The thermal stability of molten nitrite/nitrates salt for solar

thermal energy storage in dierent atmospheres

Rene I. Olivares
CSIRO Energy Centre, Newcastle, 10 Murray Dwyer Circuit, Steel River Estate, Mayeld West, NSW 2304, Australia
Received 31 August 2011; received in revised form 27 May 2012; accepted 28 May 2012
Available online 23 June 2012
Communicated by: Associate Editor Yogi Goswami
Abstract
The study of the thermal decomposition of molten nitrite/nitrates salt used for thermal energy storage (TES) in concentrating solar
power (CSP) was carried-out with a HITEC (Reg. U.S. Patent Coastal Chemical Company) type salt. This salt is the commercial mix-
ture of NaNO
3
KNO
3
NaNO
2
in the proportions 75340 wt.% (NO
2
/NO
3
weight ratio of 0.7). The study was done by simultaneous
DSC/TG-MS analysis between room temperature and 1000 C in gas atmospheres of argon, nitrogen, air and oxygen. It was found that:
The thermal stability of the salt can be signicantly enhanced by controlling the atmosphere.
By two assessment criteria, TG and DSC, the salt operated in an inert atmosphere could be used at temperature of at least 610 C and
when operated in an oxidising atmosphere up to between 650 C and 700 C.
Oxidising atmosphere was found to change the chemistry of the salt by converting some nitrite to nitrate, and although this may have
a bearing on increasing the melting point, it has the benet of rising the thermal decomposition temperature.
2012 Elsevier Ltd. All rights reserved.
Keywords: Thermal energy storage; Nitrates decomposition temperature; Thermal stability; Dierential scanning calorimetry; Molten salts; CSP
1. Introduction
A desirable medium for thermal energy storage and
energy transfer, in new tower technologies that concentrate
solar thermal energy, is a molten salt that can sustain rea-
sonable high temperatures before it thermally decomposes.
It is also required that the salt should have a low melting
point in addition to being stable at the highest possible
temperature Cordaro et al. (2011). There is some confusion
however in regards to the decomposition temperature of
alkali metal nitrate melts due to a lack of a standardised
denition of decomposition (Peng et al., 2008; Raade and
Padowitz, 2011).
The principal mode of thermal decomposition in nitrate
salts though has been agreed amongst researchers, such as
Freeman (1956), Sirotkin (1959) and Buchler and Stauer
(1966) to correspond to the main reaction: NO

3
$
NO

2
1=2O
2
. Further decomposition also takes place
with the evolution of the oxides of nitrogen, particularly
at higher temperature (Bartholomew, 1966).
In some studies (Bond and Jacobs, 1966; Freeman, 1956;
Gordon and Campbell, 1955) decomposition temperature
has been reported as that where oxygen gas or nitrogen
and nitrous oxide are detected as having been evolved. In
the work of Gordon and Campbell (1955), the alkali metal
nitrates were observed to undergo a thermal reaction at
temperatures 100300 C above their melting points as
indicated by bubbling of the molten salt. The evolution
0038-092X/$ - see front matter 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.solener.2012.05.025
E-mail address: Rene.Olivares@csiro.au
www.elsevier.com/locate/solener
Available online at www.sciencedirect.com
Solar Energy 86 (2012) 25762583
of nitrous fumes observed by Gordon and Campbell
(1955), occurred at temperatures ranging from about
200350 C above the initial bubbling reaction. This
claimed as a result of the decomposition of the nitrate
and/or nitrite to oxide. The later stage of the decomposi-
tion of these nitrates was still occurring at temperatures
as high as 900 C which was the upper limit of the appara-
tus employed in the investigation of Gordon and Campbell
(1955).
Kust and Burke (1970), conducted experiments at
300 C with a pure equimolar sodiumpotassium nitrate
melt in an oxygen rich atmosphere (pO
2
at 0.85 atm) and
measured an oxide ion O

2
concentration in the molten
salt of 2 10
7
molal. This was calculated by Kust to cor-
respond to a nitrite ion NO

2
concentration of the order
of 10
5
molal and demonstrated that nitrate ion NO

3

could decompose to a measurable extent at temperatures
as low as 295 C.
In the present work thermal decomposition was studied
from at least three dierent points of view as follows:
The temperature at which rapid weight loss is
observed in a thermo-gravimetric (TG) curve.
The temperature after melting at which an endother-
mic peak of decomposition is detected by dierential
scanning calorimetry in a DSC curve.
The temperature at which the rapid evolution of
gases, NO and/or O
2
, are detected by means of mass
spectrometric (MS) analysis.
In all these cases small to large dierences are found and
a judicious combination of criteria is required for practical
selection of the critical salt temperature for operation in a
TES eld.
1.1. Theoretical considerations
One of the primary concerns in the study of molten salts
is the chemistry and equilibrium reactions by which the
molten salt interacts with the atmosphere.
1.2. Nitrate/nitrite systems and equilibrium
In nitrate based salts, the main decomposition reaction
could be said to be the partial dissociation of nitrate ion
NO

3
to nitrite ion NO

2
and oxygen (O
2
) according
to Eq. (1):
Nitrate ion dissociation:
NO

3
NO

2
1=2O
2
1
The shift from nitrate to nitrite occurs slowly and is lim-
ited by the partial pressure of oxygen in the atmosphere
contacting the molten salt, this as per the equilibrium con-
stant in Eq. (2):
Nitrate/Nitrite equilibrium constant:
K
eq

NO

2

NO

3

pO
1=2
2
2
In the absence of H
2
O and CO
2
the equilibrium constant
is directly proportional to pO
1=2
2
.
Measured amounts of nitrite by means of ternaries
incorporating NaNO
2
or KNO
2
is a way of controlling
the activity of NO

3
and NO

2
ions in solution.
Furthermore, decomposition reactions for nitrite can
also be given as per Eqs. (3) and (4):
Nitrite ion dissociation:
2NO

2
O

2
3=2O
2
N
2
3
Nitrite ion dissociation:
2NO

2
O

2
NO
2
NO 4
The equilibrium constant in Eq. (2), for the equimolar
mixture NaNO
3
KNO
3
has been measured by Nissen
and Meeker (1983), over the temperature range 500
600 C. In contact with air (pO
2
of 0.21 atm) the equilib-
rium shift of the mixture was reported by Nissen and
Meeker (1983), as 1.1 mol% NO

2
anion at 500 C, and
5.7 mol% NO

2
at 600 C.
Carbon dioxide in the atmosphere has a marked eect
on the concentration of oxygen ions O

2
in nitrate melts
as CO
2
will convert O

2
to carbonate CO

3
according to
Eq. (5):
Carbonate formation:
CO
2
O

2
CO

3
5
The solubility of carbonate ions in binary solar salt has
been considered by Bradshaw and Siegel (2008). This is
5 mol% near the eutectic point but signicantly less in
multi-component mixtures containing calcium nitrate.
In molten ternary mixtures NaNO
3
KNO
3
Ca(NO
3
)
2
,
solid phases were observed by Bradshaw and Siegel
(2008); between 500 C and 540 C depending on the pro-
portion of calcium nitrate present. The concentration of
dissolved carbonate ions increases with temperature but
saturation levels have not been determined.
The consequences of molten nitrate decomposition can
be considered to be at least three fold:
Gaseous evolution will pressurise the top space of the
storage unit and alter its atmosphere.
Insoluble products that form will tend to plug valves,
pipes, and foul heat transfer surfaces.
Soluble oxide ions will aggravate corrosion at high
temperature.
Therefore the use of nitrate molten salts for heat transfer
or storage at high temperature, is limited by the atmo-
sphere and reactions described by Eqs. (1)(5).
Bearing in mind that molten nitrate salts also wet and
spread over almost any surface they contact, whenever
the salt at high temperature (>500 C) comes in contact
R.I. Olivares / Solar Energy 86 (2012) 25762583 2577
with containment materials such as stainless steel, corro-
sion with the liberation of nitrogen oxides can be expected,
for example, Cr 2NO

3
CrO
2
4
2NO and similarly for
reactions with Ni and Fe. If evolved gas analysis alone is
used to evaluate thermal decomposition, these gaseous cor-
rosion products could lead to erroneous conclusions
regarding reactions taking place in the melt, Nissen and
Meeker (1983).
The work discussed here concerns the low melting point
formulation of the HITEC (Coastal Chemical Co.) type
salt mixture prepared in the laboratory from pure high
grade chemicals. This formulation was studied over the
temperature range up to 1000 C in atmospheres of argon,
nitrogen, air and oxygen using simultaneously DSC/TG
and MS analysis.
2. Experimental
The HITEC type salt was simulated by mixing pure
chemicals NaNO
3
KNO
3
NaNO
2
in the proportions given
in Table 1 after drying overnight in vacuum.
The mixture of pre-dried pure chemicals was melted in a
mue furnace and allowed to equilibrate in air at 400 C
before casting into a stainless steel mould to quench and
solidify. A small sub-sample from the solidied salt was
used for simultaneous DSC/TG-MS experimentation.
The experiments were carried-out from room temperature
up to 1000 C at a heating-rate of 10 C min
1
in atmo-
spheres of argon, nitrogen, air and oxygen respectively.
About 3540 mg were loaded into a 100 lL Al
2
O
3
crucible
in a SETARAM DSC/TG-SETSYS Evolution analyser,
coupled with a Pfeier QUADSTAR-422 mass spectrome-
ter. Once the atmosphere around the sample was set, the
gas was allowed to ow at a rate of 20 ml min
1
.
After each run, signicant contamination of the DSC
platinum sensor took place leaving a severe brown stain
around the sensor that had to be thoroughly cleaned
between runs by rst soaking in hot water and then heating
to 1500 C in air to remove any residue.
2.1. Experimental error and uncertainty
Temperature and heat ow calibration of the DSC was
done as per standard method for this type of analysis
(Hohne, 1991; Sabbah et al., 1999) using certied reference
materials (CRMs) listed in Table 2 to cover the tempera-
ture range 1001050 C. All calibration curve parameters
were estimated by a least-squares optimisation routine
(build in Calisto Software SETARAM). The uncertainty
on the temperature and heat ow measurements were cal-
culated from the standard error of the estimate, s, accord-
ing to:
s
2

1
N n 1
X
Y
corr
Y
std

2
where s is the standard error of the estimate, N the number
of data points, n the number of independent variables, Y
corr
the corrected temperature of melting, T
corr
the corrected
energy of melting, DH
corr
Y
std
the melting temperature of
standard, T
std
is the energy of melting of standard, DH
std
.
From these and using the calculation procedure
described, the uncertainty for the temperature is 4.6 C
and the uncertainty for the energy is 2.8 J/g.
The uncertainty of the standard (see Table 2) and mea-
sured temperatures (noise level 5 mK) are negligible com-
pared to the standard error of the estimate, s.
3. Results
The results for the simultaneous DSC/TG-MS experi-
ments with the salt in atmospheres of argon, nitrogen, air
and oxygen are shown in Figs. 14 respectively. The gures
show superimposed in the same graph: (i) the Ion Current
Intensity (A) for the detection by the MS of the evolved
Table 1
Nitrate/nitrite HITEC (Coastal Chemical Co.) type formulation.
Compound wt.% mol%
NO
2
/NO
3
= 0.72 (wt. ratio) HITEC type formulation
NaNO
3
7 7
KNO
3
53 44
NaNO
2
40 49
Table 2
Standard certied reference materials (CRMs) DSC calibration.
CRM Heating
rate (C/min)
CRM melting
T
std
(C)
a
Measured melting
T
meas
(C)
Corrected
melting T
corr
(C)
CRM energy
of melting, DH
std
(J/g)
b
Corrected energy
of melting, DH
corr
(J/g)
In 10 156.59 0.01 151.18 148.77 28.51 0.19 28.45
158.47 156.10 28.18
Pb 10 327.47 0.02 326.52 325.06 23.00 0.06 22.98
326.74 325.28 23.07
Al 10 660.33 0.05 658.60 658.95 401.30 1.6 395.44
661.62 661.99 403.62
Au 10 1064.18 1067.36 1069.93 64.50 64.59
Pb 5 327.47 0.02 325.56 323.62
Pb 20 329.99 329.51
a
Cammenga et al. (1993).
b
Sarge et al. (1994).
2578 R.I. Olivares / Solar Energy 86 (2012) 25762583
gaseous species, (ii) the TG (mg) curve to monitor the
weight change and (iii) the DSC (mW) trace to identify
the temperature at which heat events (exothermic/endo-
thermic) occur. In all cases the gures illustrate that; a wide
endothermic heat ow which coincides with a sharp drop in
weight once a critical temperature is reached, reects a
rapid rate of decomposition of the salt.
In an inert atmosphere of argon, Fig. 1 shows that,
although a kink at 470 C is apparent in the DSC trace coin-
ciding with the evolution of NO, the thermal decomposition
in this case can be considered to substantially occur at a
temperature between the point at which rapid weight loss
begins on approaching 610 C and before the bulk of
decomposition is identied by the broad endothermic heat
event at 745 C in the DSC trace. The gaseous species
detected by the MS in this case were NO, O
2
, NO
2
, N
and N
2
. The evolution of nitrous oxide (NO) is rst noticed
at 473 C and the evolution of nitrogen species (N, N
2
) at
the much higher temperature of 780 C. O
2
and NO
2
spe-
cies evolve at temperatures between these two.
In an inert atmosphere of nitrogen, Fig. 2 shows a small
endothermic event of 9 J/g at 468 C that may represent
some incipient decomposition although no evolution of
gases or weight loss is associated with it. The thermal
decomposition in this case can be considered to substan-
tially occur at a temperature between the point at which
rapid weight loss begins approaching 613 C and before
the bulk of decomposition identied by the broad endo-
thermic heat event at 789 C in the DSC trace. These tem-
peratures are slightly higher than those observed in an
atmosphere of argon (Fig. 1). The gaseous species detected
by the MS in this case were NO and NO
2
evolving at
564 C and 610 C respectively. Given that the atmosphere
was nitrogen, the background Ion Current Intensity was
too large to detect the evolution of species N and N
2
.
The evolution of O
2
is not detected by the MS in this
experiment.
For the experiments in air and pure oxygen, Figs. 3 and
4, a noticeable weight increase associated with an exother-
mic heat of reaction is observed soon after melting, and this
consistent with the oxidation of nitrite NO

2
to nitrate
NO

3
with the rate of oxidation being a function of the
partial pressure of oxygen, pO
2
.
In air (Fig. 3) the critical temperature after which rapid
weight loss occurs is 650 C, whereas the bulk of decompo-
sition as per the large endothermic event in the DSC trace
occurs at 747 C. Oxidation of nitrite to nitrate, exothermic
event of 38 J/g, takes place over the temperature range
Fig. 1. DSC/TG-MS analysis for thermal decomposition of nitrite/nitrate salt in argon atmosphere.
R.I. Olivares / Solar Energy 86 (2012) 25762583 2579
218510 C with a peak maxima at 370 C in this case.
Nitrous oxides, NO and NO
2
, are observed to evolve at
540 C and 605 C respectively. The background Ion Cur-
rent Intensities for oxygen and nitrogen in this air atmo-
sphere are too large and prevent the detection of the
evolution of these species from the salt. Using the TG
and DSC criterion (ignoring the evolution of some gaseous
species), it can be said that the oxidation of nitrite to
nitrate has resulted in an enhancement to the thermal sta-
bility to at least 650 C in air.
Under a blanket of oxygen (Fig. 4) the critical tempera-
ture after which rapid weight loss occurs is noted at 712 C,
whereas the bulk of decomposition as per the large endo-
thermic event in the DSC trace occurs at 740 C. The oxi-
dation of nitrite to nitrate in this case, a slightly larger
exothermic event of 42 J/g, takes place over the tempera-
ture range 250551 C with peak maxima at 392 C.
Nitrous oxides, NO and NO
2
, are observed to evolve at
570 C and 585 C respectively and the evolution of nitro-
gen species, N and N
2
, at 851 C and 865 C. The back-
ground Ion Current Intensity for oxygen in this
atmosphere is too large and prevents the detection of the
evolution of O
2
from the salt. Using the TG and DSC cri-
terion (ignoring the evolution of some gaseous species), it
can be said that the oxidation of nitrite to nitrate has
resulted in an enhancement to the thermal stability to at
least 710 C in oxygen. The data read from Figs. 14 are
further summarised in Table 3.
4. Discussion
The results discussed here show that the nitrite based
salt NaNO
3
KNO
3
NaNO
2
(75340 wt.%) of the HITEC
type formulation (Coastal Chemical Co.) has a large range
of temperatures over which it can be used, particularly
when a controlled gas atmosphere blankets the molten salt
during operation. The melting temperature for this system
was assessed as 151 C and a maximum possible operation
temperature of up to 700 C for a short time can be consid-
ered, i.e. an operational range greater than 500 C.
Although the melting point of the industrially supplied
HITEC salt is reported as 142 C (manufacturer Coastal
Fig. 2. DSC/TG-MS analysis for thermal decomposition of nitrite/nitrate salt in nitrogen atmosphere.
2580 R.I. Olivares / Solar Energy 86 (2012) 25762583
Chemical Co., LLC), the mixture prepared in the labora-
tory gave a melting point of 151 C when analysed by
DSC and this is due to the fact that the master alloy was
prepared by melting the pure analytical grade chemicals
in air and allowed to equilibrate overnight at 400 C. This
would have changed the composition of the initial mix by
oxidising some of the nitrite to nitrate altering the NO
2
/
NO
3
ratio which raised the melting point of the sub-sample
tested in the experiments. Studies of melting point increases
with the sodium and potassium nitrite/nitrate system and
the eect of impurities were rst published by Alexander
and Hindin (1947). The eect on the melting point of
changes in composition as a result of altering the NO
2
/
NO
3
ratio has been reported by Bohlman (1972).
By most of the criteria used to evaluate the thermal sta-
bility in these experiments, under an inert atmosphere of
argon or nitrogen, the stability limit of the salt is approxi-
mately 610 C. Although a kink in the DSC trace at about
470 C in both cases suggests that some incipient decompo-
sition is taking place, only under the argon atmosphere is
this kink associated with gas evolution, but not weight loss.
Under nitrogen blanket no gas evolution or weight loss is
associated with this point. A nitrogen atmosphere may
assist in xing the partial pressure of nitrogen thus prevent-
ing the breakdown of the nitrite to nitrate and the produc-
tion of oxides; i.e. the reaction 5NaNO
2
!3NaNO
3
+
Na
2
O + N
2
which is thermodynamically favoured at any
temperature.
In atmospheres of air and oxygen, the salt is seen to alter
its composition by the oxidation of nitrite to nitrate soon
after melting with the rate of oxidation proportional to
the partial pressure of oxygen. This, despite the rise in melt-
ing point of the salt, would not be a problem giving that the
nitrate becomes more stable under oxidising atmosphere;
i.e, 2NaNO
2
+ O
2
!2NaNO
3
.
Previous attempts at denite data on thermal stability at
high temperature for this nitrite/nitrate system have been
ineective. In the work of Bohlman (1972) and references
within, values varying between 538 C and 593 C and tem-
peratures as high as 649 C and 704 C are reported. It is
clearly demonstrated in the present experiments that when
quoting thermal stability, due regard needs to be given to
the conditions under which this value is obtained. In partic-
ular the requirement to discriminate amongst at least three
possible criteria for evaluation, that is; (I) the point at
which rapid weight loss in a thermo-gravimetric curve is
detected, (II) the broad endothermic event representing
the bulk of decomposition in a DSC curve and (III) the
Fig. 3. DSC/TG-MS analysis for thermal decomposition of nitrite/nitrate salt in air atmosphere.
R.I. Olivares / Solar Energy 86 (2012) 25762583 2581
temperature at which rapid evolution of gaseous species is
detected. It was found from the gas evolution analysis in
this work that; rst NO is formed followed by O
2
and
NO
2
, with the evolution later at higher temperature of
the species N and N
2
. In all these cases small to large dif-
ferences are found and a judicious evaluation has to be
made to best identify thermal decomposition from a prac-
tical stand point in which the salt is expected to be used in a
TES application.
From these results discussed here it is clear that the par-
tial pressure of oxygen has a major impact on the thermal
stability of the salt by inuencing the temperature at which
the various gaseous species are generated; similar ndings
have also been reported by Hoshino et al. (1981).
Fig. 4. DSC/TG-MS analysis for thermal decomposition of nitrite/nitrate salt in oxygen atmosphere.
Table 3
Summary for the eect of atmosphere on thermal decomposition of NaNO
3
KNO
3
NaNO
2
HITEC type salt (NO
2
/NO
3
= 0.72).
Atmosphere pO
2
Melting T (C) DSC event
exothermic/
endothermic
DSC, T C
Bulk of
decomposition
TG, T C
rapid wt.
loss after
Evolved
gas species
detected
Evolved
gases T C
Maximum
possible
temperature, C
Argon 0 151 Slow decomposition
starts 470 C
745 610 NOO
2
NO
2
NN
2
473604623778782 610
Nitrogen 0 151 Slow decomposition
starts 468 C
789 613 NONO
2
564610 610
Air 0.21 151 Nitrite oxidation
peak at 370 C
a
747 651 NONO
2
540605 650
Oxygen 1 151 Nitrite oxidation
peak at 392 C
b
740 713 NONO
2
NN
2
570585851865 710
Notes: All temperatures reported have an uncertainty of 4.6 C.
a
NO

2
oxidation occurs over the temperature range 218517 C; exothermic heat of oxidation: 38 (J/g) with a weight increase of 0.20 mg.
b
NO

2
oxidation occurs over the temperature range 250551 C; exothermic heat of oxidation: 42 (J/g) with a weight increase of 0.60 mg.
2582 R.I. Olivares / Solar Energy 86 (2012) 25762583
The atmosphere was also found to inuence to some
extent the energy required for melting, that is; 71 J/g under
argon, 58 J/g under nitrogen, 60 J/g in air and the lowest
being 53 J/g under oxygen.
5. Conclusions
The investigation carried out here demonstrates that at
least three criteria can be used to discern the thermal
decomposition of nitrite/nitrates salt mixtures;
(1) The point after which rapid weight loss is detected in
a thermo-gravimetric curve, TG.
(2) After melting of the salt, the rst broad endothermic
heat event in a DSC trace.
(3) The temperature at which the rapid evolution of gas-
eous species is detected.
Judicious assessment is required by combining these
three criteria to best identify the maximum temperature
at which the salt could be used. Independent of the criteria
adopted, the atmosphere under which the molten salt is
used in a TES environment determines the maximum pos-
sible temperature of operation, such that when heated at
10 C min
1
:
The salt under a blanket of inert gas oers thermal
stability up to 610 C.
Oxidising atmosphere changes the chemistry of the
salt by converting some nitrite to nitrate resulting in
a slight increase in the melting point, which is out-
weighed by the benet of higher thermal stability
up to 700 C.
It is possible that the rate processes in the short time of
the present experiments are driven too fast and further
work is still required to verify the time at temperature in
which the salt still maintain its integrity and this will be
the subject of a next publication.
Acknowledgments
This project has been supported by the NSW Govern-
ment through the NSW Science Leveraging Fund and by
the Australian Government through the Australian Solar
Institute (ASI). The Australian Government, through
ASI, is supporting Australian research and development
in solar photovoltaic and concentrating solar power tech-
nologies to help solar power become cost competitive with
other energy sources.
References
Alexander, J., Hindin, S., 1947. Phase relations in heat transfer salt
systems. Industrial and Engineering Chemistry 39, 10441050.
Bartholomew, R.F., 1966. A study of the equilibrium KNO3(l) = -
KNO3(l) + 1/202(g) over the temperature range 550750C. The
Journal of Physical Chemistry 70 (11), 34423446.
Bohlman, E.G., 1972. Heat transfer salt for high temperature steam
generation. ORNL-TM-3777.
Bond, B., Jacobs, P., 1966. The thermal decomposition of sodium nitrate.
Journal of the Chemical Society A 1966, 12651269.
Bradshaw, R.W., Siegel, N.P., 2008. Molten nitrate salt development for
thermal energy storage in parabolic trough solar power systems. In:
Energy Sustainability, ES2008, Jacksonville, Florida, 4p.
Buchler, A., Stauer, J., 1966. Gaseous alkalinitrogenoxygen and
alkaliphosphorousoxygen compounds. The Journal of Physical
Chemistry 70, 40924095.
Cammenga, H.K., Eysel, W., Gmelin, E., Hemminger, W., Ho hne,
G.W.H., Sarge, S.M., 1993. The temperature calibration of scanning
calorimeters. Part 2 calibration substances. Thermochimica Acta. 219,
333342.
Coastal Chemical Co., L.L.C. HITEC Heat Transfer Salt. Brenntag
Company. <http://www.coastalchem.com/> (accessed June 2012).
Cordaro, J.G., Rubin, N.C., Bradshaw, R.W., 2011. Multi-component
molten salt mixtures based on nitrate/nitrite anions. Journal of Solar
Energy Engineering 133, 011014-1011014-4.
Freeman, E.S., 1956. The kinetics of the thermal decomposition of sodium
nitrate and of the reaction between sodium nitrite and oxygen. Journal
of Physical Chemistry 60 (11), 14711600.
Gordon, S., Campbell, C., 1955. Dierential thermal analysis of inorganic
compounds nitrates and perchlorates of the alkali and alkaline earth
groups and their subgroups. Analytical Chemistry 27 (7), 11021109.
Hoshino, Y., Utsunomiya, T., Abe, O., 1981. The thermal decomposition
of sodium nitrate and the eects of several oxides on the decompo-
sition. The Chemical Society of Japan 54, 13851391.
Ho hne, G.W.H., 1991. Remarks on the calibration of DSC. Journal of
Thermal Analysis 37, 19872000.
Kust, R.N., Burke, J.D., 1970. Thermal decomposition in alkali metal
nitrate melts. Inorganic Nuclear Chemistry Letters 6, 333335.
Nissen, D.A., Meeker, D.E., 1983. Nitrate/nitrite chemistry in sodium
nitratepotassium nitrate melts. Inorganic Chemistry 22 (5), 716721.
Peng, Q., Wei, X., Ding, J., Yang, J., Yang, X., 2008. High-temperature
thermal stability of molten salt materials. International Journal of
Energy Research 32, 11641174.
Raade, J.W., Padowitz, D., 2011. Development of molten salt heat
transfer uid with low melting point and high thermal stability.
Journal of Solar Energy Engineering 133, 031013-1031013-6.
Sabbah, R., Xu-wu, A., Chickos, J.S., Leitao, M.L.P., Roux, M.V.,
Torres, L.A., 1999. Reference materials for calorimetry and dierential
thermal analysis. Thermochimica Acta 331 (2), 93204.
Sarge, S.M., Gmelin, E., Ho hne, G.W.H., Cammenga, H.K., Hemminger,
W., Eysel, W., 1994. The caloric calibration of scanning calorimeters.
Thermochemica Acta. 247, 129168.
Sirotkin, G.D., 1959. Equilibrium in melts of the nitrates and nitrites of
sodium potassium. Russian Journal of Inorganic Chemistry 4 (11),
11801184.
R.I. Olivares / Solar Energy 86 (2012) 25762583 2583