Fusion Engineering and Design 13 (1990) 59-71 59

North-Holland

Properties of LiOH and LiNO, aqueous solutions

P.J. Gierszewski ‘, P.A. Finn 2 and D.W. Kirk 3
’ Cauadiatr Fusion Fuels Technology Project , 2700 Lnkeshore Rd. W, Mississauga, Ontario CANADA LSJ lK3
‘Argonne National Laboratory 9700 South Cass Avenue, Argonne, Illinois USA 60439
’ Dept. 01 Chetnical Engineering and Applied Chemisrty, University of Toronto, Toronto, Ontario, CANADA M5S IA4

Submitted 1989; accepted 15 February 1990

Handling Editor: R.W. Conn

Engineering data for l-15 molal aqueous solutions of LiOH and LiNO, are summarized. These data include values
previously published in the literature, as well as new measurements for LiOH. Data on salt solubility, density, specific heat,
thermal conductivity, viscosity, electrical conductivity, gas solubility, surface tension, heat of solution, vapor pressure, thermal
expansion, compressibility and activity coefficient are presented, with emphasis on temperatures between 20-100 o C.

1. Introduction pressures,Cooke et al [4] provide estimates for the most

Aqueous lithium salt solutions have been proposed
as a tritium breeding medium for next-generation mac-
hines [1,2] and for power reactors [3]. In the near-term,
these salts could serve as the breeder and coolant in a
driver blanket for an ITER-class machine, at operating
conditions of less than 100° C and 2 MPa in a 316L
stainless steel system.
Tritium breeding in these aqueous salt solutions in-
creasesrapidly with concentration up to around 1 molal
lithium atoms [1,3], and then starts to level off. Al-
though there are many lithium salts, LiOH and LiNO,
are currently preferred because of their corrosion, radi-
olysis, lithium atom density and activation properties.
Typical salt concentrations of interest are 2-5 molal
LiOH and 5-15 molal LiNO,.
This report presents property data for these lithium
salts under the conditions of interest to ITER-class
machines. The available data are orgnaized into a con-
sistent form; however, a critical review of the data was
not attempted.
At low salt concentrations, property variation with
salt concentration may be inferred from theory and
from similar salt solutions. Also, property variation
with temperature and pressure may be inferred from the
behavior of pure water. However, for the high salt
concentrations of interest here, these scalings may not
apply so we have limited this report to experimental
data. For LiNO, solutions at high temperatures and
important engineering properties.
2. Units
The salt solution concentration is expressed in the
literature in a variety of units. In this report, we use
molality as this is the SI unit, and is independent of
temperature and pressure. Molality (m) is the number
of moles of solute per 1 kg of solvent. Other common
units are summarized below, along with their conver-
sion factors into molality:
Molarity (M), moles of solute per liter of solution:
nr = 1000 M/( dsoln- M MW,,,,).
Weight percentage of solute in total weight of solution
(WI:
M = 10 W/(1 - W/100) MWsn,,.
Grams of salt per 100 g water (G):
m = 10 G/M Wsnl,,
where MWsa,, is the molecular weight of the salt in
g/mol(23.95,68.94 and 109.94 for natural LiOH, LiNO,
and Li,SO,, respectively), and dsolnis the density of the
solution in kg/m3.
A Normal solution contains one gram molecular
weight of the solute divided by the hydrogen equivalent

0920-3796/90/$03.50 0 1990 - Elsevier Science Publishers B.V. (North-Holland)

60 P.J. Gierszewski et al. / Properties of LiOH and LiNO, aqueous solutions

Table 1
Conversion between salt concentration units
LiOH concentration LiNO, concentration
,?I M W G M M G
MolaI golar) (Molar) (wt%) (g/100 g) (Molar) (Molar) (C%) w100 9)
4o”c 9o”c 4o”c 9o”c
0 0 0 0 0 0 0 0 0
1 0.995 0.969 2.34 2.4 0.962 0.937 6.45 6.9
3 2.98 2.91 6.70 7.2 2.72 2.65 17.1 20.7
5 4.94 4.85 10.7 12.0 4.29 4.18 25.6 34.5
10 NA NA NA NA 7.55 7.34 40.8 68.9
15 NA NA NA NA 10.1 9.78 50.8 103.4

of the substance (that is, one gram equivalent) per litre lOO”C, and is based primarily on original data by
of solution. For LiOH and LiNO,, 1 Normal equals 1 Ditmar [9] and Pickering [lo].
Molar. The solubility limit for LiNO, in water is shown in
Table 1 provides salt concentrations in these units. fig. 2 for temperatures up to 110 o C. Again there seems
to be two curves reported in the literature, here differing
by up to 12% (3 molal) at 30° C. The upper curve is
3. Solubility from original data by Campbell and Bailey [ll], also
reported in Linke [6]. The lower curve appears to be
The solubility limit for LiOH in water is shown in based primarily on Donnan and Burt [12] as reported in
fig. 1 for temperatures up to 330°C. Data are shown Stephen and Stephen [5], Linke [6], and the Intema-
from three references: Stephen and Stephen [S] and tional Critical Tables [S]. The data shows a large in-
Linke [6], both reference handbooks; and original data crease in LiNO, solubility above 30° C due to the
from Stephan and Miller [7] at higher temperatures. change from LiNO, .3H,O to LiNO, . OSH,O.
Data from the International Critical Tables [S] are not
shown, but are consistent. The solubility reported by
40 7 I
the handbooks has a spread of up to 10% (0.7 molal) at

6
30

LiN03
solubility 20
Stephan (molal)
8 Miller
.
LiOH
/
Solubillty 6
(IllOkl) Linke 11
‘\/’ 10
7:
.I ,Y
000,x
lxx
5
‘*\
Stephen O!
8 Stephen
0 40 80 120
Temperature, C
4
Fig. 2. Solubility limit of LiNO, in water. The sources are: SS
0 100 200 300 400
Temperature. C
- Stephen and Stephen [5]; ICT - International Critical Tables
[8]; CB - Campbell and Bailey [12]; and Al, A2 - two sets of
Fig. 1. Solubility limit of LiOH in water. data provided in Linke and Atherton [6].
 P.J. Gierszewski el al. / Properties of LiOH and LiNO, aqueous solutions 61

Stephen and Stephen [S] and ICT [8] are good refer- 1.4

ences for other lithium salts of interest. For Li,SO,, the

solubility is within 10% of 3 molal over 0 to 100’ C. For
LiNO,, the solubility increases uniformly with tempera-
ture from 13 molal at O” C to 210 molal at around
100°C. The solubility of Li,Cr,O, varies from about
0.7 to 1.1 molal over 30 to 100 o C [13]. 1.2
Density
(x1000
4. Density kgh3)
1.1

The density of LiOH is shown in fig. 3 for con-

centrations up to the solubility limit and between 0 to
80’ C. The main references are the International Criti-
cal Tables (ICT) [14] and recent extensive measure-
ments by Herrington et al. [15] and Roux et al. [16]. The
different sources are in very good agreement. Data is 0.9
available at many temperatures between 0 and 80° C, 0 4 a 12 16
but are only shown at 25, 55 and 80 o C in fig. 3 since LiN03 concentration (molal)
the variation with temperature is not large. The com-
Fig. 4. Density of LiNO, aqueous solutions (data at other
plete set of data from these references was curve-fitted temperatures is available in the literature). The sources are ICT
to obtain the following density correlation (consistent [14] solid circles, and Puchkov et al. [17,18] open circles.

with the data to within 0.3%), where d is in g/cm3, C is

in molality, and T is in o C:

dLiOH = 1.0012 + 0.0277C - 7.921 x 1-4Cz

1.12 +(-6.795x10-5-4.751x10-5C

-1.756 x 10-6C2)T

/’
/’ + (-3.331 X lo+ + 9.156 x lO+‘C

1.07 -’
/
f /’ +1.042x lo-‘C2)T2.
There is extensive density data available for LiNO,,
primdrily from the ICT [14] and more recent measure-
Density ments up to 350°C and 130 molal by Puchkov et al.
(x1000 .I’
kg/m3) [17,18]. These sources are in very good agreement. Fig-
/’
ure 4 illustrates the data trends between 0 and 300 o C
‘0 for 0 to 16 molal. Puchkov et al [18] provide a correla-
1.02 -
,$ / lL tion for LiNO; density that is reported to be accurate to
1.5% (about the same as the measurement error) be-
.//,
tween 25 and 300 o C and up to 40 wt% (10 molai) salt,
./O l
where d is in g/cm3, W is in weight per cent LiNO,,
./
and T is in “C:
0.97 7 ’ ’ , ’ ’ . ’ -r dLiN0, = 1.003 + 5.765 x 10-3W+ 0.375 x 10-4W2
0 1 2 3 4 5
LiOH concentration (molal) + (- 1.898 x 1O-4 - 1.096 x 10-sw
+ 0.9375 x lo-‘W2) T
Fig. 3. Density of LiOH aqueous solutions at temperatures of
25, 55 and 80 o C (data at other temperatures is available in the + (-2.497 X lo-+’ + 6.500 x lo-‘W
literature). The sources are ICT [14] solid circles; Herrington et
al. [15] open circles; and Roux et al. [la] solid squares. +0.4229x 10-9W2)T2.
 62 P.J. Gierszewki et al. / Properties of LiOH ad LiNO, aqueous solutions

100
This LiNO, data was obtained at a pressure slightly -r
higher than the solution vapor pressure.
For other lithium salts, density data may be found in
ICT [14] and correlation equations in Novotny and
Sohnel [19].

5. Viscosity
Viscosity
(x0.0001 10
Viscosity data for LiOH are reported in ICT kg/m-s)
(0, 25, 50, 75” C) [20], Hitchcock (20, 30, 40°C) [21],
and Mashovets et al. (0-275O C) [22]. One of us
(D.W.K.) also systematically measured the viscosity of
LiOH over 20 to SO’C, using a Cannon Viscometer
calibrated using deionized water. The values for viscos-
ity are in good agreement between the various sources.
Figure 5 shows the data at some of the available tem-
peratures. The viscosity for LiOH increases with pres-
1
sure by only 0.2% up to 20 MPa (water viscosity in-
0 5 10 15
creasesby about 1%) [22], for temperatures up to 100 o C. LiNO3 concentration (molal)
The data for LiNO, is shown in fig. 6, and includes
Fig. 6. Viscosity of LiNO, aqueous solutions (data at other
fairly extensive measurements up to 275OC and 26 temperatures is available in the literature). Solid circles are
molal [20,23]. Puchkov and Sargaev [23] (the most re- from ICT [20], open circles are from Puchkov and Sargaev [23].
cent and extensive data set) state that their results are in
good agreement with most literature data.

Viscosity data for LizSO, is reported in ICT [20] and

100 by Pushkov and Sargaev [24]. For 2.3 molal at 75°C

/” the viscosity is 0.0011 kg/m s [24]. This compares with

0.0004, 0.0005 and 0.0006 kg/m s for water, LiNO, and

m/=20
0’ I c #40 c
LiOH, respectively, at the same conditions.

./ 6. Electrical conductivity
.!A
q 6OC
,‘A
,‘I
Viscosily
c .A0 c-
The electrical conductivity of a solution is typically
(x0.0001 10
kg/m-s) I- expressed as either specific conductance o in l/(Qm),
0’ . 100 c or as an equivalent conductance A in m2/(s2mol) where
1’
. A = 1000 o/C, and C is the salt concentration
150 c (mol/m3). In the limit of infinite dilution, as C ap-
,.T* . l
proaches zero, the equivalent conductance approaches a
value unique to the solvent, called the equivalent con-
275 c
,.A.
::I--:il!- -. ductance at infinite dilution.
.--- LiOH solution electrical conductivity data is re-
1 - */* * ported by ICT (18, 30, 50, 60° C) [25], Darken and
0 2 4 6 Meier (25OC) [26], and Lown and Thirsk (25” C) [27]
LiOH concentration (m&l) up to 5 molal. This database was extended by one of the
authors (D.W.K.), using a CDM83 conductivity meter
Fig. 5. Viscosityof LiOH aqueoussolutions (data at other
temperaturesis available in the literature). Open circlesare (Radiometer Copenhagen), and with the cell constant
from ICT (141, solid circles are from Mashovets et al. (221, solid determined from KC1 measurements at 25 o C. Figure 7
squares are from Hitchcock [21], and open squares are recent shows the specific conductance of LiOH aqueous solu-
unpublisheddata by one of the authors(DWK). tions. At 25OC, the range of values reported is about
 P.J. Gierszewski er al. / Properties of LiOH and LiNO, aqueous solutions 63

25

20

15

conductance conductance
(l/ohm-m) (l/ohm-m)
10
25

0 0
0 2 4 6 0 2 4 6 6
LiOH concenlralion (molal) LiNO3 concenlration (modal)

Fig. 7. Specific conductance of LiOH aqueous solutions (data
at other temperatures is available in ICT [25]). The solid
squares are recent unpublished data by one of the authors
[DWK], the open circles are from ICI [25], the open squares
are from Lown and Thirsk [27], and the open triangles are
from Darken and Meier [26].
30-40/Qm at 5 molal. Our data and ICT [25] agree
within 3/0m at 50-60°C.
The pressure dependence of LiOH electrical conduc-
tivity was measured by Lown and Thirsk [27]. Over
0.98-S molal and 25-150” C, increasing the pressure
Fig. 8. Specific conductance of LiNO, aqueous solutions. Solid
squares are from Behret and Schmithals [28], open squares are
from Postler [29], and open circles are from ICT [25].
depressed the thermal conductivity of water by less than
5%.
Other data [e.g., 301 suggest that the thermal conduc-
tivity of various aqueous salt solutions falls slowly with
increasing concentration and have the same temperature
dependence as water, at least up to 5 molal and 100 o C.
0.7

from 0.1 to 300 MPa increases the specific conductance

up to 15% (less than 3% for 50 MPa). They conclude
O’,; 0 water, 100 c
that conductance in LiOH, in contrast to NaOH and
KOH occurs primarily by the proton transfer mecha- o,65i Wa’er”OOC 1 _//_/^ LiOH.36C
LiOH. 36 C )
nism. 0.65 - /
The specific conductance of LiNOs is shown in fig. 8
at 25OC [28,29]. At 0.1 molal, the conductance varies Thermal
;A- LiOH. 20 C
with temperature from 0.74/9m at 0 o C, to 0.9/8m at cond.
(W/m-K) I// /.
25 o C, to 1.4/9m at 50 o C [25]. No data was found at
temperatures above 25OC and concentrations above 7
molal. 0.13 -1.
-----.
Li2S04, 20 C

7. Thermal conductivity

The available data on thermal conductivity of these 0.55 ,

salt solutions is summarized in fig. 9. In particular, we 0 2 4 6
Salt concentration (molal)
found data on thermal conductivity of LiOH at 20’ C
[30] and 38°C [31], and LizSO at 20°C [30], but none Fig. 9. Thermal conductivity of LiOH and LizSO aqueous
for LiNO,. For these conditions (up to 5 molal), the salt solutions.
64 P.J. Gierszewski et al. / Properties of LiOH and LiN03 aqueous solutions

Over O-300 o C and 0.1-20 MPa, the thermal conductiv-

ity of water varies by only 5% [30].

8. Heat capacity
1 A 25GLiZSO4 ] .
. 0
8 .
Measurements of the heat capacity of LiOH have -m-¤ a I
been reported for concentrations up to 5 molal and
temperatures of 18-25 and 55OC [16,32,33]. The dif-
ferences between these sources at 20-25 o C is less than
5%, but comparable to the effect of the salt itself on the
heat capacity. In fig. 10, only the recent data from Roux
et al. [16], and the recommended heat capacity values at I IA I I I
25OC from Parker [34] are shown since these are the Li SC!
2 4
most comprehensive.
For LiNO,, data at 18-20°C is reported [32,33] up
to 2 molal. Again, the evaluated heat capacity at 25°C 0.1 -I I I I -I
based on these (and other) sources is shown in fig. 10 0 2 4 6 6
from Parker [34]. Petrov and Puchkov [35] appear to Salt concenlralion (molal)
report a value of 3710 J/kg K at 22 molal and 18OC.
Fig. 11. Hydrogen solubility in LiOH, LiNO, and LizSO
The heat capacity of pure water increases by up to aqueous solutions at 0.1 MPa H, partial pressure [36].
7% over 0 to 200 OC, and decreasesby only about 1%
for pressures from 0.1 to 10 MPa [30]. At the critical
point (374OC and 22.1 MPa for pure water), the heat
capacity is infinite. As the addition of the salt changes solute becomes infinite as the temperature and pressure
the critical point, the ‘apparent heat capacity’ of the approach the critical point of water.

4300 9. Gas solubility

Recent measurements of the solubility of hydrogen

and oxygen gases at one atmosphere total pressure in
LiOH, LiN4 and Li,SO, are reported by Elliot et al.
4100
[36]. No other hydrogen data has been found, and these
results are shown in fig. 11. The results indicate an
Heal
increase in solubility for LiNO, with temperature at
capacity ;\.-, LiOH. 55 C 70 o C. In pure water, such an increase also occurs but at
(J/kg-K) . 0 Roux et al a higher temperature.
-4-Y . Oxygen solubility has also been reported at 37 o C by
3900 [37] and at 25OC [38]. Figure 12 shows the data. The
Roux et al data from Khomutov and Konnik [38] is not included
since it extends only to 1.2 molal, shows a higher
solubility in LiNO, than in water, and may be sensitive
LiN03, 25 C
to oxidizing impurities because of the technique used.
D , Elliot et al. [36] and Lang and Zander [37] are in good
4 6
agreement for LiNO,, but in poor agreement for LiOH.
0 2
Salt concentration (molal) The solubility of 0, in 2.0 molal Li,SO, is reported as
Fig. 10. Heat capacityof LiOH [16,34] and LiNOs [34] aque- 0.22 and 0.28 mmol/l respectively, at 25“ C [36] and
ous solutions. (data at 20°C for LiOH is available in refs. 37 o C [37], at 0.1 MPa gas partial pressure. The solubil-
[32,33]). For LiOH at 2S” C, the recommended values from ity of 0, in pure water is 1.27, 1.08 and 0.83 mmol/l at
Parker (341 are shown as solid squares, while the later data 25, 37 and 70 a C, respectively, and 0.1 MPa 0, partial
from Roux et al. [la] are solid circles. pressure [39].
 P.J. Gierszewski et al. / Properiies of LiOH and LiN03 aqueous solutions 65

For the hydrated crystals, the heat of solution data is

more inconsistent. However, the values are around -4
to - 7 kJ/mol for LiOH . H,O, + 30 kJ/mol for LiNOs
.3H,O, and - 20 kJ/mol for LizSO,. H,O. Lithium
0 25C.LiN03,ECO
hydroxide monohydrate is formed with LiOH solutions
are crystallized at room temperature.
q 7OC, LIN03,ECO
Richards and Rowe measured the heat of dilution
Oxygen for LiOH and LiNO, at 20 o C from 2.2 to 0.14 molal
solubility [43]. However, a more recent and comprehensive
al 0.1 MPa
(mmol/L) evaluated heat of dilution table is provided by Parker
[34] and 25 o C for LiOH from 4.6 molal (- 3.8 kJ/mol
to infinite dilution) and for LiNO, from 2.2 molal
(- 1.2 kJ/mol to infinite dilution).

11. Surface tension

0.1 A limited amount of surface tension data is available

0 2 4 6 a for these salts - LiOH data at 18°C [44] and 20°C
Salt concentration (molal)
[45]; and LiNO, at 18OC 1441,and 20 and 40 QC [32]. It
Fig. 12. Oxygensolubilityin LiOH and LiNO, aqueoussolu- is summarized in fig. 13. The data is in good agreement
tions at 0.1 MPa O2 partial pressure.Data are from Elliot et al between the sources at 18 and 20°C. The surface ten-
(ECO)[36] and Lang and Zander(LZ) [37].
sion of Li,SO, is 0.077 N/m at 18OC and 1.5 molal
WI.
There are no data for solubility at higher pressures
for these salts. However, in pure water the solubility of 12. Vapor pressure and boiling point
non-polar gases such as H, and O2 can be reasonably
extrapolated to higher pressures based on Henry’s law. There is a reasonable amount of vapor pressure data
The approximate limits for application of Henry’s law for LiOH and LiNOs solutions. In order to usefully
to H, and Oa in water are 10 MPa between 0 and
100° C, and 13 MPa at 300°C [40].
0.08 . I
LiOH, 20 C
,0- 0
10. Heat of solution
0.075 - , 0/&NO3,2OC
Heat may be releasedwhen LiOH and LiNOj crystals I’
are dissolved in water, or when an aqueous solution is /=o’*
A LiNO ,4C C
further diluted with additional water. The exact numeri- ,/-A---- 3
cal values are dependent upon the initial form (e.g., Surface
tension 0.07 ‘/ -A
LiOH or LiOH . Ha0 powder), and on the final solution (NW
concentration. Formally, the heat of solution or dilution
are negative values when the reaction is exothermic. b Waler, 60. C
The heat of solution for 1 mol of powder dissolved 0.065 I
in a large amount of water (e.g., greater than 55 mol of
water, or less than 1 molal) is -20 kJ for LiOH, -2.5
kJ for LiNO,, and - 30 kJ for Li,SO, at 2S” C and 0.1
MPa, with a variation of up to 10% depending on the 0.06
reference and the exact amount of dilution [41-431. The 0 1 2 3 4 5
other alkali hydroxides also are exothermic on dissolu- Salt concentration (molal)

tion in water, while other alkali nitrates are mostly Fig. 13. Surfacetension of LiOH and LiNO, aqueoussolu-
endothermic.
66 P.J. Giers:ewski et al. / Properties of LiOH and LiNO, aqueous solutions

present the data (which varies by order of magnitude 1

with temperature), the pressure has been normalized to

that of water [30]. For LiOH (fig. 14), data is reported
by Fricke (0 and 10” C) in Mellor [46] and Gmelins
[32], Kangro and Groeneweld (20 and 25 o C) [47], ICT
(100 o C) [48], Stephan and Miller (120-350 o C) [7], and
Krumgal’z and Mashovets (300 and 350°C) [49]. There
vapor
is very little variation with temperature over 0 to 25 o C, pressure
but significant variation at higher temperatures, with 01 LiNO3
0.6
solution
some scatter in the data. The data extremes at 100 and relative
350° C are shown in the figure. The sources do not IO water
overlap much in temperature for comparison, except at
O-25 o C and 300-350 o C, where the agreement is good. 0.4
For LiNO, (fig. 15), the effect of temperature over
25-300 o C is small. Data are reported by Campbell et
al. (30-105O C) [50], Pearce and Nelson (25O C) [51],
Kangro and Groeneweld (20, 25°C) [47], Sacchetto et
al. (45-11OOC) [52], Puchlcov and Matashlcin (150- 0.2 -I
0 10 20 30
300 o C) [53], Braunstein and Braunstein (100 o C) [54], LiNO3 concentration (molal)
and ICT (30-100°C) [48]. The data from different Fig. 15. Vapor pressure of LiNOJ aqueous solutions relative to
sources overlap considerably and are in good agree- water (data at intermediate temperatures is available in the
ment. literature). The sources are: PN - Pearce and Nelson [51]; KG
The boiling point can be estimated from these fig- - Kangro and Groeneweld [47]; Sa - Sachetto et al. [52]; BB -
ures and the vapor pressure of water. At 0.1 MPa, the Braunstein and Braunstein [54]; ICT [48]; Ca - Campbell et al.
boiling point is 101-105° C for 2-5 molal LiOH and [50]; and Pu - Puchkov and Matashkin [53].
110-115°C for 10 molal LiNO, [14]. At 1 MPa, the

boiling point would be 180-190 ’ C for 2-5 molal LiOH,

and 200-210° C for 10 molal LiNO,. And at 5 MPa,
the boiling point of 5 molal LiOH is still only around
5 o C more than that for water (265 o C for water), while
it is almost 300 o C for 10 molal LiNO,.
Vapor pressure and boiling point data for Li,SO,
and Li,CrO, may be obtained from ICT [14].
vapor
press”re
of LiOH
solution 13. Thermal expansion and compressibility
relalive
IO water
The coefficient of thermal expansion is defined as
a = (l/u) (du/dT), where u is the specific volume (the
inverse of the density) and T is the temperature. For
LiOH and LiNO,, there is almost no direct reporting of
volumetric thermal expansion coefficients. However,
there are extensive density data measurements which
0.6l...I...I...I..,I are in quite good agreement between the various sources.
0 2 4 6 6
LiOH concenlration (mold) Correlations which fit this data to within 0.3% (LiOH)
and 1.5% (LiNO,) were presented earlier, and the ther-
Fig. 14. Vapor pressure of LiOH aqueous solutions relative to mal expansion coefficient can be easily derived. The
water. The vapor pressure at 0 o C (solid circles) is from Fricke
results are shown in figs. 16 and 17. The calculated
[46,32], at 25 o C (open circles) from Kangro and Groeneweld
[47], at 100° C from ICT [48], at 350°C from Stephan and coefficients seem particularly inaccurate at tempera-
Miller (open triangles) [7] and Kmmgal’z and Mashovets (solid tures below 25 o C (there is poor agreement between the
triangles) [49]. calculated coefficient at zero concentration with data
 P.J. Gierszewski et al. / Properties of LiOH and LiN03 aqueous solurions 61

average compressibility of 0.00040, 0.00037 and

O.O0032/MPa at 0.55, 1.11 and 2.22 molal, respectively,
over 10 to 30 MPa [57], while LiNO, has O.O0028/MPa
at 1 molal [58]. These can be compared with the com-
pressibility of pure water, which varies from
Volume O.O0051/MPa at O’C and llO°C, and decreases to
thermal 0.00044 at 40-60 o C [56]. For pure water, this translates
expansion into a density increase of 1% as the pressure rises from
(x0.0001/K) 0.1 to 20 MPa.

14. Activity and osmotic coefficient

In an aqueous solution, the activity of ions differs

0 2 4 6
LiOH concentration (molal)
Fig. 16. Volumetric thermal expansion of LiOH aqueous solu-
tions, computed from a density correlation.
for pure water) and are therefore not shown at lower
temperatures. This inaccuracy is probably due to the
limited density data and the strong change in the expan-
sion coefficient at these lower temperatures. The calcu-
lated results for LiNO, compare favorably with mea-
surements by Wright [55], averaged over 25-78“C, of
0.00050-0.00054/K for l-10 molal. For reference, the
thermal expansion coefficient for water is - 0.00007,
0.00021, 0.00038, 0.00052, 0.00064 and 0.00075/K at 0,
20, 40, 60, 80 and 100’ C, respectively [56].
The compressibility of LiOH and LiNO, decreases
slowly with the addition of salt. At 25”C, LiOH has an
from their concentration by a dimensionless factor rep-
resented by the activity coefficient which accounts for
nonideal behavior. The solute and solvent activity coef-
ficient approaches unity as the concentration of all
solutes approaches zero. The single ion activity coeffi-
cient is the activity coefficient of the cation or anion
alone. The mean ion activity coefficient for a univalent
compound like LiOH or LiNO, is equal to the square
root of the product of the cation and anion activities.
Only the mean activity coefficient is reported here.
Figures 18 and 19 show the activity of water and
LiNO, in an aqueous solution. The water activity is
reported by Egorov et al. (150-350°C l-33 molal)
[59], Braunstein and Braunstein (loo0 C, 4-28 molal)
[54], and Campbell et al. (30-100°C, 2-27 molal) [50].
The variation between 30” C and 150 o C is not large,

Volume Waler
thermal activity
expansion
(x0.0001/K)
0.6 -

0 4 8 12 0 5 10 15
LiNO3 concenlralion (molal) LiN03 concentration (molal)

Fig. 17. Volumetric thermal expansion of LiNO, aqueous Fig. 18. Activity coefficient of water in LiNO, aqueous solu-
solutions, computed from a density correlation. tions (data at other temperatures available in the literature).
68 P.J. Gierszewki et al. / Properties of LiOH and LiNO, aqueous solutions

and the data at intermediate temperatures are not shown

in fig. 17. The different data sets do not overlap much
in temperature, but appear to be in good agreement.
Water activity coefficients are also provided by Puch-
kov and Matashkin [53], but their results seem con-
sistently much higher than these other references, and
their data are not shown here. The salt activity is
reported by Egorov et al. (25-350 o C, l-10 molal) [59], LiOH
Robinson (25OC, 0.1-13.5 molal) [60], Hamer and Wu activity

(25 o C, O-20 molal) [61], and Pearceand Nelson (25 o C,

O-13 molal) [51], again with good agreement except for 0.6

Pearce and Nelson whose coefficients are up to 25%

higher.
Figure 20 shows the activity of LiOH in aqueous
solution at 25OC [61,32]. No values for the water activ-
ity in LiOH solutions were found. The activity coeffi-
cient for Li,SO, in solution is 0.300 at 25 o C and 3.16
molal [62], and for LiNO, it is 3.67 at 25OC and 19
molal [63].
The activity coefficient can also be estimated directly
from theory and empirical formulae. For example, using
the Kusik and Meissner approach appropriate for these
high salt concentrations [64], we estimate that the activ-
ity coefficient for LiNO, and water in a 6 molal solu-
tion are 1.4 and 0.72 respectively, in good agreement
10
0.4 -I
0 2 4 6
LiOH concenlralion (molal)
Fig. 20. Mean ion activity coefficient of LiOH in an aqueous
solution. The open circles are from Gmelins [32] and the closed
circles are from Hamer and Wu [61].
with the values from figs. 18 and 19. Applying this
theory to LiOH, the activity coefficients for LiOH and
water in 4 molal solution are 0.37 and 0.90, respectively.
For 9 molal Li,SO,, the activity coefficients are 0.56
and 0.72 for the salt and water, respectively.
The extent of dissociation of LiOH in aqueous solu-
tions is reported by Heyrovska [65] (at 25OC) and
decreasing from 0.84 at 0.1 modal to 0.69 at 1.0 molal,
and remaining at 0.69 up to at least 2.5 molal. For

Table 2
Typical impurities in commercial LiOH (wt%)
LiNOB
activily
Element Fisher Lithcoa Lithcoa 4 molaf
analytic regular purified LiOH
LiOH.HaO LiOH*H,O LiOH.H,O solution”)
C 0.08 0.08 0.01
Na 0.01 0.002 0.0007
S c 0.007 0.0035 0.0007 0.0001
Cl < 0.001 0.001 0.0002
0.1 Ca - 0.007 0.007 0.001
0 5 10 15 Fe < 0.005 0.0007 0.0007 0.0002
LiNO3 concentration (mold) cu < 0.005 - 0.00007
Zn < 0.005 - 0.00007
Fig. 19. Mean ion activity coefficientof LiNOs in an aqueous Cd < 0.005 - 0.00007
solution (data at other temperatures is available in the litera-
Pb < 0.005 - 0.0007
ture). The data at 25 o C is from Robinson (closed circles) [60], Insolubles - 0.002 < 0.002 -
Egorov et al. (open circles) [59] and Hamer and Wu (open
triangks) [al]. The data at higher temperatures is from Egorov @ Based on the LiOH source impurities. Not including water
et al. [59]. impurities or effect of on-line purification systems.
 P.J. Giersrewski et al. / Properties of LiOH and LiNO, aqueous solutions 69

Table 3 2-30 molal. Most appear to be within about 10% accu-

Typical impurities in commercial LiNG, (wtg) racy. For LiOH, the database generally covers the con-
Element BDH 10 molal ditions of most interest, although one could suggest
reagent LiNO, ‘) extending the data base up to 100 o C for density, elec-
trical conductivity, thermal conductivity and specific
Salt >99 >40
Na heat. The lack of data for LiNO, thermal conductivity is
< 0.005 < 0.002
< 0.0001 < 0.00004 not considered serious since it is not expected to differ
Mg
Al < 0.000005 <0.000004 dramatically from water under conditions of interest.
K < 0.003 < 0.0012 In a few cases, the variation in property plus the
Ca < 0.0005 e 0.0002 experimental uncertainty is large enough to be of con-
Mn < 0.000001 <0.0000004 cern. These cases are the electrical conductivity and
Fe < 0.000005 <0.000002 heat capacity of LiNO,, and the solubility of H, and 0,
co < 0.000001 co.oooooo4 in both LiOH and LiNO,.
Ni < 0.000001 <0.0000004
CU < 0.000001 c0.0000004
Zn < 0.000005 <0.000002
Rb < 0.0001 < 0.00004 References
Sr < 0.0005 c 0.0002
Cd < 0.000001 <0.0000004 PI W. Daninner et al., Status of NET shielding blanket devel-
cs c 0.0005 < 0.0002 opment, 15th Symp. Fusion Technology, Utrecht, Nether-
Ba e 0.0005 e 0.0002 lands, 19-12 September 1988.
Tl c 0.000001 <0.0000004 K. Tomabechi and the ITER Team ‘ITER: Concept Defi-
PI
Pb <0.000006 -0.000002 nition’, 12th Int. Conf. on Plasma Physics and Controlled
Nuclear Fusion Research, Nice, France, 12-19 October
n) Based on the LiNOa source impurities. Not including water
1988 (IAEA-CN-50/F-I-4).
impurities or effect of on-line purification systems.
131 C.P.C. Wong et rd., The TITAN-II reversed field pinch
aqueous fusion power core design, IEEE Symp. Engineer-
ing Problems of Fusion, Monterey, California, 12-16 Oc-
LiNO,, the fraction dissociated decreases slightly from tober 1987.
0.86 at 0.1 molal to 0.83 at 0.4 molal, and remaining at 141 P.I.H. Cooke et al., Properties of concentrated aqueous
0.83 up to at least 1.6 molal. lithium nitrate solutions and applications to fusion reactor
The osmotic coefficient of LiNO, increases roughly design, Fus. Engrg. Des. 8 (1981) 379.
linearly from 0.938 at 0.1 molal to 1.75 at 13.5 molal t51 H. Stephen and T. Stephen, eds., Solubilities of inorganic
[60,61] at 25°C. The osmotic coefficient for LiOH and organic compounds, Vol. 1, Part 1 (Pergamon Press,
increases from 0.856 at 1 molal at 0.933 at 5 molal [61] New York, 1979).
at 25OC. WI W.F. Lit&e, ed., Solubility of inorganic and metal-organic
compounds, Vol. II, 4th ed. (American Chemical Society,
Washington D.C., 1965). (Also in prior editions edited by
A. Seidell et al.).
15. Impurities
171 E.F. Stephan and P.D. Miller, Solubility of lithium hy-
droxide in water and vapor pressure of solutions above
The impurities content of commercial reagent-grade 220’F, J. Chem. Eng. Data 7 (1962) 501.
LiOH and LiNO, is summarized in Tables 2 and 3. The VI International Critical Tables, Vol. 4 (McGraw-Hill, New
sources were Fisher Scientific Co., Lithium Corporation York, 1928) pp. 233-234.
of America, and British Drug House product informa- 191 W. Ditmar, J. Sot. Chem. Ind. 7 (1888) 730.
tion sheets. 1101S.U. Pickering, J. Chem. Sot. 63 (1893) 463, 909,998.
Pll A.N. Campbell and R.A. Bailey, The system LiNOs-
ethanol-water and its component binary systems, Can. J.
Chem. 36 (1958) 518.
16. Summary
WI F.G. Donnan and B.C. Burt, J. Chem. Sot. 83 (1903) 335.
1131 R.C. Weast, ed., CRC Handbook of Chemistry and
The available property data for high concentrations Physics, 56th ed. (CRC Press, Cleveland, 1975) p. B-107.
of LiOH and LiNO, dissolved in water have been P41 International Critical Tables, Vol. 3 (McGraw-Hill, New
summarized. Over the temperature range of 20-80 o C, York, 1928) pp. 76-78, 108, 296, 326.
the properties required for engineering applications are 1151 T.M. Herrington, A.D. Pethybridge and M.G. Roffey,
available for LiOH up to 5 molal, and for LiNOs up to Densities of aqueous lithium, sodium, and potassium hy-
70 P.J. Gierszewski et al. / Properties 01 LiOH and LiNO., aqueous solutions

droxides from 25 to 75’ C at 1 Atmosphere, J. Chem. Eng. electrolytes, US National Bureau of Standards, NSRDS-
Data 31 (1986) 31. NBS-2 (1965).
[Ia] A.H. Roux, G. Perron and J.E. Desnoyers, Capacites [35] G.I. Petrov and L.V. Puchkov, Adiabatic calorimeter for
calorifiques, volumes, expansibilites et compressibilitb des measuring specific heats of liquids in the temperature
solutions aqueuses concentrees de LiOH, NaOH et KOH, range from 0 to lOO”C, J. Appl. Chem. USSR 46 (1973)
Can. J. Chem. 62 (1984) 878. 2373.
[17] L.V. Puchkov and V.G. Matashkin, Density of aqueous [36] A.J. Elliot, M.P. Chenier and D.C. Ouellette, Solubilities
lithium nitrate solutions at high temperatures (up to of hydrogen and oxygen in concentrated lithium salt solu-
350°C) and concentrations, J. Appl. Chem. USSR, 52 tions, these proceedings.
(1979) 1103. [37] E. Lang and R. Zander, Salting-out of oxygen from aque-
[18] L.V. Puchkov and V.G. Matashkin, Density of LiNO,- ous electrolyte solutions: Prediction and measurement,
H,O and NaN03-H,O solutions at temperatures in the Ind. Eng. Chem. Fundam. 25 (1986) 775.
range of 2%300°C, J. Appl. Chem. USSR 43 (1970) [38] N.E. Khomutov and E.I. Konnick, Solubility of oxygen in
1864. aqueous electrolyte solutions, J. Phys. Chem. USSR 48
[19] P. Novotny and 0. Sohnel, Densities of binary aqueous (1974) 620.
solutions of 366 inorganic substances, J. Chem. Eng. Data [39] R. Battino, ed., Solubility data series: Oxygen and ozone,
33 (1988) 49. Vol. 7 (Pergamon Press, Oxford, 1981).
[20] International Critical Tables, Vol. 5 (McGraw-Hill, New [40] D.M. Himmelblau, Solubilities of inert gases in water:
York, 1929). p. 15. O°C to near the critical point of water, J. Chem. Eng.
[21] L.B. Hitchcock, Ind. Eng. Chem. 29 (1937) 302. Data 5 (1960) 10.
[22] V.P. Mashovets, L.V. Puchkov, P.M. Sargaev and M.K. [41] R.C. Weast, ed., CRC Handbook of Chemistry and
Fedorov, Viscosities of lithium, sodium and potassium Physics, 56th ed. (CRC Press, Cleveland, 1975) p. D-72.
hydroxide solutions at temperatures up to 275 o C, J. Appl. [42] J.H. Perry et al., eds., Chemical Engineers’ Handbook, 4th
Chem. USSR 46 (1973) 1055. ed. (McGraw-Hill, New York, 1963).
[23] L.V. Puchkov and P.M. Sargaev, Viscosities of lithium, [43] T.W. Richards and A.W. Rowe, The heats of dilution and
sodium, potassium, and ammonium nitrate solutions at the specific heats of dilute solutions of nitric acid and of
temperatures up to 275O C, J. Appl. Chem. USSR 46 hydroxides and chlorides and nitrates of lithium, sodium,
(1973) 2793. potassium, and cesium, J. Am. Chem. Sot. 43 (1920) 770.
[24] L.V. Puchkov and P.M. Sargaev, Viscosities and lithium, [44] International Critical Tables, Vol. 4 (McGraw-Hill, New
sodium, and potassium sulfate solutions at temperatures York, 1929) p. 463.
up to 275OC, J. Appl. Chem. USSR 47 (1974) 95. [45] Supplement to Mellor’s comprehensive treatise on in-
(251 International Critical Tables, Vol. 5 (McGraw-Hill, New organic and theoretical chemistry (Longmans, Green and
York, 1929) pp. 231, 238, 246, 254. Co., London, 1961) p. 159 (referencing 0. Faust, Z. Anorg.
[26] L.S. Darken and H.F. Meier, Conductances of aqueous Chem. 160 (1927) 373).
solutions of the hydroxides of lithium, sodium and potas- [46] Supplement to Mellor’s Comprehensive Treatise on In-
sium at 25 o C, J. Am. Chem. Sot. 64 (1942) 621. organic and Theoretical Chemistry, Vol. 2, Supp. 2, The
[27] D.A. Lown and H.R. Thirsk, Proton transfer conductance Alkali Metals, Part I (Lowe and Brydone, London, 1961)
in aqueous solution, Part 1, Trans. Faraday Sot. 67 (1971) p. 161 (referencing R. Fricke and L. Havestadt, Z.
132. Elektrochem. Angew. Phys. Chem. 33 (1927) 441).
1281 H. Behret and F. Schmithals, Conductivity measurements [47] W. Kangro and A. Groeneweld, Konzentrierte wlsserige
with concentrated Solutions of Alkali Chlorides and Losungen, Zeit Physik. Chemie Neue Folge 32 (1962) 110.
Nitrates, Zeit Naturforsch A200 (1975) 1497. [48] International Critical Tables, Vol. 3 (McGraw-Hill, New
[29] M. Postler, Conductance of concentration aqueous solu- York, 1928) p. 132, 296.
tions of electrolytes I; Strong uni-univalent electrolytes, [49] B.S. Krumgal’z and V.P. Mashovets, Aqueous LiOH solu-
Collection Czechoslov. Chem. Commun. 35 (1979) 535. tions at high temperatures, Russian J. Inorg. Chem. lO(11)
[30] N.B. Vargaftik, Tables on the thermophysical properties (1965) 1392.48.
of liquids and gases, 2nd ed. (Hemisphere, Washington, [50] A.N. Campbell, J.B. Fishman, G. Rutherford, T.P.
1975). Schaefer and L. Ross, Vapor pressures of aqueous solu-
[31] Z. Losenicky, The thermal conductivity of aqueous solu- tions of silver nitrate, of ammonium nitrate and of lithium
tions of alkali hydroxides, J. Phys. Chem. 73 (1969) 451. nitrate, Can. J. Chem. 34 (1956) 151.
[32] Gmelin’s Handbuch der Anorganischem Chemie, 8. [51] J.N. Pearce and A.F. Nelson, The vapor pressure of
Auflage, Lithium Erganzungsband System Nummer 20 aqueous solutions of lithium nitrate and the activity coef-
(Verlag Chemie GmbH, Weinheim/Bergstrasse, 1960) pp. ficient of some alkali salts in solutions of higher con-
268-292. centrations at 25 o C, J. Am. Sot. 54 (1932) 3544.
[33] International Critical Tables, Vol. 5 (McGraw-Hill, New [52] G.A. Sacchetto, G.G. Bombi and C. Macca, Vapor pres-
York, 1929) p. 122. sures of very concentrated electrolyte solutions 1. Mea-
[34] V.B. Parker, Thermal properties of aqueous uni-univalent
 P..J. Gierszewski et al. / Properties of LiOH md LiNO, aqueow solutions 71

surements on [(l - x)H,O + x LiNO,] and . . . by a dew- dissolved electrolytes in aqueous solutions of aIkali metal
point apparatus, J. Chem. Thermod. 13 (1981) 31. nitrates at temperatures of 423-623 K, J. Appl. Chem.
[53] L.V. Puchkov and V.G. Mat&kin, Vapor pressures and USSR 54 (1981) 1031.
certain thermodynamic functions of aqueous LiNO, and [60] R.A. Robinson, Osmotic and activity coefficients of
NaNO, solutions at temperatures in the 150-300 o C range, lithium nitrate solution, J. Am. Chem. Sot. 68 (1948)
J. Appl. Chem. USSR 43 (1970) 1984. 2402.
[54] H. Braunstein and J. Braunstein, Isopiestic studies of very [61] W.J. Hamer and Y.-C. Wu, Osmotic coefficients and
concentrated aqueous electrolyte solutions of LiCl, LiBr, mean activity coefficients of uni-univalent electrolytes in
LiNO, . . . at 100 to 150°C, J. Chem. Thermod. 3 (1971) water at 25 o C, J. Phys. Chem. Ref. Data l(4) (1972) 1047.
419. [62] R.N. Goldberg, Evaluated activity and osmotic coeffi-
[55] R. Wright, The relation between the coefficient of thermal cients for aqueous solutions: Thirty-six uni-bivalent elec-
expansion and structure of solutions, J. Chem. Sot. 3 trolytes, J. Phys. Chem. Ref. Data lO(3) (1981) 671.
(1940) 870. (631 B.R. Staples, Activity and osmotic coefficients of aqueous
(561 R.C. Weast, ed., CRC Handbook of Chemistry and alkali metal nitrites, J. Phys. Chem. Ref. Data lO(3) (1981)
Physics, 56th ed. (CRC Press, Cleveland, 1975) p. F-5. 765.
[57] E.H. Lanman and B.J. Mair, The compressibility of aque- [64] CL. Kusik and H.P. Meissner, Electrolyte activity coeffi-
ous solutions, J. Am. Sot. 56 (1934) 390. cients in inorganic processing, In: Fundamental aspects of
[58] Gmelin’s Handbuch der Anorganischem Chemie, 8. hydrometallurgical processes, eds., T.W. Chapman, L.L.
Auflage, Lithium Ergnzungsband System Nummer 20 Tavlarides, G.L. Hubred and R.M. Wellek, Symp. Series
(Verlag Chemie GmbH, Weinbeim/Bergstrasse, 1960) p. 173, 74 (American Institute of Chemical Engineers, New
291 (referencing B. Lunden, Svensk kern. Tidskr 53 (19410 York, 1978) p. 14.
86). 1651 R. Heyrovska, Interpretation of properties of aqueous
[59] V.Ya. Egorov, V.I. Zarembo, N.G. Soboleva and L.V. electrolyte solutions in terms of hydration and incomplete
Puchkov, Activity of water and activity coefficients of dissociation, Coil. Czech. Chem. Comm. 53 (1988) 686.