Solar Energy Materials 9 (1983) 177-181 177

North-Holland

I N V E S T I G A T I O N S OF S O D I U M ACETATE T R I H Y D R A T E F O R SOLAR
L A T E N T H E A T STORAGE, C O N T R O L L I N G T H E M E L T I N G P O I N T

Abraham U L M A N * and Bruno V A L E N T I N

Isotope Department, The Weizmann Institute of Science, Rehovot 76100, and "Electra" (Israel Ltd.),
P.O. Box 4455, Rishon Letion 75143, Israel

Received 8 February 1983

The addition of different acetate salts and acetamide lowers the melting point of sodium acetate
trihydrate. Between 0-10% of lithium acetate dihydrate a linear relationship was observed between
the melting point and the molal concentration, and the cryoscopic constant of Kf = - 6 . 8 ° C
( + 10%) was evaluated. Information on dissociation or dimerization of the various additives could
be deduced from the results. The positive properties of sodium acetate trihydrate were retained.

1. Introduction

The concept of energy conservation has been introduced in most human activities,
even in those which do not use large fule consumptions. In this context, thermal
energy storage is crucial whenever the energy has to be used in peak hours or in
continuous fashion, i.e. in momentary interruptions of the energy source (insolation
or heat). The range of temperatures in which thermal energy storage is necessary is
very wide, from 10-15°C in the case of backup for heat-pumps in cold climates, to
over 1000°C in the case of solar towers. It is not straightforward whether the high, or
a lower temperature in a thermodynamic cycle is the effective for storage and
detailed thermodynamic and economical calculations have to be made before giving
the final answer. Moreover, in cases where the major cost is that of finance
(investment), an expensive but efficient storage system cannot be excluded.
Currently, solar energy is stored mainly by sensible heat of water or rocks, but
recently the utilization of latent heat is being studied actively [1-3], and calcium
chloride hexahydrate (CaC12 x 6 H 2 0 ) has been suggested for space heating [4,5] as
well as for greenhouses [6]. However, this salt melts at 28°C which is a rather low
temperature and thus limited in uses. We were looking for a phase change material
(PCM) in the temperature range of 40-60°C for passive as well as for active space
heating. For this temperature range there are salts, salt mixtures and organic
materials, most of which are classified as not promising, or are very expensive [7].
One salt, however, sodium acetate trihydrate (NaC2H302 x 3 H 2 0 ) seems to be
promising [8] and has some advantges: a. Phase change (melting) temperature 58°C;
b. high heat of fusion (63 kcal/kg or 114 B T U / l b ) ; c. high specific gravity, i.e. more
heat per volume unit (1.35 at 25°C); d. not corrosive; e. not hygroscopic; f. can be

0165-1633/83/0000-0000/$03.00 © 1983 North-Holland

178 A. UIman, B. Valentin / Sodium acetate trihydrate for solar latent heat storage

regarded as waste material in many industries which use acetic anhydride in organic
synthesis and thus is expected to be relatively cheap.
The problem which arises is that in a system where water to PCM heat exchanger
is used, the temperature of the water has to be at least 65°C ( A T > 7°C), otherwise
storage cannot be achieved. This is rather difficult to reach with a flat collector
(which is the cheapest alternative), so it becomes essential to lower the melting point
of NaC2H302 × 3 H 2 0 without damaging its positive properties. ,
The influence of addition of different quantities of lithium acetate dihydrate
( L i C 2 H 3 0 2 × 2 H 2 0 ) , acetic acid (CH3CO2H), magnesium acetate tetrahydrate
[Mg(CzH302) 2 × 4 H 2 0 ], and acetamide (CH3CONH2) on the melting point of
NaC2H302 × 3 H 2 0 is the subject of this report.

2. Experimental

In a typical experiment (for 7 wt%), LiC2H302 x 2 H 2 0 (7 g BDH) and

NaC2H302 × 3 H 2 0 (93 g C.P. Merck) were crushed thoroughly. Arabic gum (0.2 g)
and 2,4-dinitrobenzoic acid (0.2 g, homemade [9]) were added and the sample was
again crushed and mixed. The mixture was placed in a pyrex cylinder (5 cm
diameter) and the cylinder was placed in hot water (70°C). The temperature was
recorded on a K E N T P2500L recorder using copper-constantan thermocouples.
After all the material has melted the cylinder was placed on the bench (in all
experiments the room temperature was 26-27°C) and the temperature was again
recorded.

3. Results and discussion

The temperature behavior of the heat discharge for different quantities of

LiC2H302 × 2 H 2 0 appears in fig. 1. Three results come out of this presentation: a.
The melting point of NaC2H302 x 3 H 2 0 decreases gradually with the addition of
LiC2H302 × 2H20; b. the temperature remains constant in the heat discharge
process; c. in the concentration of 12% a considerable supercooling is observed while
the melting point does not continue to go down. Fig. 2 shows the melting point as a
function of the addition in molal concentration. In the region 0-10% the decrease in
the melting point is completely linear with the addition. This fact indicates that
molten NaC2H302 x 3 H 2 0 can be regarded as a regular liquid and that the results
can be evaluated according to the principles of the colligative properties of solutions:
T O- T = Kfm,

where T Ois the melting point of pure NaC2H302 x 2H20, T is the melting point of
the sample, gf is the proportionality on the cryoscopic constant, and m is the molal
concentration. The slope of the line gives Kf for NaC2H30 × 3 H 2 0 which is
- 6.8°C (_+ 10%).
At this point the investigation of other additives seemed to be useful for a better
 A. U/man, B. Valentin / Sodium acetate trihydrate for solar latent heat storage 179

60
~ ~ A - ~ A : .~ _A : ~ ~ A ~ _ i ~ ~-
0

laJ t.

nr" 5 0 , / • - ++- - ~ .. 6

O.

m,i A Ol LITHI~ ACETATE \,

I-- + 5X LITHIi~ ACETATE
e. 71 LITHIUr| ACETATE
:N
~--
40 • 10~ LITHIIJH ACETATE
o 12% LITHI~ ACETATE

L i i i i i

0 20 40 60 80 I00 120 140

TIME(rain)
Fig. 1. Temperature behavior of heat discharge for different concentrations of LiC2H302 X2H20 in
molten NaCEH302 x 3H20.

u n d e r s t a n d i n g of the results as well as for p r a c t i c a l uses. In fig. 3 the results are

p r e s e n t e d for 7 wt% of the different c o m p o u n d s . F o r c o m p a r i s o n the results for 7
wt% of L i C 2 H 3 0 2 X 2 H : O were also included. In the case of C H 3 C O N H 2 ( m = 1.27)
the m e l t i n g p o i n t was 5 0 ° C which is in g o o d a g r e e m e n t with Kf. Thus, a c c o r d i n g to
the a b o v e the e x p e c t e d decrease in the m e l t i n g p o i n t was 8.6°C whereas the o b s e r v e d
value was 8°C. M o r e o v e r , it can b e c o n c l u d e d that L i C 2 H 3 0 2 x 2 H 2 0 does n o t
u n d e r g o d i s s o c i a t i o n u n d e r these c o n d i t i o n s in m o l t e n N a C E H 3 0 2 × 3 H 2 0 . F o r
C H a C O 2 H ( m = 1.25) the melting p o i n t was 54°C which c a n be r a t i o n a l i z e d o n l y on
the basis of d i m e r f o r m a t i o n , which is a well k n o w n fact for c a r b o x y l i c acids [10].

60

~_. 4-
50
I i j

0,5 1.0 1,5

MOLAL

Fig. 2. Melting points of different mixtures of LiC2H30 2 X 2H20 in NaC 2H30 2 X 3H20 , as a function
of LiC2H302 x 2h 2° concentration in molal units. 5 wt% = 0.52m, 7 wt% = 0.74m, 10 wt% = 1.09m, 12
Wt% = 1.34m.
180 A. U/man, B. IS%dentin / Sodium acetate trihvdrate jor solar latent heat storage

I I I I 1 T 1 I ---7--1 I I--7-- F-T- T -r T--T--

6o I

? , , t - - ~ . , ~ : - + . _ . ~ . , -.,.:u$-.~-_+_.+._~ ..~C2 ~z.(~...~_ _

uu , , . - "-,.~" ,i..~,- -~--.--.--.-..-4--~r~-~=~.-.,~z.,,......:.~z~t_.~_.i...
5o

'~. ,~. ".,

• 7 % CH~CONHz "~'" O* ~!.,\N.. "I~
7 % Mg(OAc)2 x4H~O ~
40 + 7'=/= Li(OAc)x:PH20
o 7 % HOAc

ROOM TEMP. 28*C

I I i I l I I I I I I I I J 1 I I I J
20 40 60 80 I00 120 t40 160 180 200
T IM E (rain)

Fig. 3, Temperature behavior of heat discharge of different additives in molten NaCzH302 × 3H20.

Hence, although the formal molality is 1.25, the effective concentration is only 0.62
which gives the expected value of 4.2°C for the decrease in the melting point, in
good agreement with the experiment. In the case of Mg(C2H302) 2 × 4 H 2 0 the
situation is opposite, instead of the expected decrease of 2.4°C, the observed value
was 5.5°C. This means that the effective concentration is 0.8m and that
Mg(C2 H302)2 × 4H20 undergoes dissociation in molten NaC 2H302 × 3H20.

4. Conclusions

The above results show that it is possible to control the melting point of
NaC2H302 x 3H20, and thus to engineer the desired temperature for heat storage in
PCM. It was shown that: a. The addition of acetate salts and of CH3CONH 2 to
NaCzH302 x 2H20 lowers its melting point; b. between 0-10% of LiC2H302 ×
2 H 2 0 a linear relationship between the melting point and concentration was
observed, and Kf could be evaluated; c. all the results with additives other than
LiCzH302 × 2H20 agree with the calculated Kf value, and it was possible to draw
conclusions on the dissociation state of the different additives; d. the positive
properties of NaC2H30 z x 3H20 were retained on this addition.

References

[1] K. Gawran and J. Schroder, Energy Res. 1 (1977) 351.

[2] A.D. Solomon, Solar Energy 22 (1979) 251.
[3] A.G. Bathelt et al., ASME J. Heat Transfer 101 (1979) 453.
[4] M. Schneider et al., A N V A R - C N R S Patent No. 79 (1977) 13296.
[5] M.E. McCabe et al., NBSIR 81-2300.
 A. Ulman, B. Valentin / Sodium acetate trihydrate for solar latent heat storage 181

[6] A. Jaffrin and P. Cadier, Solar Energy 28 (1982) 313.

[7] G.A. Lane et al., in: Proc. Workshop on Solar Energy Storage Subsystems for the Heating and
Cooling of Buildings, Charlottesville, Virginia (1981).
[8] E. van Galen, in: Thermal Storage of Solar Energy (Martinus Nijhoff, Leiden, 1981) p. 147.
[9] Buehler et al., Ind. Eng. Chem. Anal. 6 (1934) 351.
[10] J.D. Roberts and M.C. Caserio, Basic Principles of Organic Chemistry (Benjamin, New York, 1964)
p. 509.