Journal of Nuclear Science and Technology

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Determination of Hydrogen Fluoride and Uranium

(VI) in Crude Uranium Hexafluoride by Hydrolysis
and Potentiometric Titration

Haruka SHINOHARA , Kimie IZAWA , Shigeo TSUJIMURA & Kenji MOTOJIMA

To cite this article: Haruka SHINOHARA , Kimie IZAWA , Shigeo TSUJIMURA & Kenji
MOTOJIMA (1967) Determination of Hydrogen Fluoride and Uranium (VI) in Crude Uranium
Hexafluoride by Hydrolysis and Potentiometric Titration, Journal of Nuclear Science and
Technology, 4:9, 482-487, DOI: 10.1080/18811248.1967.9732791

To link to this article: https://doi.org/10.1080/18811248.1967.9732791

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Journal of NucLEAR SciENCE and TECHNOLOGY, 4 (9), p. 482~487 (September 1967).

Determination of Hydrogen Fluoride and Uranium( VI)

1n Crude Uranium Hexafluoride by Hydrolysis
and Potentiometric Titration

Haruka SHINOHARA *, Kimie IZA W A*, Shigeo TSUJIMURA *

and Kenji MOTO]IMA *

R.:ceived April 10, 1967

A simple method for determining HF and U(\1) in a hydrolyzed solution of UF, hy alkalimetry
is described.
About l g of UF6 was taken in a polytrifluoromonochloroethylene tube, and hydrolyzed with
about 50 ml of water in a closed polyethylene bottle. Using a glass electrode, HF in the hydrolyzed
solution was titrated potentiometrically with an alkali solution, after the U(\11) had been masked with
ammonium sulfate. When the equivalence point for the free acid was reached, hydrogen peroxide
was added to the solution and the liberated acid equivalent to U (\1) was titrated with the same
standard alkali solution.
Assuming that the hydrolysis of UF 6 takes place stoichiometrically, the accuracy of this method
was roughly evaluated to be ± 10% for the ratio of HF/UF6 and ± I % for the value of U(\'1) in
the range of 0 to 1 mole of HF per mole of UF,.

can be used for hydrolyzed UF6. For exam-

I. INTRODUCTION
When reprocessing spent nuclear fuel by
fluoride volatility process, it is necessary to
determine HF in the UF6 product. The
radioactivity of fission products remaining in
the product raises the need for a simple,
remotely-operable method of HF determina-
tion.
Triple-point measurement of UF6<o<2> is one
of the most simple methods of determining
HF when no impurities are contained. The
drawback of this technique is that the amount
of sample material required is excessively
large for in-line application.
Infrared spectroscopy of HF has also been
studied<3><•>, and the method is actually used
for monitoring the HF concentration in UF6
gas streams. It allows HF of 0.1 to 1.0 m%
to be determined within ±0.05 m%<•l.
Gas chromatography has been used for in-
line analysis of plant streams containing HF,
UF 6 and other reactive gases, despite its
disadvantage of invariably involving consider-
able tailing of the HF peak<s>. In the recent
experiments, 4 % of HF in UF 6 was determined
with a precision of ±0.3%<•>.
Aqueous chemical analysis of F and U(VI)
ple, to determine U(I'I), an aliquot of hydro-
lyzed sample is fumed with sulfuric acid to
exclude F, the valency of U is then adjusted,
and the solution is titrated with standard
potassium bichromate solution, using diphenyl-
amine sodium sulfonic acid as indicator. F
is determined by steam-distilling another ali-
quot and titrating with thorium nitrate using
Arizarine-S as indicator. This method is
laborious and difficult for remote operation.
On a previous occasion, the authors<7l
proposed a simple method for determining
free acid, e.g. nitric, hydrochloric or sulfuric
acid, and U(VI) by alkalimetry. In the present
study, the method has further been developed
and made applicable to the determination of
HF and U(I'I) in hydrolyzed UF6 solution. The
conditions necessary for potentiometric titra-
tion were also determined.
n. ExPERIMENTAL
1. Reagents and Apparatus
( 1 ) Reagents and Apparatus used for
Sampling and Hydrolysis of UF 6
* Japan Atomic Energy Research Institute, Tokai-
mura, lbaraki-ken.

32
 Vol. 4 , No. 9 (Sep. 1967)
UF 6: UF 6 was prepared by reacting F 2
with UF4 and purifying the product by
repeated sublimation under vacuum.
Anhydrous HF: Anhydrous HF was pre-
pared by thermal decomposition of potassium
bifluoride.
Apparatus: The system for sample prep-
aration is shown in Fig. 1.
C3
C5 C6
ca
A: To vacuum line; B: Monel Bourdon gauge,
o-1,000 mmHg; Cl-C2: Cold traps for purifica-
tion of fluorides, C3--C4: Sample measuring
cylinders, 1.4Xl03cm3 and 3.8Xl02cm3 , C5-C8:
UFs or HF reservoirs, 1.3Xl02cm3 or 1.4Xl0cm3,
S: Daiflan sampling tube
Fig. 1 System for Sample Preparation
Valves: 30VM Monel valves from Auto-
clave Engineering Co.
Tubing: Monel tube of 1/8 11 inside dia-
meter.
Cylinders: Monel cylinder of 1.4X103 cm•,
3.8X10 2 cm 3 and 1.3Xl02 cm'.
Pressure gauge: Monel Bourdon gauge.
Sampling tube: Daiflon (Polytrifluoromono-
chloroethylene resin, Daikin Kogyo Co., Ltd.) tube
shown in Fig. 2
4 7
~c~:::;:;::~
55
Daiflon tube, 4 mm inner diam., 10 em long,
heated at one end and flared. A suitable position
along the length of the tube heated to trans-
parency, drawn, tail cut off, reheated and pushed
to seal off.
Fig. 2 Daiflon Sampling Tube
( 2) Reagents and Apparatus used for
Analysis of the Hydrolyzed Solution
Standard uranyl solution: Standard uranyl
solution was prepared by dissolving pure
U02CN03)2·6HzO in water. The U content of
the solution was determined either gravimetri-
483
cally or volumetrically.
Standard 0.2 N NaOH solution: Carbonate-
free saturated NaOH solution was diluted to
about 0.2N by adding carbonate-free water.
Its concentration was determined volumetri-
cally by 0.2 M sulfamic acid or potassium
biphthalate standard solution.
All other solutions were prepared from
analytical reagent-grade compounds.
Potentiometric titrator: An automatic-
recording titrator (Metrohm Potentiograph E336)
with 20 ml buret and combined glass and silver
chloride electrode (Metrohm's Type X or U) was
used.
2. Experimental Procedure
( 1 ) Sampling and Hydrolysis of
UFG·HF Mixture
The parts of the apparatus exposed to HF
and/or UFG was thoroughly cleaned to remove
all organic substances. After the apparatus
was assembled, it was leak-tested by helium
leak detector to prevent the entry of moisture
into the system; baked under high vacuum
to drive off moisture within the tubing; and
treated with F2 to prevent reaction of UFG
with the tubing material, as well as adsorp-
tion of HF thereto.
A sampling method such as pouring molten
UF 6 into a sampling tube<sJ was not practical,
due to the limited amount of sample material
available. In the present study the amount
of sample obtained was determined by collect-
ing gaseous UF 6 or HF in a cylinder of known
volume and measuring its pressure and tem-
perature. About 0.5 to 1 g of the gaseous
sample was then CJniense:l into a Daifton
tube kept at liquid nitrogen temperature. As
:>
much UF 6 as possible was made to condense
and collect at the bottom of the tube. The
tube was isolated and detatched from the
system, and immediately thrown into a 250 ml
polyethylene bottle containig about 50 ml of
water. The lid of the bottle was tightly
closed, and it was then shaken violently.
About 1 g of UF" was hydrolyze:! within 10
min at room temperature, with occasional
shaking to prevent plugging of the tu'Je by
bubbling gas. Without this shaking, hyiroly·
zation did not complete even after 24 hr.
484 J. Nucl. Sci. Techno/ ,

C2) Potentiometric Titration of the Table 1 Effect of Titration Speed on

Hydrolyzed Solution Potentiometric Titration of
HF and U(VI) with NaOH
The hydrolysis of a UF6·HF mixture can
Sample: 1.40 meq. HF+lOl mg U(VI)
be expressed by the reaction:
HF and U(VI) Relative error
xUFs+yHF+2xH20--> xU0 2F 2 + (4x+y)HF ( 1) Titration determined
speed
The uranyl fluoride-HF solution obtained
was diluted to (2~5) x 1o-•mole// of U(VI). An
(ml/min)
HF
(meq.) I U(VI)
(mg)
HF
(%)
I
U(VI)
(%)
aliquot containing about 100 mg of U(VI) was
5.2 1.52 105 +8.6 +4
pipetted into a 100 ml polyethylene beaker.
3.3 1.45 103 +4 +2
Five milliliters of 2 M ammonium sulfate solu-
2.6 1.43 102 +2 +I
tion were added as masking agent for U (VI),
1.9 1.41 101 +7x10-' 0
and the volume was adjusted to about 60 ml
1.1 1.40 100 0 -1
by adding water.
5x10-' 1.40 101 0 0
Then HF was titrated with 0.2 N NaOH
solution at a rate of 5XI0- 1ml/min until the 3X 10-1 1.40 100 0 -1
first inflection point appeared on the titration
curve. One milliliter of 3% H 202 solution When a 20 ml buret and 0.2 N alkali solution
was then added to the solution, and the are used, the titrated solution should contain
titration was continued until the second inflec- from 50 to 150 mg of U(VI) and (2.9~2.7) x 10- 3
tion point was reached. mole of HF.
The amounts of UF6(xmole) and HF(ymole) ( 3) Masking Agent for U(VI)
were calculated from the equations 4x+y=A Sodium fluoride produced during the titra-
and 2x=B, where A is the amount of NaOH tion was effective as masking agent for U(VI);
(mole) added before the first inflection point
was attained, and B that of the NaOH (mole)
added between the first and second inflection
points.

m. RESULTS
1. Examination of the Titration Conditions,
using Mixtures of Standard Solutions >
E

( 1 ) Titration Speed ...

The effect of titration speed must be con-
sidered in the alkalimetry of fluoride solution
using a glass electrode, since the time re-
quired for attaining potentiometric equilibrium
will probably be quite long. Some of the
results obtained by changing the titration
speed are shown in Table 1. The titration
speed of 0.5 ml/min was not too fast when
the Metrohm Potentiograph E 336 with a
combined glass electrode was used. But,
when a pH meter with a common glass
electrode was used, satisfactory results were
not obtained even when the speed was as
low as 0.1 ml/min.
( 2) Amount of Sample
The collecting capacity of the sampling
tube described earlier was about 3 g of UF 6.
10 8 6 4 2 0
0.2N-Na0H (mil
Inflection point for each curve shown,
though position of these curves relative to
E axis is arbitrary.
The following amounts of KF were added
to samples of 1.38 meq. HF+l01 mg U(VI)
and titrated with 0.2 N NaOH solution at
the rate of 5X10-1 ml/min; Curve A: 70
meq., Curve B: 30 meq., Curve C: 10 meq.,
Curve D: not added.
Fig. 3 Effect of large Amount of Fluoride
on Potentiometric Titration of Ura-
nyl Nitrate-HF Solutions

-34-
 Vol. 4, No.9 (Sep. 1967) 485

it was found that the inflection point of the titration of uranyl nitrate-HF solution with
titration curve became more pronounced by 0.1 M NazC03 solution. Some of the results
the addition of ammonium sulfate. are given in Table 2.
( 4 ) Effect of Fluoride ( 6) Titration of Mixtures of Standard
The effect of fluoride was studied by Solutions
changing the amount of potassium fluoride Uranyl nitrate-HF solutions were titrated
solution added to the uranyl nitrate-HF solu- with carbonate-free NaOH solution; some of
tions. Some of the results are shown in the results are given in Table 3.
Fig. 3. For samples containing exceptionally 2. Analysis of UF.-HF Samples
large amounts of fluoride, it was difficult to ( 1 ) Effect of Sampling-tube Material
determine the inflection point on the titration Borosilicate glass and Daiflon were tested
curve, because the variation of pH during as materials for tubing to collect and hydro-
the titration was very small. lyze the purified UF. samples. The potentia-
( 5 ) Effect of Carbonate grams obtained for both kinds of tubing are
The effect of carbonate was studied by shown in Fig. 4.
Table 2 Effect of Carbonate on Potentiometric
Titration of HF and U(VI) with NaOH
I Results of
A
Samples titration with Relative error
Na,COa
-----·-- ·--- --- ----- --··
HF+free U(VI) HF+free U(VI) HF+free U(VI) >
E
acid in lacid in acid in
UO,(NOa), U0 2 (NOa), UO,(NO,), T--+--.:B.J ""
(meq.) (mg) (meq.) (mg) (%) (%)
--
I
1.17 50.4 1.16 55.7 -9x1o- 1 +11
1.19 101 1.17 105 -2 + 4 c
1.20 151 1.19 155 -sx10- 1 + 3
1.22 202 1.20 206 -2 + 2 12 10 8 6 4 2 0
0.2 N-NaOH (mil
2.34 101 2.32 106 -9x1o-t + 5
2.34 101 2.32 111 -9x1o- 1 +10 Inflection point for each curve shown with
its value on NaOH axis (position of these
Table 3 Potentiometric Titration of HF and curves relative to E axis is arbitrary).
The following solutions titrated with 0.2 N
U(\1) in HF -UO,(NO,), Solution with NaOH solution at the rate of 5 X 10- 1ml/min.
CO, Free NaOH Curve A: UFa collected and hydrolyzed in
Results of borosilicate glass tube packed with borosilicate
Samples titration with Relative error glass granules of 177~250 /-L. HF/U0 2F2 =
CO, free NaOH 2.84, Curve B: UFs collected in borosilicate
···- glass tube and hydrolyzed slowly while cooling
HF+free U(VI) HF+free U(VI) HF+free I U(VI) nearly to 0°C in tube. HF/U02 F2 =3.74,
acid in acid in acid in Curve C: UFa collected and hydrolyzed in
U0 2 (NO,), UO,(NO,), U0 2 (N0 3) 2 Daiflon tube. HF/U02 F 2 =3.95.
(meq.) (mg) (meq.) (mg) (%) I (%)
-- Fig. 4 Potentiometric Titration Curves for

~.61
1.16 - 1.16 0 - Hydrolyzed Solutions of Pure UFs
Samples obtained at Various Hydro-
1.17 50.4 1.17 I 0 +2.4 lyzing Conditions
1.17 50.4 1.17 51.4 0 +2.0
1.19 101 1.19 102 0 +1 Owing to the considerable amount of heat
1.19 101 1.18 101 -sx10- 1 0 generated in the hydrolysis, the glass tube
1.20 151 1.20 151 was found considerably etched, resulting in
0 0
151 many cases in deformation of the titration
1.20 1.21 151 +8x10- 1 0
I 0 curve and reduced HF/UOzFz ratio. The
1.22 202 1.22 202 0
I
I hydrolysis performed in Daiflon tube produced
1.22 I 202 I 1.22 202 0 Io normally shaped titration curves, and HF/

-35-
 486 J. Nucl. Sci. Techrwl.,

U02F2 ratios near 4 were obtained, as seen

in Fig.4.
( 2) Determination of HF and U(V!) in
the Solution of Hydrolyzed High-
purity UF6
A series of purified UF 6 samples were
hydrolyzed, and HF and U(V!) were determin-
ed. Some of the results are shown in Table 4.
Table 4 Potentiometric Determination of HF/
U02F2 and U(V!) in Hydrolyzed Solu-
tion of Pure UF.
U (VI) was also determined gravimetri-
cally by drying the solution in platinum
crucible and then baking at 900°C for
1 hr.
Potentiometric
determination of
HF/U02F2 and U(Vl)
Samples
HF/U02F2 I U(V!)
(mg/ml)
1 3.94 11.8
2 3.95 11.2
3 4.03
12.2
4 3.97 11.6
5 3.97 12.5
( 3) Determination of HF Content in
UF6·HF Mixtures
UF6·HF mixtures were hydrolyzed, and
the HF/UOzF2 ratios determined. The results
are given in Table 5.
Table 5 Potentiometric Determination of HF/
U02F2 and U(VI) in Hydrolyzed Solu-
tion of HF-UFa Mixture with C02
Free 0.2 N NaOH
U(VI) was also determined gravimetri-
cally by drying the solution in platinum
crucible and then baking at 900°C for
1hr.
Semples Potentiometric Gravimetric
(mmHgx3.8X determination of determina-
10 2cm 3 at 25°C) HF/U02F2 and tion of
U(Vl)
W. DISCUSSION
The method described above is an exten-
sion of the work originally developed for the
determination of free acid and U(VI) in uranyl
nitrate-nitric acid solution. Since this method
is intrinsically a pH measurement of acidic
solution containing HF, the effect of deteriora-
tion of the glass electrode must be considered.
Tests on glass electrodes supplied from Japa-
nese makers, conducted in an acidic fluoride
solution of pH 3, showed that the pH-measur-
ing ability of the electrode was impaired after
1 day and was completely lost after 3 days. In
contrast, Metrohm's glass electrodes were
Gravimetric
determina- found serviceable in pH 2.5 to 4 of uranyl
tion of U(VI) fl.uoride-HF solution as long as 100 hr without
any decrease in the ability.
(mg/ml)
Very much larger errors should have to
11.7 be expected in the alkalimetry of fluoride
solutions as compared to nitrate solutions,
11.0
considering that the absorption into NaOH of
12.2
C02 present in the atmosphere would lower
11.5
the first equivalence point and raise the
12.4
second. Adsorption onto the glass electrode
of uranium peroxide produced by the addition
of H20 2 should further raise the second point.
All these circumstances combine to result in
values of HF/U02F2 ratio smaller than actual.
The use of borosilicate glass tubing was
abandoned because the conditions necessary
for obtaining a normal titration curve could
not be found. Daiflon tubing was preferable
since it required no special technique to
hydrolyze UF6 samples, and normal titration
curves were invariably obtained.
From Table 5, it is seen that the method
of analysis of crude UF 6, described in this
paper, can be applied successfully to samples
containing 0 to 1 mole of HF per mole of UF6.
U(V!) The large value of HF content seen in the

(~~~l~l) HF/ IU(V!) U(Vl) first sample in Table 5 may be taken to

UF·I HF I U02F2 (mg/ml) (mg/ml) indicate that the UF6 gas arriving from the
95 97 5.0 5.21 reservoir in the earlier runs contained more
8.8 8.7
HF than samples coming later.
97 96 5.0 5.09 9.4 9.4
The accuracy of this method was roughly
96 95 5.0 5.02 9.2 9.2
48 4.5 evaluated from Tables 4 and 5 to be ±10%
99 4.53 12.5 12.5
for the ratio HF/UFG and ±1% for the value
98 48 1 4.5 4.48 12.5 12.4
I
'
of U (VI) in the range of o to 1 mole of HF per
9J I 47 I 4.5 4.49 I
11.9 I 11.9
mole of UFG.

-36-
 Vol. •I, No.9 (Sep. 1967)
V. CoNCLUSION
F and U (VI) in hydrolyzed solution of crude
UFs were titrated with a potentiometric
titrator having a glass electrode, using carbon-
ate-free NaOH solution.
Aliquots of samples, containing from 50 to
150 mg of U (VI) combined with corresponding
amounts of HF, from 2.9 to 2.7 meq., were
titrated successfully. For mixtures containing
between 0 and 1 mole of HF per mole of UF s,
the HF/UFs ratio was determined by this
method with an accuracy of about ± 10%,
and the value of U (VI) within ± 1 %.
Ordinary glass electrodes were found un-
serviceable for pH measurements of HF solu-
tion, whereas Metrohm's Type X or U could
be used for long periods of time with unim-
paired performance.
Small values were often obtained for 4x+y
and large values for 2x in Eq.( 1 ), when the
HF/U02F2 ratio turned out smaller than the
theoretical values. Pure UF 6 should be
hydrolyzed and titrated occasionally to verify
the validity of the results; when a small HF/
U02F 2 ratio is obtained, the glass electrode
should be washed with nitric acid solution to
remove uranium peroxide and other materials
adsorbed on electrode surface.
-37-
487
ACKNOWLEDGMENT
The authors wish to express their thanks
to Mr. G. Fujisawa, Mr. A. Takahashi and Mr.
T. Soga for their assistance in the construction
of the experimental apparatus and the pre-
paration of samples. Acknowledgment is also
due to Mr. H. Yoshida and Miss S. Kurobane
for their help in the analysis of the hydrolyzed
samples.
-REFERENCES-
(1) MAYNARD, C. W., Jr.: M-1379, (1944).
(2) RODDEN, C.J.: T/D-7003, (1956).
(3) DEANE, A.M.: AERE-R-3261, (1960).
(4) SMITH, D.F.: Proc. 2nd. U.N. Intern. Conf.
Peaceful Uses of Atomic Energy, Geneva. 1958,
28. P/930, 130~138 (1958).
(5) HAMLIN, A. G., lVESON, G., PHILLIPS, T.R.:
Anal. Chem., 35, 2037~2044 (1963).
(6) WOODMAN, F.]., CLINTON, T.G., FLETCHER, W.,
et al.: Proc. 2nd. U.N. Intern. Conf. Peaceful
Uses of Atomic Energy, Geneva, 1958, 28, P/
1453, 433~435 (1958).
(7) MOTOJIMA, K., lZA WA, K.: Anal. Chem., 36,
733~735 (1964).
(8) RIORDAN,].]., HIGHFILL, J.P.: NBL-153, 58~
63 (1959).