March 1947 INDUSTRIAL AND ENGINEERING CHEMISTRY 423

stltnt prcssurib ri'ading (at room tenipc,rature'l \vas registered tJy
the gage on the cylinder.
The conversion of fluorine into SFs by the above process yielded
not less than 8 7 5 of the amount theoretically possible.
PROPERTIES O F S U L F U R H E X i F L U O R I D E
Table I summarizcs sonie of the propdrties of SF,as found i n
the literature, together with data obtained in this laboratory
The total gage pressure (meawrcd by F. S.Preston) shown by
liquid SFs Contained in stec.1 cylinders was 189 pounds at 0" c'.
and 330 poundi. at 25' C.
LITER t T C R E C X E D
(1) Ruerhner, Tan de Graaff, Sperduto. Burrill, IIcIntosh. nnil
LTrquhart. r h u s . Reo.. 69, 692 (1946).
('7) Cherlron and Cooper, Gen. Elec. Rea., 40, 438 (1937),
(3) Eucken and Schroder, 2 . physik. Chem.. B41, 30i-19 (1938'.
(4) Fuoss, J . A m . Chem. SOC.,60, 1633 (1938).
( 5 ) Kleiiim and Henkel, Z. anorg. iiiliiem. Chem., 207, 73 (1932).
(6) Moissan and Lebeau, C'ompt. rend., 130, 865 (1900); Ann. chim.
, 26, 1 4 i (1902).
p h ! p ~[7]
(7) Pearson and Robinson, J . Chem. S O C . , 1933, 1427.
(8)Prideaux, l b i t l . , 89, 323 (19@6),
Schumb and Gamble, J . Am. Chem. SOC.,52,4302 (1930).
Schurnb, P h y s . Rea., 69, 692 (1946).
Traute and Ehrmann. J . prubt. Chem., 142, 70 (1935).
(12) Watson and Ramasn-amy, Proc. Roc. SOC.(London), A156, 144
(1'336).
(13) F a t s o n , Rao, and Ramaswarn>., Ibid., A132, 569 (1931); 431,
558 (1934).
(1.1) T o s t and Russell, "Systematic Inorganic Chemistry", 11. 299.
Xew York, Prentice-Hall, Inc., 1944.
PRESEXTED :it t h e nieering of t h e l m e r i c a n Physical Sorie-y at Carribridre.
~ I L I $ < ,3Iay
, 1916. T h e x o r k described in this paper constituted a small
!jor:iun of t h e 1 l . I . T . project in high voltage rsdiography, u n d e r t h e
aiiqpices o f t h e Office u f Scientific Research a n d De\.elopment (1.1) R c'.
C ontract OEI\Isr-294:, a n d :xi15 under t h e general superrision of I<.J. Van
de Graaff of 11.1T . i n a C r o u n t of t h e wurk .ippenred in 0 . S . R I). IYni
lieport S o . 4488. Tolnnie 3 , .Junr 1, 1945.

Vapor pressure of
HYDROFLUORIC ACID SOLUTIONS
J . C. Brosheer, F. A. Lenfesty, and Kelly L. Elmore
TEYYESSEE VALLEY 4UTHORITY. WILSOLI DAM, A L 4 .

THE partial pressures of hydrogen fluoride and w-ater
Tapor over solutions of hydrofluoric acid containing 2 to
3 0 7 ~hydrogen fluoride were determined by a dynamic
metho? at 25", 40", 60", and 73" C. The results, which
are more consistent than previously published data, are
expressed by empirical equations that fit the data within
the limits of experimental error. The heats of vaporiza-
tion of hydrogen fluoride and of water from the solutions
were calculated, and the results agree with values given
in the literature.

S'' IJf the recovery of fluorine from gases cont:iiiiiiig -nxill

perceiitnges
rlj'- of hydrogen fluoride required data on the. part iiil
vapor pressures of hydrogen fluoride and water over solutions oi
data are prewnted n i t h the chart, nor is a description given of the
method by Jvhich the plotted values xere obtained.
The prehent pnper gives measured partial pressures for the com-
hydrofluoric acid. It vas expected t h a t the concentration i , f the poiients of hydrofluoric acid solutions containing 2 t o 30Tchydro-
solutions of recovered fluorine would not exceed 20'3 hydrogen gen fluoride a t 25', 40°, 60°, and 75' C. Empirical equatioms for
fluoride and t h a t the solutions would not be heated to more t h i i relating partial pressures to liquid composition are also presented.
7 5 O c.
Khaidukov, Linetskaya, and Bognovarov ( 7 ) reported measure- 1IATERIALS AND APPARATUS
ments of vapor pressures of hydrogen fluoride and water over hy-
Reagent grade hydrofluoric acid was twice distilled over po-
drofluoric acid solutions containing 5 to 3 9 7 hydrogen fluoride at tassium fluoride (6) in a platinum still. The distillate contained
several temperaturesfrom 25' to 75' C. Their dRta do not extend about 35% hydrogen fluoride and was shown h y colorimetric
:13 far as !?-as desired into the methods t o be free from silica.
range of dilute solutions, and The purified acid was diluted
with freshly boiled distilled
tlie large increments in con- water for use in the vapor pres-
cciitration make interpolations sure measurements.
uncertain. lloreover, the d s t a The apparatus W R E designed
are s o m m h a t inconsistent for measurement of the vapor
pressures by adynamic method;
among themselves and are an inert carrier gas is saturated
markedly inconsistent x-ith x i t h the vapor of the experi-
vnlues that Fredenhagen and mental solution and is then
Wellmann (4) reported for analyzed. The errors coni-
monly encountered in the
dilute solutions a t 25" C. -\ method are due to incomplete
bulletin rcicently issued by the saturation of the carrier gas or
Chiernl Chemical Conipany (5) to entrainment of the solution
iiicludcs a chart of the partial in the carrier gai, Many in-
vestigators attempted t o mini-
lii'essure of hydrogen fluoride mize these errors by passing tlie
over hydrofluoric acid solutions. gas slowly over the surface of
This chart does not extend the liquid in a long tube. This
illto the range of l o ~ vconcen- technique is tedious, however,
trations of acid at room tem- because of the slowness viith
which equilibrium isestablished
perature, and the increment. i n betveen the static liquid and
concentration are large. S o Figure 1. Saturator the gas.
424 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 39, No. 3

I. PARTIAL
TABLE PRCSBL-RES FLL-ORIDE
OF HYDROGES ASD \T.LTER
T.LPOR ACIDSOLUTIOSS
OYER HYDROFLCORIC
250 c. 40" C. 60' C. 7.50 c.
Concn. H F Concn. H F C o n c n HF Concn. H F
i n liquid, PHF, PHso, i n liquid, PHF, PH20, i n liquid, Par, PH?O, i n liquid, liHF. PH:O,
wt. % m m . Hg m m . Hg u-t.c; m m . Hg mm. Hg w t . :; m i n . Hg m m . Hg wt. 5; mm. Hg mm. H g
0.00
2.00
3.96
0:048
0.087
23.77
23.46
22.88
0 00
2.00
4.21
0:ii.j
0,231
54.81
54 06
n 2 , 53
;.::
4.12
0'366
0.670
149.8
146 6
144 6
0.00
1.96
4.20
0:659
1.39
286.9
282.4
275.9
6.02 0 131 22.30 6 10 0 343 52.04 6.15 1 03 140 9 6.20 2 14 269.8
9.86 0.256 21.12 10.38 0,651 49.04 9.06 1.71 135.7 9.00 3.42 260.1
12.80 0,380 20.59 12.33 0,830 47.42 12.00 2.42 127.8 11.90 4 94 252.3
14.60 0,452 19.67 14.00 1.07 46.60 15.00 3.39 13.5 15.20 7.20 237.9
1 6 , 60 0.595 18.87 16.80 1.41 43.91 17.90 1.65 116.6 17.45 9.12 228.9
19.88 0.772 17.88 21.00 2.11 40.07 20.90 6.14 109.2 20.90 12.45 209.7
24.90 1.28 15 40 24 12 2.95 Hi.2i 23.90 8.18 102.2 24.00 16.52 199.6
29.00 1.90 13.52 28 90 4.56 32.00 26.50 10 5: 95.2 26.70 21.46 183.1
... ... ... 99.50 13.35 86.2 29.TO 27.55 167.6

To facilitate rapid attainment of equilibrium, a saturator was
constructed with provision for continuous renewal of a large
liquid surface. The saturator, which as a modification of the
type used by Berkeley and Hartley ( 1 ) and by Rashburn and
Heuse ( 9 ) , consisted of 28-nim. fine silver tubing welded i n the
form shon-n in Figure 1. It was packed with single-turn lielice.:
of 0.5-mm. fine silver wire t h a t had been wound 011 a 6-nim. man-
drel, and fine silver disks \Yere silver-soldered over the three pack-
ing porte.
The saturator was about half filled with the acid solution and
mounted, together with a buperimposed preheater of the same
design but of glass construction, in a rocker n-ith axis oi oRcillation
perpendicular to the long tubes in the body of the saturator. The
assembly was placed in a r a t e r bath and rocked about an axis 10-
cated just belox the saturator through a total angle of 4.5'. The
rate of rocking, 10 complete oscillations per minute, x a > selected
experimentally by observing the f l o v of water in a g1
same cros.5 section as the saturator arid packed with
At each reversal in rocking, the liquid blocked the flon- of ga.
through the lon-er side of the saturator and flon-ed in a continuouq
film over the surface of the helices in the upper side, thi,ough
which the gas n-as passing. The saturator gave practically com-
plete saturation of the gas, even a t relatively rapid f l o of~ g t..~
The temperature of the water bath was regulated within
-0.02' C. and vias measured with thermometers, graduated in
0.1 C., 11-hichhad been calibrated against reference thermometer>
certified by the Sational Bureau of Standards.
The carrier gas, air t h a t had been freed of moi.sture and carboii
dioxide, was measured in a dual displacement meter. One of tlie
two water-jacketed displacement hulbs was fillcd x i t h air nncl
allowed to reach thermal equilihrium ~ h i l ethe other as being
discharged through the saturator. Each hulb held about 5 liters
and was calibrated between a mark on the connecting tube, n-liirli
led t o the reservoir of confining liquid, and a t v o - v a y stopcock,
through which connection was made either t o a manometei, or to
the saturator. The confining liquid was a mineral oil of Ion. vapor
pressure; the trace of vapor it introduced into the air n-as re-
moved in a tube of activated carbon.
The train fur ahsorption of the vapor from the saturator \vas
mounted on the rocker outside the water bath. I t consisted of
two rubber-rtoppcred, silver E-tubes arid two Stetser-Korton ab-
sorption bulbs in series. Connections from the saturator through
the silver C-tubes \\-ere made with silver tubing, and connections
don-nstreani from the second U-tube were made with glass tubing.
The tube from the saturator to t h e first C-tube xi. maintained at
a temperature 5 " to 10" C. above t h a t of t h e saturator. The sil-
ver U-tubes were packed with silver helices, over n.hich a dilute
solution of sodium hydroxide was poured, and n-ere then dried in
an oven from which carbon dioxide was excluded. The packing i n
the first tube thus was coated Tvith about 50% more caustic than
the e9timated equivalent of the acid in the ga-, and the packing in
the second tube r a s coated n-ith about two third> a s inuch as the
first. 1small piece of blue litmus paper in the g l a s tube leading
from the qecond L--tube ,showed t,hat absorption of the acid by the
caustic ivaq complete in all the experiments. The two glass ab-
Gorbers contained Drierite to absorb the water vapor not ah-
sorbed by tlie caustic.
Small n-ater-filled manometers were connected to t h e gas line,
one betn-een the displacement meter and the preheater and one
het~veenthe preheater and the saturator, t o indicate the back
pressure at these points. Figure 2 shows a general view of the
apparatus.
>lEASURE\IENT O F VAPOR P R E S S U R E S
Bec:iuv of the carry-over of hydrofluoric acid bolution in the
.atmator packing, final mixing of each new compoaition was ef-
fected in t h e saturator. -1s much as possible of thesolutionfrom
the preceding experiment \vas drained into a silver heakvr, suffi-
cient acid or water was added t o approximate the desired concen-
tration, and the solution was sucked back into the saturator. By
manipulation of the saturator the solution was flowed throughout
the packing. The iolution n-as poured back into the silver beaker,
stirred, pucked back into the saturator, and again forced into each

Figure 2. Vapor Pressure lipparatus

March 1947 INDUSTRIAL AND ENGINEERING CHEMISTRY 425

the system in a ~vorkdayt o r:lporize hydrogen fluoride and m t e r

in quantities that could tic dotnmincd accurately. At 40" C. 20
liters of gas were sufficient: nt 60" and 75" c'. 5 liters were suffi-
cient.
h f t e r the required volume of gas had been p
system, the saturator n.:is disconnec~tcti:inti t h
disassemhled and weighed. The tilver L--tubes wcrc wabhed free
of alkali and absorbed fluorine with distilled water. Fluorine
generally was determined in a n aliquot of the ~mshingsby direct
titration with thorium nitrate; prior distillation was unnecessary
in the absence of interfering ions. If the quantity of fluorine n-as
small, the entire sample, evaporated i o about 100 cc., mas titrated.
The weight of hydrogen fluoride, as calculated from the fluorine
analysis, was subtracted from the gain i n weight by the absorp-
tion train to obtain the Lveight of absorbed water. From these
n-eights the partial pressures of hydrogen fluoride and water were
calculated.
The concentration of the hydrofluoric acid solutions was de-
termined by titration with carbonate-free sodium hydroxide solu-
tion t o the phenolphthalein end point. The samples were weighed
in covered platinum crucibles, clilut ecl -with freshly boiled distilled
water, and titrated in a silver beaker.

EVALUATION O F RESULTS

As a check on the method of vapor pressure measurement, t,he

vapor pressure of distilled water vas determined at each of the
experimental temperatures. The observe
0 - PRESENT YIORK
0 - FREDENHAGEN AND WELLMAN (c), 2 5 ° C .
2y0 of the accepted values; the average
h,- GENERAL C+EMICAL CG. (5) cepted values w\-as0.85%.
0.06
A - K H A I D U G V AND CO-WORKERS (1) Table I shows the experimental data for the partial presures of
1 I
I d hydrogen fluoride and m t e r vapor over hydrofluoric acid solu-
0.041 1 1 I tions. Each value reported is the average of tn-o or more deter-
5 IO 15 25 3c
HF IN SOLUTION. WT.O
'% minations; individual measurements that devi:ited from the av-
erage by more than 2.5'70 were discarded. The average deviation
Figure 3. Isotherms of the Partial Pressure of Hydrogen of the measurements from the reported oalues x i s leas than 1%.
Fluoride over Solutions of Hydro5uoric Acid
;\lost of the anomalous values vere obtnincd during the early part
of the investigation; after experience was gained in the technique,
the results generally were consistent. The data are plotted as iso-
section of the saturator. After about twelve cycles of filling and therms in Figures 3 and 4.
draining the saturator, a sample was poured from each end of the The concentration of the hydrofluoric acid solutions was deter-
saturator and analyzed. If further adjustment of the concen- mined both before and after a series of measurements a t a given
tration was necessary, hydrofluoric acid or water iyas added, and nominal concentration. I n a few experiments in which the pre-
the mixing operation was repeated until the variation betu-een heater n-as partially filled with distilled water, the acid concentra-
samples from opposite ends of the saturator n-as within the tion decreased. I n most of the experiments, however, the pre-
titration error (0.2%). Excess solution was then poured out to heater i m s operated dry, and the acid concentration incrcnsed.
leave the saturator approximately half full. The change generally was less than 0.27, hydrogen fluoridc. The
'
The charged saturator and the preheater were rocked in the average of the analyses before and after a series of measurcments
water bath for 1hour t o bring the solution t o the experimental tem-
perature. The displacement meter was then connected to the pre-
heater. and the preheater and saturator were flushed with 2 to 3
liters of gas, which was dischargedinto the air. The resistance t o
passage of the gas through the preheater and saturator n-as less
than could be detected on the water manometers.
JVhen the flushing was completed, the absorption train was
connected t o the saturator, care being taken t h a t all connections
were gastight,. Gas from the displacement meter t,henwas passed
through the system. The flow v-as about 100 cc. per minute at,
25' C. and about 50 cc. per minute a t the other temperatures.
The Lvater manometers in the gas line aided in regulation of the
flow; with the absorption train connected, the back pressure was
about 3 mm. of water a t a flow of 100 cc. per minute and about 1.5
mm. of water a t a flow of 50 cc. per minute. As a further meas-
ure of control the gas bulbs were marked in approximate 500-cc.
units of volume.
Since the gas volume i n the saturator was about 400 cc., the
time of retention of t,he gas in the saturator was about 4 minutes 5 IO I5 20 25 30
H F IN SOLUTION, WT. */.
at a flow of 100 cc. per minute and about 8 minutes a t a flow of 50
cc. per minute. The more rapid flow was used a t 25' C. so that Figure 4. Isotherms of the Partial Pressure of Water
sufficient gas (about 40 liters or 8 bulbs) could be passed through Vapor over Solutions of Hydrofluoric Acid
426 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 39, No. 3

ii t
the same temperature was considered to be the effective concen-
tration for the series. Where the same solution was used at more
than one temperature, the change in concentration was assumed
to be proportional to the number of measurements, and averages
were estimated for each temperature.
pztF = 0 when w = 0, but values calculated for ~ H aFt values of
10 < 2 probably are without significance.
From the logarithmic equations values of ~ H and F werc
~ H Z O
calculated for selected concentrations of hydrofluoric acid a t each
of the experimental temperatures. When the results are plotted
:i: the logarithm of the partial pressure against the reciprocal of
the absolute temperature, they yield practically straight lines for
the pressure of hydrogen fluoride (Figure 5) and slightly curved
lines for the pressure of n-ater vapor (Figure 6). A similar plot of
the accepted values ( 8 )for pure n-ater also yields a slightly curved
linc. Empirical equations for the logarithms of the partial pres-
a r c s of the respective components, in terms of powers of 1000/T,
were derived by the method of least squares, and the heats of
Vaporization (kg.-cal. per mole) of the components from the
eleven compositions shown in Figure 5 were calculntrd from
t h e rquntion

Since the curves i n Figure 5 are essentially straight lines, con-

2.85 2.90 2.95 A W 3.05 3.10 3.15 3.20
+. x 103
Figure 5. Logarithm of Partial Pressure
of Hydrogen Fluoride Plotted against
Reciprocal Temperature
-tant values are obtained for the heat of vaporization of hydro-
gen fluoride from a given concentration of acid at various tem-
peratures. These values vary with concentration from 10.81 t o
11.18 kg.-cal. and are in fair agreement with values of 11.56,
8 2 5 3.30 U 5 3.40
11.46, and 11.11 kg.-cal. for 8.47, 15.62, and 33.517, solutions, re-
spectively, tabulated by Bichowsky and Rossini (2). From their
vapor pressure data Khaidukov and co-workers ( 7 ) calculated thc
heat of vaporization of hydrogen fluoride to be 11.72 kg.-cal. per
mole.

Corrosion of the fine silver saturator by the acid jolutiom wao

negligible. A portion of a 12% solution that had been in th(:
saturator for several days a t 60" and 76" C. v a s evaporated t o
dryness in a platinum dish. The solid residue corresponded t o 50
parts per million in t h e original acid. Spectrographic analysis of
the residue showed t h a t the acid contained 14 parts per million of
silver and 7.5 of copper.
The following empirical equations show the relation of the par-
tial pressures t o the weight per cent, w,of hydrogen fluoride in
solution:
+
.it 25'C.: log ( ~ H F 0.172) = -0.72956
log (34.14 - ~ H , o ) = 1.00817++00.031541~1
.010473~
At 30" C.: log + 0.455) = -0.31390
( ~ H F + 0.03489~:
1.20161 + 0.013532~.
log (70.95 - ~H*o)

At 60" C.: log ( p a p + 1.465) 0.18759 + 0 . 0 3 3 4 7 8 ~

log (212.1 - pato) + 0.01029~
1.7957
+
At 75'C.: log ( ~ H F 3.012) = 0.50190
++0.013475%
0.033194~ +x 103
log (368.3 - ~ H ~ o )1.9076
Figure 6. Logarithm of the Partial Prea-
The equations fit the experimental values witliin an averagr sure of Water Plotted against Reciprocal
deviation of 2% for the partial pressure of hydrogen fluoride and Temperature
1% for the partial pressure of water vapor. These deviations arc
ivithin the limits of experimental error. The values for K In the
+
terms log ( ~ H F R) and log ( K - pa2o) were calculated by thc
Table I1 shows fair agreement between the calculated values
for the heat of vaporization of water from the acid solutions and
method of Davis (5).
the accepted values (8) for the heat of vaporization of wster.
The equations for ~ H do
F not extrapolate t o ~ H =F 0 n hen u =
From their vapor pressure data Xhaidukov and co-workers (7j
0. Series equations for ~ H in
F terms of the first three powers of 7 1
calculsted the heat of vaporization of water to be 11.1 kg.-cal. per
can be derived. The series equations will fit the experimental dat'i
mole.
as well as do the logarithmic equations and vi11 extrapolate tiJ
The present experimental values for the partial pressure of wa-
ter vapor over solutions containingless than 10% hydrogen fluoride
are in fair agreement with values calcuIated by Raoult's law, aa-
TABLE
11. CO\IPARISON O F C A L C C L 4 T E D H ~ i OF
r suming H F molecules exist in solution. The experimental valuep
V.4PORIZATIoX O F TJ'ATCR T I T H ACCEPTED V A L L L 3 for more concentrated solutions are lower than values calculated
Heat of Vaporization, Kg.-Cal./Mole by Raoult's lanr, a s is to be expected.
23' C. 40' C. 60" C. 73' C .
F i t h thc exception of the partial pressure of hydrogen fluoride
Accepted values (8) 10 50 10.35 10.15 9.99
Range of calod. values 10.0-10.7 10.4-10.7 10.2-10.4 9.6-10 3 at 75' C., all the data presented by Khaidukov and co-worker$$
(7) are lower than corresponding data obtained in the present in--
March 1947 INDUSTRIAL AND ENGINEERING CHEMISTRY 427

vcstigation. Their partial pressures of m t e r vapor over 5 and ACKNOULEDGXIEhT

1 0 7 solutions are considerably loJyer than those calculated by
Raoult'. law. They apparently did not attain saturation of the
carrier g:is by passing i t over a static surface of solution. The
numericd clata reported by t,hem give neither straight lines nor
~ m o o t hcurves Tylien plotted as the logarithm of pressure against
the reciprocal of absolute temperature.
The pirtial prchsures of hydrogen fluoride at 25' C. reported
by Frcdenhngen a n d Kellmnnn (4)are npprosimately tn-ice the
correspondiiig vnlues obtained in the present study. Fredenhagen
and Wcllrnann calculated, but did not measure, the partial prei-
,cures of water w p o r . Tht ilso passed a carrier gas over a atatic
surface of solution; hence seems t h a t their rcxsults n-ould tend
t o 1)elow rather t h n high. They absorbed the hydrogen fluoride
from the carrier gns and dctermiiied the amount conductometri-
rally rather than by direct anal!
In the short range of o v e i h p between the preeent dntn nnd the
vapor pwsiure t1:ita presented graphically by the General Chenii-
cal Company (5),the two s e t s of data are in fnir agreement.
The authors acknowledge the assistance of John ;i.Brabson
and .hits Darron-, v h o prepared the silica-free hydrofluoric acid
used in the study.
LITERATURE C I T E D
(1) Berkeley, Earl o f , and Hartley, E. G. J., Proc. R o y . Soc. (London).
A77, 156-89 (1906).
(2) Bichowsky, F. R., and Rossini, F. D.. "Thermochemistry of The
Chemical Substances", Xew York, Reinhold Pub. Corp.. 1936.
(3) Daris, D. S.,"Empirical Equations and Somography", S e w
I-ork, McGraw-Hill Book Co., Inc., 1043.
(4) Fredenhagen, K., and TT'ellmann, >I., Z. p h y s i k . C h e m . , A162,
451-66 (1932).
( 5 ) General Chemical Co., Tech. Seraice BuU. 30A (1945).
(6)Hoffman, ,J. I., and Lundell, G. E. F., Bur. Standaids J . Resecrrch,
3, 5s1-05 (1929).
( 7 ) Khaidukor, S . ,Linetskaya, Z., and Bognol-arov, d.,J . ilplili'erl
Chem. (U.S.S.R.),9, 439-45 (1936)
(S) Lange, S . A , . Handbook of Chemist 4th Ed., Gandusky, Ohio,
Handbook Puhlishers, Inc., 1941.
(9) TYashburn, E. IT-.. and Heuse, E. O., J . --im. C h r m . S u r . . 37, w -
21 (1915).

HYDROFLUORIC ACID-WATER
and
HYDROFLUORIC ACID-HY DROFLUOSlLlClC ACID-WATER *

Paul A. Munter, O t t o T. Aepli, and Ruth A. Kossatz

P E N N S Y L V A N I 4 S 4 L T hI4NUFACTURING CO., WVYNDVOOR, Pi.

I S TIIE course of assem-

Illing basic d a t a relative
to tlic industrial production of
THE liquid-yapor equilibria of the binar! system HF-Hz0
and of the ternary system HF-HZSiFa-II20 have been de-
termined a t atmospheric pressure over a considerable
OI'ERATIOY O F EQUILIB

The
RlC3I STILL
equilibrium still em-
pure arihydrous hydrofluoric range of composition. The azeotropic mixture of the ployed for the measurement?
acid, it was found t h a t only system HF-H20 was found to have a composition of 38.26% was constructed of pure silver
meager information on the hydrofluoric acid and a boiling point of 112.0" C . at 750.2 sheet (B. 8: S. gage 18) ami
\,oiling points and the related mm. pressure. A constant-boiling solution was found in tubing joined with "hard"
liquid and vapor composi- the ternary system HF-HaSiFs-HzO a t the composition silver solder (Figure 1). It
tions for the systems HF- 1Oc/c hydrofluoric acid, 36Yo hydrofluosilicic acid, 54$?'0 c o n s i s t e d e s s e n t i a i l y of :
H,O and HF-H2SiF6-H20 is water, which boiled a t 116.1" C. at 759.7 mm. pressure. boiler A with chnrging port
available in the literature. The all-silver equilibrium still employed for these deter- B and heater well C, whicli
For the system HF-H20, minations is described. was surrounded by bafflc
most of the reported data plate D to ensure good mixing
:ire for the constant-boiling of the return condensate witli
mixture and are summarized later in Table 11'. I n addition, the boiliiig solution : columri E supporting thermocoupit
Frederihagen and Wellmann (4)determined the boiling poiiit- well F , which extended to just below the surface of the boil-
liquid composition curve, a t atmospheric pressure, for the ing liquid; condenser G; and sampler H with auxiliary coil-
system HF-H?O over the composition rnnge from 0 to 100'; denser J , condensate return line K , and rotatable sampling
hydrofluoric acid. tube assembly L. T h e silver charging-port cover and the'
S o measurements have been reported on the liquid-vapor sampling tube assembly were sealed by clamping Tvith bras?
equi1ibri:i a t the normal boiling points for the ternary system unions. Figure 2 is a photograph of the still assembly.
tIF-II&F6-H20. Some Jvork was done on the binary system The heater unit vias constructed b y winding Sichrome wire
IIiSiF6-Hn0 by Baur ( I ) , Truchot ( I I ) , and Jacobson ( 6 ) . (Alloy V, B. 8: S.gage 12, 1 w/foot) on a porcelain thermocouplP
Beyolid indicating the dissociation of hydrofluosilicic acid in the n-ire insulntor (Std. 723, Leeds & Korthrup). The windings were
vapor phase and the probable existence of an azeotropic mixture insulated by covering with Insalute cement t o such a diameter ah
i l l the system H2SiFs-HQ0, these studies provide little information to permit the heater to slip readily into the heater vie11 of t h r
relative t o the liquid-vapor equilibria. still when required. The rate of heating rras regulated by :I
The present research was carried out to supplement these Variac transformer so t h a t not more than 1 to 2 grams of mate-
meager d a t a ; it covers measurements, over a wide range of coni- rial distilled over per minute.
positions, of the boiling points and related liquid and vapor com- The t,emperature of the boiling solution was measured t o
positions, at atmospheric pressure, on the binary system HF- * 0 . l o C. by a calibrated iron-constantan thermocouple which
H 2 0 and the ternary system HF-H2SiFsH20. extended t o the bottom of the thermocouple well. ,4 little