Vapor-Liquid Equilibriumof the Binary System HF-H20

Extending to ExtremelyAnhydrousHydrogen Fluoride

N. Miki, M. Maeno, and K. Maruhashi
Hashimoto Chemical, Limited, Kaizan-cho Sakai 590, Osaka, Japan

T. Ohmi*
Department ~ Electronics, Faculty ~ Engineering, Tohoku University, Sendai 980, Japan

ABSTRACT
The vapor-liquid equilibrium of the binary system HF-H20 was determined, especially in the range of low water con-
centrations. The purity of anhydrous hydrogen fluoride used in this work was 9N (99.9999999%) with a conductivity of 0.7
• 10 -6 S c m - ' (water concentration of 0.033 ppm). We elucidated that the vapor-liquid equilibrium of the binary system
HF-H20 obeyed Raoult's law below 1 x 10 3 tool dm -3 (18 ppm) water concentration. We determined the activity coeffi-
cients of H F and H20 at the boiling point of the binary system HF-H20.

Munter et al. (1, 2) reported the vapor-liquid equilibrium Composition of the binary system HF-H20.--Figure 3
of the binary system HF-H20 at atmospheric pressure over shows the relation between conductivities and water con-
a considerable range of composition. The boiling points centrations determined by known additions of water and
and vapor-liquid compositions of the binary system by the Karl Fischer method. The conductivity of an-
HF-H20 determined by them are now utilized as the stand- hydrous hydrogen fluoride in the closed system attained
ard for hydrofluoric acid. Figure 1 shows their boiling the level of 0.7 • 10 -6 S c m - ' for continuous flowing an-
points and vapor-liquid compositions for the binary sys- hydrous hydrogen fluoride. In the range of water concen-
tem HF-H20. They only measured the equilibrium up to trations below 1 • 10 -2 mol dm -3 (180 ppm), a definite
89% hydrogen fluoride (HF) concentration, and the equi- quantity of water was added to the anhydrous hydrogen
librium has not yet been measured in the range below 10% fluoride, and the conductivity was measured. In the range
water concentration. Vieweg (3) has reviewed and unified of water concentrations over 1 • 10 -2 mol dm -3 (180 ppm),
the available data on vapor pressure over HF-H20 mix- the water concentrations were measured using the Karl
tures for the range of composition of 5~80% HF. It is impor- Fischer method. The calibration curve was obtained from
tant for promoting a technology of dehydration of HF that both results (4, 5). For the vapor-liquid equilibria, meas-
the equilibrium of the binary system HF-H20 is deter- ured water contents less than 1 mol dm -3 (18,000 ppm) by
mine d in the range of trace amounts of water. Here we the conductivity method using the calibration curve and
have determined the binary system equilibrium, espe- greater than 1 mol dm -3 (18,000 ppm) using a neutraliza-
cially in the range of low water concentrations, using the tion titration method.
conductivity method developed by ourselves (4, 5). We
have calculated the activity coefficient of HF and H20 at Measurement of Vapor-Liquid Equilibrium
the boiling point for the entire binary system HF-H20. Figure 4 shows the measurement apparatus for the va-
por-liquid equilibrium. First, anhydrous hydrogen fluor-
Experimental ide was introduced into the vessel A from the ultra puri-
Principle of measurement--Anhydrous hydrogen fluor-
ide exhibits a hygroscopic nature, so measurements of the
equilibrium were carried out under the following two con- 120
ditions: (i) an apparatus consisting of a closed circulating 2
system and (ii) measuring instruments set in the system. "0.,
Figure 2 shows the principle of the closed circulating
system. This system consists of a vaporization part and a 100
condensation part, with conductivity cells for measuring o

\
water concentrations set in both parts. In this work, the
closed conductivity cells used were entirely made of
fluorocarbon polymer with two bright platinum electrodes. 80
Materials.--The purity of anhydrous hydrogen fluoride
used is 9N level (1 ppb m a x for every anion impurity and
0.1 ppb m ax for every cation impurity), and its conductiv-
ity is 0.7 x 10 -6 S cm -1 (at 0~ that is, the water concentra-
4-'-
C~ 60 \
tion is below 1.85 • 10 -6 mol dm -3 (0.033 ppm). Anhydrous
hydrogen fluoride was charged into the apparatus from an
ultrapurifying process which is based on a new chemical
distillation principle (6). The new chemical distillation
E 40 \
principle consists of ultra dehydration and a fluorine oxi-
dation process. The complexity of the chemical formulas 20
IX
of the impurities converges to simple anhydrous struc-
tures due to the extreme dehydration of the hydrogen
fluoride, and the various valences of the impurities con-
verge to the highest oxidation state by the fluorine oxida-
tion. Consequently, all of the impurities having various 20 40 60 80 I00
chemical formulas are simplified to structures removable
from hydrogen fluoride, which can be purified perfectly by
the distillation.
HF (Wt%)
Fig. 1. Boiling points and vapor-liquid composition of the binary sys-
* Electrochemical Society Active Member. tem HF-H20. 1, Liquid phase; 2, vapor phase.

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 788 J. Electrochem. Soc., Vol. 137, No. 3, March 1990 9 The Electrochemical Society, Inc.
I T2
Vaporization part Condensation p a r t

T .
K --
.
0
HF gas
.

HI:" liq
.

<
.

J
.~

0
" Cooler
T : Thermocouple
K : Cell

Fig. 2. Schematic diagram of the closed-circulating system for vapor-

liquid equilibrium.
f "5 G

t y i n g p r o c e s s , after w h i c h a definite q u a n t i t y o f w a t e r w a s
a d d e d f r o m i n j e c t i o n hole I. A t this t i m e , t h e w a t e r c o n c e n -
t r a t i o n was m e a s u r e d u s i n g c o n d u c t i v i t y cell K1. T h e hy-
d r o g e n fluoride w a s t h e n h e a t e d to i n c r e a s e its v a p o r p r e s -
s u r e a n d e x h a u s t e d f r o m t h e p o i n t F in Fig. 4 b y r e d u c e d
II
p r e s s u r e to e l i m i n a t e t h e air in t h e s y s t e m . S u b s e q u e n t l y ,
h y d r o g e n fluoride w a s statically v a p o r i z e d , a n d t h e n t h e
v a p o r o f h y d r o g e n fluoride was c o n d e n s e d b y c o n d e n s e r G AHF outlet
to r e t u r n to t h e v e s s e l A. T h e k e y p o i n t for this e x p e r i m e n t
is t h e static v a p o r i z a t i o n m e t h o d , b e c a u s e v i g o r o u s boiling Fig. 4. Measurement apparatus for vapor-liquid equilibrium: A, ves-
disturbs the vapor-liquid equilibrium. Circulation was sel; B, tower; C, condensed hydrogen fluoride, D, capillary; E, control
c o n t i n u e d until t e m p e r a t u r e s TI, T2, a n d T~ a n d c o n d u c t i v - vessel for pressure; F, vacuum system; G, condenser; H, heater; I, injec-
ities kl a n d k2 r e a c h e d c o n s t a n t values. tion hole with fluoro-polymer rubber; T1, T2, T3, thermocouple; K=, K2,
cell.
Results and Discussion
The vapor-liquid equilibrium of the binary system
s o r b e d m o i s t u r e in t h e c o u r s e of t h e analysis p r o c e s s ,
HF-H20 h a s b e e n d e t e r m i n e d at a t m o s p h e r i c p r e s s u r e , es-
w h i c h r e s u l t e d in h i g h e r c o n c e n t r a t i o n s o f water. T h e con-
p e c i a l l y in t h e r a n g e of low w a t e r c o n c e n t r a t i o n s . Table I
v e n t i o n a l m e t h o d is n o t able to m e a s u r e a c c u r a t e l y a t r a c e
a n d T a b l e II p r e s e n t t h e l i q u i d a n d v a p o r c o m p o s i t i o n s
a m o u n t o f w a t e r in H F b e c a u s e o f its o p e n s y s t e m config-
a n d r e l a t e d boiling p o i n t s d e t e r m i n e d for t h e b i n a r y sys-
uration and the accompanying absorption of water from
t e m HF-H20.
t h e e n v i r o n m e n t d u e to e x t e r n a l l e a k a g e o f t h e m e a s u r i n g
F i g u r e 5 s h o w s t h e relation b e t w e e n t h e b o i l i n g p o i n t s
s y s t e m a n d b a c k d i f f u s i o n of w a t e r f r o m t h e o p e n e n d of
a n d v a p o r - l i q u i d c o m p o s i t i o n for t h e low w a t e r c o n c e n t r a -
t h e s y s t e m . In this w o r k , t h e m e a s u r i n g s y s t e m w a s
t i o n s in t h e b i n a r y s y s t e m HF-H20, u s i n g t h e d a t a in Table
II. T h e b i n a r y s y s t e m in t h e r e g i o n o f low w a t e r c o n c e n t r a -
t i o n s has b e e n a c c u r a t e l y d e t e r m i n e d in t h i s w o r k . T h e
Table I. Composition in liquid and vapor phase at boiling point of the
c o n v e n t i o n a l boiling p o i n t s h a v e b e e n d e m o n s t r a t e d to co-
system HF-H20
i n c i d e well w i t h o u r d a t a for h y d r o g e n fluoride c o n c e n t r a -
t i o n s u p to 89%. O n t h e o t h e r h a n d , in t h e r e g i o n o f v e r y
l o w w a t e r c o n c e n t r a t i o n s , t h e v a p o r c o m p o s i t i o n (line 2) is Liquid Vapor
c o m p l e t e l y d i f f e r e n t f r o m t h e p r e v i o u s l y r e p o r t e d data T1 kl (0~ 1 CH2O T2 7'3 k2 (0~ CH2o
(~ (• (ppm) (~ (~ (• 6Scm-1) (ppm)
(1, 2). It is c o n s i d e r e d t h a t this d i f f e r e n c e is c a u s e d b y t h e
analytical m e t h o d . T h e p r e v i o u s w o r k e r s s a m p l e d t h e con-
108.5 -- 754000 a 108.3 15.5 -- 932800a
d e n s a t e , d i l u t e d w i t h ice, a n d a n a l y z e d for h y d r o g e n fluor- 113.7 -- 580000" 113.6 15.6 -- 481000 a
ide b y titration. It is c o n s i d e r e d likely t h a t t h e s a m p l e s ab- 113.2 -- 563000a 113.0 15.6 -- 38,9500a
101.5 -- 454000" 101.4 15.4 -- 52900"
76.0 -- 340000" 75.8 15.4 41000 4600
CMzo (ppm) 57.1 -- 259000 a 57.0 15.3 28000 2700
35.5 -- 125000a 35,4 15.3 13500 1000
1.8x10"3 1.8xlO
"2 1.8xlO
-I I.SxlO~ 1.8xlO= 1.8xlO2 1.8xlO~ IBxl04 29.8 -- 84000a 29,8 15.2 8700 570
10-1 20.3 46800 5570 20,2 14.8 2022 89
19.8 25500 2390 20,0 15.1 1081 46
19.5 9041 600 19,8 15.1 350 12
19.5 947 44 19.5 15.2 20 0.64
10-2 19.5 502 20 19.5 15.0 10 0.45
_A tf
'E "Neutralization titration.
r I0"~

"90 10-4

.>_
I0 "5 / 7 Table II. Activity coefficients in the binary system HF-H20

HF
(weight Percent) Boiling
Vapor
pressure Activity
point (mmHg) coefficient

o iO-e / Liquid

24.6
42.0
Vapor

6.72
51.90
(~

108.5
113.7
Po (HF) Po (H20) 71 (HF) 72 (H20)

9614
10810
1021.5
1215.2
0.02
0.09
0.90
0.52
/ 43.7 61.05 113.2 10690 1195.3 0.10 0.45
iO-V 54.6 94.71 101.5 8175 801.6 0.18 0.12
10-7 10-6 10-5 10-4 I0-3 10-2 i0-I 10o 66.0 99.54 76.0 4321 301.4 0.27 0.04
74.1 99.73 57.1 2554 129.8 0.41 0.06
Water Concentration CHao ( tool dm -a) 87.5 99.90 35.5 1311 43.4 0.67 0.14
91.6 99.943 29_8 1090 31.5 0.77 0.17
Fig. 3. The relation of water concentration and conductivity of hydro- 99.443 99.9911 20,3 787 17.9 9.97 0.68
gen fluoride. (A, - - 9 (O~ this work; (B, - - 0 - - ) (O~ this work 99.761 99.9954 19.8 768 17.3 1.00 0.86
99.940 99.9988 19.5 760 17.0 1.00 0.90
(Karl Fiscber's method); (C, ----) (15~ Ref. (11); (D, - - - - ) (15~ 99.9956 99.999916 19.5 760 17.0 1.00 1,00
Ref. (7). 99.9980 99.999955 19.5 760 17.0 1.00 1.00

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 J. Electrochem. Sac., Vol. 137, No. 3, March 1990 9 The Electrochemical Society, Inc. 789

I} Table III. Activity coefficients in the binary system HF-H20 from the
data of Munter and Vieweg

Vapor
pressure Activity
40 (weightHF
percent) Boiling
point (mmHg) coefficient
I 2 Liquid Vapor (~ Po (HF) Po (H20) ~t (HF) ~2 (H20)

Munter (1)
10 2.0 102.8 8433 836 0.02 0.98
20 7.1 106.6 9183 950 0.03 0.91
30 19.4 I10.3 10046 1087 0.05 0.80
I/ 50 80.0 106.2 9120 939 0.14 0.33
30 70 98.8 65.5 3250 192 0.34 0.12
2 ~ 81 99.3 44.9 1769 71 0.54 0.40
89 99.5 33.3 1224 38 0.70 0.82

Vieweg (3)
10 2.01 102.8 8433 836 0.02 0.98
20 6.78 106.6 9184 950 0.03 0.91
30 19.26 110.3 10046 1087 0.05 0.80
20 40 43.52 111.7 10337 1136 0.08 0.63
50 74.25 106.2 9120 939 0.13 0.43
60 90.99 87.0 5743 469 0.21 0.38
70 98.73 65,5 3250 192 0.34 0.17
80 99.91 47,6 1923 82 0.50 0.04
80 90 99 I00
HF ( w t % )
the experimental data coincide with the theoretical line
Fig. 5. Boiling points and vapor-liquid composition for low H20 con- b e l o w 1 x 10 -~ m o l d m -3 0 8 p p m ) o f water. T h e s l o p e of
centrations in the binary system HF-H20 1, liquid phase; 2, vapor the relation between the water concentrations in liquid
phase. a n d i n v a p o r b e c a m e 1 i n t h e r a n g e b e l o w 1 • 10 -z m o l
d m -3 (18 p p m ) w a t e r in h y d r o g e n fluoride. T h i s r e s u l t led
closed, as s h o w n in Fig. 4 and, m o r e o v e r , t h e s y s t e m w a s to t h e c o n c l u s i o n t h a t t h e v a p o r - l i q u i d e q u i l i b r i u m of t h e
c o m p l e t e l y c o v e r e d b y a n i t r o g e n e n v i r o n m e n t i n o r d e r to b i n a r y s y s t e m H F - H 2 0 o b e y s R a o u l t ' s l a w b e l o w 1 x 10 -3
s u p p r e s s t h e i n c u r s i o n of w a t e r t h r o u g h e x t e r n a l leakage. m o l d m -z (18 p p m ) w a t e r c o n c e n t r a t i o n .
Figure 6 shows the relation between the water content in T h e a c t i v i t y coefficient of H20(~/s2o) i n H F h a s n o t b e e n
t h e v a p o r a n d l i q u i d p h a s e s i n t h e b i n a r y s y s t e m HF-H20. r e p o r t e d p r e v i o u s l y . A c t i v i t y coefficients of H F a n d H20
T h e c o n c e n t r a t i o n o f w a t e r in t h e v a p o r p h a s e i n t h i s w o r k h a v e b e e n d e t e r m i n e d o v e r a w i d e r a n g e of c o m p o s i t i o n at
is d i f f e r e n t f r o m t h e v a l u e o b t a i n e d b y M u n t e r a n d V i e w e g t h e b o i l i n g p o i n t s at a t m o s p h e r i c p r e s s u r e in t h e b i n a r y
o v e r t h e r a n g e of 60-90% H F c o n c e n t r a t i o n i n t h e l i q u i d s y s t e m HF-H20, as c a l c u l a t e d f r o m t h e f o l l o w i n g e q u a t i o n
phase. [2] (8, 9). T a b l e III s h o w s t h e a c t i v i t y coefficients c a l c u l a t e d
E v e r y p a r t i a l p r e s s u r e i n t h e v a p o r - l i q u i d e q u i l i b r i u m of f r o m t h e d a t a of M u n t e r e t a L a n d V i e w e g (2, 3).
t h e b i n a r y s y s t e m H F - H 2 0 g e n e r a l l y o b e y s H e n r y ' s l a w [1] P Yi
~h - at t~ [2]
Pi xi
p, = ~nP~ at t~ [1]
p~ = p a r t i a l p r e s s u r e of n t h c o m p o n e n t ~ = a c t i v i t y coefficient of i t h c o m p o n e n t
P% = v a p o r p r e s s u r e of n t h c o m p o n e n t at t~ p = t o t a l p r e s s u r e of s y s t e m
~, = a c t i v i t y coefficient of n t h c o m p o n e n t pi = v a p o r p r e s s u r e o f i t h c o m p o n e n t at t~
X~ = m o l e f r a c t i o n of n t h c o m p o n e n t i n l i q u i d x~ = m o l e f r a c t i o n of i t h c o m p o n e n t in l i q u i d
y~ = m o l e f r a c t i o n of i t h c o m p o n e n t in v a p o r
T h e d a s h e d l i n e i n Fig. 6 i n d i c a t e s t h e r e l a t i o n b e t w e e n
the water concentrations in the vapor and liquid phases T h e r e s u l t s are s h o w n i n T a b l e II a n d Fig. 7. T h e v a l u e s
o b t a i n e d b y c a l c u l a t i o n u s i n g ~/H2o= 1. I t is r e c o g n i z e d t h a t o f ~H~o c a l c u l a t e d f r o m t h e r e p o r t e d d a t a (1-3) are d i f f e r e n t

I0 -4 i0-5 lO-Z lO-J I0 ~ I0 t (mol dm-a) H2OinLiquid Phase (wt %)

A
102

i0 I
i I

o This work
9 MuntePs data
i i i

! )
E
:~ o.8
1.0
I00 80
. .
60
.
40
. .
20 0

,1-- a Vieweg*s data i1-.

~ , I0 ~ ---Raoult's law j
o 0.6
// ( 0
0
r" I0 -I

//
D-
/~r .>_
0
0.4

t'~ 10-2
r sp 9
< o., X"j
sS
~.- 10-3
._~.~-~. , .---- ,~
0
0 20 40 60 80 O0
o
-r~ 10-4 HFin Liquid Phase (wt%)
This work o ?'~ (HF) Munter's data ,, 1', (HF)
lO "ll ./' I I I I I 9 I'2 (H20) 9 1'2 (H20)
10-4 10-3 I0 -z 10-I I0~ I01 I0 z Vieweg'sdata u 1', (HF)
H20 of Liquid Phase (wt %) 9 ~'2 (H20)
Fig. 6. Vapor-liquid equilibrium of the binary system HF-H20 Fig. 7. Activity coefficients of the binary system HF-H20
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 790 J. Electrochem. Soc., Vol. 137, No. 3, March 1990 9 The Electrochemical Society, Inc.

from those calculated from our data, particularly at low HF-H20. It has been shown that the activity coefficient of
water concentrations in HF, though the reported values of H20 has a m i n i m u m value at a concentration of about 70%
~]H~ coincide well with our data in the binary system H F and approaches 1 with a decrease of water concen-
HF-H20 with decrease of water. The activity coefficient for tration.
HF (~HF) monotonically increases and approaches 1 with a
decrease of water concentration, while the activity coeffi- Manuscript submitted Nov. 10, 1988; revised manuscript
received Aug. 13, 1989.
cient for H20 (~H2o)exhibits a m i n i m u m value at about 70%
HF in the binary system HF-H20. The existence of the Hashimoto Chemical, Limited, assisted in meeting the
m i n i m u m value of "m2o is explained as follows. The liquid publication costs of this article.
structure of the HF-H20 system has already been demon- REFERENCES
strated to exhibit a m i n i m u m 'H chemical shift at about
1. P. A. Munter, O. T. Aepli, and R. A. Kossatz, Ind. Eng.
70% H F by NMR measurement, due to a m a x i m u m forma- Chem., 39, 427 (1947).
tion of H30§ and, moreover, the density of HF 2. P. A. Munter, O. T. Aepli, and R. A. Kossatz, ibid., 41,
solutions is well known to exhibit a m a x i m u m value at 1504 (1949).
about 70% HF because of the strong hydrogen bond (10). In 3. R. Vieweg, Chem. Tech. (Berlin), 15, 734 (1963).
the extremely anhydrous region of the binary system 4. N. Miki, M. Macho, and K. Mewuhashi, JpnAnal., 29, 88
HF-H20, the value of ~H2oapproaches 1, where water mole- (1980).
cules ideally dissociate. 5. N. Miki, M. Maeno, T. Ohmi, This Journal, 137, 790
(1990).
Conclusion 6. N. Miki, U. S. Pat. 4,668,497 (1987).
The vapor-liquid equilibrium of the binary system 7. R. Ukazi and I. Kageyama, Jpn. Anal., 9, 604 (1960).
8. R. L. Jewry, and W. Davis, Jr., J. Phys. Chem., 57, 600
HF-H20 has been determined, especially in the range of
(1953).
low water concentrations. 9. Chemical Handbook, Japan Chemical Association
It has been demonstrated experimentally that the vapor- (1984).
liquid equilibrium of the binary system HF-H20 obeys 10. M. F. A. Dove and A. F. Clifford, "Chemistry in Nona-
Raoult's law below 1 • 10-3 mol dm -a (18 ppm) water con- queous Ionizing Solvents," Vol. II, Part I. pp. 212-
centration. We have determined the activity coefficients of 218, Pergamon Press (1971).
H F and H20 at the boiling point of the binary system 11. Draft, International Standard ISOfDIS 3700-2 (1978).

Conductivity and Dissociation Equilibrium of Extremely

Anhydrous Hydrogen Fluoride
N. Miki and M. Maeno
Hashimoto Chemical, Limited, Kaizan-cho Sakai 590, Osaka, Japan
T. Ohmi*
Department of Electronics, Faculty of Engineering, Tohoku University, Sendai 980, Japan

ABSTRACT
We have studied the conductivity of extremely anhydrous hydrogen fluoride (AHF) and obtained a m i n i m u m conduc-
tivity of 0.7 • 10 -6 S cm -1 at 0~ We have recognized that water in A H F at concentrations below 1 • 10 -3 tool dm -3 shows
an ideal dissociation and that the limiting equivalent conductance of AHF is 436 S cm 2 mol-1 at 0~ The ideal relationship
between the conductivity and water concentration obtained in this work was extrapolated to the ultra-micro water con-
centration region. The conductivity of 0.7 x 10-6 S cm -1 corresponds to a water concentration of 1.85 • 10 -6 tool dm -3
(0.033 ppm) in the above relationship; however, this conductivity is not due to the dissociation of water but to that of hy-
drogen fluoride. We recognized that the relationship between the conductivity and water concentration of A H F coincides
completely with that of ultra-pure water in the ultra-micro conductivity region (10 -8 S cm-1).

The relationship between the dissociation of water and with a conductivity of 10 2 S cm i, which was distilled
the conductivity in anhydrous hydrogen fluoride is impor- after heating a mixture of HF and F~ to 200~176 (10).
tant for the electrochemical theory, the analytical technol- Netzer et al. described a modified fractionation system
ogy of water, and the dehydration technology of hydrogen from which they obtained hydrogen fluoride with a con-
fluoride. ductivity of about 1 x l0 -6 S cm -1 at 25~ (11).
Frendenhagen et al. studied conductivities over the The International Organization for Standardization
range from 0.013 to 0.5N water in hydrogen fluoride and (ISO) has presented a conductometric method for determi-
obtained a conductivity of 1.4 x 1O-5 S cm -1 for anhydrous nation of water concentrations in industrial anhydrous hy-
hydrogen fluoride at 15~ (1-4). drogen.fluoride over the range of 0.01-0.4% water (12).
Kilpatrick et al. improved the methods for the purifica- We have reported previously the conductivities below
tion of anhydrous hydrogen fluoride, which yielded acid 0.01% water concentration in anhydrous hydrogen fluroide
with m u c h lower conductivity, 1.6 • 10-6 S cm ~1 at 0~ (13). We now report that we have measured the conductiv-
than reported previously (5-7). ity of anhydrous hydrogen fluoride with lower water con-
Rogers examined the dehydration of hydrogen fluoride centrations and studied theoretically the dissociation of
by CoF2 and Hyman tried the fractional distillation of hy- water in extremely anhydrous hydrogen fluoride.
drogen fluoride, but their conductivities for anhydrous hy-
drogen fluoride were only at the 10 -4 S cm -1 level (8, 9). Experimental
Ukazi et al. analytically studied conductivities over the Materials.--Hydrogen fluoride was purified by an ultra
range from 0.1 to 5% water in anhydrous hydrofluoric acid purifying process to reach a very low level of impurities as
shown in Table I. The ultra purifying process, which is
* Electrochemical Society Active Member. based on a new chemical distillation principle, consists of
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