J. Inorg.Nucl.Chem., 1962,Vol.24, pp. 1287 to 1296. PergamonPressLtd.

Printedin NorthernIreland

THE DENSITY OF LIQUID NaCl A N D KCI A N D

AN ESTIMATE OF THEIR CRITICAL CONSTANTS
TOGETHER WITH THOSE OF THE OTHER
ALKALI HALIDES*

A. D. KIRSHENBAUM, J. A. CAHILL, P. J. MCGONIGAL~" a n d A. V. GROSSE

Research Institute of Temple University, Philadelphia, Pa.

(Received 21 February 1962)

Abstract~A procedure for the estimation of the critical constants of salts, provided reliable liquid
density data are available, is explained. The method is applied specifically to NaC1 and KCI, the
liquid densities of which have been determined from the melting point to the normal boiling point
The dependence of density on temperature may be expressed by the following equations :
Dsacl g/cm 3 = 2'061 -- 4.759 × 10-4 T°K 3:0.002 g/cm3
DKCl g/cm 3 = 2.062 -- 5.350 × 10 ~ T°K ~ 0.003 g/cm3
The estimated critical constants for NaCI are: To = 3400°K ± 200°K, D c = 0.22 g/cm3 :::=0.05
--50 --120
g/cm 3, V~ =.=266cm 3 ÷70cm 3, Pc = 350 atm +130atm, and for KCI: Tc =~ 3200K :~,z2OO°K,
--100 --70
D, = 0.175 g/cm 3 :k 0"05 g/cm 3, Vc = 415 cm 3 +200 ' Pc == 220 atm, +100 atm.
Estimated critical temperatures are given for the other alkali halides.

IN previous p u b l i c a t i o n s ~1'-°)a p r o c e d u r e for estimating the critical t e m p e r a t u r e o f any

metal based on a p p l i c a t i o n o f the t h e o r e m o f c o r r e s p o n d i n g states to the e n t r o p y o f
v a p o u r i z a t i o n has been discussed. I f density d a t a for the liquid metal are available the
law o f rectilinear d i a m e t e r s m a y be used to estimate the critical density a n d critical
volume. Critical pressures m a y be a p p r o x i m a t e d by e x t r a p o l a t i o n o f ideal gas v a p o u r -
pressure data. It has been e m p h a s i z e d ~1'2) that in r e g a r d to t h e r m a l stability the metals
f o r m a unique g r o u p ; since they are e l e m e n t a r y m o n a t o m i c substances the only
dissociation process which need be c o n s i d e r e d is i o n i z a t i o n a n d this is repressed b y the
high s a t u r a t i o n vapour-pressures. Calculations involving the Saha e q u a t i o n indicate
t h a t for metallic v a p o u r s the degree o f i o n i z a t i o n is small (of the o r d e r o f a few per
cent) at the critical point, p a r t i c u l a r l y in view o f the high vapour-pressure. The
critical t e m p e r a t u r e s o f the high-boiling metals, for example, are as follows: M o -
17,000°K, Re-20,500°K, T a - 2 2 , 0 0 0 ° K a n d W-23,000°K.
W i t h m o l e c u l a r species, however, the situation is n o t so simple a n d dissociation
into atoms, radicals, ions, simpler molecules o r a c o m b i n a t i o n o f these forms, m u s t be
considered, 6000°K m a y be t a k e n as the u p p e r limit for real critical t e m p e r a t u r e s o f
* This work was supported by the National Science Foundation under grant 15540.
1- Portions of this work will be included in a dissertation to be submitted by P. J. McGONIGAL
to the Graduate Council of Temple University in partial fulfillment of the requirements for the
degree of Doctor of Philosophy.
c1~A. V. GROSSE,J. Inorg. and Nucl. Chem. 22, 23 0961).
12~A. V. GROSSE,Paper No. 2159, A.R.S., Space Flight Report to the Nation, New York, Oct. 9-15,
(1961); See also A. V. GROSSE,The Liquid Ranffe of Metals and Some of their Physical Properties at
High Temperatures, Research Institute of Temple University, Oct. 19, (1960).
1287
1288 A.D. KIRSHENBAUM,J. A. CAHILL,P. J. McGONIGALand A. V. GROSSE

molecular substances since above this temperature all chemical bonds will be broken.
Many compounds will be substantially dissociated at lower temperatures and it is not
always possible to speak of a critical temperature of a compound since it could not
exist as such at that temperature. For example, CaO boils at 3800°K and, as a first
approximation, would be expected as an ionic compound to have a critical temperature
in the neighbourhood of 7600°K. Extrapolation of K~ data for dissociation into the
elements as reported by LATIMER(s) and vapour-pressure data reported by BOCKRIS et
al. ~ yield values of 350 and 1860 atm respectively for these quantities at the critical
point. The degree of dissociation calculated for CaO at its supposed critical tempera-
ture and pressure is 40 per cent. As a more extreme example of a substance which
cannot be said to have a critical point we may consider AlsO a which is substantially
dissociated into AlsO , A1202, O and O 3 at its normal boiling point of 3800°K, which
happens to coincide with the flame temperature of the A1-O2-flame (at 1 atm). (5)
On the other hand calculations based on recent K~ data (6) and linear extrapolation
of the vapour-pressure data of BARTONand BLOOM(7) show that NaCI is only 1.25 per
cent dissociated at its estimated critical temperature of 3400°K and critical pressure of
350 atm. The per cent dissociation at the critical point critical temperatures (see
Discussion) are given in Table 1. Critical pressures are estimated to be from 200 to
1000 atm, based on available vapour pressure and K~ data. It is, therefore, feasible
to speak of critical temperatures for the alkali halides (see Table 9).

TABLE 1 .----CRITICAL TEMPERATURES AND PER CENT

DISSOCIATION OF SEVERAL ALKALI HALIDES

Dissociation
Salt Te(°K) (~o)
LiF 4140 0"4
LiC1 3080 0"2
LiBr 3020 0"3
LiI 3250 0"7
NaF 4270 1.7
NaC1 3400 1"2

EXPERIMENTAL
Procedure
The density of sodium and potassium chlorides were determined from their melting points to their
normal boiling points by the Archemedian Principle. The procedure used has been described
previously in our paper on liquid lead.ta~ It was observed previouslyc9~that graphite did not react
with these salts. Therefore, graphite crucibles, sinkers and reflux condensers were used in these
experiments. Analyses of the salts after the experiments showed that there was <0.02 per cent
carbon present in the salts.
~8~W. M. LATIMER,Tables of Free Energy Functions for Elements and Compounds in the Temperature
Range 2000-5000°K, U.S.A.E.C., Oak Ridge, Tenn., 11-18-49-300-A10159(MDDC-1462).
~ J. O'M. BOCKRIS,J. L. WHITEand J. D. MACKENZIE,Physico-Chemical Measurements at High
Temperatures, p. 93. Academic Press, New York (1959).
~5, A. V. GROSSEand J. B. CONWAV,lnd.& Eng. Chem., 50, 663 (1958).
c~ JANAF Interim Thermochemical Tables, Vol. 1 and 2, Prepared under the auspices of the Joint
Army-Navy-Air Force Thermochemical Panel, W. H. Jones, Chairman, by the Thermal Labora-
tory Dow Chemical Co., Midland, Mich., Dec. 1960, with supplements through Sept. 1961.
,7~ j. L. BARTONand H. BLOOM,J. Phys. Chem. 60, 1413 (1956).
ta~ A. D. KIRSHENBAUM,3. A. CAHILLand A. V. GROSSE,J. Inorg. NucL Chem., 22, 33 (1961).
19~ A. D. KIRSHENBAUM,J. A. CAHILLand C. S. STOKES,J. Inorg. Nucl. Chem. 15, 297 (1960).
 The density of liquid NaCI and KCI 1289

The volume of the sinker at 20°C was calibrated in mercury and corrected for surface tension.
The volume of the sinkers were always corrected to the operating temperature using the thermal
expansion data reported by GOLDSTEIN, et al. ~°~ together with data known for the graphite used.*
The volume of the sinker depended upon its depth of immersion in the liquid salts. This was deter-
mined by an electric probe, i.e. by the difference between the depth of the liquid salt and the distance
of the sinker from the crucible base. t8,°~
The losses in wt. of the sinkers were corrected for surface tension using the surface tension
equations reported by BLOOM et al. (11) namely ~'NaCl 190'8 -- 0.093t and 7Kcl -- 155"2 -- 0.073t
=

where t is in °C and 7 in dynes/cm.

Materials used
The total impurities were 0.027 per cent in the NaC1 and 0.020 per cent in the KCl. The main
impurities were:
NaCl KC1

Bromide 0.005 ~ 0"005 ~/o

Chlorate I 0.003 ~ 0.003 ~{,
Nitrate / 0-003
Iodide 0.002 ~ 0.002
Sodium -- 0.003 %
Potassium 0.002 ~ --
Thus, the purity of the NaCl was 99.973 per cent and of the KCI was 99"980 per cent.
RESULTS
T h e e x p e r i m e n t a l d a t a o b t a i n e d f o r N a C 1 a n d KC1 are p r e s e n t e d in T a b l e 2. A
least s q u a r e s t r e a t m e n t o f t h e d a t a g a v e t h e f o l l o w i n g l i n e a r relationships'."

oliq.
NaCI = 2.0610 - - 4-759 × 1 0 - ~ T ° K ~ 0.002 g / c m a
D ~ 1 = 2-0624 - - 5"350 × 1 0 - 4 T ° K :k 0.003 g / c m a.

T h e m o l a r v o l u m e s a n d v o l u m e coefficients o f e x p a n s i o n o f NaC1 a n d KC1 are

g i v e n in T a b l e 3. A c o m p a r i s o n o f o u r d a t a w i t h t h o s e r e p o r t e d in the l i t e r a t u r e are
TABLE 2.--EXPERIMENTALLIQUIDDENSITIES
NaG1

Temperature Density Temperature Density

(°K) (g/cm 3) (°K) (g/cm ~)

1149 1'516 1502 1.347

1162 1'503 1590 1.305
1202 1.486 1552 1.323
1208 1.483 1573 1.312
1404 1'388 1670 1.267
1459 1'367

KCI

1101 1.4710 1317 1.364

1112 1-4707 1410 1.303
1184 1.4277 1420 1-297
1197 1'422~ 1507 1.264
1294 1.3688 1607 1.202

* Dixon E-821, fine grain petroleum coke base stock with a transverse linear coefficient of
expansion from 100 to 600°C of 35 × 10-7]°K and a parallel coefficient of expansion of 20.8 × 10-7]°K.
~10~A. Goldstein, T. E. Waterman and H. J. Hirschhorn, Thermophysical Properties of Solid
Materials Vol. 1, p. 59-158. W A D C Technical Report 58-476, (1960).
(11) H. Bloom, F, G. Davis and D. W. James, Trans. Faraday Soc. 56, 1179 (1960).
1290 A. D. KIRSHENBAUM,J. A. CAHILL,P. J. McGONIGALand A. V. GROSSE

TABLE 3.--MOLAR VOLUMESAND COEFFICIENTSOF EXPANSIONOF NaCI AND KCI

Molar volume Cubical Coeff. of Expan.
Density (g/cm 3) (cma/mole) × 105 (°K-I)
Temperature
( °K) NaC1 KC1 NaCl KC1 NaCl KCI

1073 (m.p.) 1.5504 -- 37-70 -- 30.70 --

1063 (m.p.) -- 1.494 -- 49.90 -- 35.81
1100 1"538 1.473 38-01 50.61 30.94 36.32
1200 1.490 1.420 39-23 52.50 31.94 37.68
1300 1.442 1-366 40.54 54.58 33.00 39.17
1400 1 "395 1.313 41.90 56.78 34-11 40.75
1500 1.347 1.259 43 '40 59.22 35.33 42-49
1600 1-300 1.206 44.96 61.82 36.61 44-36
1680 (b.p.) -- 1.163 -- 64.10 -- 46.00
1738 (b.p.) 1.247 -- 46.88 -- 35.81 --

p r e s e n t e d i n T a b l e s 4 a n d 5. T h e r e is excellent a g r e e m e n t o n the densities o f N a C I a n d

KC1 at t h e i r m e l t i n g p o i n t s b e t w e e n o u r d a t a a n d those r e p o r t e d in the literature. T h e
l i t e r a t u r e t e m p e r a t u r e coefficients, h o w e v e r , d o v a r y slightly for NaC1 (3.8-6.26 ×
10-4). W e give p r e f e r e n c e to o u r dD/dt v a l u e s since t h e y c o v e r t h e w h o l e r a n g e o f
5 5 0 ° K , f r o m the m e l t i n g p o i n t to t h e n o r m a l b o i l i n g p o i n t .
TABLE 4.------COMPAKISONOF LITERATUREVALUESFOR THE LIQUIDDENSITYOF NaCI
Temperature Temperature Density
Investigator range (°K) coeff. × 104 at m.p. Reference

This work 1150-1700 --4.759 1.5504

LORENZ, FRIESand J A r S 1125-1225 --3"8 1"521 Z. phys. Chem. 61,
472 (1908)
JAEGER 1100-1450 --6"261 1'549 Z. Anorg. Chem.
101, 180 (1917)
HONDA 1200-1600 --5'07 1'557 Z. Anorg. Chem.
154, 238 (1926)
SAUERWALD 1300-1600 -- 5"00 1"564 Z. Anorg. Chem.
135, 327 (1924)
ARNDT and GESSLER 1075-1175 --5'4 1'54 Z. Elektroch. 14,
666 (1903)
BRUNNER 1100-1300 -- 5"4 1"554 Z. Anorg. Chem. 38,
avg. ='1-548 375 (1904)

A c c o r d i n g to BOCKRIS et aL az) the d e n s i t y o f solid s o d i u m a n d p o t a s s i u m chlorides

h a v e the f o l l o w i n g t e m p e r a t u r e r e l a t i o n s h i p s :

NaCI: D s -----2.168 - - 1.267 × l l - 4 t - - 1.754 × 10-7#(-4-0.002 g / c m 3)

KCI: D e = 1.985 - - 5.459 × 1 0 - ~ t - 1.836 × 10-7tz(-+-0.001 g / c m 3)

w h e r e t is in °C. T h e densities a n d m o l a r v o l u m e s o f NaC1 a n d KC1 at their m e l t i n g

p o i n t s are:
D ( g / c m 3) V~,(cm3/mole)

N a C I (solid) 1.955 29.90

(liquid) 1.5504 37.70
KC1 (solid) 1.827 40.81
(liquid) 1.494 49.90
tx2~ j. O'M. BOCKmS, A. PILLA and J. L. BARTON,Jr. Phys. Chem. 64, 507 (1960).
 The density of liquid NaCI and KCI 1291

TABLE 5.---COMPARISON OF LITERATURE VALUES FOR THE LIQUID DENSITY OF KCI

Temperature Temperature Density

Investigator range (°K) coeff. × 104 at m.p. Reference

This work 1100-1600 ° --5.350 1.494

NEILHAMER and PEAKE 1075-1300 ° --5"8 1"502 J. Chem. Engng. Data 6,
197 (1961)
MASHOVETZ and 1075-1400 ° --5-7 1.499 Proc. 1st All-Union conf.
LUND1NA Non-aqueous solutions
1935, pp. 191-212
PEAKE and BOOTHWELL 1075-1200 ° --5"8 1'502 J. Amer. Chem. Soc. 76,
2653 (1954)
BRUNNER 1075--1300 ° --5"7 1"507 Z. Anorg. Chem. 38, 350
(1904)
ARNDT and GESSLER -- --5.4 1.498 Z. Elektrochem. 14, 666
(1903)
JAEGER and KAHN 1075-1225 ° --5"95 1"509 Proc. Acad. Sci. Amster.
10, 381 (1916)
KLEMM -- --5"6 1'517 Z. Anorg. Chem. 152, 295
avg. = 1-504 (1926)

TABLE 6.--VOLUME CHANGE OF NaCI AND KC1 ON MELTING

AV/V.,(%)
Reference
NaCI KCI

26"06 ± 0'06 2 2 " 2 7± 0'08 This paper

25"58 4. 0.07 2 0 " 2 04.4-0'05 BOCKRIS, PILLA and BARTON, J. Phys. Chem. 64, 507 (1960)
-- 2 1 " 0 4 . 0"5 LANDON and UBBELOHDE, Trans Faraday. Soc. 52, 647 (1956)
30.0 23"0 Eucg~N, Z. Angew. Chem. 55, 163 (1942)
25.0 4. 0.5 17"3 ± 0"5 SCHrNKE and SAUERWALD,Z. Anorg. Chem. 237, 313 (1956)
22"8 4. 0.7 16"8 4- 0"5 EUCKEN and DANNOHL, Z. Elektrochem. 40, 814 (1934)
23.2 -4- 2"0 17-5 4. 2.0 BREDIG and JOHNSON, Report ORNL-1940, p. 19

Therefore, the volume change on melting (A V/V~) are 26-06 and 22.27 per cent respec-
tively for NaC1 and KCI. A comparison of these values with those reported by previous
investigators are given in Table 6.
DISCUSSION
Diagrams covering the entire liquid ranges of NaCl and KC1 have been constructed
from the experimental liquid density data and vapour densities obtained by extrapo-
lation of the data of BARTONand BLOOM.(7) The general method for the preparation of
these diagrams has been previously discussed. I1) Dimeric species were taken into
account in the calculations. The amounts were obtained by extrapolation of the data
given by DATZ, et al. ¢x3~ These diagrams are reproduced in Figs. 1 and 2. Densities of
vapour and liquid above the normal boiling points of NaCI and KC1 are shown in
Table 7.
The liquid densities were calculated according to the equation
Dliq. = 2D ~ -- Dwv '
where D ~ represents rectilinear diameter. The equations for the rectilinear diameters
are:
DoWN,el--- 1"0305- 2-3795 × 10-4T(°K)
Dc~xcl--- 1 . 0 3 1 2 - 2.675 × 10-4T(°K)
(131 S. DATZ, W. T. SMITH, JR. and E. H. TAYLOR, J. Chem. Phys. 34, 558 (1961).
 1292 A D KIRSHENBAUM.J. A. CAI-IILL, P. J. McGONIGALand A. V. GROSSE

M.R C R I T I C A L CONSTANTS FOR NoCI

- l O T 4 °K
TC = 3 4 0 0 eK = 2 0 0 °K
1 . 5 - - VC= 2 6 6 c m s 50
* 7 0 cm 3
D c = 0 . 2 2 g/cm 3 =O,05g/cm 3
PC = 3 5 0 ofm - 120
* 130 otto

I
I
I
c~ r I
I
t
k- I
I CRITICAL
I ~ REGION
z
I
w
a I? /"

,
0.5 - -
I
, , R~,~:,~,~:~/
I
I
I l
i
I
i..., GAS ///~/~ ~
I
I
0
1500 2000 2500 3000 3500 4000
TEMPERATURE =K
FIG. 1.--Liquid range diagram for NaC1.

M.R C R I T I C A L C O N S T A N T S OF'KCI
-1049 *K
TC = S E O O = K e2OO=K
1,5 " I00
Y¢ = 4 1 5 ¢ m l ~ 2 0 0 cm I
Dc • (~ 175 g/cm=*O.05 g / c m =
- 70
Pc • 2 2 0 at're. * I 0 0 atrn.

~E hO
I
l
I ~ ~
,
2D~ I.~
CRITICAL
REGION ~.
II
0.5

l RECTILINEAR

l
! . - - - - - ~ ~y / / / ~
Old.o, GAS

0
I100 1500 2000 2500 3000 3500
TEMPERATURE eK

FIG. 2.--Liquid range diagram for KC1.

 The density of liquid NaCI and KCI 1293

TABLE 7.--SATURATED VAPOUR AND LIQUID DENSITIES OF NaC1 AND KC1

ABOVE THEIR NORMAL BOILING POINT

Sat. vapour density (g/cm 3) Liquid densit (g/cm3)

Temperature
("K) NaCI KCI NaCI KCI

1680 (b.p.) -- 0.000595 -- 1.162

1738 (b.p.) 0.000577 --- 1-233 --
1800 0.000837 0.00117 1.203 1.098
2000 0'00225 0.00290 1.107 0.989
2200 0.00495 0"00636 1.009 0.879
2400 0.0100 0.0125 0-909 0-766
2600 0.0174 0.0208 0.807 0.650
2800 0.041 0.034 0.701 0.530
3000 0.059 0.050 0.622 0.407
3200 0.10 -- 0.480 --

The critical temperatures were estimated to be in the centers of the critical regions
shown in Figs. 1 a n d 2. The upper limit for the critical region is definitely established by
the intersection o f the liquid a n d ideal v a p o u r density curves at the rectilinear diameter.
The lower limit is n o t so well defined b u t m a y be taken as that temperature at which
the calculated v a p o u r density is one-fifth as great as the calculated liquid density. I n
the case of NaC1 a n d KC1 this temperature is a b o u t 400 ° below the upper limit. The
error in the critical temperature in each case is taken to be ~ 2 0 0 ° K . The critical
constants determined from the diagrams are presented in Table 8.

TABLI~ 8 . - - C R I T I C A L CONSTANTS OF N a C I AND K C I

NaCl KCI

This work ERRING This work EYRING

Tc 3400° ~: 200°K 3600~K 3200 !. 200~K 3092~K

De 0"22 ~ 0"05 g/cm 3 0,20 g/cm3 0.18 L 0.05 g/cm 3 0.173 g/cm 3
-50 cm3
- -- 100 cm3
I/ 266 ~ 70 293 cma 466 t 200 431 cm3
-120 atm
- - 70 atm
P, 350 + 130 235-5 atm 220 : 100 135.5 atm
(pvcl
~ / 0"332 0'233 0"390 0"230

These constants, obtained on a semiempirical basis, agree reasonably well with

those o b t a i n e d theoretically by EYRING a n d co-workers ~14) who developed a partition
f u n c t i o n for fused salts based on the concept of significant structures in the liquid state.
F o r purposes of c o m p a r i s o n EYR~NG'S data are also shown in Table 8. The m o l a r
volumes at the boiling p o i n t as calculated by EYRIN6 are 51-15 cm 3 for NaCI a n d
71-20 cm 3 for KC1 c o m p a r e d to our experimental values of 46.87 cm 3 and 64. l0 cm 3,
respectively.
In view of the great similarity of physical a n d chemical properties of the alkali
halides generally we assume that their critical temperatures can be estimated with a
fair degree of reliability by application of the law of corresponding states to the entropy
of vaporization, ASvav., vs reduced temperature curve for NaC1. The procedure is
(141 C. M. CARLSON, H. EYRINGand T. REE, Proc. Natl. Acad. Sci., 46, 333 (1960).
1294 A.D. KIRSHENBAUM,J. A. CAHILL,P. J. McGONIGALand A. V. GROSSE

similar to that previously described for metals. {1) This curve, which appears in Fig. 3,
was constructed from our estimated critical temperature for NaC1 and the AH,,ap. data
of KELLEY(xr} which, for our purposes, at least are not significantly different from the
more recent data of BARTON and BLOOM. (7)
44

N Hs
4o k

f - -

\
28
\ cc,,

N
Z
t0

24
\ V
FLUOROCARBONS
RELATED COMF :)UND

0
0.
~t
> ZOo'

'@\N
O
I-
Z
w

0
O.J 0.2 o.n 0.4 o.s O.B ar o.e 0.9 J~o
REDUCED TEMPERATURE
FXO. 3.--ASval~ vs. reduced temperature.

These estimated critical temperatures are listed in Table 9; the normal boiling
points and entropies of vaporization are those reported by BR[W[R. (15)
JOLmT(17) has recently published a procedure for estimating the critical volumes of
the alkali halides which involves the assumption that at the critical point each alkali
halide molecule occupies a cube whose edge is twice the internuclear distance at room
temperature. The critical volumes calculated by this method for NaCI and KC1,
108 cm 3 and 152 cm 8, respectively, are much lower than the values given in Table 8.
JOLIET'S results appear to agree rather well with those of SASLAWSKY(la) and LORENZ
txn) L. BREWER et aL, in: The Chemistry and Metallurgy of Miscellaneous Materials, Thermodynamics
(Edited by L. L. QLaLL) NNES Vol. IV-19B, McGraw-Hill, New York (1950).
(16) K. K. KELLEY, Bureau of Mines Bulletin 383, (1935).
txT) j. F. JOLIET, C.R. Acad. Sci. Paris 252, 719 (1961).
(la) SASLAWSKY,Z. Phys. Chem. 109, 111 (1924).
 The density of liquid NaC1 and KC1 1295

TABLE 9.--BOILING POINTS, ENTROPIESOF VAPOURIZATION,REDUCED

TEMPERATURESAND CRITICALTEMPERATURESFOR ALKALIHALIDES

Salt Tb(°K) ASvap. g atom.

cal. deg. ) Tre~. Tc(°K)

LiF 1954 26.1 0.473 4140

LiCI 1653 21.7 0-537 3080
LiBr 1583 22.4 0.525 3020
LiI 1444 28.2 0.445 3250

NaF 1977 26.9 0.463 4270

NaC1 1738 23.5 0.508 3400
NaBr 1665 22.8 0.520 3200
NaI 1577 24"2 0.498 3160

KF 1775 23.2 0.513 3460

KCI 1680 23-1 0.515 3200
KBr 1656 22.4 0.525 3170
KI 1597 21.7 0.537 2980

RbF 1681 23.5 0.512 3280

RbCI 1654 22"3 0.527 3140
RbBr 1625 22.8 0.520 3130
Rbl 1577 22.8 0.520 3035

CsF 1524 22"5 0'523 2915

CsCI 1573 22-7 0.518 3040
CsBr 1573 22-9 0.517 3045
Cs[ 1553 23.1 0.515 3020

a n d HERZ. (19) H o w e v e r , it should be n o t e d t h a t SASLAWSKY'Svalues are calculated from

an expression which involves the critical t e m p e r a t u r e which in turn is o b t a i n e d f r o m
the LORENZ relationship, T c = Tin/0.44, which c a n n o t be valid for alkali halides since
at the critical t e m p e r a t u r e s this expression yields v e r y l o w values for the v a p o u r densities.
A c c o r d i n g to the LORENZ e q u a t i o n NaC1 a n d KC1 w o u l d have a b o u t the same critical
t e m p e r a t u r e , 2400°K; at this t e m p e r a t u r e the v a p o u r densities w o u l d be only 0.010
g/cm 3 for NaC1 a n d 0.012 g / c m 3 for KC1.
It w o u l d thus seem t h a t JOLIET'S a s s u m p t i o n s are incorrect.
It is o f interest to consider the r e d u c e d density vs r e d u c e d t e m p e r a t u r e curve for
typical salts as exemplified by NaC1 a n d K C I a n d to c o m p a r e it with three o t h e r classes
o f substances, namely, ideal o r perfect liquids ( a r g o n a n d other noble gases)/2°1
metals/21) a n d f l u o r o c a r b o n s ( a n d derivatives), ~22'23) h o m o p o l a r liquids with partic-
l a d y small i n t e r m o l e c u l a r forces. These curves are shown in Fig. 4. It is a p p a r e n t t h a t
each o f the f o u r types o f substances has a curve distinct f r o m the others. This is n o t
to say t h a t as the n u m b e r o f examples increases there will n o t be a b a n d for each type.
However, it is to be expected t h a t the mean curves will show differences. The r e d u c e d
density vs r e d u c e d t e m p e r a t u r e b e h a v i o u r o f the substances is n o t simply related to their
structures. H o w e v e r , the similarity o f the r e d u c e d vapour density curves is a p p a r e n t
a n d is u n d o u b t e d l y due to the fact t h a t at the large i n t e r a t o m i c o r i n t e r m o l e c u l a r
119)LORENZand HERZ,Z. Anorff. Chem. 138, 330 (1924).
(20) E. A. GUGGENHEIM,J. Chem. Phys. 13, 253 (1945).
~zl~p. j. MCGONmAL, A. D. KIRSHENBAUMand A. V. GROSSE,J. Phys. Chem., 66, 737 (1962).
~..,2~R. M. YARRIYGTONand W. B. KAY, J. Chem. Engng. Data, 5, 24 (1960).
~23~j. H. SIMONS,Fluorine Chemistry, Vol. 1, p. 438. Academic Press, New York (1950).
1296 A.D. KIRSHENBAUM,J. A. CAHILL,P. J. McGONIGALand A. V. GROgSE

f-%,
I
°"1/ /\
1°' °
Joiill
1 //\
,,

o.6~ FLUOROCARBONS AND 1 N

.RELATE£ COMPOUI~)$ / METALS
O.S

0.5~
0 hO E.O 3.0 4.0 5.0 6.0 7.0
Dred.
FIG. 4.--Reduced density vs reduced temperature.

distances which exist in the gaseous state the characteristic attractive forces are very
much lessened.
A similar and typical separation into classes of substances is shown in Fig. 3 which
is a plot of entropy of vapourization vs reduced temperature. It is to be noted that the
behaviour of typical homopolar compounds like CC14, CO2 or benzene is essentially
the same as that for associated liquids like HzO and NH a.
CONCLUSIONS
The method described above allows a reasonable consistent estimation of the
critical properties of salts. The agreement of our semi-empirical method with the
results of EYRINGt14) is encouraging. The greatest discrepancy is in the estimation of
the critical pressures. Further experimental work on liquid and vapour densities,
especially at high pressures, beyond the normal boiling point, is obviously indicated
to extend density data to higher temperatures and to support or narrow down the
critical constant estimates presented in this paper. Methods for making such measure-
ments are currently under study at this Institute.