ORNL-1252.txt

UNCLASSIFIED ORNL-1252

W s

3 4456 03L0O9S57 5

 

  

GENERAL INFORMATION

   

CONCERNING FLUORIDES

   

By

   

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UNCLASSIFIED

 

 
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Index No. ORNL-1252

Subject Category: Chemistry

GENERAIL INFORMATION CONCERNING FLUORIDES

Mary E. Lee

February 19, 1952

AIRCRAFT NUCLEAR PROPULSION DIVISION

OAK RIDGE NATIONAL LABORATORY
Operated by
CARBIDE AND CARBON CHEMICALS COMPANY
A DIVISION OF UNION CARBIDE AND CARBON CORPORATION

Oak Ridge, Tennessee

Contract No. W-T405-eng-26

MARTIN MARIETTA ENE STEMS LIBRARIES

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Index No. ORNL-1252

O o1 v Lo oM

, Chemistry
Internal Distribution:
C. E. Center
C. E. Larson
W. D. Lavers
A. M. Weilnberg
W. B. Humes
E. D. Shipley
R. C. Briant
B. W. O. Dickinson
. E. S. Bettis
10. A. P. Fraas
11. L. A. Mann
12. A. J. Miller
13. H. F. Poppendiek
14, H. W. Savage
15. W. K. Ergen
16. E. H. Taylor
17-22. W. R. Grimes
23. F. Kertesz
2L, W. D. Manly
25. M. A. Bredig
26. A. S. Householder
27. M. E. Lee
28. E. G. Bohlmann
29. J. L. English
30. C. D. Susano
31. Frances Sachs
32. Elizabeth Carter
33-36. T. W. Laughlin (AEC-ORO)
37. C. H. Secoy
38. G. H. Clewett
39. J. A. Swartout
4o. E. Wischhusen
4. J. Courtney White
4o, J. P. Blakely
43, G. M. Adamson
4453, ANP Reports Office
54.56. Y-12 Technical Library
5T7-58. ORNL Chemistry Library
59-62. Reports Office, TID
External Distribution:
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GENERAL INFORMATION CONCERNING FLUORIDES

 

Abstract

This report is a compilation of abstracts, taken from
Chemical Abstracts (1907 thru Sec. U, 1952), containing
information concerning the fluorides of aluminum, barium,
beryllium, calcium, cesium, lead, lithium, magnesium, po-

tassium, rubidium, sodium, strontium, and uranium.

UNCLASSIFIED
UNCLASSIFIED L

CcA 6, 17h-4

Measurements of Specific Heats at Low Temperatures
with the Copper Calorimeter

F. Koref

Amn. Physik, 36, 49-73

. .The following substances, for certain temperature intervals (given
in parentheses) have the following mean at. or mol. heats: Li, (-191 to
-80), 3.61; (0 to -78), 5.15: (+19 to -T5), 5.44: Na, (-191 to -83), 5.60;
(0 to -77), 6.34; K, (-191 to -80), 6.14; (O to -78), 6.51; NaF, (-191 to
-82), 7.31; (O to -75), 10.43; KF, (-192 to -82), 9.06; (O to -76), 11.21;
CaFy (=190 to -84), 9.69; (0 to -T3), 1k.90; Ca(OH)e, (-191 to -80), 11.30;
(0 to -78), 17.53; (+18 to -T3), 18.41;.cccvcccncaans

CA 7, 1849-6

Equilibrium in Binary Systems of Fluorides
N. A. Pushin and A. V. Baskov
J. Russ. Phys. Chem. Soc., 45, 82-101

A study of the solidification curves of several binary systems of fluorides
gave the following results; AlF3 gives definite compounds, A1F3 . 3MF, in
which M = Li, Na, X, Rb, Cs. With Na, K and Rb it also forms compounds,
2 AlF,+ 3 MF existing in 2 modifications, and separated by a particular tem-
peratire. For Na this temperature is 6000, for X 3009, for Rb 350°. fThe
systems NaF-FPbF,, and NaF-CdF, are represented by 2 very slightly concave
(toward the X-axis) curves intersecting at the eutectic point. No solid
solutions were observed in the systems investigated.

CA T, 2512-5
Electrometallurgy of Aluminum
P. P. Fedotiev and V. L. Ilyinskiil
7. enorg. Chem., 80, 113-5k
An investigation of NaF and AlFé mixtures showed the following m. ps.:
’

6859, a minimum. The vola%iligy of A1F3 did not allow of higher readings....

UNCLASSIFIED
ca 8, 31-8

Theory of the Production of Aluminum
R. lorenz, A. Jabs and W. Eitel (Frankfurt a/M)
Z! arlorgo Chemo 3 -8—3_, 39"50

A thermal and optical study of the systems Al,0; - cryolite and NaF-
cryolite (cf. Fedotiev and Ilyinskii, CA 7, 2512 and Pascal and Jouniaux
CA 7, 2904). The system NajAlFg (m.p. 999°) - Als0; was followed up to
50 mol. % Al505; mixed crystals were formed on the NazAlFg side conteining
20% A1203 and The eutectic was at 973-8° and 32-3% A1203. The results for
the system Na,AlFg-NaF agree with those of Fedotiev and Ilyinskii, with
the exception”that the eutectic was found to be at 886° and 23% NajAlFg, and
a narrow field of mixed crystals is shown on the NaF side.

CA 9, 405-6

Specific Heats. II Alkali Halides
J. N. Bronsted {Copenhagen)
Z. Elektrochem. 20, 554-6 (1914)

The specific heats of 17 halides have been determined at a mean tem-
perature of 10° in a Cu calorimeter. With the exception of CsCl, the mol.
heat increased with mol. wt. for the same halogen, and for a single halogen,
with the weight of the metal. The individual values were LiF 9.66, NaF
10.96, NaCl 11.85, NaBr 12.10, NaI 12.31, KF 11.60, KC1 12.04, KBr 12.27,

KI 12.30, RbF 12.04, RbCl 12.25, RbBr 12.29, RbI 12.34, ¢sF 12.09, CsCl
12.56, CsBr 12.38 and CsI 12.39.

CA 9, 2024-6

Investigations on the Temperature-Coefficients of the
Free Surface-Fnergy of Liquids between -80° and 1650°.
VII. The Specific Surface-Energy of the Molten Halides
of the Alkali Metals.

F. M. Jaeger (Groningen)

Verslag Akad. Wetenschappen 23, 611-27 (191%4)

The surface tension of a number of molten salts of the alkall metals
was determined with the same app. which has been previously used for
other liquids (cf. CA 9, 738). The necessary measurements of the d. of
the various salts as a function of temperature required for the calcn. of
the molar surface-energy have not yet been completed and will be published
later. The variation with temperature of the specific surface-energy in
ergs/cm? (Xt) of all the salts may be represented by the expression X =
a - b(t - tg) +c(t - t5)© in which tg is the m.p. and a, b and c are
constants. The values of tg, a, b, and ¢, resp., of the various salts
are as follows: LiF, 840, 255.2, 0.126, 0; Licl, 608, 1k0.2, 0.076, O;
NeF, 990, 201.6, 0.106, O; NaCl, 801, 114.1, 0.071, O; NaBr, 768, 106.5,
6

0.069, 0; NaI, 660, 88.2, 0.053, 0; KF, 858, 1k3.2, 0.087, C; KC1l, T80,
97.4, 0.072, 0; KBr, 734, 88.8, 0.070, 0; KI, 681, 78.3, 0.064, O; RbF,
765, 132.0, 0.131, 0.00012; RbCl, 720, 98.3, 0.086, 0; RbBr, 685, 90.7,
0.069, 0; RbI, 642, 80.3, 0.065, 0; CsF, 692, 107.1, 0.088, 0.000k4; CsCl,
64, 91.3, 0.077, O; CsBr, 631, 83.6, 0.063, 0; CsI, 620, 91.6, 0.056, O.
From these results 1t is apparent that Xy as a function of t is very nearly
a straight line in all cases. The following conclusions are drawn from
the observations: (1) in the case of the four halides of the same alkali
metal the temperature coefficient b of X decreases continually with in-
creasing at. wt. of the halogen atom; (2) at the same temperature the value
of X for the same halide of all the alkalil metals decreases gradually

with increasing at. wt. of the alkali metal; at the same temperature X

for the four halides of the same alkali metal gradually decreases with in-
creasing at. wt. of the halogen atom. The relations, however, do not
possess a simple additive character. Finally, reasons are given for
believing that the liguid ILi salts possess a higher degree of molar com-
plexity than the salts of the other alkali metals........-

CA 9, 2828-4

Thermal Analysis of Mixtures of Alkali Hydroxides
with the Corresponding Halides

I. Compounds of Potassium

Giuseppe Scarpa

Atti accad. Lincei 2L, 1, T738-46 (1915)

It has long been known that some metallic oxides can combine with
their respective halogen salts to form definite and stable compds. (called
hydroxyhalides). Considerable work has been done on these compds. in the
wet way but very little has been done at high temps. on the behavior of
the oxides with the halides. Ruer (Z. anorg. Chem. 49, 365(1906) studied
the system PbO-PbCl,, Sandonnini (Atti accad. Lincei 23, I, 959 (191k4)
studied PbO-PbBr, and PbO-PbF, and Truthe (CA 6, 2372) studied Cus0-CusCls.
The 1st pairs form well-defined hydroxyhalides while the last 2 show no
formation of compds. S. has extended these data and this paper is a re-
port on the K compds. The systems KOH-KF, KOH-KCl, KOH-KBr, KOH-KI were
investigated. The study of these systems i1s made difficult by the fact
that it is hard to find a container that is not attacked by KOH and by
the fact that KOH tends to absorb large amts. of moisture and CO, from
the air. The mixts. were placed in a Ag crucible (since this material is
little acted upon by fused KOH in the absence of 0 at moderate temps.);
this is placed in an Fe cylinder, covered with a porcelain cover and the
whole put in a resistance furnace in a current of Ho0- and COo-free N.

A Ag-Ni thermoelement made and calibrated in the lab was used to measure
the temps. since a Pt-~-PtRd couple is attacked. The Ag-Ni couple was
covered with a small Ag cylinder in making the solidification p. detns.

and the slight changes in the Ag and Ni were found to be without ap-
preciable effect on the e.m.f. For temps. above 900° (for KOH-KF mixts.
containing much KF) & Pt crucible and Pt-PtRh couple were used with success.
The KOH used was 89.53% KOH, 1.4T% KoCO3 and 9% Hp0; the latter was re-
moved by heating it 45 min. at 500° in the furnace in an atm. of N. The
m.p. of this KOH was 380° (Hevesy (CA 4, 2763) found 360° and Neuman and
T

Bergve (CA 8, 3533) found 345°) and the point of transformation was 260°
(Hevesy, 2480). The KF solidified at 857° (Plate (CA 2, 502) found 859.9°
and Karandezen (Centr. Min. Geol. 1909) found 867°). The solidification
ps. of all the mixts. of KCH and KF stand between those of the 2 compo-
nents which are completely miscible in the solid state and give mixed
crystals of 1 kind only. Thus the point of transformation of KOH that
results from the solidification p. curve gradually falls with the increase
of the concn. of KF. The KC1l used in the study of KOH-KCl m. 776°. 1In
this system the primary crystn. curve falls from the solidification p. of
KC1 to that of KOH and shows an elbow at 430° at 67 mol. % KOH. The mixts.
from 36 to 67 mol. % KOH show, besides the primary arrest, a secondary
arrest of crystn. at 430°; the mixts. from O to 25 and 47 to 100 mol. %
KOH show an interval of crystn. due to the formation of mixed crystals.
This system belongs to the 4th type of Roozeboom since it gives 2 kinds
of mixed crystals and a miscibility break. The point of transformation
of KOH is markedly lowered by KCl and at 82 mol. % KOH is 120°. The
point on the descending crystn. curve limiting the solid soln. of KC1l

in KOH could not be accurately detd. The KBr used in the system KOH-KBr
solidifies at T60°. The solidification diagram of this system shows that
the 2 components, if the formation of mixed crystals in the mixts. con-
taining only small amts. of KOH is disregarded, are completely miscible
in the liquid state. The eutectic arrest is at 300° with 75 mol. % KOH
and disappears at O and 85 mol. % KOH. The point of transformation of
KOH is rapidly lowered at first by the addition of KBr but becomes nearly
constant at 2050 with 90 mol. % KOH. The KI used in the system KOH-KI
solidifies at 695°. The primary crystn. curve descends from the m.ps. of
the 2 components and intersects at the eutectic at 250° at 73 mol. % KOH.
The point of transformation of KOH lies a little above the eutectic arrest.
The system KOH-KF gives solid solns. in all proportions; KOH with KC1l and
KBr gives solid solns. of 2 kinds with a miscibility break; KOH and KI
gives a simple eutectic.

II. Compounds of Sodium, Ibid. 955-61

In continuing the expts. described above the systems NaOH-NaF, NaOH-NaCl,
NaQOH-NeBr and NaOH-Nal were studied. The methods and technic were the
same. The NaOH attacks Ag less than KOH and since it is stable at high
temps. higher temps. could be used without any decompn. taking place.

The NaOH used was 97.46% NaOH, 1.64% Na oC03 and O. 9% HyO. The m. and
solidification points of NaOH are 3100 and 290° (Hevesy found 318.k4° to
299.5° and Neumenn and Bergve found the solidification p. to be 300°);
the m.p. of NaF was 1005©C. The system NaCH-NaF showed the formation of
mixed crystals with miscibility break, while KOH-KF gave 2 kinds of solid
solns. The primary curve of crystn. lies between the solidification ps.
of the 2 components and shows a slight break of 90 mol. % NaOH. For
mixts. from 20 to 90 mol. % NaOH there is a 2nd arrest at 360°. The pt.
of transformation of NaOH is somewhat lowered and forms, with the limit
of the solid soln. of NaF in NaOH, a eutectic which shows a max. at 80
mol. % NaOH and which disappears at 5 and 100 (?) mol. % NaOH. In mixts.
of 5 to 80 mol. % NaOH it was possible to det. the duration of the eu-
tectic arrest, but from 80 to 100 mol. % NaOH the arrest due to the trans-
formation was also present. The system NaOH-NaCl shows a diagram similar
to the preceding. The NaCl m. 8060. The primary crystn. curve shows

a break at 350° and 75 mol. % NaOH; from 10 to 75 mol. % NaOH there is

_a 2nd arrest at 360%. The pt. of transformation of NaOH is rapidly
lowered by small amts. of NaCl with the solid soln. of NaCl in NaOH as the
1imit and the formation of an eutectic arrest which is at a max. at 73 mol.
4 NaOH and disappears at 5 and 100% NaOH.  The solidification p. of NaBr
is 776°. The system NaOH-NaBr shows complete miscibility in the liquid
state. The primary crystn. curve shows 2 branches which intersect at the
eutectic, 260° and 80 mol. % NaOH. There is not even a slight tendency

to form solid solns. The Nal m..665°. The system NaOH-NaI gives a de-
composable compd.” From the solidification p. of Nal the primary crystn.
curve descends regularly to 65 mol. % NaOH where there is a distinct
break; then it descends further and intersects the descending solidification
p. curve from the solidification p. of NaOH in a eutectic at 220° and 83
mol. % NaOH. In the mixts. up to 65 mol. % NaOH there is a 2nd arrest

in the solidification p. curve at 300° which has a max. duration at 40 mol.
% NeOH. This arrest coincides with the formation of a compd. decomposable
on melting; 2 NaOH+ 3 Nal is probably its formula. The pt. of trans-
formation of NeOH in a mixt. containing 3 mol. % NaIl is practically the
same as that of pure NaOH. Thus the systems NaOH-NaF and NaQOH-NaCl give
s0lid solns. of 2 kinds with a miscibility break; NaOH-NaBr gives a

simple eutectic; NaOH-NaI gives a compd. decomposable at fusion (probably
2 NaQH - NaI).

CA 10, 1477-6

Thermal Analysis of the Mixture of the Alkali
Hydroxides with the Corresponding Halides III.
Compounds of Lithium

Giuseppe Scarpsa

Atti accad. Lincei 24, IT, 476-82(1915)

In 2 preceding papers (CA 9, 2828) the behavior of KOH and NaOH with
the K and Na halides was described; it was found that the tendency to
give compds. increases from K to Na. S. has now extended these expts.
to Li to see if with its smaller electroaffinity compared with Na there
is a further increase in this tendency. The same methods and app. were
used a8 before. The LiOH used contained 98.5% LiOH, 0.5% LiC03 and
0.T% H»O. The Li salts were dehydrated in a Pt crucible. The m.p. of
LiOH was found to be 462° (DeForcrand, Compt. rend. 142, 1255(1906) found
4450); that of LiF is 840C. The system LiOH-LiF shows complete misci-
bility in the liquid state and gives solid solns. in limited proportions.
The primary crystn. curve drcps from that of LiF to a eutectic at 4300
at 80% LiCH and rises to the f.p. of LiOH. The freezing curve shows the
eutectic arrest from 5 to 85 mol. % LiOH. LiCl m. 605°. The primary
crystn. curve of the system LiOH-LiCl drops from the f.p. of LiCl to a
eutectic at about 290°, showing a break at 50 mol. % LiOH and then
rising to the m.p. of Li0OH. The eutectic arrest for mixts. of 45-100
mol. % L1OH lies at about 285° and shows a max. duration at about 65 mol.
% LiOH. Mixts. from O to 50 mol. % LiOH show another arrest at 315°
which has a max. duration at 40 mol. % LiOH. This arrest corresponds
to the formation of a compd. decompg. on fusion, which is probably 2
LiOH-3 Licl, wiBr m. 550°. The diagram of the system LiOH-LiBr is
similar to .hat of LiOH-LiCl. The eutectic lies at 275° with 45 mol. %
LiOH. Mixts. of O to 70 mol. % LiOH show & eutectic arrest which disappears
between 75 and 100 mol. %; at the latter compns. there is an arrest at 310°
which is max. at 75 mol. % and corresponds to the decomposable compd.

3 LiOH- LiBr. LiI m. 440°. The primary crystn. curve of the system LiOH-
LiI drops from the m.p. of LiOH to the eutectic 180° at 45 mol. % LiOH

and shows a strong break at 75 mol. % LiOH and then rises to a temp. of

310° at 80 mol. %, which must be due to the formation of a compd. not

stable at the m.p.; it must be 4 LiOH. LiI. The results show that the
tendency to give compds. between the alkali hydroxides and the halogen salts
of the same metal increases graduslly on passing from K to Na to Li or

with diminishing electroaffinity of the ion. This agrees with the theory
of Abegg and Bodlander (Z. anorg. chem. 20, 453(1903)) on electroaffinity
and formetion of complexes. The results of the 3 papers are summarized
thus:

Fluorides Chleorides Bromides Todides
LioH XX 2LiOH- 3LiCl 3LiOH-LiBr YTA10H-LiI
NaOH XX XX Vv 2NaQH- 3NaIl
KCH X==X XX vV v

xx indicate mixed crystals with a bresk, x--x mixed crystals in any
proportion, V formation of a simple eutectic.

CA 11, M1h-5

Investigations on the Temperature Coefficient of the

Free Molecular Surface Energy of Liquids between -800°

and 16500, Xv. The Determination of the Specific

Gravity of Molten Salts and of the Temperature Coefficient
of their Molecular Surface Energy.

F. M. Jaeger and Jul. Kahn (Groningen)

Proc. Acad. Sci. Amsterdam 19, 381-97 (1916)

The methods used for the determination of density are described.
The d. of liquids was determined with s pycnometer, or, in the case of
compounds, such as the low-boiling aliphatic amines, which absorb CO2
and HoO with avidity, with a volumeter. With inorgenic salts of high
melting point the d. was determined by the hydrostatic method, using a
float of Pt, suspended by a fine Pt wire from the pan of an analytical
balance. Following are the results for the compounds whose sp. surface
energy vas given in CA 9, 2024; first the temperature range used is
given, then the empirical formula expressing the d. as a function of the
temperature, then the value ofSH/St in ergs per degree; when only one
value of the latter is given it was sensibly const.

o
LiF, 887-1058°, d’°h

[

1.798-0.0004375(t-850), 0.40-0.58

C
1icl, 626-732°, at 1.501-0.000432(t-600), 0.47
l
0
LiNO3, 288-546°, at),

NeF, 1017-1214°, &%)
G

NaCl, 823-885°, b,
O

NaBr, 787-880°, d%),

NaI, 675-724°, d'tz
O

NayS0),, 926-1046°, dth

Na MoO),, 804-1063°, av

to
Na, W0y, 917-13300, ar,

o
NaNO3, 350-550°, a%

o
NaPOg, 905-1007°, dth

o

KF, 913-1054°, dtu

t

’ O
RbF, 820-1006°, d )

0
CsF, T20-824°, dtll

o

L

0

L

Kcl, 785-878°, at

KBr, 751-802°, at

o

KI, T00-751°, dth

O
K,S0), 1102-1291°, dth

o
CsBr, 662-Tu42°, dth

o

il

"

10

1.755-0.000546 (t-300), 0.45

1.942-0.000564 (£-1000), 0.52
1.549-0.0000626 (£-800), 0.48

2.306-0.00072 (t-780)-0.0000008(%-780)%, 0.53
2.698-0.0001061 (t-700), 0.63

2.061-0.000483 (t-900), 0.30

2.795-0.000629(t-T00) 1.2 between T00-800,
0.98 (800-1035), 0.56 (1035-11T1)

3.673-0.0009275 (£-930) + 0.000000337
(t-930)2, 0.64 (700-1000), 0.98 (1515-1600)

1.914-0.000672(t-300), 0.24 (320-360),
0.34 (350-425), 0.45 (425-600)

2.193-0.0004k4(£-800), 0.43 up to 1200°,
0.61 up to 1270, and 1.1 at 1500

1.878-0.000669 (t-900), 0.33 (900-960),
0.45 (960-1060), 0.83 (1275-1310)

2,873-0.00096T(t-825) -0.000000247(t-825)°,
1.0 (802-887), 0.56(887-1037), 0.40 at
higher temp.

3.611-0.001234(£-T700), 0.72 up to 930°,
diminishing tc 0.36 at 1100°

1.539-0.0005947 (£-750), 0.68

2.106-0.000799 (t-750), 0.76

2.431-0.001022 (£-700), 1.58 (730-765),
0.67 (765-815), 0.41 at higher temp.

1.872-0.000545 (£-1100), 0.90

3.125-0.00134 (t-650), 0.90 (660~700),
0.57 (860-970)
11

3.175-0.001222 (t-640), 0.82

it

O
csI, 639-701°, 4%,

1

8,50y, 1040-1220°, dtz 3.034-0.000711 (t-10L40) -0.00000049k
(t-1040)2, 1.91 (1036-1100), 1.16 (1100-
1220), 0.70(1220-1425) 0.43 up to 1530°

2.824-0.001114 (t-400), 1.18 to 600;
decreasing rapidly to 0.42

H

O
CsNO3, Lu5-575°, dth

CA 16, 1039-8

Vapor Pressure of Some Salts II
H. V. Wartenberg and H. Schulze
Z. Elektrochem. 27, 568-T3 (1921); cf. CA 15, 2376

Measurements have been made of the vapor pressures of 1iCl, CsCl,
RbCl, LiBr, CsBr, RbBr, NaF, KF, LiF, CsF, RbF, Nal, CsI, and RbI at a
number of temperatures between the b.p. of the salt and 200-300° below the
b.p. The vapor-pressure curvee of the different fluorides are widely
separated from one another; those of the other classes of salts lie
closer together the higher the at. wt. of the halogen.

CA 16, 2431-9

The Regularity of the Molecular Volumes

of Inorganic Compounds

Fr. A. Henglein

Z. snorg. allgem. Chem. 120, 77-84 (1921); cf. CA 16, 1343

.s..the densities of lithium, sodium and potassium fluorides are
2.587, 2.726 and 2.669, resp.

CA 16, 3799-6

Studies at High Temperatures XV The Vapor Pressures

of the Alkali Fluorides

Otto Ruff, Gerhard Schmidt and Susanne Megdan

Z. anorg. allgem. Chem. 123, 83-8 (1922); cf. CA 16, 190

Vapor pressure-temperature curves for the fluorides of Cs, Rb, K, Li
and Na are given between pressures of about 50 mm. Hg and 1 atm. For
exptl. methods cf. CA 16, 190. The curves are roughly parallel, and the
order of metals given above is the order of decreasing vapor pressure
at any temperature. For any glven pressure Rb has a curve sbout 160°
above Cs, K about 80° above Rb, Li about 180° sbove K, and Na ebout 30°
higher yet. The centigrade boiling points are:
12

LiF NaF KF RbF CsF
1670 1705 1498 1408 1253

Heats of vaporization, the Ramsay-Young consts., and critical temperatures
(from the Guldberg-Guy rule) are calculated.

CA 16, 4118-1

Vapor Pressure of Some Salts III
H. V. Wartenberg and 0. Bosse
7. Elektrochem. 28, 384-T7 (1922); cf. CA 15, 2376

The vapor pressure of AgCl, the chloride, bromide and sulfide of Cu,
the chloride, bromide and fluoride of Pb and the chloride, bromide, fluoride
and sulfide of T1 has been measured at different temperatures by the
method previously employed. Determinations have been made of the vapor
d. of the fluorides of K, Rb and Cs at different temperatures. These data
show that alkali fluorides exist as simple mols. in the vapor state.

CA 17, 2376-5

Measurements of the Density of Aluminum Halides,
with Mercury as the Pycnometer Liquid

Wilhelm Biltz and Walter Wein

Z. anorg. allgem. Chem. 121, 257-65 (1922)

Assuming A1F3 d. = 3.10, mol. vol. = 27.1

CA 17, 3273-1

Fusibility of the Ternary System: NaF, CaFo, AlF3
P. P. Fedotieff and W. P. Iljinsky
Z. anorg. allgem. Chem. 129, 93-107 (1923)

The results of the study are given in the accompanying diagram. The
black portions denote the unrealizable regions. The invariant points
occur at 780, 705, and 675°.

CA 19, 1368-4

Thermal Apnalysis of the System LiF-MgF2
G. Tacchini
Gazz. chim. ital. 2&, T77-80 (1924)

Sardonnini (Gazz. chim. ital. 41, 377 (191L4); cf. CA 7, 3284) studied
the system LiCl and MgCl, and found that it gave a continuous series of
mixed crystals. T. examined the system LiF-MgF,. 30 g. of mixts. of the
pure salts were fused in a Pt crucible by means of a small Pt-resistance
elec. furnace. The results are given in a table and a dlagram. The temp.
13

{

on cooling was followed to 300° but showed no eutectic arrest in any of
the mixte. The curve for the beginning of crystn. falls from 840°, the
m.p. of LiF, to a min. of 670° at 68.2 mol. % MgF,, rises slightly to 690°
at 78.99 mol. % MgF, and then rises sharply to lOgO0 at 88.5 mol. % MgFo.

The app. was not suited for observing the m.ps. of higher mixts. of MgF,,
which is estd. to be about 1400° (Beck, CA 4, 279). The form of the
diagram and the lack of a eutectic in all mixts. lead T. to conclude that
mixed crystaels are formed in all ratios. Owing to the fact that the
components have different cryst. forms it is believed that the mixed
crystals are decomposed but thermal evidence of this decomposition could
not be obtained.

CA 19, 2581-9

Solid Solutions of Compounds of Elements of
Different Valencies

G. Bruni and G. R. lLevi

Atti accad. Lincei (V), 33, ii, 377-84 (1924)

The results of X-ray analysis confirm the conclusion reached from
those of thermal analysis (c¢f. Tacchini, CA 19, 1368) that Li and Mg
fluorides form solid solutions, the mixed crystals undergoing decompo-
sition at a low temperature. At the ordinary temperatures, solid solutions
of the LiF type contg. up to 20% MgFo may be prepd. The replacement of
a certain No. of MgF, mols. by a corresponding No. of double LiF mols.
causes neither appreciable change in the LiF space lattice nor the ap-
pearance of new lines in the corresponding X-ray photograms, but, Jjust as
in other similar cases, the formation of the mixed crystals is accom-
panied by a slight increase in the volume of the elementary cell.

CA 19, 2890-6

The Crystalline Reticuli of Lithium and
Magnesium Fluorides and their Isomorphism

A. Ferrari
Atti accad. Lincei (6), 1, 664-T1 (1925)

The structure of MgF, was determined by the powder method. The results
show that it has a rutile type of structure with the following dimensions
for the elementary cell containing the MgF, mol.: a = L.65 A.U., C = 30.06
A. U., ¢/a = 0.6596. The d. deduced is 3.14. The vols. of the elementary
cells containing 4 mols. in the case of LiF and 2 in that of MgF, are
practically equal.
CA 20, 559-T

A Study of the Fluorides and Double
Fluorides of Aluminum

Martin Tosterud

J. Am. Chem. Soc. 48, 1-5 (1926)

Hydrated Al fluoride of compound Al F¢- 18 H,0 was prepared from Al
hydrate and aq. HF. Anhyd. Al¥F, was prepared by heating the hydrate to
2000, X-ray photographs show & transitlon at 115-120°. The compounds
L xF - Al F¢ and 4 ROF - Al Fg were prepared in the cryst. form by subject-
ing the gelatinous substance tc a temperature of 270° in a closed system.
Two forms of the K salt, one monoclinic and the other orthorhombic, were
found; the Rb salt was orthorhombic. Cond. measurements suggest the
existence of an NH)Al fluoride and NaAl fluoride.

CA 20, 2111-1

The Thermochemistry of Fluorine. II.
H. V. Wartenberg
7. anorg. aligem. Chem. 151, 326-31 (1926)

From older data in connection with new heat of formation the following
heats of formation are calculated. LiF 144.7, NaF 136.2, KF 134.2, ROF
132.8, CsF 131.5, BaF, 278.9, TIF aq. 80.5, CaF, 289.4, srF, 289.3, MgF,
264.3, ZnF, 193, CdF, aq. 173.7, FeFp aq. 177.2, MoF, aqg. 206.1, CoF, &q.
172.8, NiF, aq. 17103, AlF3 331.5, FeF3 aq. 253.1, CwFp aq. 129.8, AgF
50.1, PbFo 156 kg-cal.

CA 21, 2436-9

Researches on the Electrometallurgy of Magnesium and
its Alloys. Pressure of the Binary System Lithium
Fluoride-Magnesium Flucride

V. P. Hyniski and P. F. Antipine

Trav. inst. russe chim. appl. 1925, No. 84, 3-8;
Chimie et industrie 17, 601 (1927)

The fusibility of the system LiF-MgF, was determined by mixing given
weights of the previcusly dried salts, melting in & Pt-Ir crucible, and
obtaining the cooling curve by means of a Pt-Pt-Rh couple by taking read-
ings every 15 sec., the rate of cooling being 20° per min. Pure LiF m.
837°, pure MgFo, 1225°. The eutectic mixt. contains 53% MgF, and m. 718°.
Between O and 53% MgF, there is no eutectic, showing that LiF gives con-
tinuous solid solutions with MgF,. At 90% MgF, there is another eutectic
point, showing that there are no solid solutions along this branch of the
curve. The solidified mixtures with high LiF contents are white and have
a porcelain-like structure. Cryst. structure appears with increase in MgF,,
and with 85-90% on cooling the crucible is filled with MgF, needles. All
the mistures contract on cooling. The fused eutectic readily dissolved
15

10% of MgO, and the cooling curve of the system MgF,-LiF-MgO indicated that
crystn. started at 753°; hence, the soly. of Mg0 is suff1c1ent to allow for
its electrolysis in the eutectic at T753°.

CA 21, 3801-8

The Fusibility of the Mixtures of Lithium and
Magnesium Fluorides

V. P. Ilyinskii and P. F. Antipin

Ann. inst. enal. phys. chem. 3, 464 (1926)

The eutectic lies at 7189, so0lid solns. being formed on the LiF side.

CA 22, T32-8

Electrodeposition of Magnesium from Molten Fluorides
George (Grube
Z. Elektrochem. angew. physik. Chem. 33, 481-7 (1927)

The ternary system for BaFp, MgFo, NaF was studied and the results
were plotted in a diagram to determine the point of lowest m.p. About 1%
of MgO could be dissolved in the different fusion mixtures. A eutectic
m. 800° with the compn. BaFp, BaF,: MgFp, MgF, . NeF and contg. 1% MgO gave
a deposition of Na with Mg. The eutectic m. 5500 with the compn. MgF»,,
BaF, ¢« MgFo, MgFo - NaF and contg 1% MgO deposited Mg only. 900° is the
best working temp. for this system A cathode c.d. of 5 amp per sq. cm.
yields 509 Mg; 6 amp. per sq. cm.: 53%; 7 amp. per sq. cm.: u8% Mg.
A fusion contg. 20% MgFg and 80% BaF2 (m. 890°) with a cathode c.d. 5
amp. per sq. cm. at 920° gave 52% yield of Mg. In most cases the Na is
deposited rather than Mg, but in the cases in which Mg is deposited the
Na is probably held in the complex Mg-NaF3 as part of the ion N&Fg.

CA 22, 3851-8

Salt-Like Hydrides. IIT.
M. Proskurnin and I. Kazarnovskii
Z. anorg. allgem. Chem. 170, 301-10 (1928)

App. is described in which the d. of the hydrides can be determined
pycnometrically with the exclusion of air. The d. of the hydrides of Na,
K, Rb and Cs is determined and given as follows: for NaH 1.38 0.0k,
KH 1.47, RbH 2.60 £ 0.07, CsH 3.42 £ 0.1. Molssan's values are much too
low. In taking up H, a large contraction of the metal lattice takes
place, which is greater for the alkali hydrides than for the alk. earth
hydrides. Thus with LiH the vol. contraction in % is 24.6, with NaH
26.6%, KH 40.0%, RbH L40.7%, CsH 44.9%, CaH, 4.2%, BaH, 13.3%. Comparison
of the mol. vol. of the hydrides with the halogenides shows a great
similarity between the hydrides and fluorides. Mol. vol. of LiH is 9.8,
LiF 9.98, LiCl 20.53, while for CaH, mol. vol. is 24.8, CaF, 2k.6, CaCl2
50.0. The ion radius of the H ions is 1.45 A. U.
16
CA 23, TLT-5

Dilatometric Measurement of the Thermal
Expansion of Unstable Crystalline Ssalts
W. Klemm, W. Tilk and S. V. Mullenheim

Z. anorg. allgem. Chem. 176, 1-22 (1928)

vever 4,25 MgFp 3.13, ZaF, 4.95, LiOH 1.43, NaOH 2.02, KOH 2.12
Anion VOJ.BQ MgFE 6."", ZIIFE 5-8, LiOH lo.h" 'NaOH 8-0, KOH 3-6.

| CA 23, 1058-3

Fluorescence and Solid Solution
Mabel K. Slattery
Proc. Nat. Acad. Sci. l&, TT77-82 (1928)

NaF and LiF, activated to fluorescence by the addn. of small amts. of
U, show no difference in crystal structure from the pure salts. This may
be due to replacement of ILi or Na by U in the lattice at random points,
no distortion being expected since U has a quite small atomic radius.
Mixts. of LiF and NaF (5% to 50% LiF) and & small and uniform amt. of U
were fused. The fluorescent lines show a shift from the positions found
in the pure fluorophors, but this shift is the same for all mixts., the
increase in intensity of the LiF lines being the only change in going
from the 5% to the 50% LiF mixt. Also the amt. of shift of the NaF x-ray
diffraction lines is the same for all mixts. It thus appears that some
L1 had entered the NaF lattice but the remainder had crystallized
separately. It finally appears that an increase in crystal dimensions
causes an increase in wave-length of the fluorescent emission.

The Fluorine Tension of Metal Fluorides and
the Chemical Constants for F and HF

Karl Jellinek and A. Rudat

Z. anorg. allgem. Chem. 175, 281-320 (1928)

..... heat of formation PbF, 155,600.

CA 23, 48T4-9

Melting Point Diagrem of Cryolite-Barium Fluoride

Naoto Kemeyame and Eiichi Masuda

J. Soc. Chem. Ind. (Japen) 31, 1134 (1928); Suppl. Binding
32, 271B (1928)

The cryolite used contained 24.30% Al,0, and 0.04% matter insol. in
H,S0y and HCl. BaF, was prepd. by double defompn. of BaClp and NaF, and
17

the purified product contained 0.19% NaF and 99.48% BaF,. The NaF used
was purified by pptg. contaminating sulfate with benzidine chloride.
Cooling curves show a eutectic point at 8350, the eutectic mixt. being
composed of BaF, 62.5% by wt. No compd. was found.

 

 

BaF, in the mixt. Beginning of freezing Butectic point
0 by wt. 101 L.,
20 982 819.5
40 931 830
55 877 837
61 8l 83k
64 840 835
67.5 856 835
70 875 833
77.5 oll 828
85 1025 820
100 1324 coean

CA 24, 2927-3

The Mixed-Crystal Series Calcium Fluoride-
Strontium Fluoride

Erich Rumpf

7. physik. Chem., Abt. B. T, 148-54 (1930)

It was shown by means of Debye-Scherrer photographs that the mixed-
crystal series CaF,-SrF, satisfies the additivity rule of Vegard.

cA 24, L4208-3

Equilibrium in the Fused State between Potassium,
Sodium, and their Fluorides

E. Rinck

Compt. remd. 190, 1053-% (1930); cf. CA 24, 1787

The reaction between fused Na and K and their fluorides was studied
by heating the various mixtures inm Ni tubes. At 1000° the equil. const.
has a value cf 0.29.
18

CA 25, L164-1

Densities of Molten Cryclite and of Molten

Mixtures of Cryolite and Barium Fluoride

Naoto Kameyama and Atsushli Naka

J. Soc. Chem. Ind., Japan 34, Suppl. binding 140-2 (1931)

The ds. of molten cryolite and molten mixts. of cryolite and BaF,
were detd. by the buoyancy method; they decrease with increasing temp.
The interpolated ds. at 10500 are as follows (the 1st. no. in each case
indicates the percentage by wt. of BaF, in the melt, and the 2nd the d.
in g. per cc): 0, 2.03; 21.8, 2.37; 50.0, 2.91; 62.5, 3.19; T1.6, 3.Tk.

CA 26, 5000-9

The Melting Diagram of the Systems: KF-A1F3 and
LiF-AlF3

P. P. Fedotiev and K. Timofeev

Z. anorg. allgem. Chem. 206, 263-6 (1932)

In both systems stable compds. of the cryolite type 3KF - AlF3, m.
1025°, and 3 LiF - AlF,, m. T90°, were found. In melting KF with AlF
there is probably an Unstable compd. KF -A1F3 with transition point at
2T5°, there is no evidence of a similar compd. of LiF with AlFs.

cA 27, 2410-8

Determination of Corrosion of Iron, Chromium

and Nickel and of Corrosion- and Heat-Resistant

Alloys of these and other Metals

R. Mueller, G. Hahn and H. Krainer

Berg-U. Huttemmann, Jahrb. 80, Tk-8 (June 10, 1932); Met.
Abstracts (in Metals and AlToys) 4, 32

The electrolysis of melts of fluorides requires heat- and corrosion-
resisting materials. In a melt of MgF, at 950°, Fe was the least and Ni
the most resisting, with Cr in between; after 6 hrs. Fe showed an av. loss
of 10.3%, Cr 9.3%, and Ni a very slight increase in wt. due very likely
to a thin film formed on the surface. Cr-C steels show at first with
increasing C content a deterioration; with higher C content near the
eutectic point an improvement takes place. Ni steels show with increasing
Ni content an increase in corrosion resistance. Si has a slight improving
influence. Cr and Ni increase the resistance considerably. Addn. of Al,
Mo or Cu seems also to have a favorable effect. Replacement of Ki by Co
leads to strong corrosion. In general, under the influence of molten
MgF>, pure Ni is the most resistant, highly alloyed Cr-Ni steels are a
close second, while the typical heat-resisting C-Si steels are compara-
tively strongly attacked. The actual loss in material for all tests is
tabulated.
19
CA 27, 3660-6

Determination of Freezing Points of the

System MgF,-BaF,-Calp

G. Fuseya, M. Mori and H. Imamursa

J. Soc. Chem. Ind. Japan 36, Suppl. binding 175-6 (1933)

For obtaining g wmolten bath of low fusing point suitable for producing
Mg from MgO, the MgF,-BaFo-CaF, system has the advantage of no co-depo-
sition of Ba or Ca with Mg. In this system the lowest f.p. lies at 40% MgF,,
i2%723g2 and 18% CaF, and at 817° the addn. of 10% NaF lowers the f.p.
o o

cA 28, 400-5

Thermal Analysis of the System Lithium Fluoride-
Lithium Metaborate

I. IT. Kitsigorodskii, T. A. Popova and Q. K. Botvinkin
Ann. inst. smal. phys.-chim. {Leningrad) 6, 135-9;

J. Phys. Chem. (U.S.S.R.) 4, 380-2 (1933)

A thermsl investigation of the system LiF-LiBO, was undertaken with
the object of finding s glass capable of transmitting ultra-violet rays.
The melting diagram contains a max. corresponding to the complex compd.

2 LiF+ LiBOy. Two pclymorphic transformations in this compd., at 5450 and
5850, were detd., also two in LiF, at 812° and 762°, and one in LiBOo at
7850, Eutectics were found at 688° for LiF-2 LiF. 3 LiBO,, contg. 66%
LiBOp, and at 7109 for LiB0,-2LiF - 3 LiBO,, contg. 80% LiBOo.

CA 28, 1241-2

The Relationship between the Densities of Some

Salts in the Solid and the Liquid State. Determinations
of the Diameters and Densities of Molecules of

Salts and of the Atoms of Alkali Metals.

A. E. Makovetzkii

J. Phys. Chem. (U.S.S.R.) 4, 423-30 (1933)

The ds. of solid alkali halide salts were obtained by calen. from
data for 4. of salts in the liquid state. On this basis empirical rela-
tionships are found.

CA 29, 32-2

Specific Heats of Light-Metal Fluorides at High Temperatures
A. N. Krestovnikov and G. A. Karetnikev
Legkie Metal 3, No. Y, 29-31 (1934)

The sp. heats of MgF,, BaF, and NasAlFg were detd. between 3000 and
1000° and that of NaF between 300-80079.° Results: NaF 0.247h + 1.88 x
20

107% + 2.53 x 10°842; MgF, 0.2151 + 1.73 X 1074 + 2.66 x 10542, BeF,
0.1091 + 0.711 x 10-9t + 2.96 x 10~5t2; NagAlFg 0.2459 + 2.51 x 10-l¢-
1.255 x 10-1t2,

CA 29, 976-4

The Vapor Pressures of Zinc, Cadmium, Magnesium,
Calcium, Strontium, Barium, and Aluminum Fluorides
Otto Ruff and Leon Le Boucher

Z. anorg. allgem. Chem. 219, 376-81 (1934)

The b. ps., heats of evapn. and Trouton consts. are: MgF, 2260,
69.8 cal., 27.9; CaF, 2500, 80.3, 29.0; SrF, 2460, 78.2, 28.6; BaF,
2260, 69.8, 27.9; ZnFo 1500, 5.7, 25.8; CdFe 1748, 53.5, 26.4; AlF3
sublimes at 1260, 78.0, -. If the vapor-tension curves are plotted
(asbscissas: 1/T; ordinates: log p), they are practically straight
lines and intersect at 1/T = 10-* and log p = T7.48.

CA 29, 3570-)4-

Effect of Chemical Combination on Atomic Constants
in Crystalline Binary Compounds

Ugo Panichi

Mem. accad. Lincei (6), 5, 471-578 (1934)

Several more or less qual. relations gained from a consideration
of the changes which certain phys. consts. (at. vol., at. refraction,
at. lattice energy) undergo in the act of forming a cryst. binary compd.
AyB,, chiefly of a metal and a nommetal, are discussed. New ds. are
reported: Cal, 4.30, SrF, 4.06, AgF 7.10 and AlI3 sbout b,

CA 29, 5728-4

The Equilibrium Diagram of the System Barium
Fluoride-Magnesium Fluoride

Usaburo Nishioka and Masazo QOkamoto
Kinzoku-no~Kenkyu 12, 220-5 (1935)

The equil. disgram of the system BaF,-MgF, was constructed by
measurements of sp. gr. and n of the salt mixts. in addn. to thermal
and x-ray analyses. In this system a compd. BaF,: 2 MgF, (41.5% MgF,)
vas formed through the peritectic reaction, MgF, + melt %21% MgF,) <= BaF5*
2 MgFp, at 930°. The compd. and BaF, formed a simple eutectic (IT7%
MgF»), the eutectic point being 912°. By quenching the melt of this
salt mixt., a glassy mass could not be obtained.
21

CA 29) 6h97‘3

Specific Heat of Calcium Fluoride at

High Temperatures

A. N. Krestovnikov and G. A. Karetnikov

Legkie Metal 4, No. 3, 16-18 (1935); cf. CA 29, 32-1

Between 3000 and 1000° the sp. heat = 0.24871 + 4.251 x 10-6t +
5.844 x 10~7t2.

CA 29, TTT0-9

Equilibrium Diagram of the System BaFo-MgFo
Masazo Qkamoto and Usaburo Nishioka
Science Repts. Tohoku Imp. Univ. lst Ser., 24, 141-9 (1935)

The equil. diagram of the BaF,-MgF, system was detd. by means of
thermal and x-ray analyses, microscopic examn., and measurements of sp.
gr. and n. In the system a compd. BaF,° 2 MgF, is formed at 930°. fThis
compd. in turn forms a eutectic with BaF, at 9120 with 83 wt. % of the
latter.

CA 30: h095'9

Electrometallurgy of Aluminum
Paul Drossbach
Z. Elektrochem. 42, 65-70 (1936); cf. CA 28, 6639-6

Temp. - compn. diagrams are given for the binary systems, Na3AlF6-
Li3AlF6, Na3AlF6=A1203 and L13A1F6-A120 and for the ternary systéem
composed of "all 3 compds. Exptl. electrolyses were made with mixts. of
65% NaoAlF¢, 30% LizAlFg and 5% Al503. Data are given on the polarization
potent?al and current yield under various conditions of c¢.d., temp. and
distance between electrodes. The max. current yileld obtalned was 86%.

The operation and elec. connections are described for a tube voltmeter
for use with both a. ¢. and 4. c.

CA 30, L097-1

Reactions QOccurring in the Production of Aluminum
by the Electrolysis of Cryolite-Alumina Melts
Paul Drossbach

Z. Elektrcchem. 42, 144-7 (1936)

The e. m. £. at 950° for the decompn. of AlF, into its elements is
given as 3.4 to 3.7v. and for NaF, 4.4t to 4.6v. ese values are calcd.
from available thermodynamic data. The primary reaction in the electrol-
ysis of cryolite and alumina is the decompn. of NaF (cf. CA 18, 3516).

Al and 0, are formed by the depolarizing action of Alx0s3. Bl
22

CA 30, 4097-3

Decomposition Potentials of Molten Potassium
and Sodium Fluorides

V. S. Molchanov

Legkie Metal. 4, No. 5, 28-31 (1935)

By use of a special graphite cell the decompn. potential of KF and
NaF wes detd. by breaks in the current-potential curve. Results: KF, 9009,
2.13v.; 9400, 2,00v; 980°, 1.70v.; NaF, 860°, 2.95v.; 920°, 2.80v.; 9689,
2.63v. and 10220, 2.45v.

CA 31, 2894-5

Anomalous Mixed Crystals in the System SrF2~LaF3
J. A. H. Ketelsar and P. J. H. Willems
Rec. trav. chim. 56, 29-35 (1937)

The system SrFo-laFa was examd. by means of x-rays and d. detns.
Between O and 30 mol. % %aF anomalous mixed crystals of the fluoride
structure of pure SrF, are formed, the lattice parameter increasing from
5.782 to 5.827A. The isomorphous replacement of Sr++ by Lat++ is ac-
companied by a filling of vacant spaces in the lattice structure by F
ions, similar in charscter to the formation of the so-called luteo struc-
ture.

CA 31, 4569-3

Reaction in Equilibrium of Water Vapor, at High
Temperatures, with Some Metallic Fluorides
Louis Domange :

Ann. chim. 7, 225-97 (1937)

....The heats of reaction (with water vapor) in cal. are: MgFo,
900-11000, -L44300; CaFop, 900-1100°, -48500; BaFop, 900=1100°, -37250; PbFo,
600-750°, -37200. The heat of formation of each of these fluorides
was calcd.

CA 32, LOT-1

Crystallization of Calcium Fluoride from Melts
E. V. Tsekhnovitser
J. Phys. Chem. (U.S.S.R.) 10, 88-99 (1937)

CaFp was melted in ZrO, crucibles at 1%00-1500° and on crystn. gave
individual crystals up to 5 mm. and those of dendritic fluid type up to
10 mm. Slight decompn. takes place at 1500° leading to a Ca0 content of
3%. Above 1300° the reaction CaF, + 2 NaCl—>CaCl, + 2 NaF takes place,
both products being veolatile.
23

CA 32, 1582-6

Decomposition Potential of Aluminum QOxide

in Fused Fluorides

I. P. Tverdovskil and V. S. Molchanov

J. Applied Chem. (U.S.S.R.) 10, 1011-19 (in German 1019) (1937)

The decompn. potentials of cryolite at 1030°, 1058° and 1110° are,
resp., 1.98, 1.80, and 1.55v.; for the mixt. NaF 90 + AlF, 10% (mol.%),
2.16v. at 1000°; for NaF 51.5 + AlF, 48.5%, there are 2 pdints of in-
flection, 1.4l (for 1000°0) and 2.70v. (at 885°); for the mixt. Na AlFg
plus 12% (by wt.) Al50, 1.37 and 1.45v. at 965° and 1000°, resp.; and
for 20% Alp0q, 1.50 ané 1.55v., resp. The results showed a rectilinear
relation with the temp.; thus the electrolysis is a homogeneous process
in almost all electrolytes under investigation. The depolarization action
of Al505 on F at the anode caused an accumulation of AlF,, and the 0
liberated at the anode formed COo. Data are tabulated ahd plotted. 29
references.

CA 32, 3247-5

Double Decomposition in the Absence of a Solvent. XXXVI.
Irreversible Reciprocal System of Sodium and Potassium
Fluorides and Bromides

N. S. Dombrovskaya and Z. A. Koloskova

Ann. secteur anal. phys.-chim., Inst. chim. gen. (U.S.S.R.)
10, 211-28 (1938); cf. ca 31, 1686-4

The irreversible reciprocal system KF + NaBr =NaF + KBr was studied
(cf. Bergmen and D., CA 31, 1686-2). According to the thermochem. re-
action effect equal to 11.6 kg.-cal. the equil. is shifted toward the side
NaF + KBr. By means of a stable diagonal section of NaF + KBr, represent-
ing a simple eutectic system, the square of the system (obtained by
projecting the crystn. surface on the prism base, representing the prop-
erty diagram of the system) is divided into 2 independent ternary systems ;
(1) FaF + KBr + KF with 1 termary eutectic point at 570° and 7.5% NeF +
56% KBr + 36.5 KF, and (2) NaF + KBr + NaBr with 2 fields: (1) NaF and
(2) solid solns. of bromides. A considerable no. of sections in this
region showed that the line of mutual crystn. divides these fields in the
form of a very oblique curve with a min. at 583° and the compn. 16.5%
NaF, 29.5% KBr and 54% NaBr. The space diagram shows the presence of 3
fields of crystn: 1 field of continuous solid solns. and 2 fields of
the components NaF and KF. The crystn. vols. of the solid phases are in
accord with the direction of the reaction of double decompn.
24

CA 32, 4290-8

Beryllium Fluoride
Seri Holding S.A.
Fr. 822,302, Dec. 28, 1937

Be fluoride practically free from oxide is prepd. by heating dry
Be(OH), with pure dry NH\HF, in theoretical amt. The temp. is preferably
50 5000 so that sublimation of the Be flucride is preveuted.

CA 32, 5271-8

Surface Tension of Molten Mixtures Containing Cryolite
Emile Elchardus
CO-mPto renda 206, 11"6052 (1938)

The surface tension (x) of cryolite alone or with addn. of amts. not
exceeding 20% of NaF or AlF., was detd. by measuring the pressure necessary
to force a bubble of gas through the molten mixt. at a temp. approx. 20°
above the m.p. Addn. of AlF; lowers, of NaF raises a, while that of Al,0
has little effect. On passihg downward through the m.p. « first decreases
then rapidly increases and then decresses again; or conversely increases
with increased temp.; this is attributed to rapid increase in ionic dissocn.
near the m.p. Cryolite when solid is Na AlFg; on fusion, apart from ionic
dissocn., it becomes & mixt. of AlF; and"NaF. A labile form exists,
probably (Na3A1F6)2, which melts 8° lower than the ordinary NagAlFg.

CA 32, T686-2

Beryllium Fluoride
Serl Holding (Soc. anon.)
Fr. 826, k05, Mar. 31, 1938

Dry Be(OH)» or BeQ is caused to react at a high temp. (700-750°)
with gaseous HF, which should be dry or contain not more than 20% of
moisture. BeF, may be prepd. in a continuous manner.

CA 32, T808-7

The Heat Capacity and Entropy of Barium Fluoride,
Cesium Perchlorate and Lead Phosphate

K. S. Pitzer, W. V. Smith, and W. M. Latimer

J. Am. Chem. Soc. 60, 1826-8 (1938)

The heat capacities were measured from 15° to 300°K. With these
data, and by use of the Debye sp. heat equation to extrapolate from 0°
to 159K, the entropies were calcd. by graphical integration of C
f(log T). For BaF,, Pb 3{Poy) and 0501oh, §0291.1 = 23.03 + 0.1, 85.45 +
0.4 and 41.89 + 0.2 cal deg- i -1, resp. -
25

CA 33, 3227-9

Mixed-Crystal Formation between Several Fluoride
Salts of Different Formula Types

E. Zintl and A. Udgard

Z. anorg. allgem. chem. 240, 150-6 (1939)

Mixts. of the binary systems LiF-MgFy, CaFp~ThF), CaFp-YFg and SrFo-
Laf4, were studied. The prepn. of the constituents is given. For the
first pair mixts. contg. 5, 10 and 15 mol. % MgF, were tested with x-rays,
characteristics lines of the latter already being strong for the 5% mixt.
No mixed crystals could be found at 9 mol. %$. The lattice const. of LiF
does not change on melting with MgF,. Calcns. on data for a mixt. of 33.5
mol. % YF; and 66.5 mol. % CaF, indicate crystals of the interstitial type.
From a 66.6 mol. % SrF, and 33.3 mol. % LaF; a lattice const. of 5.849A.
and & d. of 4.88 indicate the interstitial ¥ype of cryst. Three mixts. of
9.22, 18.6 and 27.3 mol. % CaF, for the fourth pair were prepd. From the
lattice const. and d. the interstitial-type crystal was again indicated.
The vacant lattice position type was also considered but found incompatible
with the data.

CA 33: 3228'3

Mixed Crystals of Cryoliths with Clays
E. Zintl and W. Morawietz
7. anorg. allgem. Chem. 240, 145-9 (1939)

Three mixts. of NajAlFg and O¢-Alpy03 were prepd. which contained 5,
10 and 15% of the last.” The 15% mixt. 8howed corundum lines with x-rays
but they were not present in the others. Measurements of d. gave 2.97h,
2.980 and 2.977 for pure NasAlFg, 5% and 10% Alp0O;, resp. Of the various
cases considered only that gor formation of Na3Al§6 and Al;A10g gave
calcd. ds. comparable to the values found. The coupling of Al and Na is
explained.

CA 33, W525-7

Electrolytic Refining of Aluminum
J. Z. Zaleskli and A. Kotowicz
Przemysl Chem. gg, 536-48 (1938)

Expts. on electrolytic refining of Al in 3, horizontal, fused layers
were performed in lab. as well as on a semitech. and industrial scale.
The lab. investigations consisted in the detn. of the m.p. and the sp. gr.
of the ternary system AlF.- BaF,- NaF, as well as of the m.p. of the ex-
hausted anode alloys and of the sp. gr. of the fresh anode alloys, both
in liquid state....
26

CA 33, 8367-2

Beryllium Fluoride
Carlo Adamoli (to Perosa Corp.)
Can. 383, 438, Aug. 15, 1939

BeFo nearly free from oxide is prepd. by reaction of dry NHLHF, with
dry Be(0H), in substantially stoichiometric proportions at 450-500°.

CA 33, 8367-3

Anhydrous Beryllium Fluoride
Carlo Adamoli and Gino Panebianco (to Perosa Corp.)
Can. 383,440, Aug. 15, 1939

Gaseous HF is made to react with Be(OH)> at high temp. in spp. im-
permeable to HF.

cA 34, 1237-7

Vapor Pressures of Some Salts at High Temperatures
I. I. Naryshkin
J. Phys. Chem. (U.s-8.R.) 13, 528-33 (1939)

From the exptl. data on the vapor pressures at temps. from 750 to
10000, the values of A and B in the August equation, log p = -(A/T) + B,
are: 8810.6, T7.982 for NaCl; 8133.0, T7.580 for KCl; 9756.0, 8.463 for
KF; 11387.7, 8.654 for NaF; and 5000, 4.35 for AlF3. The heats of evapn.
and the extrapolated b. ps. are: NaCl, 40.2 cal.,”1454°; KC1, 37.2,
1457°; KF, 44.6, 1473°%; NaF, 51.9, 1702°; AlFs, 59.0, (sublimes). These
values are fairly close to the av. values of Other workers°

cA 34, 6143-1

Magnetic Susceptibilities of Some Fluorildes
Abdul Awwal Chowdhury
Current Sci. 8, 550 (1939)

By using a Gouy balance, the following mess-susceptibility (X 106)
data were obtained: MgFp, 0.40 (289); AlF g -0.16 (29.29); CdFp, -0.25
(29°); crF3, 91.20 (320); FeFg, 122.00 (32%); CuFp, 23.00 (32.29); znFp,

-0.37 (26.6°); CoF3, 10.90 (29°) ; BiF3, -0.23 (29.8°); "HgFo(oxy),"
-0.26 (299); "HgFo(ous)," -0.24 (29°); KBeFp, -0.60 (28.6°).
27

CA 35, 361-7

Determination of Crystal Densities by the Temperature -
of - Flotation Method. Density and Lattice Constant of
Lithium Fluoride

Clyde A. Hutchison and Herrick L. Johnston

 J. Am. Chem. Soc. 62, 3165-8 (1940)

A method is described for detg. the ds. of crystals to the fifth
decimal place, which is a combination of "temp. flotation" of small
crystals with calibration of the flotation liquid by hydrostatic weighings.
By this means the d. of LiF was found to be dss = 2.63905 £ 0.0001. This
value of the d. was used to compute the lattice const. of LiF. With the
at. wt. of F taken to be 19.00 and Avogadro's No. taken as 6.064 x 10°3,
this yields aps = 4.01736 * 0.00004A. However, an addnl. uncertainty
that may be as " high as 0.00050A. is involved because of an uncertainty of
0.01 unit in the at. wt. of F. Corrected to a wave-length scale which
also uses N = 6.06k x 1023 and takes the d. of NaCl (20°) as 2.1638,
recent x-ray measurements of Straumanis (cf. CA 32, 412L4-8) yield ayg =
4.01732 + 0.00004A. in complete agreement with the above figure. An
addnl. uncertainty of at least 0.00020A. is involved because of a min.
uncertainty of 0.0002 unit in the d. of NaCl. The possible future util-
ity of a combination of d. and x-ray measurements on LiF in providing a
standard of wave-length measurements, in detg. the precise value of
Avogadro's No. or in comparing the at. wt. of F with that of Cl is in-
dicated.

CA 35, 2055-9

Activity Coefficients of Sodium and Potassium
Fluorides at 25° from Isopiestic Vapor-Pressure
Measurements

R. A. Robinson

J. Am. Chem. Soc. 63, 628-9 (19k41l); cf. CA 35, 367-2

A table gives the molalities of solns. of KCl and NaF or KF that
are isopilestic at 259; from these data the activity coeffs. were calcd.;
the coeff. for KF is very close to that of NaCl, whereas NaF has a
much lower coeff., close to that of RbI.

CA 35, 351L-6

Density of Fused Salts of the Systems KF-NaF,
KqAIFg-NasAlFg and (K3A1Fg + NagAlFg)-BaF-Alp0
G. A. Abramov

Trans. Leningrad Ind. Inst. 1939, No. 1,

Sect. Met. No. 1, 49-58 (in Eng. 59)

For the mixts. KF-NaF the d. for each compn. decreases linearly
with rising temp. and the 4. - temp. curves are almost parallel to one
28

another. The mol. vols. of these mixts. at 1000° decrease linearly with
increasing mole fraction of NaF. The d. of K A1F6-Na3AlF6 mixts. in-
crease linearly with drop in temp., whereas their mol. vols. as a function
of the compn. at 1000° and 1100° deviate slightly from the law of addi-
tivity. The mol. vols. v, at any temp. can be expressed by: vy = 136-36.5a
+ [0.04Ta + 0.069 (1-a)] (t-1000), where t is temp. and a is content of
Na,AlFs in mole fractions, assuming that the mol. vols. are subject to

thé law of additivity. The d. decreased linearly with rising temp. for
the mixts. of (K3AlFg + NagAlFg)-BaFp- The Na and K cryolites were taken
in equimol. proportions. eir mol. vols. as a function of compn. at
1000° and 1100° decrease linearly with increasing mole fraction of BaFj.
The mol. vol. can be computed from vy = 136(l-a-b) + 99.5a + 35b +

[0.069 (1-a-b) + 0.012b + 0.04Ta] (t-1000), where a is mole fraction of
NagAlFg and b is mole fraction of BaFp in the mixt. Addn. of AlsO3 de-
creased the d. in all cases. The drop was large in presence of large
amounts of BaF, in the mixt.

CA 35, 3514-9

Density of the Fused Salts of the Ternary Systems

NaF-AlF3-CaF2 and NaF-AlF3~BaF2

G. A. Abramov and P. A. Kozunov

Trans. Leningrad Ind. Inst. 1939, No. 1, Sect. Met. No. 1, 60-T3

The d. of both systems increases linearly with decreasing temp.,
and with increasing amts. of CaF, or BaFp the d. rises considerably. The
mol. vols. of NaF and cryolite with CaF, or BaF, are subject to the
law of additivity. The mixts. of NaF and AlF, have a max. d. situated
near the compn. corresponding to cryolite. Tgis max. is shifted to the
side of NaF, the shift being greater the higher the temp. It is shown
that cryolite dissocs. into Na ions and a complex ion contg. Al. The
complex ion dissoc. into simple ions particularly with rising temp.

CA 35, 3549-9

Behavior of Fluorides of Sodium and Aluminum and

Cryolite During their Fusion

K. P. Batachev

Trans. Leningrad Ind. Inst. 1939, No. 1, Sect. Met. No. 1, L0-8

NaF is considerably volatile and changes compn. during fusion in
the open. 1In fusing cryolite in the open there is a fractional evapn.
of the AlF, along with the substitution of F for 0. The vapors of A1F3
are converted to d-alumina in the surrounding air. Anhyd. AlF., can be
prepd. by distn. in an incompletely hermetrically sealed app. %n an atm.
of AlF3 and HF.
29

cA 35, 4664-9

The Phase Diagrams for the Systems KF-MgFo
and RbF-MgFo

H. Remy and W. Seemann

Rec. Trav. Chim. 59, 516-25 (1940) (in German)

In the KF-MgF, system, the compds. KF- MgFo (I) and 2 KF - MgFo (II)
were found. From melts with 50 to 78.5 mol. % KF, mixed crystals of I
and KF first sepd., then rearranged on further cooling to give II, or
mixed crystals of II with I, or with KF. The products obtained in this
range were pale green. With more than 78.5% KF, there were no mixed
crystals, IT and KF sepg. directly from the melt. In the RbF-MgFs
system, there were no mixed crystals; the compds. RbF- MgF, and 2 RbF «
MgFo> were found. The products contg. 50-75 mol. % RbF were greenish.

CA 37, 303-2

Fusibility Diagram of the System LiF-KF-MgF,
A. G. Bergman and S. P. Pavlenko
Compt. rend. acad. sci. (U.R.S.S.) 30, 818-19 (1941) (in English)

The phase diagram of the system is given and discussed in detail.

CA 37, 823-1

Fusion Diagram of LiF-KF-NaF

A. G. Bergmen and E. P. Dergunov

Compt. rend. acad. sci. (U.R.S.S.) 31, T753-4 (1941) (in German)
cf. CA 37, 303-2

The ternpary system, of which the components m. 84k, 856 and 990°,
resp., consists of 3 binary systems, KF-NeF with a eutectic at T10° contg.
KF 60 and NaF 40 mol. %, LiF-NaF eutectic at 652° contg. NaF 39 and LiF
61 mol. %; and LiF-KF with a eutectic at 492° contg. 50 mol. % of each.
The ILi binaries form neither solid solns. nor double compds. The
diagrem of the ternary system consists of 3 distinct crystn. areas. Of
the total area NeF occupies 55, KF 23.7 and Li 21.3%. The eutectic
triple point is at 454O. At this point the compn. is NaF 11.5, KF 42
and LiF 46.5 mol. %, or 11.7, 59.2 and 29.1% by wt., resp. The sp. gr.
at the eutectic point is 1.99-2.13 at 460-860°. The results indicate
that this ternary system is suitable for fused-salt baths at 460-1000°.
30

CA 37, 823-3

Fusion Diagram of the System LiF-NaF-MgFo
A. G. Bergman snd E. P. Dergunov
Compt. rend. acad. sci. (U.R.S.8.) 31, 755-6 (1941) (in German)

The binary system LiF-MgF, has a eutectic at 7420 contg. 33 mol. %
of MgF,. This system forms a continuous chain of solid solns. NaF and
MgFo form & compd. NaF- MgF,, m. 1030°. fThis compd. forms a eutectic
with NaF, m. 830°, NaF 75 mol. %, and a eutectic with MgF,, m. 10000,
MgFo 64 mol. 4. The ternary system LiF-NaF - MgF» has a eutectic point
708°, at which it contains 62 mol. % of LiF. The system LiF-NaF-NaF-
MgF> has a eutectic at 6309, at which it contains MgF,10, NaF 43 and LiF
47 mol. % or 17.1, 49.4 and 33.5% by wt., resp. The system LiF-MgFo-
NaF - MgFo has a eutectic at 684° and a compn. MgFo 29, NaF 12 and LiF 59
mol. %, or 47.0, 13.11 and 39.89% by wt.

CA 37, 2982-7

Thermal and R8ntgenographic Studies of the

System BeF,-MgF,

Giovanni venturello

Attl accad. sci. Torino, classe sci. fis., Mat. nat. 76,
I, 556-63 (1941); Chem. Zemtr. 1942, I, 111k ‘“

The system BeF,-MgF,> plays an important role in the industrial pro-
duction of Be. After introductory remarks on the prepn. of BeFp from
BeO and HF with the application of NHLF, results of a thermal investi-
gation show a solidus line indicating complete miscibility of the two
fluorides. The region studied extended from pure MgF, to pure BeFp. In
the region about and above 90% BeFo the messurements are uncertain.
X-ray measurements in general confirm these results. They show the
presence of BeO formed from the partial transformation of BeFo under the
exptl. conditions employed. Debye x-ray diagrams with photometric
curves are given.

CA 37, 3661-6

The Heats of Formation of Chromium (III) Fluoride,

Chromium (IV) Fluoride, Chromium (III) Chloride and
Magnesium Fluoride

H. V. Wartenberg

Z. aporg. allgem. Chem. 249, 100-12 (1942); cf. CA 36, 6097-6

-++. A combination of data gives the thermochenm. equation Mg +
2 HF - aq—oMgFp + Hy + aq. + (109.5 + 0.7) kg:cal. Finally a value of
261.4 + 1 kg.-cal. per mol. is obtained for the heat of formation of
MgFs.
31

CA 37, b9T1-2

The Electrolysis of Molten Salts
P. Drossbach
Matallwirtschaft 21, 61-3 (1942); Chem. Zentr. 1942, II, 13

. .The structure of molten salts is discussed. Measured polari-
zation potentials are given for fused LiF and PbFo.

CA 39, 852-4

Entropies in Homologous Series of Saltlike Solids
W. D. Treadwell and B. Mauderli
Helv. Chim. Acta 27, 567-T1 (1944) (in German)

Spgg = 14.286 (log K + B log A) + (-25.244) for NaF-KF
K is mol wt. of the cation; A, that of the anion
B = 1 for 1-1 salts, B = 2 for 2-1 salts

CA 39, 1351-9

Heat Contents at High Temperatures of MgF, and CaFp
B. F. Naylor
J. Am. Chem. Soc. 67, 150-2 (1945)

High-temp. heat contents above 298.16°%K. of MgF, and CaF, (fluorite)
were detd. from room temp. to about 1773°K. From these data heats of
fusion and m. ps. also were obtained. The results are summarized by
algebraic equations and a table giving the heat content and entropy in-
crements above 298.169K. at 100° intervals. The sp. heat relations are
MgF, (s): Cp = 16.93 + 0.00252T-(220,000/T2), MgFo(l): Cp = 22.57,
CaFo(C): Cp = 14.30 + 0.00728T(k46,900/T2), CaFE(ߤ: Cp = 25.81 +
0.00250T and CaF,(l): Cp = 23.88.

CA 39, 1807-1

Lattice Spectrum, Specific Heat and Thermal Expansion

of LiF and NaF

Bisheshwar Dayal

Proc. Indian Acad. Sci. 20A, 138-44 (19L4k4); cf. CA 39, 459-L

The lattice spectrum, sp. heat, and thermal expansion of LiF and
NaF are calcd. by methods based on Raman dynamics of crystal vibrations.
The mutual repulsion of the nearest F ions is considered in addn. to
those existing between the neighboring ions Li and F for the calcn. on
LiF. An exponential form of the repulsive potential is assumed, and
the consts. are evaluated from exptl. data. Good agreement is obtained
for LiF.
32

CA 39, 4542-6

Thermal Anaiysis of the System NaF-BeF,-
X-ray Phase Analysis of the System NaF-BeF,

A. V. Novoselova, M. E. Levina, Yu. P. Simanov and A. G. Zhasmin
J. Gen. Chem. (U.S.S.R.) 1k, 385-402 (1944) (English summary)

By means of x-ray and thermal analysis of the system NaF-BeF, the
following double salts were established: NapBeF) which melts congruently
at 6159, whereas at 220 and 330° its polymorphic transformations occur;
NaBeF, which melts with decompn. at 360-70°; NaF - 2 BeF, which decomposes
at 2880 without melting. BeFs, prepd. from (NHu)g BeF), by distn. of NH)F,
suffers polymorphic changes at 4259 and 528° and softens at 600°, with
occurrence of transparency at 780°. Molten BeF,, on cooling, solidifies
to a glass without formation of any of its cryst. forms. On solidification
of melts of BeF, with NaF the former seps. in a cryst. form. An analogy
was detected between the x-ray data of this form of BeF, and that of o-
quartz; this material has the following const. with hexagonal cell
structure; a = 4.724., ¢ = 5.18aA.

CA 40, 3953-6

Anomalous Behavior of Fused Cryolite
T. R. Scott (Council Sci. and Ind. Research, Melbourne, Australia)
Nature 157, 480-1 (1946)

Natural cryolite (Na;AlFg) fused in Pt gives a "wetting" melt that
may creep over the edge of the crucible. The addn. of 0.02% Pb or Bi
and comparable amts. of Tl makes the melt nonwetting. Tl is volatile,
and its effect is temporary. The addn. of 5% of other compds. does not
interfere with the effect of Pb or Bi. With K3A1F6, 5% Pb or 0,25% Bi
is required to mske the melt nonwetting. Melts of synthetic cryolite
prepd. in Pb vessels are nonwetting; prepd. in rubber or Pt, are wetting.
Melts of NapSOl, NaF, NasWO), and KoS0) are affected like cryolite;
melts of NaCl and NaPO; are not. PbF, forms a wetting melt in Pt which
becomes nonwetting on %he addn. of twice its wt. of cryolite. No
theoretical explanation if given.

cA 40, 49oh3-7

Fusion Diagram of the System KF-NaF-MgFo
A. G. Bergman and E. P. Dergunov
Compt. rend. acad. sci. (U.R.S.S.) 48, 329-31 (1945)

The KF-NaF-MgF, system studied is one of the L triple systems
forming the faces of the compn. tetrahedron of a quadruple system of
Li, X, Na, and Mg fluorides, which is being investigated primarily to
find fluoride fluxes for the refining of nonferrous metals and their
alloys. The compds. in the KF-NaF-MgF, system det. the nature of the
quadruple system as & whole, as the fourth component, ILiF, does not
form any addnl. compds. and serves only as & solvent. The method used
33

was the visual-polythermal method, where the temps. at which the first
crystals appear and the last disappear are detd. by means of a Pt/Pt-Rh
thermocouple. The formation of 3 compds.-2 KF . MgF,, KF - MgF,, and NaF-
MgF, - divides the compn. triangle into 4 simple systems. The resulting
3 eutectics correspond to the following temps. and compn. (in mol. %):
eutectic (1) at 975° - 53.5% MgFo (I), 33.0% NaF (II), and 13.5% KF (III);
eutectic (2) at 798° - 22.5% I, 62.5% II, and 15.0% III; and eutectic (3)
at 685° - 6.5% I, 34.5% II, and 59.0% III. The transition triple point
occg;s at 710° and has the following compn.: 11.04 I, 39.0% II, and

50.04 III.

CA 41, 2313 g

Results of Low-Tempersture Research. I. The

Molecular Heat of Lithium Fluoride between 18° and 273.20 abs.
Klaus Clusius (Univ. Minchen)

Z. Naturforsch 1, 79-82 (1946)

The Debye continuum theory is only qualitatively valid for LiF at
these low temps. The characteristic temp. ép has a min. of 607° at 80°
abs., increasing to 648° at 273° abs., and 752° at 18° abs. At 18°
abs. the av. at. heat (one-half mol. heat) C, is 0.0065 cal/g. atom,
vhich is about 1/1000 of the value at room temp.

CA b2, 4811 e

The ILow-Temperature Heat Capacities, Enthalpies,

and Entropies of UF) and UFg

F. G. Brickwedde, H. J. Hoge, R. B. Scott (Natl. Bur. of Standards)
J. Chem. Phys. 16, 429-36 (1948)

The heat capacity of UF) was measured from 20 to 350°K. and that
of UFg from 14 to 3709K. Molar heat capacities are tabulated at 5°
intervals and extrapolated to O°K. From them the entropies and enthal-
ples of the compds. are found by integration and are tabulated. The
triple-point temp. of UFg is 337.2129K. and the heat of fusion is 19,193
Jjoules per mole.

CA 42, 6194 b

The Electrolytic Conductivity of Crystals IV. An
Experimental Study of the Mixed-Crystal System: SrF2-LaF3
Ugo Croatto and Maria Brumo (Univ. Padova, Italy)

Gazz. chim. ital 78, 95-105 (1948)

In continuation of investigations of the fluorite lattice (cf. CA
38, 41T72-3, 6152-9) pure SrF, and anomalous mixed crystals of SrFp-LaFy
were studied conductometrically. Pure SrF, and LaF,; were prepd. by
pptn. from their aq. nitrates by pure HF, filtratioh, repeated evapn.
with HF, and heating to a red heat. The mixed crystale were prepd. by
3L

repeated pulverization and heating, at 1100° of mixts. of SrF, and LaF
until x-ray examn. showed that equil. was reached. Roentgenographic ana
d. data on the mixts. are tabulated. The technique of making the cond.
measurements is described in detail, and the results obtained at various
temps. are given in graphs and tables. By application of the general
principles developed in the previous part, it was possible to calc. on a
quant. basis the lattice disorder and relative energy consts. of pure
SrFy, the transference Nos., and the mobility of the individual points
of cond. The lattice disorder was found to be of purely ionic nature.

CA k2, 6695 i

Complex Formation between Alkali Metal Fluorides

and Fluorides of Metals of the Fourth Group

E. P. Dergunov and A. G. Bergman (N.S. Kurnakov Inst.
Gen. Inorg. Chem. Acad. Sci. U.S.S.R., Moscow)
Doklady Akad. Nauk S.S.S.R. 60, 391-4 (1948)

The binary system KF-ThF) shows eutectic points at 664° (17 mol. %
ThFy), 750° (33), 878° (57), and 954° (80), and maxima corresponding
to K3ThF7 (870°), KThF5 (906°), and KF « 3 ThF), (960°), the latter being
a new type of compd. The system RwaThFh has the eutectic points 6640
(15 mole % ThFy), 762° (37), 848° (54), and 1000° (80), and mexims
corresponding to Rb3ThFq (974°) RbThFs5_ (852°), and RbF . 3 ThF), (1004°),
Stability of complexes of the type Me 1 ThF~ increases with the ionic
radius of the cation; the Rb salt is more stable than the K salt, and
Na and Li salts could not be obtained. Complex compds. of the type
M21 ThFg, analogous to (NH))s SiFg, are nonexistent; hence, the type
M3l ThF; cannot be structurally related to (NHh)g-SiFs NHLF, especially
as the zormer show an unprecedently sharp max. on the melting diagram.
The ternary system KF-RbF-ThF) shows an uninterrupted series of solid
solns. of the 3 complex compds. with KF and with RbF, indicating perfect
isomorphism of the K and the Rb complexes. The KF-RbF- -ThF), triangle
is divided into 3 tetragons, KF-K-ThF~-Rb ThF ~-RbF, K3ThF7-KThFs-
RbTth-Rb3ThF7, and KThF:--KF - 3 TfiFh—g bF . 3 ThFu~RbThF5, and one tri-
angle Kf . 3 ThFu-ThFu-Rbg 3 ThFy.

CA 42, 6696-c

Complex Formation between Alkali Metal Fluorides
and Fluorides of Metals of the Third Group

E. P. Dergunov (N.S. Kurnskov Inst. Gen. Inorg.
Chem. Acad. Sci. U.S.S:R., Moscow)

Doklady Aked. Nauk S.S.S.R. 60, 1185-8 (1948)

Melting diagrams are given for the binary systems: HaF«YF3, deep
min. at about 700°, 30 mole % YF3; LiF-YF3, eutectic T440, 17 mole %
IF3; KF-YF3, eutectic 756°, 1k, compd. K,YFg m.996°; RbF-YF3, eutectic
7520, 9, compd. Rb3YFg m. 106h° CsF-YF3, eutectic 673%, 4, Compd.
35

Cs3YFg m.1075%; NaF-laF3, deep min. at 8089, 27 mole % LaF;, incongruent
colpd. NalaFl, inflectidn pt. 920°; KF=L&F§, eutectic 620°, 22, in-
congruent compd. KLeF), inflection pt. T7709; RbF-LaF3, eutectic 5829,
20.5, incongruent compd. RbLeF),, inflection pt. 68493 CsF-LaF3, 1st
eutectic 600°, 12, compd. (congruent) Cs3LaFg m.795°, 2nd eutectic 726°,
34. Congruently m. compds. with sharp maximas are thus: K3YFg, Rb3¥Fg,
Cs3YFg, and Cs;LaF6; incongruently m. compds.: NalaF), KLaF), and RbLaF),.
The deep min. In the system NaF-YF,, indicative of solid soly., con-
firms the isomorphism of the ions §a+(o.9aA.), CA++(1.06A.) and YHH
(1.06A.). The tendency to form complex compds. of the cryolite type
falls from Al to La, i.e., with increasing ionic radius. Thermal sta-
bility of compds. with the same complex anion increases from Li to Cs,
i.e., with increasing radius of the cation.

CcA 42, 71901

Double Fluorides of Potassium or Sodium with
Uranium, Thorium, or Lanthanum

W. H. Zachariasen (Univ. of Chicago)

J. Am. Chem. Soc. 70, 2147-51 (1948)

Many double fluorides were found in the system KF-UF), KF-ThF), KF-
LaF3, NaF-UF),, NaF-ThF) and NaF-LaFq by the x-ray diffraction method.
The observed diffraction intensities can with good approximation be
attributed to the heavy atoms since the scattering powers of K, Na, and
F are small compared to those of U, Th, and La. Since g small number
of degrees of freedom is involved, the number and positions of the
heavy atoms within the unit cell can be detd. from the intensity meas-
urements. The vol. of the unit cell, V, and the number of heavy atoms
within it, Ny, are thus accurately known exptl. quantities. The vol.
of the unit cell for fluorides of the heavy elements under considera-
tion can with good approximation be attributed to the F atoms alone,
with the heavy-metal atoms fitting the interstices between the anions.
The vol. requirement of a ¥ atom may be set at Vp = 18A.3; exptl. values
are for UFg 18.1, UF), 19.4 UgFg 16.9, «-UFg5 19.0, S-UF5 17.0, UFg 19.3,
LaF3 18.2. 7 The mean values for the vol. requiremeuv of a K or a Na
atom obtained from a number of known crystal structures are Vi = 214.3
and Vy, = TA.3. V = NyV, + NgVp, where N, and Ny are, resp., the
number of alkali atoms and of F atoms per unit cell, and V, is the vol.
requirement of an alkali atom. N,, Ny, and Np are not independent,
since the valences must be balanced. Thus N, and can be detd. in
terms of the experimentally known V, Vg, Vas and . In the systems
AF-XFYy, Ny = (V-UNxVp)/Vy + Vp) and Np = (V + UNgVy) /vy + V)5 in the
systems AF-XF3, Ny = (V-3NxVp)/(Vp + Vp) and Ny = (V + 3NgV,)/(Vy + Vg).
In addn. to the terminasl compds. the following phases were observed:

In the KF-UF) system: KUgFps, KUgFy3, KUpFg, KUFs5, «-KpUFg, B1-KoUFg,
Po-KoUFG, «-K3UF7, and «'-K3UFy7; in the KF-ThF) system: KIhgFpg, KThoFg,
KThF5, «-KoThFg, P1-KoThFg and KgThFg; in the KF-LaF 3 system: o -KLaF),
P1-KLaFl; in the NaF-UF) system: NaUFs, «-NasUFg, Po-NaoUFg, 7-NapUFg,
and NagUFe; in the NaF-ThF) system: NaThoFg, Bo-NaoThFg, 8-NaoThFg, and
Na)ThFg; in the NaF-LaF, system: @o-NalaF). Crystal structure data are
given also for KNp2F9, éPu2F9, NaPuF5J RbPuF5, KPuF5 and NaPuF), .
36

CA 42, 7190h

Complex Formation and Solid Solutions in the

Ternary System Potassium Fluoride, Rubidium

Fluoride and Magnesium Fluoride

E. P. Dergunov and A. G. Bergman (Inst. Gen. Inorg.
Chem., Acad. Sci. U.S.S.R., Moscow)

J. Phys. Chem. (U.S.S.R.) 22, 625-32 (1948) (in Russian)

KF, m. 8569, and RbF, m. 7800, form a continuous series of solid
solns. without a min. KF and MgFo form 2 compds., namely, KMgF., m. 1090°,
and K-MgF) (a transition point at 8720); the 2 eutectics are a¥f 12.5 mol
% MgF, and 785C and at 68% MgF, and 10280. The RbF-MgFo system forms the
compds. RbMgFs, m. 9129, and RboMgF), m. 7920, and the eutectic at 19%
MgFo and 686° and at 62.5% MgF, and 883°. 1In the ternary system, KMgF 3
forms solid solns. with any amt. of RbMgF,, and KoMgF), with RboMgF), .

Pure MgF, was prepd. by heating NHhmgF3 a% 7000,

CA 43, 8763 a

Thermodynamics of the System KHF»-KF-HF, Including
Heat Capacities and Entropies of KHF» and KF
Edgar F. Westrum, Jr., and K. S. Pitzer

J. Am. Chem. Soc. T1, 1940-9 (1949)

.-..In the range 330-530°K., the data for KF can be represented by:
Hp-Hpgg, 160 = 11.266T + 1.929 x 10-3T2 + 6.88 x 1o-fi;—1-3761.5, Cp =
11.266 + 3.858 x 10-37-6.88 x 10%T-2,

CA 44, 3924

Dielectric Constants and Polarizabilities of Ions
in Simple Crystals and Barium Titanate

Shepard Roberts

Phys. Rev. 76, 1215-20 (1949); cf. CA 43,4061e

The dielec. consts. and polarizabilities of ionic crystals are
correlated by means of the Clausius-Mosotti equation. Polarizability
changes but slightly with temp. By use of the principle of additive
polarizabilities, dielec. consts. are calcd. for PoFp, SrClsy, Ko0, Lin0,

Nag0, Rbo0, AgF, T1I, CuF, Cul, AgI and KMgFs.
37

CA Lk, 892¢g

Sintering cf Salts and Cxides
A. Ya. Zvoryskin and N. I. Timokhina
Zhur. Priklad. Khim. (J. Applied Chem.) 22, 1063-7 (1949)

In further development of the rule of Tammann and Z. (CA 23, T47)
egtablishing the empirical ratio of the temps. of beginning sintering of
solid powders and their temp. of fusion, tg/te = 0.4k for salts, and 0.8
for oxides and silicates, powders sintered at definite temps. above tg
were tested for mech. strength S by detn. of the min. wt. necessary to
crush a specimen of lower diam. 11, upper diam. 19, height 25 mm. For NaF,
NaCl, NaBr, KCl, KBr, and KI, tg; = 285, 20k, 181, 216, 190, and 1379,
heated at 5000, S = 25.0, 47.5, 92.4, 65.6, 87.1 and 371.7 g/0.95 sq. cm.,
increasing, within each halide series, with decreasing lattice energy of
the salt. CaF,, heated at 400-T00°, reached only small S of 9.2-56.4.....

CA bk, 896 i

Crystal Modifications of Lead Fluoride
Ya. Sauka v
zhur. Obshchei Khim. (J. Gen. Chem.) 19, 1453-8 (1949)

Large crystals, up to 3 mm., can be obtained by slow pptn. occurring
when dil. solns. of Fb(NO3)p and of NHLF are made to diffuse into each
other. The product is a mixt. of the 2 known forms of PbF,, cubic and
orthorhombic. The proportion of the cubic form is the higher the slower
the reaction. With very dil. solns., almost pure cubic (octahedral) FbFo
was obtained. Replacement of Pb(NOz), by Pb(OAc), favors the cubic form.
Interdiffusion of concd. solns. yieids almost pure rhombic PbF,. By
goniometric detns., the latter belong to the class of rhombic dipyramids.
The rhombic form goes over monotropically into the cubic form. The
transition point was redetd., by X-ray and microscopic examn., to 3159,
considered more accurate than previous detns. (400, 200, or 280°). The
d. of the cubic and rhombic forms are detd. to 7.750 and 8.445 resp.

The cubic form can be obtained and maintained at lower temps., altho it
is thermodynemically stable only above 3159. Along with the 2 forms of
PbFo, the ppt. contains a small amt. of mixed crystals, the compn. of
which PbFp - 0.16 Pb(NOg)p + 0.13 HpO, corresponds to no definite compd.,
and which gradually refrystallize into either cubic or rhombic FbFo.

cA 44, 1306 4

Tables of Osmotic and Activity Coefficients of
Electrolytes in Aqueous Solution at 25°

R. A. Robinson and R. H. Stokes

Trans. Faraday Soc. 45, 612-2L (1949)

The data are tabulated for H, Li, Na, K, Rb, Cs, Al, Sc, Cr3+, Y,
la, Ce, Pr, Nd, Sm, and Eu chlorides; H, Li, Na, K, Rb, and Cs bromides
38

and iodides; Na and K fluorides; H, Li, Na, K, Rb, Cs, Ag, Tl*, Cr3t, and

Thi nitrates; 1i, Na, K and Cs hydrox1des, H, L1, ga and T1 perchlorates,

Na and K chlorates; Na and K bromates; Cu2+t +,cd2+, Mnet, Ni2+, A1,
andCr3*sulfates, 1i, Na, K, Rb, Sc, and Tl acetates, 1i, Na, and K toluenesul-
fonates; Na and XK thiocyanates; NeHoPOY; KuFe(CN)g; KHoPOL and sucrose.

CA 44, 1313 f

Comparison of the Catalytic Activities of Some

Solid Salts in the Recombination of Hydrogen Free

Atoms (Atomic Hydrogen) and Hydroxyl Free Radicals

(Free Hydroxyl Radicals)

Mikko Tamura and ShoJji Shida

Rev. Phys. Chem. Japan, Shinkichi Horiba Commem. Vol. 1946, 115-20

The negative catalytic effect of some solid salts on the combustion
of H, and some org. compds. may be caused by the recombination of H atoms
and OH radicals on the solid surfaces. To test this theory, water vapor
was passed thru a Wood's discharge tube, past a thermometer coated with
the solid salt, thru a trap cooled with solid CO, and alc., and finally
was pumped out by a vacuum diffusion pump and sn 0il pump. The rise in
temp. was measured for KF, KCl, KBr, KI, KCl, NaCl, RbCl, LiCl, NaF, LiF,
LipCO3, NaoSOy, NapCO3, NaNO3, KpSO), NHLCI, KNO% MeClo, Ca(NOa)g, CaFo,
Pt, KQCO3, and glass. The order of catalytic activity decreased in the
order Rb, K, Na, Li for carbonates, halides, and nitrates and in the order
metal, carbonates, nitrates, halides for K and Na salts. The fluorides
and sulfates of K and Na are inactive. In general, the more pos. the
cation and the less neg. the anion, the more active the salt. For the
alkali halides, the smaller the lattice energy, the greater the catalytic
activity.

CA Ll, 1316 g

Chemical Investigations of Silicates

XII. The System Lithium Fluoride-Beryllium Fluoride
and its Relation to the System Magnesia-Silica

Erich Thilo and Hans Albert Lehmann

Z. anorg. Chem. 258, 332-55 (1949); cf. CA 35, 505L-1

The m.p. diagram of the system LiF-BeF, (I) was observed to find
how closely it serves as a Goldschmidt model for the system Mg0-SiO, (II),

‘in which the ion radii are nearly the same but the valences are doubled.

Mixts. in the system I were prepd. by heating LiF and (NHy), BeFj to-
gether, and the melting curves were followed to 50 mole % BeF». Incon-
gruent m.ps. were observed for L13Be2F (L459) and LiBeF3 (365°). LiBeyFg
may exist. The compds. formed in I are explained by the unsatn. and
polymerization of BeF,, considered to be covalent with the Be lacking

two electron pairs. The similarity to II is very close, with disconti-
nuities at almost the same compns. Ratios on the abs. temps. of 5
39

characteristic points in I and II are all close to 2.88. Crystal structures
of 4 analogous compds. in I and II are discussed from data of the literature
and the authors. Powder X-ray data are given for LiBeF4, and powder and
rotation data for LisBeF), but structures are not worked out. Analyses in

I were limited to a detn. of Be in (NHu)g BeF) by conversion to sulfate

and reduction to BeQ with hydrogen or illuminating gas at 625° or above.

The compds. LiF (845°) and LisBeF) (4750) were congruent melting, with a
eutectic (L620) at 31% BeFs.

CA 4k, 1321 i

The Heats of Vaporization of Uranium Hexafluoride
Joseph F. Masi
J. Chem. Phys. 17, 755-8 (1949)

UFg was vaporized in a heavy-wall, Ni-plated calorimeter. The heat
of vaporization of the solid was measured at 7 temps. and of the liquid at
L temps. covering the range from 4O to 90°. The app. was tested before
beginning the measurements by obtaining the heats of vaporization of water
at 3 temps. The scattering of the data on UFg is about l%. The measured
heats of vaporization were used to obtain a consistent correlation of the
vapor pressures, heat of fusion, and triple point given in the literature.
The results are expressed as vapor pressure equations and an equation of
state for the satd. vapor. From these equations and the National Bureau
of Standards values for the thermodynamic properties of the solid and
liquid, the entropies of the ideal gas are calcd. and compared with those
given in the literature from spectroscopic data and mol. structure. The
heat of vaporization and entropy at 273.169K. is 12,023 cal/mole and
87.56 cal/mole degree. At the m.p. (337.21°K) the entropy is 94.20 cal/
mole degree. The heat of vaporization is 11.429 and 6859 cal/mole in
the solid and liquid state, resp.

CA 4k, 1322 f

Dissocn. Energy of Fluorine
E. Wicke
Z. Elektrochem. 53, 212-16 (19L9)

The heat conducted by F at 10 mm. pressure from a hot Ni wire to a
cool wall was the same as for N at all temps. up to 10000, showing that
little dissocn. occurs at this temp. The result is consistent with the old
value of 63 kcal. for the dissocn. heat of F, but inconsistent with the
new value 33 kcal. of Schmitz and Schumacher (CA L2, 2869 4). The in-
terpretation of the C1F absorption spectrum, on which S. and S. base
their value, is discussed and shown to be doubtful.
L0

cA 44, 1322 ¢

Heats of Formation of Several Fluorides
H. V. Wartenberg and G. Riteris .
7. anorg. Chem. 258, 356-60 (1949); cf. CA 43, 8255 h

The heat of the reaction ClF4 + 3 NaCl = 3 NaF + 2 Clp was calori-
metrically detd. as 86.8 + 0.3 kcal. (exothermic). Then with the aid of
recently detd. heats of formation of NaCl and NaF, 1/2 Clp + 3/2 Fp =
C1F3 + 28.4 + 0.3 kcal. From the hydrolysis reaction calorimetrically
measured as COFp + HoQ = 2 HF aq. + COo + 26.73 + 0.2 kcal., and known
heats of formation of HF and COp there was obtained C + 1/2 Op + Fpo =
COF2 + 150.35 + 0.5 kcal. The compd. CF), was reacted with K in a
special app. contg. an elec. arc, and the heat observed:

4 K + CFy = C (graphite) + & KF + 307 * 3 kcal. Then

C (graphite) + 2Fo ™ CFL + 231 * 3 kecal.

CA 44, 1801 4

Ultraviolet Absorption Spectra of Rubidium and
Cesium Fluorides and the Heat of Dissocn. of Fluorine
A. D. Caunt and R. F. Barrow (Univ., Oxford, Engl.)
Nature 164, 753-4 (1949)

To det. the dissocn. energy, D. of mol. fluorine, the absorption
spectra of RbF and CsF were measured in the quartz ultraviolet. At
about 900° for RbF and T50° for CsF, continuous absorption is detectable,
with max. absorption at 2150A. for RbF and at 2100 for CsF. As the
temp. 1s raised, diffuse bands appear at longer wave lengths. Some
30 for RbF to 2980 and 25 for CsF to 2710 have been measured. From
these Dig - (RbF) and Dyg (CsF) were detd.; coupled with the heats of
formation, Q(MF), the latent heat of vaporization, L,g (MF), they give
a value of D(F,) of 50 % 6 kcal., which is incompatible with one of
40 + 3 kcal. as detd. from C1F. Further work is necessary to bring
these values more into line but it appears certain that the bond strength
of mol. fluorine is considerably less than that of mol. chlorine.

CA 4k, 231k £

Tmproved Crystallization of Lithium Fluoride

of Optical Quality

Donald C. Stockbarger (MIT, Cambridge)
Discussions Faraday Society 1949, No. 5, 299-306

Pure LiF is prepared by bubbling CO, through saturated ag. LisCO
solution at room temperature and mixing the LiHCO4 which is formed wi%h
HF solution. The LiHCOg3 is added to the HF slowly with agitation, and
the addition is stopped while acid is still present in excess. LiF
crystals are prepared by lowering the melt, which is contained in a Pt
41

crucible, through a temperature gradient in an air furnace. The major
difficulties are the control of the temperature and line voltage, the
avoidance of reaction with water vapor, and the avoidance of color in the
resulting crystals. Superior crystals can be grown at greater expense

in a vacuum furnace. These crystals have much better transmission char-
acteristics in the ultraviolet and infrared than crystals grown in air.

CA 4k, 2811 g

A Theory cf Dielectric Polarization in

Alkali Hglide Crystals

Shepard Roberts (G. Elec. Co., Schenectady, N. Y.)
Phys. Rev., T7, 258-63 (1950); cf. CA 4k, 392 4

A theory of dielec. polarization is described in which each ion in
an alkali halide crystal is considered as a sep. entity capable of being
distorted internally by an elec. field. Three stiffness coeffs. suffice
to describe the interaction between the local elec. field and the polariz-
able ion. The Lorentz internal field is valid for this calcn. Optical
and dielec. polarizabilities per mol. and infrared absorption frequencies
in alkali halide crystals calcd. by this method are in substantial agree-
ment with exptl. Electronic polarizabilities of free (gaseous) ions are
also calcd., and a novel "pseudo-piezoelec."” effect is predicted.

CA 4k, 2839 a

Heat Capacities at Low Temps. and Entropies

¢f Magnesium and Calcium Fluorides

S. S. Todd (U.S. Bureau of Mines, Berkeley, Calif.)
J. Am. Chem. Soc. 71, 4115-16 (1949)

The heat capacities of MgF, and CaF, were measured throughout the
range 52 to 298CK. Their entropies at 298.169K. were calcd. to be 13.68
+ 0.07 and 16.46 * 0.08 cal/degree/mole, resp.

CA W4, 2839 a

Low-Temp. Research. VII. The Specific Heat of the
Alkali Halides Lithium Fluoride, Sodium Chloride,
Potassium Chloride, Potassium Bromide, Potassium
Icdide, Rubidium Bromide, and Rubidium Iodide between
100 and 273° Abs.

Klaus Clausius, Jochen Goldmann, and Albert Perlick
Z. Naturforsch. la, U2h-32 (1949); cf. CA 43, 825hb

The sp. heats were measured in a vacuum calorimeter (cf. CA 30,
3707-9). Cp, Cy, and the characteristic Debye temp. 6 are given. Curves
are presented to show the deviation from the prediction of the Debye
theory that 6 = const. LiF, NaCl, and KC1l were investigated at suffi-
ciently low temps. (G/T > 12) to include the region of the T3 law. The
42

values of © were, on the contrary, found to reach a min. Just sbove this
region, then to increase very rapidly with decreasing temp.

CA 4k, 3320 g

An Anomalous Dielectric Effect of Vacuum-
Sputtered CaF, Layers

Erkki A. Laurila (Finland Inst. Technol, Helsinki)
Phys. Rev. T7, 405-6 (1950)

The change in the capacitance, a.c. and d.c. resistances, and the
dielec. const. with time (5 sec. to 14 days) are tabulated for layers of
CaFo 1000, 3000, and 10,000 A. thick.

CA Lk, 3327 g

Crystal-Chemical Studies of the 5 f Series of Elements
W. H. Zachariasen (Univ. of Chicago)
Acta Cryst. 2, 288-91 (1949); cf. CA 43, 648kh

XI. The crystal structure of «-UF5 and of A-UFg, Ibid 296-8

- is tetragonal body-centered with a; = 6.512 * 0.001, ag =
4. 463 = 0.801 ¥X and 2 stoichiometric mols. per unit cell, space group
Coyp - I 4/m. In the proposed structure each U atom is bonded to 6 F
atome. The UFg octahedra are linked by shared corners into endless
strings along the a axis. fi-UFs is also tetragonal body-centered.
The unit cell contg. 8 stoichiometric mols. has dimensions a; = 11.450
+ 0.002. ag = 5.198 + 0.001 kX space group D12,5 - I L2d. A structure
is proposed in which each U atom is bonded to TF atoms. The interat.
distances are: «-UFg, U-6F = 2.20A.; p~UF5, U-TF = 2.23A.

XII. New compds. representing known structure types. Ibid 388-90
The crystal structures of 55 new compds. of U4f and 5 £ elements rep-
resenting 14 known structure types were detd.: NaCl-type = NpO, PuO, AmoO,
NpN, PuN, PuC;
CaFp-type = PalOp o(?), NpOp, PulOp, AmOp, ACtOF, PulF, X-KoThFg, c-KoUFg,
«-NaoThFg, x-NasUFg, @ -KLaF),, @ -KCeF),; LaF3-type = ActF3, UF3, NpFg,
PuF3, AmF3, CaThFg, ThOFp, SrThFg, BaThFg, PbThFg, STUFg, BalFg, and
P'bUF6; PbFCl-type = ActOCl, ActOBr, PuOCl, PuOBr, PuQI, PrOCl, NdOCl,
NdOBr, and YOCl; ZrF) type = ZrF), HfF), ThF), UF), NpPF), PuF), CeF);
Lax03 type = Act203 ’ Th2N3 ; Sodium uranyl acetate-type = neptunyl and
plutonyl compds.; K3ZrF7-type = K3UF7, CuoMg-type = CePto; CaTiO3-
type = CeAlO3; UOzFp-type = NpoOoFp; LaPOy-type = Act PO4 - 0.5 H20;

UCl) -type = NpCl),.
43

XIII. The crystal structures of UoFg and NaThQFg, Ibid 390-3

The compd. UoFqg is body-centered cubic with a = 8.4545 + 0.0005 kX,
space group T3d - Ig3m, and 4 stoichiometric mols. per unit cube. The
positions of the U atoms were detd. from the observed intensities and
the positions of the F atoms from spatial considerations. Each U atom
is bonded to 9 F with U-G9F = 2.31A. The U atoms are structurally equiv.
The double fluoride, NaThgFg, is body centered cubic with a = 8.705 %
0.005 kX, space group TJ3 - I %3 m. The positions of the Th and F atoms
are practically the same as for the U and F atoms in the UpoFq structure.
Suitable positions for the Na atoms were found. The interat. distances
are Na - 6F = 2,34 A. and Th -9F = 2.40 A.

CA 44, 3389 f

The Dry Chemistry of Plutonium Fluorides

S. Fried and N. R. Davidson (Argonne Nat'l. lLab., Chicago)
Nat'l Nuclear Energy Ser., Div. IV, 14 B, Transuranium Elements.
Pt. I, 784-92 (1949)

PuF), does not react with dry O, at temps. up to 600°, whereas PuF3
at 600° apparently undergoes the reaction 4 PuF; + Oo+==3 PuF) + PuO,.
PuF), decomps. to PuF3 + Fp, presumably, at abou% 900° in vacuo. This
decompn. takes place 1n vessels of Pt, BeO, and CaFp,. PuF)} does not de-
comp. to PuF, in vacuum in contact with Pt at 600°. It is suggested
that the PuF) decompn. i1s a disproportionation, 2 Pth-—+PuF3 + PuF5,
followed by decompn. of the PuF5.

CA 4k, 3389 g

Alkali Plutonium (IV) Fluorides
H. H. Anderson (Argonne Lab., Chicago)
Nat'l. Nuclear Energy Ser., Div. IV, 1k B, Transuranium Elements,

Insol. alkali Pu fluorides were prepd. by wet pptn. methods. Anal-
yses established the formulas NaPuFs5, KPuF and RbPuFes for compds. found
isomorphous with KUFs. The CsPu2F9 « 3 HpO was obtained under analogous
conditions, and KPuegg was found in a sample of unknown history. NHuPuF5 and
LiPuFs are probable compds. found under analogous conditions. The
potassium compd. is the least sol.
hly

CA U4, 3391 &

The Effect of K and La Jons on the Solubility

of Plutonium (IV) Fluoride

M. Cefola and C. Smith (Argonne)

Nat'l. Nuclear Energy Ser., Div. IV, 1lu4B, Transuranium Elements,
Pt. 1, 822-4 (1949) cf. CA 42, 821 b

Observations that pul** fluoride is insol. in the presence of K and
La ions and sol. in the absence of these iomns suggests that double fluo-~
rides are formed in the latter case. Pptns. of Puh+ with La from a MHF-
0.4t M HNO3 soln. yielded a compd. corresponding to the double fluoride
LasPuFpg+ x HoO (I). Attempts to prep. a cryst. form of I were unsuc-
cessful. Prepns. of KPuFc were shown by X-ray analysis (cf. CA 42, 7190
g) to have a rhombohedral structure isomorphous with KUFs,'KThF5, and
NaUFc .

5

CA 44, 3680 ¢

Alkali Aluminum Fluorides _

Erling Brodal and Henning Guldhav (to Aktieselskapet
Norsk Aluminum Co.)

Norw. 72,831, Sept. 19, 1949

Alkali Al fluorides, particularly cryolite, are made by dissolving
fluorspar in alkali, adding alkali aluminate and pptg. with COp, the
quantity of COp, is limited so that some free alkali remains in soln.,
and this is then used for prepg. fresh alkali aluminate by leaching
sintered or smelted Ca aluminate. The soln. may be used alternately
for extg. the alkali-fluorspar sinter and the Ca aluminate, and when
its alkalil content has increased sufficiently (e.g., to 150 g/1) the
excess alkali is pptd. with COo as bicarbonate and heated to convert
the bicarbonate to carbonate, which is then returned to the process.

CA 4k, 3681 ¢

Beryllium Fluoride

Warren S. Peterson and Charles B. Willmore (To Aluminum
Co. of Am.)

U. S. 2,487,270, Nov. 8, 1949

Be is extd. as BeF, from beryl or similar Be ores by first removing
all but 10-15% of the Si in the ore by smelting with Fe and C, forming
granules of the slag, and treating these last with anhyd. HF, first at
450-500° to remove the rest of the Si as SiF), and then at about 650° to
convert the Be to BeFo. If Al is present, it will also be converted in
this last step and must be sepd. later. The presence of C to reduce
Ho0 formed during the last step is desirable.
45

CA Mk, 3792 b

New Band Spectra of Diatomic lead Halides
K. Wieland and R. Newburgh (Zurich, Switz.)
Helv. Phys. Acta 22, 590-1 (1949)

Absorption spectra were obtained in heated wvapor for PbCl35, PbBr79,
and PbI. The bands are degraded to the violet (B-system). A further
system (A- bands), degraded to the red was observed for PbI, in both ab-
sorption and emission. Vibrational consts. were calcd. The dissocn.
energées, Do, in kcal. per mole are : FbF, 80.0; PbCl, 72.0; PbBr, 68.5;
PbI, 65.5.

cA 4h, 3829 f

The Influence of the Cation Radius on the Energy

of Formation of Addition Compds. II. The System
Alkali Carbonate-Alkali Fluoride and Alkali Sulfate-
Alkali Fluoride

O. Schmitz-Dumont and Irmgard Heckmann

Z. anorg. Chem. 260, 49-6L (1949); cf. CA ko, h312-k

Temp-compn. studies were made of the systems MF-MoCO; and MF-MpS0)
(M = alkali metal). LiF, NaF, and CsF formed only simple eutectics with
their corresponding carbonates The LiF-LioSOL system did not form a
congruent-melting compd. KF, RbF, and CsF formed compds., of the general
formula M3SOLF. A theoretical discussion of the influence of the cation
radius on the energy of formation of the compds. is given. KF and RbF
formed congruent-melting compds. of the formula M3CO3F with their corre-
sponding carbonates.

CA 44, 4210 i

Purification of Certain Alksline Earth Halides

and Crystal Products thereof

Donald C. Stockbarger and Arthur A. Blanchard (to Research Corp.)
U. S. 2,498,186 Feb. 21, 1950

A soln. contg. 60 parts HF is added with stirring to a suspension
of 100 parts CaCO; and 4 parts PbCO3 in 3 1. H50 in a lead bucket. After
gettling, the supernatant liquid is decanted. A little addnl. HF is
added to the residue and the mixt. evapd. to dryness. The dry ppt., con-
sieting of CaFo, with sbout 4% PbFo and & small emt. of absorbed HpO, is
transferred to a graphite crucible and fused in an elec. vacuum furnace.
The PbFo acts as scavenger for the commonly occurring sulfides, sulfates,
silica and oxide impurities, and ie volatilized with them and the HoO,
leaving a clear, colorless, purified melt of CaF,. The CaF, is allowed
to cool in vacuo and yields a large cryst. body of optical quality free
from impurities which cause light scattering. Other alk. earth fluorides
L6

as well as MgFo, may be prepd. similarly by using the corresponding car-
bonates. Optical crystals of natural fluorite can be produced by thor=-
oughly mixing the finely crushed mineral with PbF, and fusing.

CA 44, L4321 ¢

Phase Relations and Structural Phenomena in the

- Fluoride - Model Systems LiF-BeF, and NaF - BeFo

Della M. Roy, Rustum Roy, and E. F. Osborn (State College, Pa.)
J. Am. Ceram. Soc. 33, 85-90 (1950)

Phase equil. data are given for the system LiF-BeF, and for the BeF,
end of the systems NaF-BeF, and RbF - BeFp. The results show them to be
weakened models of the systems Zn0-S510, and Cad - 51i0,, resp., altho the
liquid immiscibility does not appear in the fluoride systems as it does
in the silicate systems. The m.p. of the cristobalite form of BeF,,
produced by the distn. of (NH)), BeF), was detd. as 543 * 50, and that of
the willemite model (LigBth) as 458 + 50, A tridymite form did not ap-
pear. Data for the compd. NaoLiBeoF- showed that its structure is similar
to that of melilite hardsytonite (CansZnSinO7). The value of data on re-
fractory oxide systems obtained by studying their fluoride models is ap-
parent from the similarity of these systems to their silicate counter-
parts.

CA L4, 4359 a

New Fluorine Compounds

Walter Huckel

Nachr. Akad. Wiss. Gottingen, Math.-physik. Klasse 1946,
No. 1, 55-6

The fluorination of metals with F and C1F,; in a V 2 A-steel-lined
autoclave proceeds easily, often at room temp. HgF, (120° for 3 hrs) is
prepd. in good yield. AgFs, CuFo, TlF3, CoF3, PtF), and PbF3 are also
prepd. Bulk Cr is unaffected. (FCN)3, b. 1500, is prepd. in good yield
from HgF, and ICN at 160°.......

CA bk, 4790 £

A Kinetic Study of the Thermoluminescence of LiF
Charles A. Boyd (Univ. of Wisconsin, Madison)
J. Chem. Phys. 17, 1221-6 (1949)

The isothermal decay of the thermoluminescence of single crystals of
LiF activated by X-rays has been detd. at various temps. The results are
interpreted in terms of a simple reaction-rate mechanism based on a
picture of the thermocluminescent process similar to that of Johnson (CA
33, 914k4). The analysis of the isothermal decay studies is in agreement
with the results of "glow curve" expts. on similar LiF samples where the
W7

intensity of luminescence is measured as the temp. of the crystal is
heated at a const. rate. Two principal types of electron traps in LiF
are found to have trapping energies of 19,800 cal/mole and 45,300 cal/
mole., resp.

CA hk, 5750 g

The Ternary Fluoride NaYF)
F. Hund (Univ., Munster, Ger.)
7. ancrg. Chem. gél, 106-15 (1950)

Two forms of NaYF) were prepd. @-NaYF}, high-temp. form, is produced
by chilling a melt of YF, in excess NaF or by pptn. frcm YClj soln. by a
large excess of NaF soln. P-NaYF), is soft, white, d. = 3.87,"m. 1100°,
cubic with lattice const. a, = 5.448 + 0.001A.; 2 mols. per unit cell.
2Na+27Y in (a) 000; 0 1/2 1/2; 1/2 0 1/2; 1/2 1/2 0; &F in (c) 1/b4 1/k
/%5 1/% 3/ 3/4; 3/h 1/4 3/4; 3/ 3/4 1/h; 3/4 3/h 3/4; 3/4 1/b 1/h;
1/% 3/% 1/4; 1/% 1/h 3/4. o-NaYF},, low-temp. form, ivory-white, brittle,
d. = 4.23, is formed by long tempering of f-NaYF) at 550 - 600° or by
slow cooling of the melt of YF3 and excess NaF; it crystallizes in a new
lattice with many X-ray lines.

CA 44, 6696 i

The Growth of Artificial Crystals and their Properties
M. Gans

Congr. groupement avance. methodes ansl.

spectrograph. produits met. (Paris) 11, 61-% (1949)

Two methods of crystal growth are outlined: (1) The method of
Stockbarger is used by Hershaw Chemicals; pure salts are place in a cy-
lindrical Pt crucible termipating in a conical end. This crucible is
placed in a 2-compartment furnace, the upper part slightly above, the
lower part{ slightly below, the crystn. temp. The crucible is then slowly
lowered thru the furnace. (2) The method of Kyropoulos is used at the
O.N.E.R.A. labs. in Toulouse; crystn. is initiated by a crystal seed
and the crystal is cooled at a very slow rate. The following tables
are given: (1) the infrared transmission of glass, quartz, mica, spinel,
sapphire, LiF, CwF,, SrF,, BaF,, NaCl, KCl, KBr, AgCl, KI, and T1(Br,I);
(2) linear dispersion in the infrared of quartz, LiF, CaF,, NaCl, KC1,
and KBr; (3) ns and sbsorption coeffs. of LiF, CaCl,, and KBr.
L8

CA 44, 7124 4

The Compressibility, Viscosity, and Surface
Tension of Aqueous Solutions of Alkali Halides
H. Krishnamurty (Andhara Univ., Waltair)
Current Sci. (India) 19, 87 (1950)

A preliminary report on the detn. of the adiabatic compressibility
B, viscosity 7, and surface tension o by ultrasonic measurements for
solns. with various concns. of KI, KBr, KF, and NaF., The empirical re-
lations, %= 2.0 x 102 pandg = ,ov-3/é x 1.2 x 10“6, where o is dens. and
v is the ultrasonic velocity, are independent of temp. and concn. for all
the halide solns.

The adiabatic and apparent molar compressibilities of alkali halides,
Ibid 87-8. The apparent molar compressibility ¢ for the KI, KBr, and KF
and NaF solns. follows from the values for B. P is not related to concn.
by Bachem's equation (CA 30, 79706) in the lower concn. ranges, but in-
stead passes thru a max. at approx. 0.3 M. In the same concn. range ¢
is not a linear function of the sq. root of concn. as predicted by Gucker's
equation (CA 27, 5233).

CA 4k, 720k 4

Problems of the Use of Chemical Fused Salt

Baths for the Separation of High- and Low-Melting Metals
Edmund R. Thews and Martin Stromeyer

Chem. Tech. 2, 157-61, (1950)

CA Uk, T60T e

The Surface Tension of Solids
R. Shuttleworth (Bristol Univ., Engl.)
Proc. Phys. Soc. (London) 634, 44k-57 (1950)

For a one-component liquid, surface free energy and tension are
equal. The surface tension of a crystal face is related to, but not
equal to, the surface free energy. Thermodynamic formulas of surface
physics are reviewed. The surface free energy appears in the expression
for the equil. contact angle and in the Kelvin expression for the excess
vapor pressure of small drops, but the surface tension appears in the
expression for the difference in pressure between the 2 sides of a curved
surface. The surface tensions of inert-gas and alkali halide crystals,
calc. from expressions for their surface energies, are neg. The surface
tensions of homopolar crystals are zero if it is possible to neglect
the interaction between atoms tMat are not nearest neighbors. Surface
tensions are calcd. for the (100) faces of the crystals of Ne, A, Kr,
and Xe and for the (100) faces of NaF, NaCl, NaBr, NaI, KF, KC1l, KBr,
KI. Except for NaF the calcd. values are neg.
k9

CA 4k, 7608 g

Elastic Constants of Lithium Fluoride
R.V.G. Sundara Rao (Indian Inst. Sci., Bangalore)
Current Sci. (India) 18, 336 (1949)

Acoustic velocities in sections (100 and 110) of LiF crystals were
detd. by the ultrasonic wedge method (CA 39, 4783-2) and the modified
plate method (CA 43, 8787p). The elastic consts. calcd. from the mean
acoustic velocities in units of 101l dynes/sq.cm. were: Cj1, 11.9; Cqp,
4.58; Cyy, 5.42. The bulk modulus K in similar units was 7.02. The
elastic moduli in units of 10-13 cm®/dyne were: 813, 10.T; S12, 2.97;

18.5. The Cy13 and Cyp Values agree with those of Schaefer and
Bergmann (Ultrasonics, 19%§, p. 180) but the C)), value does not.

CA W4, 8068 h

Soluble Aluminum Fluoride

"Montecatini" Societa Generale per 1' industria mineraria

e chimica (Franco Sciacca and Luigi Notarbartolo, inventors)
Itel. 426,332, oct. 24, 1947

AIF3- 3.5 HoO 1is crystd. from AlFq solns. by adding a rether large
quantity of the same salt at a temp. o% 22-500 with stirring. In an
example, to 10 cu. m. of AlF, soln. (20°Bé) is added 1000 kg. of salt
(contg. 52% AlF3) at 30-50°,7under 12 hrs. stirring.

cA U4, 8211 a

The Fluoride Ion as a Base in High-Temp.

Reactions with Polyphosphates

0. F. Hill and L. F. Audrieth (Univ. of Ill., Urbana)
J. Phys. and Colloid Chem. 54, 690-6 (1950)

Reactions of NaF and various Na phosphates in the fused state were
studied. The fluoride lon behaves as a strong ionic base in effecting
the depolymerization of fused polymetaphosphate and polyphosphate ions.

CA 44, 8217 h

The Ternary Adiagonal, Reciprocal System of the
Fluorides and Chlorides of Sodium and Barium

E. I. Banashek and A. G. Bergman

Doklady Akad. Nauk SSSR 56, 485-6 (1947); Chem. Zentr.
(Russian Zone Ed.) 1948, I, 1167

The surface of the liquidus curves in the system NaoF, - NaCl -
BaFp - BaClo is divided into 5 cryst. fields. The greater portion of
Y

50

this surface {about 51%) represents the field of the compd. BaFs . BaCls.
Three triple points were established: a eutectic contg. BaClo 59, NaCl
36, and NaoFo 5% at 617°; a transition point with BaF, 37, NaCl 43.5, and
N;%FE 120 5%‘: at 654C; and a eutectic contg. NeoFp 49, BaCl, 32, and NaCl
19% at 630°.

CA 44, 827k c

The Vapcr Pressure of Plutonium Halides

T. E. Phipps, G. W. Sears, R. L. Seifert, and 0. C.

Simpson {Argonne, Chicago)

National Nuclear Energy Ser., Div. IV, 1iB, Transuranium Elements,
Pt I, 682-703 (1949)

Vapor pressures of PuF,, PuCl,, and PuBr, were measured by a modifi-
cation of the Knudsen effusion method. The vapor-pressure equation is
10g Ppy = E - F/T. Consts. E. and F, resp., for the halides are: PuFg
(solid) 12.468, 21,120; (liq.) 11.273, 19400; PuCly (solid) 12.726,
15,910; (liq.) 9.509, 12,590; PuBr (solid) 13.386; 15,280; (1liq.) 10.321,
12,360. Thermodynamic quantities are for PuF,, PuCly, and PuBr,, resp:
AH of sublimation, 96.6 % 0.5, 72.8 + 0.6, ahd 69.97+ 0.3: AH of vapor-
ization, 88.7 + 6.2, 57.6 + 0.4, and 56.5 *+ 0.2; A H of fusion, 7.9 %
0.5, 15.2 # 0.7, and 13.4 + 0.3 kcal/mole.; A S of fusion 5.5 * 0.4, 14.7
+ 0.7, and 14.0 % 0.4 cal/mole/degrée.

CA 4, 8275 n

Aluminum Fluoride Hydrates

Werner Fischer, Eleanore Bock, and Karl Meisel
(Tech. Hochschule, Hannover) |

Z. anorg. Chem. 262, 54-60 (1950)

Detailed descriptions are given for the prepn. of hydrated AlF
by solution of (a) Al(OH)3,_ (b) ignited Al,03 (600°) and (c) Al metdl
in ag. HF. The first two starting materials lead to basic salts, which
are not in chem. equil. with the soln. These solns. may contaln a
peptized colloid that causes the compn. of the resulting fluoride to
depend upon the previous history of the material. Neutral Al¥F, hydrates
(mono - and tri-) are obtained from solns. of Al metal dissolveéd in
aq. HF. The monohydrate is obtained by long drying on a steam bath;
the trihydrate is obtained by exposure of the monohydrate to air satd.
with water vapor, followed by drying over concd. HoSOy. Debye X-ray
diffraction photographs support the claims for the mono- and tri-
hydrates, but cast doubt upon the existence of a 3.5 hydrate.
51

CA 4k, 8611 4

Fluoride Glass
Kuen-Han Sun and Maurice L. Buggins (tc Eastman Kodak Co.)
U. S. 2,511,224, June 13, 1950

Moisture-insusceptible glass contg. over 32% AlF, and BeF, and
fluorides and other anions of multivalent elements transmit light thru
the visible spectrum and far into the ultraviolet and infrared regiomns.
cf. CA 30, 4288-8; 43, 5165 f.

CA b4, 8713 b

Effect of Pressure on the Low-Frequency Dielectric
Constant of Ionic Crystals
Sumner Mayburg (Univ. of Chicago)

Phys. Rev. 79, 375-82 {1950)

Data on the pressure dependence of the dielec. const., € , of 5
compds. at 1000 c¢.p.s. and room temp. are given as & function of hydro-
static pressure, 0-8000 bars. The dielec. consts. decrease with an
initial slope (3 1 e¢/3 p) T (X10-5bar~1): Mg0, -0.320 * 0.019; LiF,
-0.448 + 0.028; Nacl, -0.98 % 0.06; KCl1, -1.05 # 0.08; KBr, -1.1T *
0.09. Present lattice theories are capable of explaining these data
only if the inner field decreases with increasing pressure.

CA 4k, 8ThO e

Solubilities of Salts in Water at High Temperature
Harold Simmons Booth and Richard MacPherson Bldwell
(Western Reserve Univ., Cleveland, O.)

J. Am. Chem. Scc. T2, 2567-75 (1950)

A technique for the measurement of solubilities at high temps. and
pressures was developed, in which filtration of the satd. soln. is
effected by quenching the high-pressure vessel. The solubilities of
CaF,, BaF,, and LiF and SrSQ), were measured up to, or past, the crit.
temp. of water. The previously investigated solubilities of -CasSQ) and
Nao,50)y at high temps. were checked and extended. The dependence of
the soly. of LiF in water above its crit. point on the d. of the solvent
was measured at several temps. The very low solubilities of the salts
investigated in the region of the crit. point made it seem unlikely that
the recrystn. from their pure aq. solns. of these salts would be a
practical method for the making of synthetic crystals of optical quality
unless at appreciably higher temps. and pressures. The precision of
the results obtained compared well with other measurements in the same
region, most of which required far more complex app.
52

CA hLk, 9233 g

Equilibrium in the System NaF-AlF3nH20

V. S. Yatlov and E. N. Pinaevskaya

Zhur. Obshchei Khim. 19, Fo. 1 24-31 {1949);

J. Gen. Chem. U.S.8.R. 19, 21-6 (1949)(Eng. Trans.);
cf, CA Ty 1849; 17) 3273.

The system was studied at 25° and at 75° by the thermostatic method
of detg. solubilities and by investigating the elec. cond. There are 5
regions where the stable solid phases are: (1) AlF, - 3 Ho0; (2) solid
solutions of A1F3 - 3 HpO in chiolite, which latter compd. appears to
have the formula 3 NaF - 2 A1F3, corresponding to the compd. found in the
binary system NaF-AlF», rather than 5 NaF - 2 AlF,, corresponding to the
naturally-occurring mineral; (3) chiolite; (4) solid solutions of chiolite
in NeF, with no indication of the compd. 11 NaF - 4 A1F3 previously reported
(CA 38, 3542-1), but having an upper limit of soly. corresponding to a
Na/Al ratio of 2.7 - 2.8; (5) NaF (not investigated). Binary fluorides of
Na and Al dissolve in water with decompn. and, consequently, R NaF - AlF
was not found. The compd. NaAlFj, was not isolated, but it is possible
that it is formed as a monohydrate in concentrated solutions of A1F3.

CA kb, 9234 a

Ternary Reciprocal System of Fluorides

and Chlorides of Lithium and Calcium

G. A. Bukhalova and A. G. Bergman

Doklady Akad. Nauk S8.S.S.R. 66, 67-70 (1949)

The 4 binary systems were studied previously (ef. CA 2, 502; 18, 1Lkk5).
All form simple eutectics except the system CaFo-CaClo, where there is a
peritectic point in addition to the eutectic. The reciprocal system has
6 crystn. regions where the solid phases are, respectively, LiF, CaFo . CaClp,
CaCl,, and®and & - LiCl. There are 3 eutectic points, lying on a slightly
curved line, having values of temperature (©C), equiv. % Ca, and equiv.
% F, and with solid phases in equil. as follows: 472, 22.5, 43.0, LiF +
CaFg + Licl; 450, 51.0, 6.5, CaClp + CaF, - CaClp + LiCl; and 485, 35.0,
25.0, CaFo + CaFo - Ca012 + LiCl. Between adjacent eutectic points there
are relative maximum: 492, 30, 30.0, LiCl + CaFp; and 492, 40.0, 20.0, LiF +
CaFo - CaClp.

CA 4k, 923k ¢

Irreversible-reciprocal System of Fluorides and Iodides

of Scdium and Potassium, of the Transition-to-singular Type
F. P. Platonov

Trudy Moskov. Sel'sko-Khoz. Akad. im. K.A. Timiryazeva
1946, No. 36, 42-56

The L 1ateral binary systems, and 2 diagonal binary systems, and 6
quaternary cross-sections were investigated to characterize the reciprocal
 

23

system. The system NaI-NaF is a simple eutectic system, the m. p. decreasing
from 667° for Nal to a eutectic m. 603°, contg. 18 (mole)% NaF, then rising
to 990o for Nal'. The KF-KI system is of the same type, the m.p. decreasing
from 850° for KF to a eutectic m. 5449, contg. 34% KF, then rising to 680°
for KI. Nal and KI form a continuous series of solid solutions, with m.p.

of mixtures going through a min. of 5830 at 42% KI. KF and NaF form a
simple eutectic m. T10°, contg. 40% NeF, and there is a limited range of
solid solutions, with KF dissolving in NaF to the extent of approximately

4%, and NaF in KF about 10%. The steble diagonal cross-section NaF-KI forms
a simple eutectic, m. 631°, contg. 12% NaF. This is a stable system, since
the solid phases are the pure components NaF and KI, and none of the prod-
ucts of their reaction appears in the diagream. The metastable diagonal cross-
section KF-Nal has 3 crystn. regions: a Nal region from Nal down to a
eutectic m. 5789, contg. 12% KF; a KF region from KF down to a eutectic m.
678°, contg. 78% KF, and a central region characterized by a maximum at 8400,
50% KF, and corresponding to the reaction product NaF. In this central
region, below the liquidus curve there are other metastable equil. with the
result that the curve showing the temperature of complete solidification
decreases from the eutectic at 678° to another eutectic-like point at about
540°, 60% KI, then goes through a maximum of 620° at 50% KI, decreasing to

a broad min. of 560° at 30% KI, and rises gradually to the eutectic at 5789,
From these data and those of the quaternary cross=-sections, a 3-dimensional
model was constructed for the reciprocal system, and the conventional planar
representation by projection of the model on the compn. plane. The stable
diagonal NaF-KI divides the diagram into 2 ternary systems: (1) the NaF-KI-
KF system contg. 3 regions where the solid phases are NaF, KI, and KF, resp.,
and a ternary eutectic point at 5420 contg. 95.5% K, 64.5% I; (2) the system
NeF-KI-Nal contg. 2 crystn. regions where the solid phases are NaF and solid
solution of Nal in KI, with a min. in the copptn. curve at 560 . The entire
reciprocal system thus has 3 crystn. regions, where the solid phases are NaF,
KF, and solid solutions of Nal and KI. In the NaF region, which occupies
most of the diagram because of its smaller soly., the isotherms below T00°
intersect at very oblique angles, an indication of the irreversibility of the
system and of the fact that this irreversible-reciprocal system is of the
transition-to-singular type. A comparison of the system NaF-KCl, NaF-KBr,
and NaF-KI shows that increasing heats of reaction (7.6, 9.1, and 10.6 kecal.,
resp.) are assocd. with increasing areas of crystn. of the stable components
in the resp. systems in planar representstions (73.73, 77.85, and 82.54% of
the total area, resp.) and by increasing vols. of crystn. in 3-dimensional
models (82.79, 86.78, and 87.89%, resp.)

CA Lk, 9272 e

Electromotive Phenomensa Between Metallic Aluminum

and Various Aluminum Salts. JI. The Occurrence of An
Electromotive Force Between Aluminum and Solid Salts
Horoski Nozaki and Ken Miyauchi

J. Chem. Soc. Japan, Ind. Chem. Sect., 51 3 - 4 (1948)

The e.m.f. of the cell Al/salt/Pt is measured at or below TOOC under a
pressure of 1 - 2 mm. Hg. Salts studies are: NasAlFg (I), NeF (II), AlFg3
(111), NagAlFg with 25% AlpO3 (IV), Alp03 (V), c o (VI), and NaCl (VII)
54

In every system the e.m.f. reaches a maximum at asbout 660°, while short-
circuit currents reach a maximum at slightly higher temperatures. Under stm.
pressure the maximum e.m.f. values of the systems lie within a narrow Zzone
(2.0 - 2.3 v.), but under reduced pressure the max. e.m.f. values are small
but differ from each other; I 1.68, IT 1.86, IIT 1.65, IV 1.59, VII 1.LO,

VI 0.54, and V 0.52 v. Maximum short-circuit currents also differ considera-
bly, the values for the systems IV, VII and II being 92, 21, and 2%, resp.,
of I. The maximum e.m.f. of the cell Zn - Na3AlF¢/Pt is 0.3 v. and the
maximum short-circuit current is only 6% of that of I.

CA L4l4, 9293 a

Exchange Decomposition in the Absence of Solvent-Complex
Formation, Solid Solutions, and Exchange Decomposition in
Melts of Strontium and Barium Fluorides and Chlorides

A. G. Bergman and G. A. Bukhalova

Zhur. Obshchei Khim. 19, 603-11; J. Gen. Chem. U.S.S.R. 19,
553-62 (1949) (Engl. Translation) -

The L4 pure substances have m.ps.: SrF,, 1400°; BaF,, 1280°; SrClp, 868°;
BaClp, 9580, SrCls and BaCl, form solid solutions over the entire concn.
range with a min. m.p. at 847°, 30% BaClp. SrFo and BaF, form a similar
system, with a mfn. at about 1270°, 70% BaFo - SrF, and SrClp form the compd.
SrCly « SrFp m. 962°, and there are 2 eutectics: 753°, 13% SrFp; and 9620,
63% SrFo. The compd. undergoes a phase transition at 890°, intersecting the
liquids curve at 25.5% SrFpo. BaF2 and BaCly form a similar system: BaFp -
BaClp m. 1008°; eutectics at 854°, 19% BaF, and 936°, 73.5% BaFo; and tran-
sition point 940°, 30% BaF,. The system SrCly, - SrFp - BaClp . BaFj, is
characterized by solid solutions over the entire concn. range, with a min.
m.p. at 9060, 36% BaClp - BaFp. The diagonal binary system SrClp - BaFp.
has 4 crystn. regions where the solid phases are: (1) solid solutions of
SrCls in BaClp; (2) and (3) « - and P~ cryst. modifications of solid solutions
of SrCly, - SrF, in BaClp - BaFp; (4) solid solns. of SrFp in BaFp, causing
breaks in the liquidus curve at 730°, 3.5% BaFo; 862°, 15% BaFo; 9230, 62%
BaFo. The other diagonal system BaClo - SrFo also has 4 regions: (1) all 4
pure compds.; (2) and (3) - and f- cryst. modifications of solid solutions
of the two binary compds.; (L4) solid solutions of SrFs in BaFo, causing
breaks in the liquidus curve at 800°, 15.5% SrFo; 890°, 31.5% SrFo; 917°,

57% SrF,. On the basis of the binary diagrams and of i quaternary mixtures,
planar and 3-dimensional models were constructed for the reciprocal system.
The latter shows the crystn. surface to be composed of 4 parts. There is an
almost planar surface dropping down rather steeply from the SrF, - BaFp side
to a trough, where the solid phase is a series of solid solutions of SrF, in
BeFo. Next there is a saddle, in the central portion of the diagram, the
peaks of which correspond to the 2 binary compds., and the surface then drops
to another trough; in this region the solid phases are the « - and f-modifica-
tions of solid solutions of the 2 binary compds. Finally, there is an almost
planar surface up to the SrCl, - BaC12 side, where the solid phase is a series
of solid solutions of the chlorides. As a result of the relatively small

heat of reaction of 4.6 kcal., and because of the stable complex compds.
formed in this system, the important relationships are not along the diagonals
but are in sections divided by the line connecting the 2 binary compds.
25

CA b4, 9761 4

The Configurational Free Energy of Binary Solid
Solutions of Alkali Halides

V. Hovi

Soc. Seci. Fennica Commentationes Phys. - Math. 15,
No. 15, 1 - 8 (1950) {inEnglish)

An expression is derived in sccordance with the principles of modern
statistical thermodynamics for the configurational free energy of binary
s0l1lid solutions of alkali halides in which only local order appears; the
formulas for a numerical evaluation of the expression are given.

CA 44, 9823 a

The Electrolysis of Fused Salts I. Electromotive
Force Observed in the Salt-Metal Systems

Hiroski Nozaki

J. Electrochem. Soc. Japan 16, 31 - 3 (1948)

The emf observed in some metal-salt systems enclosed in a Pt crucible
under atmosphere or reduced pressures are: 1.65 v. at 6750 for Al-AlF
1.68 v. at 630° for Al-cryolite, and 1.67 v. at 7259 for Al-NaF. The ghort-
circuit current is 100 ma. in the lst system when an Al rod 25 mm. in length
and 20 mm. in diameter and a Pt crucible of 45 mm. depth and 40 mm. in dia-
meter are used. In the 2nd system the corresponding current is very small.
In the 3rd system metallic Na is produced at both electrodes.

IT. Consideration of the appearance of the electromotive force in the salt-
metal system and its relation to electrolysis, Ibid 33-6

The emf observed in the 1lst system above can be explained by the solu-
tion of & new Al compd. which is assumed to have a lower valence, e.g.,
Al,Fg + Als=6 AIF. The main parts of the emf. of the 2nd and the 3rd
systems are probably due to the same reaction in addition to exchange
reaction as Na3A1F6 + Ale==3 Na + AloFg and 2 NaF + Al+=— 3 Na + Na3A1.F6.
These conclusions are also supported by the unpublished thermodynamic calcns.
of N's collaborators. The results obtained from the Na cryolite and NaAlpFg
systems also coincide with the above explanation.

III. Electrolysis of aluminum and sodium fluorides. Ibid. 60-2

Current voltage curves in the electrolysis of fused salts were detd. at
gtout 1000° in a graphite crucible with the molten metal at the bottom as the
cathode and a Pt wire in the fused salt as the anode. The inside wall of the
crucible was covered completely with a MgO lining to prevent the wall from
acting as the cathode. In the system with the Al cathode and cryolite the
current was very small, increased rapidly from 1.63 v. approaching a comnst.
value, and again increased linearly from 5.5 v. It was concluded that the
lst discontinuity was due to the decompn. of the A1013 - m Al dissolved in
the fused salt as assumed above, while the 2nd was due to the decompn. of
cryolite. In the system NagAlFg + AlpFgE (mol. ratio 8:2) and NazAlFg + 6 NaF
56

(mol. ratio 7:3) the lst discontinuities were at 3.6-7 and 2.8 v, resp. In
the system of NaF with & Na cathode the lst discontinuity of the lst run was
not clear, probably because of the solution of the Na formed in NaF, while
the 2nd indicated the decompn. of NaF at about 4.0 v., corresponding to the
theoretical value of 4.2 v. In the 2nd run in the same system, a finite
current was cbserved at O v. from the existence of Na already formed in the
fused NaF.

CA Lk, 9852 e

Intermediate Uranium Fluoride Compds.:
-UF , 8- UF_, UoFg, and ULFq-

P. A. Agron, ét al

U. S. Atomic Energy Comm. MDDC-1588,

8 pp (Jan. 16, 1948)

The occurrence of two allotrcpic forms of UF:- was established by means
of x-ray diffraction and chem. analysis. Chem. and x-ray analysis showed
that a black fluoride originally designated "Black UFy" was UpFg, and proved
the existence of U,F]7. The conditions of prepn. and properties of the
compds. are outlined.

CA k4, 10549 4

Electrical Conductivity of Aluminum Electrolysis
Baths With a Molten Cryolite Base

A. Vayna (Industria Nazle. Alluminio, Mori, Italy)
Alluminio 19, 215-24 (1950}

A modification of the cell of Jaeger snd Kapma (CA 15, 2772) was used
to measure the cond. of molten binary solutions of cryolite with AlpO3, NaF,
CeaFp, and AlF,, resp., at several temperatures near 1000°, and of ternary
solutions of ¢ryolite and A1203 with each of the other 3 compds. at 980°
and 1000°. Alk. baths (excess NaF) have the highest and acid baths (excess
A1F3) the lowest cond.; conds. of neutral baths and of those containing CaF2
are intermediate. Addition of Al,O, lowers the cond. of all baths, perhaps
because it raises their viscosity (Rlluminio 19, 133 (1950)). The data, pre-
sented graphically, are discussed with reference to heat production and auto-
regulation in com. Al production.

CA 44, 10560 e

The Vapor Pressure of Plutonium Halides
T. E. Phipps, G. W. Sears, et al (Argonne)
J. Chem. Phys. 18, 713-23 {1950) - see CA hk, 827k c
o7

CA 45, 430 a

The Energy of Formation of Aluminum (I and II) Halides
F. Irmann (Eidg. Tech. Hochschule, Zurich, Switz.)
Helv. Chim. Acta 33, 1L49-57 (1950) (in German)

Heats of formation AHygg of cryst. AlX and AXX, (X = F, C1, Br, I)
were calculated by means o% %he Born-Haber cycle. Lattice energies were
calculated from the Born equation and were corrected by a small term obtained
from similar compds. for which accurate AHpogg values are known. A similar

cycle was used to calculate heats of formation and of dissocn. into atoms for
gaseous AlX . Rough estimates were made of the heats of formation of gaseous
AlX, . The values of AHogg (kcal/mole) for the crystal and for the gas, resp.,
are; AlF, - 103, -50; Algl, -50, =5, AlBr, -36, 12; AlI, -19, 33; AlF,. -18k,
-11k4; AlCl,, -80, -30; AlBr,, -58, -8; All,, =27, 23. The heats of dissocn.
(kcal/mole% are: AlF, 148; A1C1l, 109; AlBr, 90; AlI, 68. For the monohalides,
the uncertainties inwAHz g are estimated to be * 10 and * 5 kcal/mole for
crystal and vapor, resp.  Values for the dihalides are less certain. The values
are used to discuss the relative stabilities; the cryst. monochalides are only
slightly less stable than the trihalides, but the cryst. dihalides are defi-
nitely less stable. Gaseous mono- and dihalides are both less stable than the
trihalides, but the cryst. dihalides are both less stable than the trihalides.

A rough statistical calen. of entropies for gaseous AlX and A1X3 made no
change in the trend. About 50 references.

CA 45, 434 4

Measurements of the Absolute Values of the
Cross-sections for Ionization of Uranium
Tetrachloride and Hexafluoride by Electrons
W. E. Berkey, E. H. S. Burhop, J. D. Craggs,
J. Keene, and H. 5. W. Massey

Nat'l. Nuclear Energy Ser., Div. I, 5, 127-4k

Foi 100-v. electrons the ionization cross-section of UCly, is about
5 x 107 > sq. cm., approx. ten times the value for argon. No value could
be quoted for UFg because of extreme variations in results.

Ionization and Dissocn. of Uranium Tetrachloride
and Hexafluoride by Electron Impact

E. H. S, Burhop, H. S. W. Massey, and C. Watt,
Tbid 145-65

The relative intensities of the ions UCln+, UCln++, cit, c1-, Uan,
UFp Y, UF, ™, Ft, F~ produced by electron impact are studied. Electron
energy, current d, and pressure were varied. Appearance potentials were
measured for all these ions.
58

CA 45, 476 1

The Large Fused-electrolyte Cells for the
Production of Aluminum

L. Ferrand

J. four elec. 59, 11k-17 (1950)

Detailed discussion.

CA 45, 489 b

Nonvolatile Inorganic Fluorides

H. J. Emeleus (Cambridge Univ., Engl.)

Fluorine Chemistry (Academic Press, Inc.,

New York) 1, 1-76 (1950)

Volatile inorg.fluorides, Anton B. Burg (U. South
Calif., Los Angeles) T7-123

Halogen fluorides. H. S. Booth (Western Reserve Univ.,
Cleveland, 0) 189-200

CA 45, 923 f

Anomalous Mixed Crystals Between #-NaYF), and YF
F. Hund (Tech. Hochschule Stuttgart, Neckarhausén, Ger.)
Z. enorg. Chem. 263, 102-11 (1950); Cf, CA 4k, 5750 g

YCl, solution was added to NaF solution to give X P Na¥F) - y ¥F
(X+ y »"1;x=0.9910 to 0.4170). Debye-Scherrer patterns show that the
lattice const. ay increases from 5.44 A to 5.52 A as y increases, but that
the structure retains its symmetry and there are no marked intensity changes.
Both observed and calcd. ds. and intensities agree if the model used has a
fixed cation lattice, and the extra F ions are put in interstitial holes,
but there is little correlation for a model with fixed anion lattice and
cation holes. The space group is Fp3,, and for a YFj-rich crystal the atoms
are in the following positions: 1.18 Na + 2.82 Y statistically distributed
in 000, 0 1/2 1/2, 1/2 0 1/2, 1/2 1/2 0; 1.64 F statistically distributed in
1/2 1/2 1/2, 1/2 00, 01/2 0, 00 1/2; and 8 F in.1/k 1/k 1/k, 1/4k 3/4 3/h,
353 1§t 3/4, 3/4 3/4 3/% 1/4, 3/4 3/% 3/4, 3/h 1/% 1/4, 1/4 3/4 1/4, 1/
1/4 3/4, '

CA 45, 967 g

The Fluorides of Niobium, Tantalum, Tungsten
and Rhenium

H. J. Emeleus and V. Gutmann (Univ. Chem. Leb.,
Cenbridge, Engl.)

J. Chem. Soc. 1950, 2115-18; cf. CA Lk, 5242 g

Attempts were made to prep. the lower fluorides of these elements from
the metals and from other lower halides by reaction with HF. A lower chloride
of Wb (cf. Sue, CA 33, 8132-9) reacted sbove 500° and Nb powder reacted at
29

250-300° to give NbFs. Nb previously heated in H at 250° gave mainly NbF
but also an unidentifiedblue film, possibly the lower fluoride of Ruff an
Schiller (CA 6, 839). Ta or Ta preheated in H gave a mixture of nonvolatile
TeF3 (10%) and volatile TaFg5 (90%) at 300°. WBrp, prepd. from WBr5 end H,
gave partial reaction at 550° to undetd. products and at 600° gave WFG and
W; metallic W was unattacked up to T7O0°. Re also did not react, and ReClj
at 350° gave Re and possibly a little ReFg. WFo and ReF, may form, but are
unstable at these temperatures.

CA b5, 1414 f

Thermodynamic Properties and Equilibrium at High
Temperatures of the Compds. of Plutonium

L. Brewer, L. Bromley, P. W. Gilles, and N. L. Lofgren
(Univ. of Calif., Berkeley)

Nat'l. Nuclear Energy Ser. Div. IV, 14B, Transuranium
Elements, Pt. II, 861-86 (1949)

Values of the thermodynemic data for Pu compds. are given, including
m.p., b.p., and vapor-pressure data. Alsoc given are: the consts. for the
free energy of vaporization equation together with heat and entropy of
vaporization at the b.p., values of the free-energy function, (aF -AI—I298)
/T, and AH,qq, the heat of formation, and the heat, free energy, and
entropy of ?ormation for the aq. ions. Values given are often estimates
detd. by analogy with U and rare earth metals. The high temperature chemistry
of the compds. is discussed. The equil. concns. of halogen or halide in Pu
and halogen systems at 3 different pressures; namely, 1, 10’3, and 10-° atm.
are presented.

CA 45, 1836 a

The Crystal Modifications of Lead Fluoride
Ya. Sauka (Latvian State Univ.)

J. Gen. Chem. U.S.S.R. 19, 1453-7 (1949)
(Engl. Translation) See CA 44, 896 1

CA 45, 1890 c
Dehydration of Alkali Metal Acid Fluorides
Robert C. McHarness and Anthony F. Benning (to the U.S.
of America as represented by the Atomic Energy Comm. )
U. S., 2,527,320, October 24, 1950

Correction of Patent No. (see CA 45, 52 a)
60

CA 45, 2278 b

Revieed Dielectric Parsmeters of Alkali and

Halide Ions

Shepard Roberts (G. E. Research Lab.,

Schenectady, N. Y.)

Phys. Rev. 81, 161 (1951); cf. CA Lk, 392 4, 2811 f.

The ionic parameters, nuclear charge, nuclear compliance, electronic
compliance, dielec. polarizability, and optical polarizability are tabu-
lated for Li, Na, X, Rb, Cs, F, C1l, Br and I.

CA 45, 2380 d

Metallurgical Reactions of Fluorides
Herbert H. Kellogg (Columbia Univ.)
J. Metals 191, Trans., 137-41 (1951)

Graphs representing the standard free-energy of formation as a
function of temperature for fluorides of Cl, Se, Te, C, S, As, Ag, H,
v, Cd, U, B, Mn, Si, Al, Mg, K, Na, Ba, Ca, and Li are presented, along
with estimated values for the standard free-energy of formation of Au, Hg,
Cu, Co, Bi, Sb, Fe, Ni, Sn, Zn, Cr, Ti, Zr, and Be fluorides. A few of the
many possible uses of these data in metallurgical calculations are dis-
cussed, including the fluorination of oxides, sulfides, and chlorides,
and the reduction of metal fluorides.

CA 45, 3740 n

Lining for Fused Salt Electrolysis Cells
Adem I. S. Duncan, J. G. Moore, and Imperial
Chem. Industries Lt4d.

Brit., 647,313, December 13, 1950

In cells for the electrolysis of fused salts or salt mixtures, a
lining is provided for the protection of the refractory wall of the cell
from attack by Cl, Nas0, etc. A satisfactory lining or shield is made
of mild steel. The lining prevents contact of the fused electrolyte with
the refractory wall and thus eliminates contemination of the electrolyte.

CA 45, 4993 b

Precision Lattice Constants and Coefficients of
Thermal Expansion of PbF2

Ya. Sauka (Riga State Univ.)

Zhur. Fiz. Khim. 25, 41-8 (1951)

By means of Straumanis' asym. method (CA 43, 8859 a) lattice consts.
of single crystals of PbFo are detd. At 189, a = 5.92732 + 0.00001 A. for
the cubic modification (I% and a = 3.89098 + 0.00003; b = 6.42689 + 0.00002
C = 7.6357h + 0.00018 A. for the orthorhombic variety (II). From detns.
61

at 3 different tempegatures, the expansion coeffs. are calecd.: (= 2§.8 x
1070, & = 86.4 x 1070, for I and oy = 31.9 x 10-6, oc, = 37.1 % 1070, o 5
= 13.6 x 10-6, 4 = 82.6 x 1076 for TI.

CA 45, 5014 b

Thermodynamic Functions of AlLC3, Si, 8i0p, SiC,

AlF, and NasAlFg

L. 1. Ivanova .

zhur. Obshchei Khim. (J. Gen. Chem.) 21, khk4-52 (1951)

The thermodynamic functions were calcd. from heat capacities, partly
taken from the literature, partly calcd. by Debye's formmla. Selected data
of Cp, Hg - Hys Sp - S, and - (Fp - Fy) are: For 1/4 AlF3, at 100, 500,
1000, 13009%K.; 3.%, 11fi, 1.52, 0.5; 5.2, 1915, 8.41, 2290; 7.4, 5029, 12.67,
7611; 8.6, 7229, 1k.T77, 11972. For 1/10 Na3AlFg at 100, 500, 1000, 13009%K.;
3.00, 112, 1.50, 38; 6.13, 2122, 9.11, 2433, 7.29, 5524, 13.81, 8286; 7.kl
7728, 15.73, 12721.

CA 45, 6476 e

An Example of a Particular Solidification Diagram
in a Reciprocal System of Fused Salts

Andre Chretin, Pierre Silber, and Mohammsad Ishaque
Compt. rend. 232, 1217-18 (1951)

Curves of cooling were plotted for the system KC1l + NaF= NaCl +
KF. Five solid phases with 3 series of mixed crystals were found. KC1
and NaF crystallize separately, forming a stable couple. The diagram
shows a eutectic for KCl, KF, and NaF at 5820 with 49% F and 90.5% K.
Another equil. corresponds to & temp. min. (at 6120 with 50.5% K and
9.25¢% F) of crystn. of the solid soln. NaCl-KC1l with the addn. of NaF.

CA 45, 6483 e

Study of Ionic Crystals under Electron Bombardment
D. E. McLennan (Univ. Toronto)
Can. J. Phys. 29, 122-8 (1951)

Alkali halide crystals bombarded within an electron microscope
show a generalized photographic effect. In macro-crystals (0.2-0.002
cm.) equil. F-center formation slowly reversible after bombardment
ceases, and stable entrapped metal colloids in the crystal lattice
were observed. Jonization pulses were noted only during bombardment.
In micro-crystals (10-0.01 i) electron-diffraction techniques showed
the presence of metal, oxide, or carbonate after bombsrdment of
halide. A postulated sequence of events under bombardment includes
ionization, capture of Cl- electron to produce C1°, migration of C1°
to exterior of crystal and disintegration of crystal from center out.
62

CA 45, 6485 a

Electronic Structure of the F-Center in Alkali

Halide Crystals

Toshinosuke Muto

Rept. Inst. Sci. and Technol. Univ. Tokyo 1, 140-5 (1947);
cf. C.A. 44, 87751 -

Two perturbation methods for solving the Schrodinger equation
for an electron captured in the F-center are suggested; the 1lst method,
which corresponds to the at. wave function approximation, is based
on the assumption that the potential due to the surrounding iomns in
the crystal lattice is approximated by the periodic static potential
due to perfect lattice (that part due to the missing neg. ion is sub-
tracted). The 2nd one, which corresponds to the mol.wave function
approximation, is based on the assumption that the potential is ap-
proximated by the sum of that due to the nearest ions and that due
to the other ioms.

CA 45, 6485 b

Theory of the F-Absorption Band in Alkali Halide Crystals
Toshinosuke Muto

Rept. Inst. Sci. and Technol. Univ. Tokyo 2, 37-42 (1948);
cf. preceding abstr. -

Theoretical. At sufficiently higher temps. than the Debye char-
acteristic temp. of the NaCl crystal, the F-absorption max. shifts to
the longer-wave-length side linearly with rising temp., and at suffi-
ciently lower temps. more slight dependence on temp. is to be observed.
The breadth of the absorption band increases with rising temp. un-
symmetrically on both sides of the band center.

CA U5, 6485 ¢

Theory of the Kerr Effect in Colored Alkali

Halide (Preliminary Report)

Mitsukuni Watanabe

Rept. Inst. Sci. and Technol. Univ. Tokyo 2, 139-40 (1948)

The Mott-Tibbs model for F-centers in alkeli halide crystals
(Tibbs, C.A. 34, 1907-1) suggests that the Kerr const. in colored
alkali halide crystals becomes infinite at the wave length corre-
sponding to the energy difference between 1ls-2p, or ls-28 levels.
63

CA 45, 6515 b

Electrolytic Cleaning of Metals
Hugh G. Webster (to J. H. Shoemaker)
U. 8., 2,547,510, Apr. 3, 1951

A bath for the electrolytic cleaning of oxide and scale from
ferrous metals consists of NaOH 85, NaCl 10, Na aluminate 1, NaCKN 2,
and NaF b4 parts.

CA J"‘5) 6525 g

New Compounds Containing Active Fluorine
Hans Bode (Chem. Staatsinst., Hamburg, Ger.)
Naturwissenschaften 37, 477 (1950)

Reaction of F, with halides of K, Rb, and Cs gives, not fluorides,
but MF, for K and Rb and MF; for Rb (?) and Cs as intermediary products.
The MF, compounds are optically isotropic and cubic. CsFz is aniso-
tropic and probably rhombic. The compds. liberate I from KI solns.;
they color free NiCl, red with formation of My(NiFg); they are white
and hygroscopic. By reaction of F, with mixed alkali halides, compds.
such as KF3:RbF3 and RbgSbFpy (in the presence of Sby03) are formed.

CA 45, 6535 ¢

Fluorine and Fluorocarbons

G. W. Busch, R. C. Carter, and F. E. McKenna (Univ. of Chicago)
Natl. Nuclear Energy Ser., Div. VIII, 1, Anal. Chem. Manhatten
Project 226-48 (1950) -

The chemistry of F is reviewed with particular regard to properties
that can be used for detg. the element. Many F compds. can be decompd.
by heating with powd. silica % Ho80y or HC1lOy- The HpySiFg formed
distils off and is thus removed from the mineral. To avoid the action
of F or HF on the container, special Pt app. is required of which 4
illustrations are shown. Fusion with NaoCO; gives water-sol. NeF.

UF), can be dissclved in a mixt. of H3B03 ana HC1, AlCl3 % HC1, H3B03 %
HpSO), or HCL # HNOg «..on...

cAa 45, 6833 ¢

Fluorine-Resistant Lubricant
John F. Gall (to Penn. Salt Manufg. Co.)
U. S., 2,548,471, Apr. 10, 1951

A fluid mixt. of 1-7 moles of HF to 1 mole of KF possesses good
lubricating properties and is inert to gaseous or liquid F. The compn.
mey be used from O to 300°. Smaller proportions of HF are sufficient
at higher operating temps.
6k

CA 45, 6931 £

X-Ray Luminescence Spectra of Alkali Halides
Aparesh Chatterjee (Calcutta Univ.)
Indian J. Phys. g&, 265-70 (1950)

Spectrograms covering the range of 2750-7000 A. are shown for X-
ray-excited crystals of NaF, NaCl, NaBr, KBr, KI, KBr + T1Cl (Mech.
mixt.) and KBr + Tl (solid soln.). Other alkali halides showed little
or no glow when irradiated; however, all showed a characteristic color
change. The emission bands were not characteristic of any impurities
present, and hence represent lattice emission. The importance of
lattice-emission spectra in elucidating the electronic energy states
of solids is discussed.

CA L5, 6989 b

Aluminum Welding Fluxes
Mike A. Miller and Warren E. Haupin (to Aluminum Co. of America)
U. S., 2,522,104, Mey 8, 1951

Improved arc stabilization, fluxing action, and slag removal were
obtained with new flux compns. of nonhygroscopic salts with the follow-
ing typical analysis: NaCl 33, KCl 34, LiF 15, AlF, 10.5, NaF k4.5, Ca
or Sr sulfate 3%. In coating the welding rod, the bare Al rod is
heated to 1020CF. before dipping into the flux bath, which varies from
1110 to 1200°F. In U. S., 2,552,105, the flux compn. contained NaCl
33, KC1 33, LiF 15, AlF; 7.5, MgFpo 8 and Ca or Sr sulfate 3.5%. 1In
U. s., 2,552,106, the flux compn. contained NaCl 30, KC1l 33.5, LiF 1k,
AlF3 T, MgFp 9, NaF3, and Ca or Sr sulfate 3.5%. Cf. C.A. 4k, 63801i.

CA 45, 7852 ¢

Distribution of the Thorium Isotope U X, Between

Lanthanum Fluoride Crystals, and its Saturated

Solutions in 3 and 12% Nitric Acid at 100°

V. G. Khlopin and M. S. Merkulova

Doklady Akad. Nauk S.S.S.R. 65, 861-4 (1949) cf. CA bk, 6241 b

The system UX; (Th)F)y-LaF3 is particularly interesting because it
is analogous to the system YF;-CaFo, in the formation of "anomalous mixed
phases" (cf. CA 24, 1005). The distribution equil. is detd. from both
sides by approach from an active satd. soln. with inactive crystals and
from an inactive soln. with active crystals. The equil. is established
in 48 hrs., but even after 8 hrs. the av. of the coeffs. K(p) (the ratio
of the enrichment and impoverishing coeffs.) for both types Of reactions
is detd. with sufficient accuracy. With decreasing concn. of the Th
isotope in the soln., K continucusly decreases to zero. This is the
same phenomenon that was Observed in systems of an inorg. host crystal
65

with an org. foreign substance included (cf. CA 35, 3870-7). The low
limit of miscibility characterizes the cryst. soln. in such a case as
a pseudo- (anomalous) mixed-phase pehnomenon. |

CA 45, 7857 i

Thermodynamics of Fluorine-Chlorine Exchange Reactions -
Systems NaF-NaCl, BaF,-BeCly, NiFo-NiCly, and PbCIF-FbCl
G. C. Hood and M. M. Woyski (Univ. of Wisconsin, Madison
J. Am. Chem. Soc. T3, 2738-41 (1951)

The metal fluorides were prepared by reaction of anhyd. HF with the
corresponding chlorides. Analysis of the kinetic data permitted calcn.
of free energies for the exchange reactions. Thus, an evaluation was
made of the thermodynamic fluorinating ability of each fluoride. In de-
creasing order of ability to fluorinate, these were found to be BaFp,
NaF, PbCIlF, NiF, and HF.

CA 45, 7863 i

The Nonreversible, Reciprocal, "Two-ridge" System of

the Fluorides and Chlorides of Barium and Potassium

E. I. Banashek and A. G. Bergman

Doklady Akad. Nauk S.S.S.R. 57, 905-6 (1947); Chem. Zentr.
(Russian zone Ed.) 1949, I, 2; cf. CA 4k, 8217 h

A study made of the 4 binary systems belonging to the quaternary
system: Ba - K - C1 - F verified the results of Ponomareff (CA 9, 1435),
Plato (CA 2, 502, 3019), and Gemsky (CA 8, 2536). The visual poly-
thermal method was used for the investigation. Two diagonal and 23
interior lines (of intersection) form the square liquidus diasgram of
the reciprocal system. The pure salts are represented at the corners
of the square. The most sharply defined, stable line of the system
is the KoCl,-BaFo line. The next in order of stability is the K,Clp~
BaF,-BaCl, line. The BaF, region occupies 50.12% of the field; next
is the BaF,*BaCl, region %28.13%). These two fields are characterized
on the space model by two sharply defined ridges (space folds). There
are U eutectics at 575° (BaFo, KoFs, KoClp), 616, 625, and 728°. The
last 3 contain no KoFo. The nonreversible, reciprocal system of the
diagonal type is characterized by the formation of the compd. BaF, ¢
BaCl,, which does not affect the direction and displacement of the
displacement reactions. This is also true of the chlorides, which
occupy only 0.75% of the liquidus field.
66

CA 45, 8315 i

A Quantum-Mechanical Treatment of the Lithium
Fluoride Crystal

G. C. Benson and G. Wyllie (Bristol Univ., Engl.)
Proc. Phys. Soc. (London) 64A, 276-82 (1951)

A simplified quantum-mech. model for the LiF crystal is described.
The lattice parameter, cohesive energy, and compressiblity are calcd.
by use of 3 different choices of wave function for the F~ ion in the
crystal; these are (1) the Hartree wave functions for the free ion F~,
(2) wave functions orthogonalized to the ls-orbitals of the 6 nearest
neighbor Li ions, (3) functions similar to 2 but based on wave functions
for the free ion, that have been contracted to give agreement with the
- diamagnetism of F~. The results obtained in (1) are in fair agreement
with the empirical values. ILarge discrepancies are observed when the
more complete wave functions (2) are used; this indicates that the
Hartree wave functions for the free ion are too diffuse. Results of
(3), which agree well with expt., substantiate this interpretation.
It is assumed that the metal and halogen ions are arranged in the usual
cubic lattice array and that the structure is completely ionic. Purely
central forces act between ions, and the force between two ions that
are not nearest neighbors is considered to be the ordinary electro-
static term. Only uniform lattice deformations are allowed, and the
energy assocd. with the thermal vibration of the ions is not considered.
Repulsion between the closed shells of the halogen ions is probably
gignificant in most Li halides. An exam. of the ratios of the radii
of the various halogen ions to that of the Li% ion indicates that only
in the case of F is there some justification for neglecting this effect.

cA 45, 8339 4

Equilibrium "Liquid-So0lid" in the Ternary System
Formed by the Fluorides of Na, K and Ca

Pierre Silber and Mohammad Ishaque

Compt. rend. 232, 1485-7 (1951); cf. CA L5, 6LT6 e

The study by thermal analysis (curves of cooling) shows for CaFo-
NasFo, a eutectic (a) at 810° (51% NaoFp); for NasFo-KoFp, two series of
mixed crystals with a eutectic (b) at 722° (61% KoFp); for KoFo-CeFo,

a double salt CaF,* KF, after fusion at 1068° forms a eutectic with
each salt (c) 26.T% CaF, at 782° and (4) 76.9% CaFp at 1060°. Four
solid phases appear: for CaF,, a double salt KF - CaFp and two series
of mixed crystals NaF - KF: series I rich in NaF and series II rich in
KF. The corresponding areas in the plot are bounded by 5 lines for
the 2 sclids which det. 2 points; (e) at 682°, 14% CaF,, 50% KoF, and
36% NasFo; and (f) at 772°, 3b% CaFp, 19% KoFp, and 47% NasFo.
67

CA U5, 8368 £ -

Sodium?® from the Gamma-Ray Bombardment of
Sodium Fluoride

R. K. Sheline (Univ. of Chicago)

Phys. Rev. 82, 95k (1951)

Alverez has regorted (CA 45, 956f) the reactions Ne?C(p,n)Ne®C;
Na=0 ———=dd / 20 ‘has an al hamdecay By using 76 m.e.v.
betatron gamma- rays, the reaction Na®3 (,3n) - NaQ was obtained.
The /3/ half-life is 0.23 £ 0.08 sec. The end point of thgd*“ spec-
trum lies in the range 3.5-7.3 m.e.v.

CA 45, 9978 a

Thermal Expansion of Crystals. IV. Silver Chloride,

Lithium Fluoride, and Magnesium Oxide

S. S. Sharma (Indian Inst. Sci., Bangalore)

Proc. Indian Acad. Sci. 324, 268- T4 (1950); cf. CA 45, T8k2e

Coeffs. of linear expansion are given for the compds.: AgCl to
3259, ocy = 0.03136 - 0.071588t é 0.0 2038t ; LiF to 3809, ocy =
0.043376 £ 0.072054% £ 0. oloh885t MgO to T10°,0C ¢ = O. Ou109§ /
0.0g5865 # 0.0771052t“. Gruneisen's consts. calcd. for AgCl above
room temp. and for LiF from -222° to 4OO° vary markedly with temp.

cA 45, 10024 4

Silicate Models. II. The System Sodium Fluoride-Beryllium
Fluoride and its Relations to the System Calcium Oxide-Silica.
Erich Thilo and Hans jurgen Schroder (Humboldt Univ., Berlin)
7. physik. Chem. 197, 39-62 (1951); cf. C.A. U4, 1316g

The system NaF-BeFo was studied by thermal analysis to a BeFo
content of 61 mole %; only solid solns. exist above this compn. The
results are completely analogous to those for the Ca0-S5i0, system.
The temps. in ©K. of almost all invariant points in the fluoride
system when multiplied by 2.82 are converted to the corresponding
points in the silicate system. The definite compds. found and their
m.ps. are: NaF 990°, NasBeF) 578°, NaBeF g 372°, Na 3BegF 3480 (in-
congruent). The eutectic NaF-NaoBeF) occurs at 31 mole ; BeF» and
m. 560°; NagBeoF7-NaBeF3 at 44.3% and m. 340°. 1In the subsystem
NaF -Na~BeF), there is formed by a solid~state reaction NagBeF
alpha and beta modifications of NaoBeF) were definitely iden ifled
3 addnl. modifications were established with high probability, and
the beta and alpha modifications of NaBeF, were detected. The
various transition temps. were detd. Incidental results show that
the thermal decompn. of (NH))oBeF) occurs in 2 steps; the interme-
diate product NHLBeF3, stable between 230 and 270°, has a charac-
teristic x-ray diagram.
68

CA 46, 837 ¢

Surface Tension of the Cryolitic Molten Baths
A. Vajna (Lab. ric. ind. nazl. allum, Mori, Italy)
Alluminio 20, 29-38 (1951); cf. C.A. 45, 5043 e

The baths contg. CaF, have a surface tension greater than the alk.
baths and these greater than the acid baths. The neutral baths are
intermediate. The obtained results of the surface and interface
tensions of the phases in contact (solid-liquid-gas, liquid-liquid,
and liquid-liquid-solid) are used to explain some peculiar phenomena
happening in the electrolytic industrial cells; chiefly the amodic
effect.

CA 46, 1222 g

Potassium Titanium Fluoride
Henry C. Kaweckli and Edwin J. Bielecki (to Beryllium Cor.)
U. S., 2,568,341, Sept. 18, 1951

The process is described for the production of high-purity NasTiFg,
KoTiFg, and (NH))oTiFg from Fe-bearing titaniferous raw materials,
ilmenite ores, or a slag concentrate. The raw material is digested
with sufficient HF (60% com. grade) in water soln. to form a soln. contg.
TiF), and FeFp, and the insolubles are sepd. A salt of the alkali whose
fluotitanate is desired is added to the soln. at 709, with excess HF.
The alkali salt should have an anion (chloride or nitrate) which will
form a ferrous salt more sol. than FeSQy. The desired fluotitanate is
crystd. out of the soln. to which 5% HoSO) has been added for each 50%
HF by wt., to produce large crystals. After decantation, the crystals
are filtered or centrifuged.

CA 46, 1336 g

The Theory of Electrolytic Solutions. II. Integral

Heat of Dilution of Electrolyte.

Tatsuro Watari (Tokyo Imst. Technol).

J. Electrochem. Soc. Japan 19, 189-92 (1951); cf. CA 45, 3222i, 8328b

By taking into account the undissocd. mol. MfA' and its mono-
hydrate Mf(HQO)A', the integral heat of uni-univalent electrolytes is
calcd., and applied to LiCl, KF, and NaCl.
GENERAL INFORMATION CONCERING FLUORIDES

Index

69

The numbers following the subject headings indicate the page on

which the reference is found and the abstract number on that page.
instance, under Actinium oxide 42-2 indicates page 42, the second

abstract on the page.
A

Actinium oxide
Actinium oxybromide
Actinium oxychloride
Actinium oxyfluoride
Actinium phosphate
Actinium trifluoride
Activity coefficients
Alkali metal acid
fluorides
Aluminum
Aluminum bromide
Aluminum carbide
Aluminum chloride
Aluminum fluoride

Crystal data
Density
Electromotive
phenomena
Entropy
Free-energy of
formation
Heat of dissocia-
tion
Heat of evaporation
Heat of formation
Magnetic suscepti-
bility
Molecular volume
Preparation
Sublimation
temperature
Systems

Vapor pressure

422
Lo-2
ho-2
h2-2

N =
TR
Moo

t 1

1
(ol AV WHEMPDNDWMPDPDW N W E

M U1V =3 2~ o\

'

H W e L O\ =\

O N
S [
n

n

1 !
MR FMNOND Www

S O

nw Mo

37-3

4h-3

55-2

k-3
20-2
26-3
32
56-3
25-2
25-2

55-2
61-2

61-2

23-2

63-3
12-3
21-k
27-3
00-3
58-2
28-2
27-3

For

64-2

142
252
28-3
53-2
64-2
70

Aluminum hydroxide 50-3

Aluminum iodide 20-3

Aluminum oxide 1 16-4 21-3 21-4 23-.1 24-2 25-2

20-1  50-3 53-2  56-3

Aluminum sulfate 30-1

Americanium oxides ho-2

Americanium trifluoride 42-2

Ammonium acid fluoride 24-1

Ammonium aluminum

26-1

fluoride 14-1  52-1
Ammonium beryllium
fluoride 32-1 38-3 h6-2 67-3
Ammonium chloride 38-2
Ammonium fluoride 30-2 32-1 37-2
Ammonium magnesium
fluoride 36-1
Ammonium plutonium
fluoride 43-3
Ammonium silicon
fluoride 34-2
Ammonium titanium
Pluoride 68-2
Antimony fluorides 60-2
Antimony trioxide 63-2
Argon 48-3
Arsenic fluorides 60-2
B
Barium 19-1
Barium chloride 16-4 4o k4 54h-2 65-1 65-2
Barium fluoride 14-2 15-3 16-4 17-1 18-1 19-1 19-k
20-1 20-2 20-4 21-2 22-3 244 25-3
27-3 28-1 28-2 47-3 494 53.3 5h4-2
58-2  60-2 65-1 65-2
Boiling point 20-2 ‘
Density 18-1 20-4 21-2 25-3 28-1 28-2
Entropy 2L-Y4
Free-energy of
formation 60-2 65-1
Heat of evapora-
tion 20-2
Heat of formation = 14-2 22-3
Heat of reaction 22-3
Melting point 25-3  54.2
Preparation 16-4 65-1
Specific heat 20-1 24-4
Systems 15-3  16-4 17-1 18-1 19-1 20-4 21-2
22-3 25-3 27-3 28-1 28-2 Lh9-4 s5h-2
5-2

Trouton's constant 20-2
Vapor pressure 20-2
Barium hydride

Barium thorium
fluoride

Barium titanate

Barium uranium
fluoride

Beryl

Beryllium

Beryllium fluoride

Crystal data
Free-energy of
formation
Melting point
Preparation
Systems
Beryllium hydroxide
Beryllium oxide
Beryllium sulfate
Bismuth
Bismuth trifluoride
Boiling points
Boric acid
Boron fluorides
Bromine

¢

Cadmium fluorides
Cadmium sulfates
Calcium

Calcium sluminate
Calcium carbonate
Calcium chloride
Calcium fluoride

Boiling point
Catalytic activity
Crystal data
Density
Dielectric effect
Electromotive
phenomena
Entropy
Free-energy of
formation
Heat of evapora-
tion

15-k

§2-2
36-3

ho-2
1h-3
30-2
2h.1
51-1
32-1

60-2
38-3
2k-1
30-2
2k-1
24-3
39-1
32-2
26-4
12-1
63-3
60-2
60-1

26-1
32-1
24-3
26-1

14-2

47-3
12-4
22-3
41-3
52-2
68-1

17-2

4h-3
26-2
60-2
51-1

20-2

52-2
14-2
22-4
yo-1
23-2

22-14

30-2

26-4

15-4
25.1
yo_2

25-1

321

32-1
67-3

43-2

58-2

28-2

38-3

4.3

60-2

Tl

4h-3
Heat of formation
Heat of fusion
Heat of reaction
Melting point
Preparation
Sintering tempera-
ture
Solubility
Specific heat
Surface tension
Systems

Trouton's constant

Vapor pressure
Calcium hydride
Calcium hydroxide
Calcium iodide
Calcium metatitanate
Calcium nitrate
Calcium oxide
Calcium sulfate
Calcium thorium

fluoride
Calcium zinc silicate
Carbon (graphite)
Carbon dioxide
Carbon fluorides
Carbon-silicon steel
Carbon tetrafluoride
Carbonyl fluoride
Catalytic activity
Cerium aluminate
Cerium chloride
Cerium-platinum
Cerium tetrafluoride
Cesium
Cesium bromide

Cesium carbonsate
Cesium chloride

Cesium fluoride

Boiling point
Critical tempera-
ture

Crystal data
Density

Heat of formation

Heat of vaporiza-
tion

B
HfFww

no
Y

V1 w = MDD OW O ot
EROGPS FrOaSSERBFE X

t

t

§
FPMPOPWLWMPODPDFODHFHFDPDWMNOORERWEHEPDEMNDID WEFEFNDNDWEHEFODDOND FHEFEWE

RS DS D S E S ERESRE o 5KE

b O\
ouw
o e

-
T

~
P
~

21-1

17-2
56-3

O . ONWN

1
R & ED

o) WL
e iy
+w

62-1
Lo-2

Lo-2

31-3

19-1
64-3

67-3

10-1
62-3

11-2
6-1

35-1
62-1

62-2

41-3

22-3
66-2

4h-2

11-2

37-3
10-1

ho-2
62-2

62-3

25.1

37-3

61-4
11-2

41-2
62-3

63-2

28-2

T2

52-2
Ramsay-Young
Constant
Specific heat
Specific surface
energy
Systems
vVapor pressure
Cesium fluosulfate
Cesium hydride
Cesium hydroxide
Cesium iodide

Cesium lanthanum
fluoride

Cesium nitrate

Cesium oxide

Cesium perchlorate

Cesium plutonium
fluoride

Cesium sulfate

Cesium yttrium
fluoride

Chlorine

Chlorine monofluoride

Chlorine trifluoride

Chromlic chloride

Chromic fluoride

Chromic nitrate

Chromic sulfate

Chromium

Chromium-carbon steel

Chromium-nickel steel

Cobalt

Cobaltic fluoride

Cobaltons fluoride

Copper

Copper bromide

Copper-magnesium
alloy

Copper sulfide

Critical temperatures

Cryolite

Crystal data

Cupric fluoride

§

o
Py

HE DOV W
S

W

HEWWODW £FW
1
WWHHFWHWRW

=
Y
no

'

$2EEEY
W kWM N

&

30-3
58-2

1

W N W
VI B N0 10 FNn £
FOOENDR &R DP

o7-2
60-2
60-2

58-2

16-L4
25-2
Yh-2
15-4
23-2
29-3
38-2
47-3
51-3
62-3

55-1

11-2

60-1

60-2

58-2

37-3

60-3

60-2

19-4
28-1
55-2
17-2
2542
32-1
Lo-2
49-1
59-3
64-1
58-2

hi-2

61-4

73

61-4

21-4
28-3
61-2
20-3
28-1
3h4-1
h1.2
20-3
61-4
Cupric sulfate
Cuprous chloride
Cuprous fluoride
Cuprous iodide
Cuprous oxide
Cyanogen fluoride
Cyanogen iodide

D

Decomposition potential
Densities of fluorides

Dielectric effect

E

Electromotive
phenomena

Entropy

Europium chloride

F

Ferric fluoride
Ferrous fluoride
Fluorine

Fluorspar
Fluosilicic acid
Free-energy of
formation
Fused salt baths

G

Glass
Gold fluorides
Gruneisen's constants

H
Bafnium fluoride

Heat of formation
Heat of fusion

?\0\\'114:‘-!:‘
MR WPEHFEWMPDMNDPD

£ ON O\EG\-F"UOI—‘I—‘
I

ODC|DU)

L2-2
14-2
31-3

12-2
58-2

11-3
20-3
27-1
48-1
42-1

61-2
60-

W

51-1

60-2

12-2
20-4
27-3

51-2

56-3
31-3

58-2
60-2
L0-1
60-1

65-1

22-3

21-2
28-1

36-2

60-2
68-2
Lo-2
61-3

30-3

41-3

4o-1

16-1
25-1
29-3

>T-1

Lo-2

Th

18-1
25-2
3h-1

61-2
Heat of reaction
Heat of vaporization
Hydriodic acid
Hydrobromic acid
Hydrochloric acid
Hydrofluoric acid

Hydrogen perchlorate
Hydroxyhalides

I

Iodine

Iron

K

Kerr constant
Krypton

L

Lanthanum

Lanthanum chloride
Lanthanum fluoride

Lanthanum
Lanthanum
Lanthanum

oxide
phosphate
plutonium

fluoride
Lead
Lead acetate
Lead bromide
Lead carbonate
Lead chloride
Lead fluoride

Crystal data

Density

Dielectric constant

Dissociation energy

Free-energy of
formation

Heat of formation
Heat of reaction
Polarization
potential

w

\J'IO\I'\)—QOI;\)-F'O\\HO\—Q
HWMPMPPPMPODNDPDWNDND

=
oy

£ =W W
P i

N H oON
b Fo
w

31-1

23-1
20-2

4hy-1

25-1
64-3

4h-3

33-k

22.3

75

Lo-2
40-1  40-3  U4-3  L45-3
60-2 63-3 63-4 65-1
68-2
34-1 35-1 35-2 Le-2
14-2 16-3 22-3 31-1
b5-1 45-3  58-2 59-3
60-4
Systems

vapor pressure
Lead fluorochloride
Lead monobromide
Lead monochloride
Lead monofluoride
Lead monoiodide
Lead monoxide
Lead nitrate
Lead orthophosphate
Lead thorium fluoride
Lead trifluoride
Lead uranium fluoride
Lithium
Lithium acetate
Lithium beryllium

fluorides
Lithium bicarbonate
Lithium bromide

Lithium carbonate
Lithium chloride

ILithium fluoride

Boiling point

Catalytic activity

Critical tempera-
ture

Crystal data

Density

Dielectric constant

Free-energy of
formation

Heat of formation

Heat of vaporiza-
tion

Melting point
Polarization
potential
Preparation

Ramsay-~-Young
constant

I
HHEFMPDPWMPODFEFEOPODHEHEEFERENDMNDD

W =

PHFWMPPMPDNDEHEFHFNDWRDWNPDWPDWW

O\ W O W
8 b b 00 b f b R % b0 k1

W W W N

W&
ww

6-2
65-1

58=2

58-2

19-3

o
®E oo = O
VS

!

Ao e b

i
PP PDWMPDPDVIDWMND DWW

O\mgwml—-l—'
-l‘-"\-fll

13-1

41-2
40-3

59-3

59-3
60-1

w

i

=
I\)\P\J'i -~

\
!
N w

OD\PO’.)LAJ\H
HMP&EPDWMDMPDW

a\\n w4
RE&

60-2

61-4

Li-2

[0
v
=

11-2

N
o U
! 1

|_.l

!
RDMPDWWEFEMPDWND

O =3 CIDO\OUO

AN FWwW

=3
I

29-3

66-1

25-1
41-3
62-1

25-1

30-1

DV W 1 2
N

27-1
Lh-1
62-2

27-1

38-3

76

62-2

37-3
62-2

11-3
15-2
25-1
32-3
L1-4
ol-3
62-2
Solubility
Specific heat
Specific surface

energy
Systems

Thermal expansion

Vapor pressure
Lithium hydride
Lithium hydroxide
Lithium iodide

Lithium metaborate
Lithium nitrate
Lithium oxide
Lithium perchlorate
Lithium plutonium
fluoride
Lithium sulfate
Lithium toluene-
sulfonates

¥

Magnesium
Magnesium chloride
Magnesium fluoride

Boiling point
Corrosion by
Crystal data
Density

Entropy

Free-energy of
formation

Heat of evapora-
tion

Heat of formation

Heat of fusion
Heat of reaction
Magnetic suscepti-
bility

Melting point
Preparation
Specific heat

I 1 1 1

WHHEN£WDE R
wamo$owm5mm
N WWWWMPFMNND VR

o
7

20-2
14-2
31-3
22-3

26-4
13-1
25-1
19-4

22-3

33-2

10-1
12-5
19-2
34-3

30-3

h1-4

13-2
21-3
8-3

W

55-1

36-1

61-k

143
20-1
29-1
33-1

29-1

14-3
29-2
h6-2

62-1

15-2
29-3
52-2

62-2

15-3
20-4
30-1
§1-3
Systems

Trouton's constant

Vapor pressure
Magnesium oxide
Magnesium sulfate
Manganese difluoride
Manganous sulfate
Melting points

Mercuric fluoride
Mica

Mild steel
Molybdenum

N

Neodymium chloride
Neodymium oxybromide
Neodymium oxychloride

- Neon

Neptunium nitride
Neptunium oxides

Neptunium tetrachloride

Neptunium tetra-
fluoride

Neptunium trifluoride

Neptunyl fluoride

Nickel

Nickel chloride

Nickel fluoride

Nickel steel

Nickel sulfate

Niobium

Niobium chloride

Niobium pentafluoride

Nitric acid

90

Oxygen

P

Perchloric acid
Platinum

12-5
21-2
32-3
20-2
20-2
15-1
38-1
14-2
38-1

-3
28-3
53-1
26-14

b7-3

60-3
18-3

37-3

. ho-2

4o-2
48-3
L2-2
h2-2
h2-2

42-2
ho-2
ko2
17-3
63-2
142
18-3
38-1
58-L
58-4
59-1
63-3

43-2

13-2
22-3
36-1

671

12-5
55-2

13-3
25-1

38-3
60-2

8-1
30-1

58.2

60-2

32-2
63-3

14-3
29-1

51-2

65-1

38-2

55-2

40-3

22-4
36-1

43-2

78

20-4
30-2

47-3
Platinum-iridium
alloy

Platinum tetra-
fluoride

Plutonium bromide

Plutonium carbide

Plutonium chloride

Plutonium nitride

Plutonium oxides

Plutonium oxybromide

Plutonium oxychloride

Plutonium oxyfluoride

Plutonium oxyiodide

Plutonium penta-
fluoride

Plutonium tetra-
fluoride

Plutonium trifluoride

Potassium

Potassium acetate
Potassium beryllium
fluoride
Potassium bromate
Potassium bromide

Potassium carbonate
Potassium cerium
fluoride
Potassium chlorate
Potassium chloride

Potassium dihydrogen
orthophosphate

Potassium ferricyanide

Potassium ferrocyanide

Potassium fluo-
carbonate

Potassium fluoride

Activity coefficient

Boiling point
Catalytic activity

=
:

[
MMM PMRONNMDMPPDW )

l\)f\)l\)l\)Ol\)Og

SR Ew W
N D

=
L
o

=
PRIV PR PEETY
NHEPWHRFFRFNDD D

WEMPONWVWWNDE P

09-2
59-2
29-2

59-2

Lh-1
50-2
19-3

41-2
55-1

FOTES Py
FPOMPWMPOHEEFEPND

NN FW MY

i

UL L L
NDEHEMPPDMPPDWEHEND

RDWMPRWMPMDE
AN LW N -
NP OV P ONEFE O

29-2
Lh-1

RO\ W W N
® O OO =3
WHWHDLD P

79

62-3

10-1
17-3
27-3
32-3
36-2
23-1
62-2
Critical temperature

Crystal data

Decomposition
potential
Density

Entropy

Free-energy of
formation

Heat of dilution

Heat of formation

Heat of vaporiza-
tion

Melting point

Ramsay-Young
constant
Solidification
point

Specific heat
Specific surface
energy

Systems

vapor pressure
Potassium fluosulfate
Potassium hydride
Potassium hydroxide
Potassium iodide

Potassium lanthanum
fluoride
Potassium magnesium
fluoride
Potassium monoxide
Potassium neptunium
fluoride
Potassium nickel
fluoride
Potassium nitrate
Potassium plutonium
fluoride
Potassium rubidium
fluoride
Potassium sulfate
Potassium thiocyanates
Potassium thorium
fluorides
Potassium titanium
fluoride
Potassium toluene-
sulfonates

1C-1
31-2
60-2
68-3
14-2

12-1

38-2
k3-3

32-2

35-2

Ly-1

38-2

L2-2

n oW N
RRGY &
wWPpPPP W

y5.2

hh-1

38-1
10-1
48-1
62-3

n

63~

48-1

-1
-1
1

v W
+Ww
Potassium uranium
fluorides
Potassium yttrium
fluoride
Potassium zirconium
fluoride
Praseodymium chloride
Praseo ijymium oxy-
chioride
Preparation of
fluorides

Protoactinium oxide

D

Quartz

R

Ramsay-Young constant

Rhenium

Rhenium difluoride

Rhenium hexafluoride

Rhenium trichloride

Rubidium

Rubidium acetate

Rubidium antimony
fluoride

Rubidium bromide

Rubidium carbonate
Rubidium chloride

Rubidium fluocarbonate
Rubidium fluoride

Boiling point
Critical tempera-
ture

Crystal data

Density

Heat of formation

Heat of vaporiza-
tion

Melting point

L7-3

1 1

W O\ a2
® OO0 \D oo
HFHERHP s

ON

FEV DV DWW

+ O O\

-

| i
HEMRMHFMPNDNOMEFEFNDNDWNDMD

61-k

43-3

L.l

61-4

62-1

81

62-1

62-2
Ramsay-Young
constant
Specific heat
Specific surface
energy

Systems

Vapor pressure
Rubidium fluosuifate
Rubidium hydride
Rubidium iodide

Rubidium lanthanum
fluoride
Rubidium magnesium
fluoride
Rubidium monoxide
Rubidium nickel
fluoride
Rubidium nitrate
Rubidium plutonium
fluoride
Rubidium sulfate
Rubidium thorium
fluorides
Rubidium yttrium
fluoride

S

Samerium chloride
Sapphire

Scandium acetate
Scandium chloride
Selenium fluoride
Silicon

Silicon carbide
Silicon dioxide
Silicon tetrafluoride
Silver

Silver chloride
Silver difluoride
Silver fluoride
Silver iodide
Silver-nickel alloy
Silver nitrate
Sodium

Sodium acetate

Sodium aluminate

Sodium aluminum
fluoride

—
M

|
-

e
lllig-{:?\ Y

=i
FNOFPOoMDND D

o)t

W
\
—~

W
On
=

~
oo b0

FUW A AAWW W

FHEFRFLDWNDODWRODRHWW NDW DWW WW

MONEFEOOFE O3

-

61-4

43-3

35-1

443

L46-2
58-2

47-3
58-2
20-3

29-1
12-2

11-2
62-2

61-2

61-2
60-2

67-2
36-3

19-3

14-1
2ly..2
35-1

34-2

27-2
62-3

63-3

58-2

35-2

34-3

38-1

60-2

43-1

18-1
27-3
03-2

36-1

41-2

95-2

82

45-2

h1-4

60-1
Sodium beryllium
luoride

Sodium bromate

Sodium bromide

Sodium carbonate
Sodium chlorate
Sodium chloride

Sodium cyanide
Sodium dihydrogen
orthophosphate

Sodium fluoride

Activity coefficient

Boiling point

Catalytic activity
Critical tewmpera-

ture
Crystal data

Decomposition
potential
Density

Electromotive
phenomena
Entropy
Free-energy of
formation

Heat of formation
Heat of reaction
Heat of wvaporiza-

tion
Melting point

Preparation

W N wWw
10 8 b byt b

WO OCoF
HEWMDMOVMNODHFNNENDNDRE -

AN\

Vo b e
WHEWWMPDEFODWEREWERFED D

PNDWONON W VN
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i v i

AN\ EFWWN N -
UJODI\)\J’I\J'III—’—JI\)—JI—‘-F"
HWEFEFMOFMNMMODEFRFWWW

25-3

10-1
61-4

63-3

10-1
38-2
k9-}
62-2

\J'II—'-N'H,'U\O o\

UL | i
WROHPOPVDFWHH PP

!

w ow

28-3

VI P
Uo-s'!-\'!f'\)CDw\Ol\)\J'l

'
WMPROMNOFRFEFPDWEPD

o\ O\
=
P
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28-1
yi-2
64-1

25-3

29-3

37-1
62-2

27-1
4i1-2
23-2
64-1

P11 8

OV FWWNNO P
-I'-"I—'\J'ICDODI})CD-F'\O-F'\J'!
MNFFPFPPFPMDODDEPOW

27-3

30-1

83

28-1

32-1
Ramsay-Young
constant
Sintering tempera-
ture

Specific heat

Specific surface
energy

Systems

Thermal expansion

vVapor pressure
Sodium hydride
Sodium hydroxide
Sodium iodide

Sodium lanthanum
fluoride

Sodium lithium
beryllium fluoride

Sodium metaphosphate

Sodium molybdate

Sodium monoxide

Sodium nitrate

Sodium perchlorate

Sodium plutonium
fluoride

Sodium sulfate

Sodium thiocyanates

Sodium thorium
fluoride

Sodium titanium
fluoride

Sodium toluene-
sulfonate

Sodium tungstate

Sodium uranium
flucride

Sodium uranyl acetate

Sodium yttrium
fluoride

Solidification points

Specific heats

Specific surface
energy

Spinel

Strontium chloride

=
P
=

L
T3
e

i T § 1 1 1
- WMHOHFPPFODMPPPODPODPDWDDW

& R W o\ £W
cn\n—au1PJP-#Wf\nraxnfi34r\n

W
\n
!

B
5o
H o

10-1

W
"
W

10-1
38-1

35-2
10-1
38-1
35-2
68-2
38-1
10-1

42-2

\.
t
Mo

=

w
l l\)U‘I\P-F:‘O

o\
\.n\lng|
F RPRPFODFRFWRHRWH

=
T

\n

W
U wone
v H e

w
»
no

42-2

32-2

h2-2

36-2
10-1

54-2

|_l
P
=

n
!

VN W N
AV =
PO LPWW H N

4h-1

45-2

21l-1
L1-4

48-1

N WD E
(I)\O-P'(lI)UJI'\)(I)
W FWwNh P Fa

51-3

2kh-h

48-3

31-3

8L

31-4
85

Strontium fluoride 14-2  17-2 20-2 20-3 22-2 25-1 33-4
34-1 47-3 5h.2  58-2
Boiling point 20-2
Crystal data 17-2  20-3 22-2 25-1 34-1
Density 20-3 22-2 25-1 34-1
Heat of evapora-
tion 20-2
Heat of formation 14-2
Preparation 25-1 33-4
Systems 17-2 22-2 25-1 33-4 54-2
Trouton constant 20-2
Vapor pressure 20-2
Strontium sulfate 51-3  64-2
Strontium thorium
fluoride ho_2
Strontium uranium
fluoride ho_2
Sucrose 38-1
Sulfur fluorides 60-2
Sulfuric acid 63-3 68-2
Systems Yo 4.3 5-1 6-2 7-1 8-1 8-2
9-1 12-4 12-5 13-2 13-3  14-1 14-3
15-2  15-3 16-2 16-4 17-1 17-2 17-3
18-1 18-2 19-1 19-2 20-4 21-2 21-3
21-4 22-2 22-3 23-1 23-2 242 25-1
25-2  25-3 27-3 28-1 28-2 29-1 29-2
29-3  30-1 30-2 31-2 32-1 32-2 32-3
33-4 34.2 34-3  35-2  36-1 38-3 44-2
4s.2  h6-2 Y7-2  49-3  Lo-k 51-1 52-1
52-2  53-1 53-2 54-2 55-1 55-2 56-3
58-3  61-3 64-3 65-1 65-2 66-2
T
Tantalum 59-1
Tantalum penta-
fluoride 59-1
Tantalum trifluoride 59-~-1
Tellurium flucrides 60-2
Thallium 32-2  6Lk-1
Thallium acetate 38-1
Thallium bromide 12-2  47-3
Thallium chloride 12-2  64-1
Thallium monofluoride  12-2  14-2 58-2
Thallium monoiodide 36-3  47-3
Thallium perchlorate 38-1
Thallium sulfides 12-2
Thallium trifluoride 46-3
Thallous nitrate 38-1
Thorium 35-2  43-1
Thorium flucride 25-1  34.2 35-2 L42-2 58-2
Thorium nitrate
Thorium nitride
Thorium oxyfluoride
Tin fluoride
Titanium fluoride
Trouton's constant
Tungsten

Tungsten dibromide
Tungsten difluoride
Tungsten hexafluoride
Tungsten pentabromide

v

Uranium

Uranium fluorides

Uranium hexafluoride

Uranium pentafluoride

Uranium tetrachloride

Uranium tetrafluoride

Uranium trifluoride

Uranium X. thorium
fluoride

Uranyl fluoride

y

Vapor pressure

| >4

Xenon

Y

Yttrium chloride
Yttrium fluoride
Yttrium oxychloride

2z

Zinc

Zinc fluoride

Zinc oxide

Zinc sulfate
Zirconium dioxide
Zirconium fluoride

35-2
35-2
33-3
35-2
ho-2
33-3
35-2

64-3
L2-2

11-2

48-3

_UNCLASSTFIED
68-2

Yo-2 43-1
43-1 56-2
39-2 Yo.2
ho-2 56-2
57-2

35-2 hooo
Yoo 58-2
11-4 12-2
Yy7-2 58-3
34-3 35-1
16-1 20-2
58-2 60-2

UNCLASSIFIED

60-2
o7-2
58-2

56-2

- 60-2

20-2

26-4

58-2  60-2

60-2

58-2 60-2 63-3
26-3 27-2

58-2 58-3 64-3
58-2  60-2