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1971 J. Phys. D: Appl. Phys. 4 441

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J. Phys. D: Appl. Phys., 1971, Vol. 4. Printed in Great Britain

The thermal conductivity of molten salts

K. CORNWELL
Department of Mechanical Engineering, Heriot-Watt University, Chambers Street,
Edinburgh 1
MS. received 22nd September 1970
Abstract. Experimental values of the thermal conductivity of molten salts are
reviewed and found to deviate appreciably from values predicted by semi-empirical
theories to the thermal conductivi<y of liquids. The author shows that for univalent
molten salts a simple correlation exists between the thermal conductivity at the melting
point and the mean ionic weight of a univalent molten salt. Mixtures of molten salts
have a thermal conductivity which is less than the proportional mean of the constituent
salts.

1. Introduction
This study was undertaken as part of an investigation into the possibility of using molten
salts for thermoelectric generation (Cornwell 1970). It is difficult to measure the thermal
conductivity of liquids at high temperatures and for this reason there are few data reported
in the literature. A search for some method of estimating the thermal conductivity of
molten salts using the theories and values available led to a correlation with the mean
ionic weight.
Molten salts are being used to an increasing extent as high temperature heat transfer
fluids and the design of suitable heat exchangers involves a knowledge of the thermal
conductivity of the salt. This study is reported in order to collate the experimental data
and to make available a method of estimating the thermal conductivity of a molten salt.

2. Semi-empirical theory
Modern theories generally assume that the thermal conductivity of molten salts is pre-
dominantly due to two mechanisms : the vibration mechanism arising from short-range
order of the molecules in the liquid state and the translational or diffusion mechanism due
to the motion of the ions. It was originally postulated that ionic diffusion (or the electrical
conduction mechanism) made a substantial contribution (Gambill 1959, Sundheim and
Rosenstreich 1959), but the high ratio of thermal diffusivity to mass diffusivity and the
high value of the Lorenz number indicate a low contribution from diffusion. Turnbull
(1961 b) has shown this to be the case and found the ratio of diffusion conduction to total
conduction to be less than 5 %. Any theory which is to lead to useful results must therefore
be based on the vibrational mechanism. It is for this reason that molten salts have thermal
conductivity values of a similar order to solid dielectrics.
Bridgeman (1949) adapted his equation for the thermal conductivity of insulators to
liquids. Basically he assumed that liquid molecules were arranged in a cubic lattice with
a spacing d and an energy of 3kT per particle flowing from row to row at the speed of
sound U. This led to the following equation for the thermal conductivity:

Rao (1941) also assumed a liquid to be composed of a cubic arrangement of particles

vibrating at a certain frequency. By analysing the heat flow mechanism and using the
441
442 K. Cornwell
Lindemann theory relating the frequency to the melting point he predicted the thermal
conductivity at the melting point to be given by the following equation :

K=constant x - (
$4,3)

where T, is the melting point (K), M is the molecular weight and V is the atomic volume.
In the case of dissociated molten salts the discrete particles are ions and not molecules.
The thermal conductivity should therefore be based on the mean ionic weight M / i (where
i is the number of different ions) and the mean ionic volume y/i.
Turnbull (1961 b) applied both of these formulae to molten salts. Bridgeman’s expression
could only be applied to three of the salts he studied owing to lack of data on the velocity
of sound. The predicted thermal conductivity values were certainly of the correct order
of magnitude but deviated by up to 30 % from the measured values. Rao’s expression was
applied to ten salts and gave correlation within 22 % for eight of them. But data reported
since the publication of this paper show large deviations from this expression. White and
Davis (1967) attempted to apply the law of corresponding states for the transport coefficients
to alkali nitrates by correlating the density, viscosity and thermal conductivity changes
with temperature. Only a limited degree of correlation was established.

3. Review of experimental data

The available data on the thermal conductivity of molten salts near the melting point
are given in table 1. Thermal conductivity values reported before 1959 were obtained
using apparatus based on a steady heat flow through a plane or cylindrical liquid film.
Turnbull (1961 a) critically reviewed the data up to this date.

Table 1. The thermal conductivity of molten salts near the melting point
Salt Mean ionic weight T K X 103 Reference
(“C) (W cm-l K-l) k 5 %
LiN03 34.5 252 5.82 White and Davis 1967
NaN03 42.5 307 5.66
- 329 5-52 Bloom et al. 1965
KN03 50.6 334 4.31 White and Davis 1967
- 343 4.98 Bloom et al. 1965
- 343 4.28 Turnbull 1961 b
RbN03 73.8 311 3.77 White and Davis 1967
CsNOs 97.5 314 2.85
AgN03 85.0 210 3.7 extrap. Bloom et al. 1965
- 210 3.77 Turnbull 1961 b
AgBr 93.9 460 2*77+10% Cornwell 1970
(NaCl) 29.2 801 8.8 k 2 5 % Turnbull 1961 b
ZnClz 44.1 320 3.05
KHS04 68.1 206 3.39
NaHS04 60.1 179 4.60
NH4HS04 57.6 145 3.94
NaNOz 34.5 209 6.0 extrap. Bloom et al. 1965
KCNS 48.6 175 2.72 Turnbull 1961 b
NaOH 20.0 319 9 . 2 ?C 10% Lucks and Deem 1956

The experimental results of Turnbull (1961 a, b) were obtained using a transient hot
wire method. He estimated the accuracy of his results as )3%. Ewing et al. (1962)
reported measurements on the thermal conductivity of € 3 2 0 3 and ‘Flinak’ (NaF + KF + LiF
in the ratio 11.5: 42: 46.5 mole %). He also ascertained experimentally the effect of
radiation in steady radial and axial heat flow rigs and found it to be considerable. Bloom
 The thermal conductivity of molten salts 443
et al. (1965) measured the conductivity of some nitrates and nitrate mixtures using a radial
steady heat flow apparatus and estimated the accuracy as + 5 % . The results of White
and Davis on solid and liquid alkali nitrates were also obtained using a radial steady heat
flow apparatus. They estimated their 9ccuracy as 3-5% and in the cases of NaN03 and
K w o 3 suggested reasons for the deviations of previous investigators.
White and Davis (1967) criticized the transient hot wire method of measuring the thermal
conductivity of molten salts. The author examined the application of the transient hot
wire method to molten salts and found that with certain modifications to the apparatus
consistent values could be obtained, but at an estimated accuracy of only k 10 % (Cornwell
1970). This method can therefore only be used to produce approximate thermal con-
ductivity values for molten salts.
The temperature coefficient of the thermal conductivity is usually small and positive
(with conductivity values increasing at the rate of 0.2 to 0.4 W cm-1 K-1 per 100 "C).
Exceptions are NH4HS04 and ZnCln which have negative temperature coefficients.

4. The correlation with mean ionic weight

From the discussion of the semi-empirical theories it would appear that there is no
satisfactory method of predicting the thermal conductivity of a molten salt. Nevertheless
it has been established that the lattice vibrational mechanism is responsible for the major
part of the thermal conductivity. It is therefore probable that the mean mass of the
vibrating particles is the major factor determining the thermal conductivity.

I I I
20 30 40 50 60 70 80 90 110
Mean ionic weight M/I
Figure 1. The thermal conductivity of pure ionic salts (log scales).

Figure 1 shows values of the thermal conductivity plotted as a function of the mean
ionic weight for the pure molten salts listed in table 1. The correlation between these two
properties is very evident and the equation to the line drawn in the figure is given by :

The low conductivity of KCNS is probably caused by the complex structure leading to a
damping of the lattice vibration modes. Zinc chloride has not been included as it is only
partly dissociated at the melting point (Bockris et al. 1960). The only data available is on
univalent molten salts and the correlation can therefore only strictly be applied to univalent
salts until further measurements are reported.
444 K. Cornwell
The correlation of the thermal conductivity with the mean ionic weight is to some extent
consistent with Rao’s expression (equation (2)). If the substitution V=Mie is made
(where e is the density) and M is replaced by Mii as discussed earlier, equation (2) becomes

The square root of the melting temperature (in K) does not vary greatly from salt to salt
and the density is to some extent dependent upon the molecular weight. This formula
therefore implies that the conductivity at the melting point is largely dependent upon the
mean ionic weight and decreases as the mean ionic weight increases.

Table 2. The thermal conductivity of molten salt mixtures near the melting point
Salt mixture (mole ratio) K x lo3 (W cm-l K-l) Measurement Reference
Mean Measured (k5 %) temperature
( “C)
AgN03+NaN03 (49 : 51) 4.7 3.73 278 Bloom et al. 1965
AgN03 + KNo3 (54 : 46) 4.0 3 * 6 extrap. 150
KN03+NaN03 (71 : 29) 4.7 3.60 330
KNo3 + NaN03 (40 : 60) 5* 1 3.80 333
- 5.28 140 Turnbull 1961 a
LiCl + KCI (59 : 41) - 6.90 353
AgCl + AgI (47 : 53) - 1.82rt 10% 300 Cornwell and Dyson 1969
NaCl+ FeClz (46 : 54) - 2.60 158 Turnbull 1961 a
NaCl + ZnClz (42 : 58) 5.5 3.68 270
NaHS04 + KHS04
(53.5 : 46.5) 4.1 4.27 125
tKN03 +NaNOz + NaN03
(44 : 49 : 7) 5.2 4.98 142 Turnbull 1961 a
5 . 6 k 10% 142 Lane et al. 1958
4.6+ 10% 142 Vargaftik 1952
$NaF + KF + LiF
(11.5 : 42 : 46.5) - 6.0 500 Ewing et al. 1962
t Heat transfer salt ; $ ‘Flinak’.

5. Mixtures of molten salts

Mixtures of molten salts generally have a thermal conductivity which is less than the
proportional mean of the constituent salts. This is to be expected owing to the general
increase in the disorder of the short-range quasicrystalline lattice of the molten salt on the
addition of another salt. This in turn increases the resistance of the salt to the lattice
vibration modes which are transferring heat energy. Experimental thermal conductivity
values for salt mixtures are given in table 2, together with the proportional mean of the
conductivities of the constituents near their melting points.

Acknowledgments
The author would like to thank Dr R. W. Dyson for helpful suggestions regarding this work.

References
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