UNITED STATES DEPARTMENT OF THE INTERIOR

GEOLOGICAL SURVEY

The Densities of Saturated Solutions of

NaCl and KC1 from 10° to 105°C

by
I/ 2/
V. L. Thurmond-' , R. W. Potter II- , and M. A. Clynne

Open File Report

84-253

This report is preliminary and has not been reviewed

for conformity with U.S. Geological Survey editorial standards.

Any use of trade names is for descriptive purposes only

and does not imply endorsement by the USGS.

This study was supported by the Department of Energy under

Interagency Agreement DE-A197-79ET4461

Present address: Rosenstiel School of Marine and Atmospheric

Science, University of Miami, 4600 Rickenbacker Causeway, Miami,

Florida 33149

2/
Present address: Occidental Research Corp., P. 0. Box 19601,
Irvine, California 92713.
ABSTRACT
Experimental data and regression coefficients for equations
describing the density of saturated NaCl and saturated KC1 solutions in
the temperature range 10-105°C are presented and compared with the
available literature values. Data were obtained using calibrated
hygrometers.

INTRODUCTION
The migration of fluid inclusions up thermal gradients in rock salt
i.e., migration toward a waste canister, is potentially a serious
problem with respect to the safe disposal of radioactive waste in mined
salt repositories. In order to accurately predict the quantities of
brine which will arrive at a waste canister during the thermal pulse, a
quantitative model of the migration rate of brines as a function of the
pertinent environmental parameters is needed. The basic equations for
the migration of fluid inclusions in salt (Anthony and Cline, 1974;
Bradshaw and Sanchez, 1969; Gaffney, 1978) have been derived assuming
that diffusion is the dominant transport mechanism of NaCl across the
inclusion. These models assume a saturated NaCl solution is the
included fluid and require its density as an input parameter. The data
base employed for the calculations is the set of densities for
NaCl-H20 saturated solutions measured by the Earl of Berkeley
(1904). These data cover the range of 0° to 107°C and have been
linearly extrapolated to 300°C for use in the migration calculations
(Bradshaw and Sanchez, 1969). Recent studies indicate systematic
departures between the NaCl solubility values obtained by the Earl of
Berkeley and those which we measure (Potter and Clynne, 1978; Clynne
and Potter, 1979). In view of the uncertainties in the existing
literature data, in particular the systematic deviations of the Earl of
Berkeley's numbers from our studies, and the need for an accurate data
base for the migration equations, we have undertaken a study of the
densities of saturated NaCl and saturated KC1 solutions from 10° to
105°C.

EXPERIMENTAL METHOD
In this study, glass hydrometers which can be read to 0.0001
g/cnr were used to measure specific gravity. The hydrometers were
calibrated for use at 15.56°C. Hence, correction for the thermal
expansion of the glass must be applied to measurements at other
temperatures. The experimental apparatus is illustrated in Fig. 1, and
the procedure used was as follows:
1. A saturated solution of reagent-grade salt was prepared in a
500 ml cylinder, with excess salt added to assure saturation.
2. A hydrometer and a thermometer were placed in the solution, and
the assembly heated in the bath to the desired temperature.
3. The solution was stirred vigorously for several minutes to
eliminate thermal and compositional gradients.
4. The specific gravity and temperature were read.
5. Steps 3 and 4 were repeated until constant values were
measured.
 For temperatures up to 100°C, a platinum resistance thermometer
accurate to +_0.02°C and precise to +0.005°C was used. At temperatures
above 100°C, NBS mercury-in-glass thermometers which could be read to
+_0.01°C were used.
Cylinders containing the salt solutions were immersed in a 25 liter
pyrex tank filled with ethylene glycol. The temperature of the bath
and the temperature of the solutions were monitored simultaneously with
separate thermometers to assure thermal uniformity. The temperature of
the bath was regulated to ^0.01°C.
A hand-held electric stirrer was used to insure saturation of the
solution after changes in temperature. Equilibrium between the salt
and saturated solution was verified by additional stirring and
rechecking the measurement. The entire series of measurements was
repeated preceding from high temperature to low temperature Specific
gravity measurements were converted to densities using the ASME steam
tables.
To test the accuracy and precision of the experimental method, we
measured the density of pure water over a range of temperatures. Of
prime concern was the accuracy of the coefficient of thermal expansion
(2.5 x 10~5 cnrVcm3/l°C) of the hydrometers. A comparison of
measured values with those from the ASME steam tables (Table l) showed
that the two sets are in agreement within the respective tolerances.
The mean deviation of our measured values from the pure water data is
+0.8 x 10~^ g/cm3 while the precision of the experimental method is
+_1 x 10~4 g/cnr*. The accuracy of the data is taken as ^2.4 x
10~4 g/cnr*; however, it should be noted that the method reproduced
the international standard values for pure water within +2 x 10~^
g/cm 3 .

RESULTS
The experimental densities obtained for saturated NaCl and
saturated KC1 solutions are given in Tables 2 and 3 respectively. The
values were fit to an equation of the following form:

P = I 3£t£
i=0

where p is the density in g/cnr, t£ is the temperature in degrees

Celsius, and aj_ are empirical coefficients derived from least squares
regression. The empirical coefficients and the mean deviation of the
experimental data from a smooth curve are given in Table 4.

DISCUSSION OF RESULTS:
Table 5 compares the results of this study with results obtained by
previous investigators. In general, the densities obtained in this
study are greater than those of previous workers except those reported
by Haas (1976). His values were obtained by correlating the available
density data for unsaturated NaCl solutions and extrapolating to the
NaCl saturation curve of Potter, Babcock, and Brown (1977). The
deviation of the results reported here from those of Haas (1976),
Postnikov (1968), and Cornec and Krombach (1932) (except for the
108.5°C KC1 value) are within the stated precision and accuracies of
their values. The data of Blasdale (1918) appear to be discordant with
the results of all the other workers. The values of Ingham (1928) and
Volz-Fladrich (1962) deviate from our values by 3 to 4 times their
stated precision. The systematic deviation of the Earl of Berkeley's
(1904) values probably results from a systematic error in the water
densities he used to calibrate his apparatus.

CONCLUSIONS:
The data set presented here appears to be the most reliable set
available inasmuch as the experimental method reproduced the standard
density values for pure water. The correlation of Haas (1976) for the
density of saturated NaCl solutions from 80° to 325°C adequately
represents the data for saturated NaCl solutions within its stated
precision. From 10° to 85°C the data presented here (Table 6) should
be employed in migration equations, while at T>85°C it is recommended
that the values of Haas (1976) be used for the migration equations
rather than values extrapolated from the Earl of Berkeley's data set
(Bradshaw and Sanchez, 1969). Using the new set of densities will
yield migration rates which are a few tenths of a percent faster than
those calculated by Bradshaw and Sanchez.
 REFERENCES

Anthony, T. R. and Cline, H. E., 1974, Thermoraigration of liquid

droplets in salt: Fourth Symposium on Salt, v. 1, A. H. Coogan
Ed., p. 313-321. The Northern Ohio Geological Society, Inc.,
Cleveland, Ohio.
Blasdale, W. C., 1918, Equilibria in solutions containing mixtures of
salts. I. The system water and the sulfates and chlorides of
sodium and potassium: Journal of Industrial and Engineering
Chemistry, v. 10, p. 344-353.
Bradshaw, R. L. and Sanchez, F., 1969, Migration of brine cavities in
rock salt: Journal of Geophysical Research, v. 74, p. 4209-4212.
Clynne, M. A. and Potter, R. W., II, 1979, The solubility of some
alkali and alkaline earth cholrides in water at moderate
temperatures: Journal of Chemical Engineering Data, v. 24, p.
338-340.
Cornec, E. and Krumbach, H., 1932, Equilibres entre le chlorure de
potassium, le chlorure de sodium et 1'eau depuis -23° jusqu'a
+190°: Annales de Chimie, v. 18, p. 5-23.
Earl of Berkeley, 1904, On some physical constants of saturated
solutions: Royal Society of London Philosophical Transactions,
Series A., v. 203, p. 189-215.
Gaffney, E. S., 1978, Brine migration: Report # PT-U78-0242, Pacifica
Technology, Del Mar, Calif., 24 p.
Haas, J. L., Jr., 1976, Physical properties of the coexisting phases
and thermochemical properties of the H20 component in boiling
NaCl solutions: U.S. Geological Survey Bulletin 1421-A, 73 p.
Ingham, J. W., 1928, The apparent hydration of ions. Part I. The
densities and viscosities of saturated solutions of sodium and
potassium chlorides in hydrochloric acid: Journal of the American
Chemical Society, v. 50, p. 1917-1930.
Postnikov, V. A., 1968, Density and viscosity of saturated aqueous
solutions of certain substances: Zhurnal Prikladnoi Khimii, v.
44, p. 236-238.
Potter, R. W., II, Babcock, R. S., and Brown, D. L., 1977, A new method
for determining the solubility of salts in aqueous solutions at
elevated temperatures: Journal of Research of the U. S.
Geological Survey, v. 5, p. 387-395.
Potter, R. W., II and Clynne, M. A., 1978: Solubility of highly
soluble salts in aqueous media - Part I. NaCl, KC1, CaCl2»
Na 2S04, and K 2S04 solubilities to 100°C: Journal of
Research of the U. S. Geological Survey, v. 6, p. 701-705.
Volz-Fladrich, H., 1962, Physical-chemical investigation of the systems
MgCl 2 -HCl-H2 0, NaCl-HCl-H2 0, and KC1-HC1-H2 0: Freiberger
Forschungshefte, v. 134, p. 1-85.
Table 1. Comparison of the experimental values of pure water with the
internationally accepted values from the ASME steam tables*

T°C p measured p ASME A = p ASME - p meas

g/cm3 g/cm3 g/cm3 x 104

19.60 0.9983 0.9983 0

28.55 .9960 .9961 1
36.75 .9936 .9934 -2
43.70 .9908 .9908 0
50.17 .9880 .9880 0
58.77 .9837 .9838 1
68.73 .9785 .9784 -1
75.44 .9745 .9745 0
81.38 .9710 .9708 -2
89.49 .9655 .9656 1

Table 2. Experimental densities for saturated NaCl

solutions and the deviations from the
least-squares regression.

T°C Experimental p deviation

g/cm3 g/cm3 x 10^

14.02 1.2049 2
17.37 1.2031 -2
25.37 1.1998 0
33.02 1.1964 -1
40.97 1.1928 -2
47.46 1.1902 0
49.83 1.1891 -1
49.93 1.1892 1
56.11 1.1866 2
60.80 1.1846 2
60.86 1.1846 2
60.91 1.1846 2
68.24 1.1812 0
68.27 1.1811 -1
70.25 1.1801 -2
70.27 1.1801 -2
73.54 1.1791 2
78.85 1.1765 -2
88.27 1.1726 0
88.53 1.1725 0
96.4 1.1692 1
96.7 1.1689 -1
103.4 1.1662 1
103.7 1.1661 0
 Table 5. Comparison of the equations derived from the experimental densities with the
densities determined in previous studies. (A = observed - calculated)

NaCl KC1

Reference T°C AxlO4 Reference T°C AxlO4

g/cm3 g/cm3

Earl of Berkeley (1904) 0.35 -16 Earl of Berkeley (1904) 0.7 -10
ii 15.20 -22 19.55 -9
11 30.05 -22 11 32.80 -11
11 45.40 -20 11 59.85 -12
" 61.70 -17 11 74.80 -13
11 75.65 -16 11 89.45 -21
11 90.50 -15 11 108.0 -30
11 107.0 -13 Blasdale (1918) 0 -41
Blasdale (1918) 0 -38 25 +57
it 25 -9 50 +2
11 50 -21 75 -46
11 75 + 18 11 100 -2
it 100 +55 Ingham (1928) 25 -12
Ingham (1928) 25 -18 Cornec & Krombach (1932) 0 -1
Cornec & Krombach (1932) 0 -18 20 -11
ii 20 -18 40 -5
" 40 -14 11 60 -2
it 60 -8 80 -11
11 80 -1 11 100 -31
ii 100 -15 108.5 -60
" 108.7 -17 Volz-Fladrich (1962) 0 -5
Volz-Fladrich (1962) 0 -14 i. 25 -14
ii 25 -19 35 -14
11 35 -19 45 -15
" 45 -20 Postnikov (1968) 10 -6
Postnikov (1968) 20 -1 11 20 -21
11 30 +13 30 -10
11 40 -4 40 -15
ii 50 -11 11 50 -8
11 60 +2 11 60 -2
ii 70 -4 11 70 10
ii 80 -1 80 21
Haas (1976) 80 +9
ii 85 +10
ii 90 + 12
ii 95 +14
ii 100 +5
ii 105 +7
ii 110 -1
 Table 3. Experimental densities for
saturated KC1 solutions and the deviations
from the least-squares regression.

T°C Experimental p deviation

g/cm-* g/cm-*

13.15 1.1687 0
13.52 1.1692 1
23.35 1.1780 0
30.06 1.1831 0
36.88 1.1873 -2
44.99 1.1925 3
53.86 1.1965 0
61.96 1.2000 0
69.24 1.2026 -2
79.61 1.2061 -1
89.65 1.2090 3
98.8 1.2101 -2
103.3 1.2107 1
104.2 1.2108 0

Table 4. Coefficients for the least-squares regression of the experimental

densities and the mean deviation of the data from a smooth curve

a3 a4 y sx!04

NaCl 1.21088 -4.38857xlO"4 6.124017xlO" 8 1.2

KC1 1.15301 1.3942 xlO" 3 -1.6718 xlO" 5 1.3514xlO" 7 -4.997x10"!° 1.0

Note: These equations are valid from 10°C to 105°C and can not be extrapolated with
any reliability.
Table 6. Smoothed values for the densities of
saturated solutions of the respective
salts.

T°C Psat Psat

NaCl KC1
g/cm3 g/cm3

10 1.2065 1.1653
15 1.2043 1.1706
20 1.2021 1.1753
25 1.1999 1.1794
30 1.1978 1.1831
35 1.1956 1.1864
40 1.1934 1.1894
45 1.1913 1.1922
50 1.1891 1.1947
55 1.1869 1.1970
60 1.1848 1.1992
65 1.1826 1.2012
70 1.1805 1.2030
75 1.1783 1.2048
80 1.1762 1.2063
85 1.1736 1.2077
90 1.1719 1.2089
95 1.1697 1.2098
100 1.1676 1.2105
105 1.1655 1.2108
 measuring circu

A
0
CT1*"T
r11 I
o , Temperature

r 1 a p=J
controller
Aluminum lid

b_^>* . **+ -^
Platinum
resistance

j i
mi thermometer

^iL
«
s. j
Hydrometer
N /
Pyrex cylinder

Saturated
solution

Glycol bath

*r t\
^ ftV Salt crystals

Figure 1. Schematic diagram of the experimental

apparatus used in this investigation.

10