxygen and water, these being the chief undesirable
impurities, by placing indicating Drierite from a closed container into a
flat open dish to get the water and by starting up an oxygen removal device
consisting of a tube furnace containing a cartridge of copper filings and
equipped with a 15 CFM blower The filings were brought to red heat and the
atmosphere in the dry-box circulated over them Purity offithe atmosphere,
which determines the purity of the melt, 1s indicated by the appearance of
the plummet when 1t 1s withdrawn from the melt The plummet, though dis-
colored, will have a clean smooth surface when taken from a clean melt No
difficulty was encountered with condensation on the wire except during measure-
ments on mixtures containing ZrF) When working with these salts, the plummet
was removed between weighings and the tube containing the melt was covered
to retard the zirconium snow effect
L e
s -15 - i i
EXPLANATION OF THE CORRELATION
Although more than fifty different fluoride mixtures have been developed