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 loJrer 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 Trlien 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 trro 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 CITED
(1) Berkeley, E a r l o f , a n d H a r t l e y , E. G. J., Proc. R o y . Soc. ( L o n d o n ) .
A77, 156-89 ( 1 9 0 6 ) .
(2) B i c h o w s k y , F. R., and Rossini, F. D.. " T h e r m o c h e m i s t r y of The
C h e m i c a l S u b s t a n c e s " , Xew York, Reinhold P u b . Corp.. 1936.
(3) D a r i s , D. S.," E m p i r i c a l E q u a t i o n s a n d Somography", S e w
I-ork, M c G r a w - H i l l Book Co., I n c . , 1043.
(4) F r e d e n h a g e n , K., and TT'ellmann, >I., Z. p h y s i k . C h e m . , A162,
451-66 ( 1 9 3 2 ) .
( 5 ) G e n e r a l C h e m i c a l Co., Tech. Seraice BuU. 30A (1945).
(6)H o f f m a n , ,J. I., a n d L u n d e l l , G. E. F., Bur. Standaids J . Resecrrch,
3, 5s1-05 (1929).
( 7 ) K h a i d u k o r , S . ,L i n e t s k a y a , Z., a n d Bognol-arov, d.,J . ilplili'erl
Chem. ( U . S . S . R . ) , 9, 439-45 (1936)
(S) L a n g e , S . A , . H a n d b o o k of C h e m i s t 4 t h Ed., Gandusky, Ohio,
H a n d b o o k P u h l i s h e r s , Inc., 1941.
(9) TYashburn, E. IT-.. and H e u s e , 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

PENNSYLVANI4 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 Irere
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
 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 39, No. 3

TABLE
I. (:.lLIRRATIOS O F h'1I.L THERMOCOUPLE
IS O f E R . A T I o N
Sorrnal Bailing P o i n t , ' C
Jtniidard Literature Observed (cor.)
Methanol 64.45 64.5
Benzene 80,09 80.1
\T-a t e r 100.0 100.3
Toluene 110.8 110.7

nnphthnleiie 01' toluene was Elaced in the bott'om of this well t o

improve thermal contact. The electromotive force of the ther-
mocouple ivaa measured to =t1 microvolt by a Rribicon Type €3
potentiometer and spotlight galvanometer. The behavior of
t,lie tliermocouple duririg operation was checked by determining
the boiling poiiits in tlie equilibrium still of tmice-distilled samples
of \\-:itcir, nictli:iiiol, lmizeiie, arid toluene: Table I gives results
Of t1iCSt t The condensers of t h e still assembly were cooled
I)?. forceti cii,culwtioii of either ice n-ater (0' C.) or R ~ a t e r - e t h y l -
m c gl?-col mixture (-20" C ) ,depending on the probable boiling
n t tlie coiideiisnte.
~ ~ i i i of
To :ivoid refliiziiig of tlir vapors in the upper boiler arid the
coluniri during opcxitiun, the still assembly, escept for the con-
denser and sampler, \vas enclosed in a transite air oveii (Figure 3).
The temperature of the oren was maintained at bevernl degrees
above tlie boiling point of the liquid in the boiler.
The still was charged with approsimately 175 grams of t'he
solution under test. After the charging port was sealed and the
I 1

IC 1
Figure 1. Diagram of Silver
Equilibrium Still
sampling tube clamped in the u p position, which permitted the
condensate t o return t o the boiler and also vented the still to the
atmosphere, the heater \\-as inserted and the boiler heated gradu-
ally until t,lie temperature of the boiling solution became prac-
tically constant. The temperature of the transit'e air oven
surrounding the still was simultaneously raised to several de-
grees above the boiler temperature.
When constant temperature had been maintained for 15 t o 30

Figure 2. Silver Equilibrium Still Figure 3. Transite .4ir Oven and Still
'
March 1947

TABLE11. LIQUIDAND V A P O R COMPOSITIOSS

Liquid
5.47
10.1
20.6
POIKTSOF SYSTEM
Compn,, n-t,7o HF
Vapor
0.87
2.03
7.06
HF-H,O
Observed
Boiling
Barometric
Pressure,
.4ND

P o i n t , C. 1 I m . Hg (Cor.)
100.8
102.2
106 8
740.5
745.1
i59 7
BOILIXG

Sormal
Boiliy
Point, C.
101.6
102.8
106.8
-
I N D U S T R I A L A N D E N G I N E E R I N GI C H E M I S T R Y

0 inches
I 2 9
429

24.7 11.6 107 8 i47 2 108.4

30.1 19 4 110.1 i54.6 110.3
36.2 32 8 111.6 757.0 111.7
36.8 34.4 111 9 758.4 112 0
37.6 36.4 112.2 i62 i 112.1
38.22 38.15 112 1 i54.9 112.3
38.27 38.26 112 0 750.2 112 4
39.2 41.1 111 9 756.1 112,l
42.2 50.1 111 5 762.6 111.4
47.0 65.7 108 3 i51.7 108.7
49 2 ... 106 7 757.1 106.8
52.9 82.6 101 3 749.8 101.7
54.8 87.4 98 5 749.6 98.9
58.6 92.9 90 7 i54 4 90 9
60.7 97.3 86 1 747.1 86.6
64.1 99.0 78 5 748.4 79.0 Figure i. Diagram of Weighing
66.2 98.7 74 0 i45.9 74.6 Bottle Construction
72.0 98.8 61 6 i46.2 61.6
81.4 99.3 44 9 753.4 45.1
89.0 99 5 33 3 754.5 33.5

TABLE111. LIQUID
POI ST^
Liquid Compn , \\-t, e;
HF H ~ S I FHzO~
0.22 24.1 75.7 0 16 2 55 9i 3 104 4 749.3
0 76 29 7 69.5 0 16 5.33 94.5 107.3 758 9
0 85 3 3 . 2 65.9 0 17 9.75 RO 1 108.8 753.5
1 . 8 9 36 2 61.9 0.19 18.0 81.8 111.2 z53.9
2.69 38.3 59.0 0 27 2 5 . 9 i3.8 112., io0 2
4 . 4 0 26 0 69.6 3.32 1 3i 95.3 108 1 763 2
4 . 6 0 38 0 57.4 0 06 3 0 . , 69.2 114 3 757.2
5.60 3 3 . 7 60.7 5.19 12.3 82,s 113.1 753 1
6 33 37.9 55.8 0 98 3 9 . 1 59 ? 115 2 i55.8
6 . 5 1 38 5 55.0 0 24 4 6 . 3 53 o 115.5 758 4
7 . 5 6 37 3 55 1 3.61 39.3 57 1 115 3 747.0
i.3; ;;p
7 86 37 2 54.9
55.1
5 45
5.43
36 4
36 5
58 1
58 1
115.3
115.7 -748
- - i9
135
69 0 5.98 0.46 93.5 108.4 750.1
8.88 37.9 53.2 3 46 50.2 46.3 115.2 752 6
9.13 36.7 54 2 7 76 36 1 06 1 115.~ 752.2
9.28 38 1 52.6 3.65 51.8 44 5 115.2 744 1
9 83 25.8 64 4 8.55 0 40 01 0 113 5 744 4
10.1 36.0 53 9 9.84 36 0 54.2 116.1 759.7
10.8 :34 2 55 0 12.8 27.4 59.8 115.9 759 8 Figure 3. Photograph of U eiphing Bottle
12.5 33.0 54 5 18.3 23.3 58 4
12.9 34.4 02 7 16.7 35.4 4i 9
15.4 31.6 53 0 25.6 23.4 51 0
15.6 29 8 54 6 26.9 14.1 59 0
17.3 32.9 49 8 26.7 36.8 36 5
18.6 16.4 65 0 14.3 0.59 85 1
18.6 29.0 52 4 33.7 19.9 46 4
19.6 17.2 53 2 35.4 11.8 52 8
22.9 38.7 38 4 5.18 93.2 1 6
a3.9 24.5 51 6 44.8 12.0 43 2
25.3 5.25 69.4 17.3 0.11 82.6 110.0 757 3
26.1 32.4 41.5 37.3 58.2 4.5 100.9 755 9
26.7 14.9 58.4 36.4 1.21 62.4 113 2 762 1
27.6 15 3 57 1 40.4 1.63 58 0 113.2 761 0
28.3 ii.6 60.i 35.0 0.10 64.9 112.5 752 8
29.8 16.1 54.1 49.9 2.38 47.7 111.9 745 4
33.0 36.0 31.0 0.61 98.4 1.0 62.5 750 8
33 6 26.0 40.4 57.6 36.7 5.7 95.9 759 0
36.3 20.7 43.0 74.6 13.9 11.5 100 1 754 1
37.2 16.7 46.1 71.6 8.87 19.5 104.4 761 0
39.1 5.04 55.9 54 1 0 . 4 1 45 5 111 2 758.1
40 5 2 i 5 32 0 26 5 72.6 0 9 70 1 744.3
45.7 12.0 42.3 Si 7 3.98 8 3 94 0 758.3
49.2 18.6 32.2 66 6 32 2 1 1 76 2 757.5
53.1 25 3 21.6 0 92 96.0 J 1 33 7 749.6
54.1
60.0
60.7
16.5
17.1
8.96
29 4
22.9
30.3
63 0
26 3
92 2
35.1
73.0
2.10
A:
5 7
63 8
46 9
67 1
755 1
756.9
756.9
69.6 9.31 21.1 43.3 56 2 0 5 46 6 760.1
70.6 11.9 17.5 5 97 93.6 0 4 32 7 749.1
92.0 0.69 7.3 77 4 21.8 0 8 25 5 750.6

IV. AZEOTROPIC
TABLE HF-H,O
MIXTUREO F SYSTEM
Compn., Boiling Pressure,
W t . 70 HE' Point, ' C. M m . Hg Investigator
35.37 120 Atin. Bineau ( 2 )
37.0 120 Atm. Roscoe (8)
48.17 126 Atm.
43.2 iii 7 50 Deussen ( 3 ) Weight c6 of H F 111 Liquid ( I ) and Vapor ( 8 )
35.4 115.2 Atill. Fredenhagen ds Kellmann (4)
38.18 110.8 732 hIuehlberger ( ? ) Figure 6. Boiling Points and Liquid-
38.26 112.0 750 This investigation Vapor Compositions of the System
HF-HzO
430 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 39, No. 3

minute., the +,impling tube n as uiiclainpd a i d t r i i i i c d t o tlic
don-n positioii for sampliiig the condensate. A conveiiieiit weight
of condensate \vas collected for analysis after the first fen- drops
vere discarded. T h e atmospheric pressure and temperature
vere recorded :it the same time. Immediately after tlie condcii-
sate was sampled, t h e heaters were shut oft', thc btill n-ni diz-
mounted and cooled in water, and a sample of the boilcr liquid
was poured o u t through the charging port for arinl~
The condensate nnd boiler liquid were sampled in a double-
nalled weighing bottle of about 20 ml. capacity, fitted ~ i t ha
ground stopper. T h e bottle and the stopper n-ere cast from As-
plit cement, a n acid-proof resin cement. A small amount of
crushed ice TTRS generally included in the n-eighing bottle t o avoid
\.apor losses during collection of thc sample. Tlic double-
n-all coiistruction prevented the condeiisatioii of Iiioiqture oil
tlie outsidc during weighing of the chillrti coiiteiit+.
Foi .,impliiig distillates high 111 acid content ( > 4 0 r c ) , the
lid of the weighing bottle was modified by inserting through its
center a tight-fitting silver tube which extended within 0.5 em.
of the bottom of the weighing bottle. T h e internal diameter of
tliis tube was such t h a t i t fitted snugly over the silver tubc of the
still sampling assembly; the result was an essentially closed
path from condeiiser to sampling bottle. During the mighings,
the silver tube of the sampling bottle was closed by a small silver
plug. Figures 4 and 5 how details of the sampling hottlc c o n -
struction.
Tlie :ic.id boliitioiic w i ' e prepared when fensible, from 48%
Ilytlrofluoi,ic :icicl (Ualtcr's xpecial, c.11. grade) and frunl 30Yc
liydrofluo~ilicicacid ( l k k c r ' s :innlyzed, C . P . grade). Oiily lots of
hydrofluoric ncid containing 1e:s than 0.05cc liydroflrio~ilicic

.it. Ternary constant boiling point

0 Liquid composition, weight 90'

---
+ Vapor composition, weight 70
Tie lines
Liquid isotherms
.....,.
Y
Vapor pressure trough
Constant boiling point of system HF-HzO
-1
- Approximate constant boiling point of system IIzSiF~-IlzO
March 1947 INDUSTRIAL AND ENGINEERING CHEMISTRY
acid were used. T h e more concentrated acid solutions Tvere
prepared in pure silver beakers from anhydrous hydrofluoric
acid (Pennsylvania Salt Manufacturing Co.) b y dilution and by
reaction with powdered silica (Baker's analyzed, C.P. grade).
T h e hydrofluoric acid solutions were analyzed by titration
with standard sodium hydroxide solutions (silica- and carbonate-
free), using phenolphthalein as indicator. T h e hydrofluoric
and hydrofluosilicic acid mixtures were analyzed by a method of
cold and hot titrations with standard sodium hydroxide, using
phenolphthalein as indicator, according to the procedure de-
scribed by Scott ( 0 ) and Sherry et al. ( 1 0 ) .
DISCUSSIOS OF RESCLTS
Table I1 presents the liquid and vapor compositions and re-
lated boiling points as determined for the 5ystem HF-HZO. T h e
normal boiling points in column 5 were cnlculated from the ex-
perimental d a t a on the assumption of a n average entropy of
vaporization of 23 calories per degree-mole for these solutions.
The liquid and vapor compositions, in veight per cent, and the
normal boiling points are plotted in Figure 6.
Table 111 lists t h e boiling points and related liquid and vapor
compositions as determined for t h e ternary system HF-H2SiFs-
Hs0. These data are plotted in Figure 7 along with the approsi-
mate liquid isotherms.
T h e constant-boiling mixture of the system HF-H20 T K I ~
found to have a composition of 3 8 . 2 6 5 hydrofluoric acid and a
boiling point of 112.0" C. a t 750.2 mm. pressure. These values
are compared with previously published d a t a in Table IV and
are in good agreement with results secured by Muehlberger ( 7 ) .
T h e boiling point curve for the system HF-H,O as determined
in thi. work is a t considerable variance TTith t h a t determined hy
Fredenhagen and Wellmann ( d ) , except in the regions approach-
ing the pure components. Lacking suitable corrohorntive dat:i,
i t is concluded t h a t the boiling point curve as determined in this
work is the more reliable in view of: (a) the agreement secured
between the boiling points of the test liquids as determined in the
still (Table I) Kith the published values, ( b ) the good agreement
of t h e d a t a for the constant-boiling mixture with those secured
b y Muehlberger, and (c) the smooth curve given b y the boiling
points and t h e close extrapolation of this curve t o the boiling
point of pure hydrofluoric acid.
In the ternary system HF-H2SiF6-H20, a masimum boiling
point was found having a cornposition of 10yc hydrofluoric acid,
36% hydrofluosilicic acid, and 54% Kater, and a boiling point of
116.1" C. a t 759.7 mm. pressure. This point lies in a vapor
pressure trough which extends across the phase sy=tem from the
HYDROGEN-FLUORINE TORCH
Homer F. Priest and Aristid V. Grossel
WAR R E S E i R C H LABORATORIES, COLU\IB14 U \ I \ ERSITY. A E W YORB, N. Y .
A S SOOK as the problem was solved of Dtoriiig fliiori:it=
under pressure ( 5 ) , the means was avrtilable for studying
fluorine flames and constructing a fluorine torch. Since fluorine
is the most reactive element known, we expected it t o produce
the highest possible flame temperatures. This follows for two
interdependent reasons: First,, reactions n.ith fluorine show the
highest molar heat evolution, and second, because of the high
strength of fluorine bonds, t h e dissociation of the reaction prod-
ucts is curtailed.
The first point is illustrated by a comparison of the heat of
1 Present address, Houdry Process Corporation, Marcus H o o k . Pa.
43 1
L3zeotropic mixture of HF-H20 to t h a t of H2SiF6-H&. as indi-
cated by the dotted line on Figure 7. The composit,ion ( 4 1 5
!iydrofluosilicic acid and 59% water) and the boiling point,
111.5" C.) indicated for the aaeotropic mixture of the system
HzSiF6-H20 are only approximate values; attempts t o deter-
mine these d a t a accurately were unsuccessful, because of the
tendency of such solutions with lon- free hydrofluoric acid content
to deposit silica in the boiler or in the condenser of the still d u r -
ing distillation.
T h e boiling point ridge divides the phase diagram into two
regions so t h a t a solution of a composition lying in one region
cannot be distilled under normal pressure to yield ,z condensate
having a composition lying in t h e other region.
T h e results secured for the liquid and vapor compositions of
solutions in the more acid regions of the ternary system (that ib,
for solutions containing over 60% free hydrofluoric acid or over
30"' free hydrofluoric and 30% free hydrofluosilicic acids) are not
equilibrium values since t h e still condenser did not condense
all the vapor phase. Severt'heless, since in t,he method of sam-
pling employed, practically all of the vapor and the eondensate
y e r e collected for analysis, it was concluded t h a t the composi-
tions found gave a reliable approximation of tlir liquid-vapor
equilibria of such solutions.
.iCBSOW LEDGhI E S T
The authors hereby express their thank5 to the PenwylvLtniu
Salt llanufncturing Co. for permission t o puhlilh these esperi-
mental data. An nclinowledgmeiit is made of the :issistance of
R.H. Rnlston in sume preliminary studies on the subject systems.
LlTERATURE CITED
Baur. E., Z . phuaik. Chem., 48, 453 (1904).
Bineau, -L,Ann. chim. phys., [3] 7 , 257 (1843).
Deussen. E., 2.anorg. Chem., 49, 297 (1906).
Fredenhagen, IC., and Wellmann, M., 2.p h y s i k . Cheni., A162,
454 (1932).
( 5 ) Gore, G., Landolt-Bornstein Tabellen, p. 273 (1905).
(6) Jacobson, C. X., J . Phus. Chern., 27, 577, 761 (1923): 28, 506
(1942).
(7) hluehlberger, C. IT., Ibid., 32, 1858 (1928).
(8) Roscoe, H., J . Chem. SOC.,13, 162 (1860); - i n n . Chern. 1 1 .
Pharrn., 116, 218 (1860).
(9) Scott, TI'. W,, "Standard Methods of Chemical .lnalysis", 5th
ed., Vol., 11, p. 2209, New York, D. Van Nostrand Co., 1939.
(10) Sherry, W.B., Swinehart, C. F., Dunphy, R. A., and Oghum
S. C., IXD. ENG.CHEM.,ANAL.ED.,16,483 (1044).
(11) Truchot, C., Compt. rend., 98, 821 (1884).
PRESESTEO before the Symposium on Fluorine Cheniistry as paper 93.
Division of Industrial a n d Engineering Chemistry, 110th Meeting of tlie
.$\IEHIC.4\. C H E \ l I C h t SOCIETY, Chicago, 111.
combustion ( f ) of one mole of hydrogen in fluorine and in oxygen,
as shon-n below:
H?+ F: +2HF(,,,) + 128.0 lig.-cd.
(1)
Hz + HnO(,ss, + 57.8 kg.-cal.
-t
1,1202 (2)
Thus, in the case of fluorine the heat generated, for the sam(>
volume of hydrogen, is 2.2 times greater than for oxygen. Simi-
larly, tlie heats of combustion of methane or acetylene with
fluorine are tTTice :IS high as those with oxygen, for
CH4 + iF, --+ CF4 + 4 H F + 415 1rg.-cal. (3,