Applied Energy 115 (2014) 483–490

Contents lists available at ScienceDirect

Applied Energy
journal homepage: www.elsevier.com/locate/apenergy

Study on phase diagram of fatty acids mixtures to determine eutectic

temperatures and the corresponding mixing proportions
Pin Zhao, Qinyan Yue ⇑, Hongtao He, Baoyu Gao, Yan Wang, Qian Li
Shandong Key Laboratory of Water Pollution Control and Resource Reuse, School of Environmental Science and Engineering, Shandong University, No. 27 Shanda South Road,
Jinan 250100, Shandong, People’s Republic of China

h i g h l i g h t s

 A series of fatty acids mixtures were prepared by heating-ultrasonic method.

 The phase diagram was plotted and analyzed.
 The thermal data was tested by DSC.
 The theoretical data was obtained by Schroder Van Laar equation.
 The scope to find the ternary eutectic point can be narrowed greatly.

a r t i c l e i n f o a b s t r a c t

Article history: This study was focused on preparation and characterization of fatty acid eutectic mixtures as phase
Received 16 April 2013 change materials (PCMs). The four common fatty acids: stearic acid (SA), palmitic acid (PA), myristic acid
Received in revised form 18 October 2013 (MA) and lauric acid (LA) were selected as representative to prepare binary and ternary eutectic mixtures
Accepted 28 October 2013
by heating-ultrasonic method. The melting points of LA–MA, LA–SA, SA–MA, SA–PA, MA–PA, LA–MA–SA,
Available online 21 November 2013
MA–SA–PA mixtures with varying combination proportions were determined and then analyzed by
drawing the phase diagrams to determine the eutectic points and the corresponding mixing proportions.
Keywords:
The results showed that the eutectic temperature of ternary fatty acids was lower than binary fatty acids’;
Fatty acids eutectic mixtures
Phase diagrams
ternary mixture possessed the same thermal properties with pseudo-binary mixture in both melting
Eutectic point temperature and latent heat of phase change; the Schröeder-Van Laar equation can be taken as a basis
Mixing proportions for mixing proportion of pseudo-binary fatty acid and ternary fatty acid systems; the ternary eutectic
The Schröeder-Van Laar equation point on the ternary phase diagram was just in the vicinity of a small triangle which was formed by
the connection between the three vertices and the three eutectic points of binary fatty acid in the
corresponding across flats. Moreover, ternary and pseudo-binary mixtures had advantage in energy con-
servation applications such as building heating/cooling and indoor temperature controlling especially
when the temperature in need was low.
Ó 2013 Elsevier Ltd. All rights reserved.

1. Introduction swings, improving thermal comfort and decrease electrical peak–

valley difference [1–6].
As a new energy-saving and environment-friendly technique, Based on their chemical components, PCMs can be classified
latent heat thermal energy storage by using phase change materi- into two different kinds of categories: (i) organic compounds
als (PCMs) has achieved an increasing attention. PCMs can be ap- and (ii) inorganic compounds [6,7]. Most of inorganic PCMs are
plied widely to the field of energy conservation such as corrosive to most metals, undergo supercooling and have poor
construction, solar energy, waste heat and waste cold as a novel reversibility, while organic PCMs are recommended widely due
energy conservation material. In the process of the urbanization to their satisfying thermal and heat transfer features. The fatty
in some developing countries like China, more and more new acids are most promising organic PCMs, due to their advantages
buildings and public facilities are needed. Applying to PCMs to of chemical and physical stability, low cost, high latent heat of
building materials can contribute to moderating temperature fusion, non-toxicity, non-flammability, non-subcooling, non-cor-
rosiveness, small volume change and good thermal reliability
after a great number of melt/freeze cycles [8,9]. Furthermore,
⇑ Corresponding author. Tel.: +86 531 88365258; fax: +86 531 88364513. fatty acids can be extracting from the common vegetable and
E-mail address: qyyue58@yahoo.com.cn (Q. Yue).
animal oils, therefore they can be supplied continuously

0306-2619/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.apenergy.2013.10.048
484 P. Zhao et al. / Applied Energy 115 (2014) 483–490

[5,9–12]. However, the melting point of the single fatty acid is 2.2. Characterization
quite high for applications such as building heating/cooling and
indoor temperature controlling [13–16]. In general, the low- The melting points of the mixtures were obtained by using
melting organic mixtures of saturated acids are attained by mix- Binocular microscope melting point apparatus (XT-4 Beijing No.
ing, namely eutectic mixtures. 000,000,113 Beijing Tech Instrument Co., Ltd.). Samples were
Many studies on the preparation and the properties of binary heated at a heating rate of 0.2 °C per min. The uncertainty of the
PCMs have been carried out. Shilei et al. [17] investigated wall- measurements was less than 1.0 °C.
board incorporated the eutectic mixture of CA–LA and tested its Differential scanning calorimetry (METTLER TOLEDO DSC1
thermal stability by phase transition cycles; Sari [18] tested the STARe system) was used to test the thermal properties of fatty acid
melting points of binary eutectic mixture made with LA–MA, LA– mixtures. Samples were heated from 10 °C to 70 °C at a heating
PA, and MA–SA, proving that the mixtures had shown reasonably rate of 2–5 °C per min in a static nitrogen atmosphere. The latent
good thermal properties and thermal reliability; Li et al. [2] pre- heat of fusion was attained by calculating the area under the peak
pared a series of binary phase change materials by mixing fatty by numerical integration. Drawing a line at the point of maximum
acids and calculated their phase-transition temperatures and cor- slope of the leading edge of the DSC peak and extrapolating the
responding mixing proportions by Schröeder-Van Laar equation. base line on the same side as the leading edge of the peak, the on-
This calculation method can be taken as a basis for determining set temperature was obtained, which was the temperature that
mixing proportion of binary phase change materials. Feldman mixture started to melt obviously. It can be regarded as the melting
et al. [19] prepared several products by esterification of different point. The uncertainty of the melting temperature was estimated
commercial mixtures of SA and PA with methyl, butyl and propyl to be lower than 0.2 °C. The calorimetric sensitivity was 0.04 lW.
alcohols and investigated heat storage capacity and phase transi- Due to the experimental conditions, the melting points of
tion temperature. majority samples were measured by Binocular microscope melting
However, taking the comfortability of the residential surround- point apparatus in order to save time.
ings into consideration, single fatty acid and the binary fatty acid
mixture, whose phase-transition temperatures are usually high, 2.3. Preparation of fatty acid mixtures
cannot meet the requirement of moderating the indoor tempera-
ture. According to the law of lowering the melting point, the eutec- Fatty acid mixtures were prepared by heating-ultrasonic
tic temperature of mixture is lower than any one of the method. The fatty acids were weighed according to the certain
components in mixture. The mixture of three components has proportion on an analytical balance (AL204 METTLER TOLEDO,
the lower melting point than the corresponding mixture of two made by Metter-Toledo Group) with a ±0.2 mg accuracy: certain
components. Study on ternary compounding of fatty acid is yet intervals (10%) from 0% to 100%, and uniformly mixed together.
limited. The mixtures were vacuumed firstly, then melted and blended in
As we all known, LA, MA, SA and PA, as common fatty acids, are the drying oven. Then the mixtures were cooled to the room
often employed in preparing fatty acids eutectic mixtures. In this temperature and conserved under sealed condition.
work, under different combination ratios, eutectic mixtures of
LA–MA, LA–SA, SA–MA, SA–PA, MA–PA, LA–MA–SA, MA–SA–PA
3. Results and analysis
mixtures were prepared by using heating-ultrasonic method as
representative of fatty acids eutectic mixtures, and then the ther-
3.1. Characteristics of eutectic system
mal properties were measured by differential scanning calorimetry
(DSC) and Binocular microscope melting point apparatus. Based on
Eutectic system has the following characteristics [20]: 1. Com-
the test results, the comparison of pseudo-binary fatty acid system
ponents do not react with each other; 2. Different components
and ternary fatty acid system were discussed; the phase diagrams
are completely immiscible in solid state, while completely miscible
of LA–MA, LA–SA, SA–MA, SA–PA, MA–PA, LA–MA–SA, MA–SA–PA
in liquid state; 3. Phase transition of every single component oc-
mixtures were plotted and investigated; the location of eutectic
curs only when it reaches the specific phase transition tempera-
point in phase diagrams were determined. The novel way to nar-
tures, especially for solid-liquid phase transition.
row the scope of the ternary eutectic point on the ternary phase
diagram would make the work of finding the ternary eutectic point
more effectively. In addition, the research conclusions about LA– 3.1.1. Properties of typical binary eutectic system
SA–MA and SA–MA–PA ternary eutectic mixture were promoted A typical and the simplest binary eutectic phase diagram is
into general rules about fatty acids eutectic mixtures. This research shown in Fig. 1 [21]. The A and B represent the different crystals.
would provide some theoretical support and application reference j and g represent the solid state of A and B, respectively. Point C
for the future works about compounding polynary eutectic mix- stands for the melting point of pure A, with the dosage of B increas-
tures of fatty acids as PCM, and make up for the vacancy of existing ing, melting point of A gradually decreases until it reached point E
research. along line CE. Point D stands for the melting point of pure B, and
when more and more A is added to B, the changing trend of B is
similar with that of A. A and B melt or crystallize at the same point
2. Materials and methods of E. Point E is regarded to the eutectic point. Because the mixed
phase change medium in eutectic point proportioning has stable
2.1. Raw materials performance, a defined single melting point and heat of fusion, it
is popular in application.
Fatty acids including stearic acid (SA, 0.94 g/mL, min 98% pure), The proportion and the corresponding phase-transition temper-
palmitic acid (PA, 0.85 g/mL, min 98% pure), myristic acid (MA, ature can be calculated through an empirical formula: the equation
0.86 g/mL, min 98% pure) and lauric acid (LA, 0.88 g/mL, min 98% of Schröeder-Van Laar [12].
pure) were all obtained from Sinopharm Chemical Reagent Co., ln xi ¼ Hi =Rð1=T i  1=TÞ ð1Þ
Ltd. (Shanghai). All the four fatty acids had good chemical stability,
good thermal stability, non-flammability, low corrosion and non- Note: Hi is the molar melting heat of component i at the melting
toxicity. The basic thermal properties are listed in Table 1. point T (J/mol), Ti is the melting point of component i (K); the
 P. Zhao et al. / Applied Energy 115 (2014) 483–490 485

Table 1
Thermal properties of fatty acids used in the preparation of the eutectic mixtures.

Samples Molecular formula Melting point (°C) Latent heat of fusion (J/g)
Stearic acid (SA) C18H36O2 69 222.2
Palmitic acid (PA) C16H32O2 62 212.1
Myristic acid (MA) C14H28O2 54 178.8
Lauric acid (LA) C12H24O2 42 175.8

T microscope melting point apparatus, and the results are shown

as Fig. 3. It can be seen that the melting point of single fatty acids
was reduced by the addition of other one; however, both fatty
D acids melted simultaneously at the eutectic points which was
L 31.35 °C, 38.93 °C, 48.06 °C, 44.65 °C and 54.00 °C, respectively.
C These different curves have the same characteristics: the pure fatty
acid had the highest melting point. With the increasing dosage of
g+L another fatty acid, the melting point became lower and lower until
j+L
N reached the eutectic point. The eutectic points of binary fatty acid
M E eutectic mixtures were obtained though the curves shown in
j+E S g+E S Table 2. However, the curves shown in Fig. 3 were just the liquidus
100%A Mass line. The inflexion point in the liquidus line could account for
100%B
composition the occurrence of eutectic reaction in the process of mixing
clearly [22].
Fig. 1. Phase diagram of binary eutectic system (L-liquid, S-solid). From Fig. 3, we could also see that the lowest temperatures of
binary systems were all higher than 32 °C and it exceed the com-
fortable temperature range for human body.
formula is deduced from the binary system, so i generally valued as The theoretical eutectic points and the corresponding mixing
1 or 2. T-temperature of Eutectic point (K), xi is the composition proportions of the binary fatty acid system were obtained by
of eutectic mixture (mole percent). R is the gas constant applying the equation of Schröeder-Van Laar. Table 2 shows the
(8.314 J/mol K). comparison between the experimental and theoretical results.
The differences between the experimental and theoretical eutectic
3.1.2. Properties of typical ternary eutectic system points are 1.02 °C, 1.13 °C, 0.16 °C, 0.23 °C and 0.29 °C respectively.
The mixture containing three different crystals forms the ter- The largest one is 1.13 °C in the LA–SA binary system. The theoret-
nary eutectic system. The phase diagram of ternary eutectic system ical mass ratios are very close to the experimental ones, and the
can be expressed in the form of equilateral triangle as shown in differences are 0.1976, 0.1360, 0.1390, 0.0062 and 0.0340, respec-
Fig. 2. Three vertices of triangle represent three different pure crys- tively. This verified equation of Schröeder-Van Laar did apply to
tals. The points in the edge were the mixtures of binary fatty acid, binary eutectic mixtures.
and the content of each component are also shown in this figure. On the other hand, for the same eutectic mixture, the theoreti-
For example, the point of M in line AB means that the mass fraction cal and experimental eutectic points were tested in the other liter-
of component A was 60% and the mass fraction of component B atures as well, which were presented in Table 3 [23]. When the
was 40%. The points inside the triangle were the mixtures of results of the studied mixtures are compared with previously pub-
ternary fatty acid, and the content of each component were deter- lished data, it can be seen that there is generally good agreement,
mined though the auxiliary lines. Taking point N as an example, but small differences between the results are obvious. For example,
line 1, line 2 and line 3 are parallel to the three sides AB, AC and in this study, the eutectic ratio and melting temperature for the eu-
BC, respectively. The contents of A, B and C were obtained from tectic mixture of MA–PA were measured to be 60:40 (mass ratio)
line 3, line 2 and line 1, respectively. Line 3 and line AB intersect and 44.65 °C. However, for the same eutectic mixture, Sarı [24]
at the point M, which represents that the mass fraction of found the eutectic ratios to be 58:42 wt.%, the melting tempera-
component A was 60%. Using the same method, the mass fraction tures to be 42.6 °C.
of component B and C can be obtained, which were both 20%. The The differences in the results were most likely to be two rea-
connection between apex angle and the arbitrary point on across sons: the amount of impurity of the single acid in the mixture
flats possesses an important property. Such as line AQ, the and heating rate performed to the samples through the DSC and
mixtures in this line have the same mass ratio of B to C, it is 7–3. Binocular microscope melting point analysis as well as the exper-
On the basis of full understanding of the binary and ternary eu- imental error which may be caused by other operational
tectic systems, we studied property of fatty acids mixture by the parameters.
method of phase diagram analysis, to find the suitable PCMs for
moderating the indoor temperature.
3.3. Properties of ternary fatty acid eutectic system
3.2. Properties of binary fatty acid eutectic system
3.3.1. Pseudo-binary fatty acid system
In this study, a series of the binary systems: LA–MA, LA–SA, In Fig. 4, to the mixture in line A–E, the component of MA and
MA–SA, MA–PA and SA–PA in different combination proportions SA was regarded as a pseudo-single component, which was fixed
were prepared. The solid samples, which were weighed within in mass ratio of 1:1; a series of the pseudo-binary system of LA
±0.2 mg, were melted and stirred at 105 °C for 30 min, and then and MA–SA were prepared in accordance with the synthesis meth-
the liquid mixtures were vibrated for 2 min. After cooling to room od of binary mixtures. The same to the line C–F, the pseudo-single
temperature, in order to determine the eutectic ratio, melting tem- component of LA and MA were blended in mass ratio of 1:1; then it
peratures of these binary mixtures were measured by Binocular was mixed with SA in different combination ratio to prepare the
486 P. Zhao et al. / Applied Energy 115 (2014) 483–490

100%A
100(0)
90 10

80 20

70 30

%
line 1

ion
60 40

Ma
sit
M line3 N

po

ss
com

c
line2

om
50 50

po
ss
Ma

sit
io
40 60

n%
30 70

20 80

10 90

100%B 100%C
0(100) 90 80 70Q 60 50 40 30 20 10 100(0)
Mass composition %

Fig. 2. Phase diagram of ternary eutectic system.

Table 3
70 LA-MA Thermal properties of binary fatty acid system in literature.
LA-SA
65 Binary fatty acid Mass ratio eutectic point (°C) References
MA-SA
MA-PA LA:MA 67:33 35.7 [21]
60
Melting points ( C)

SA-PA 66:34 34.2 [17]

o

55 LA:SA 75.5:24.5 36.7 [8]

80:20 39.2 [21]
50 MA:SA 64:36 44.1 [17]
MA:PA 58:42 42.6 [22]
SA:PA 35.8:64.2 52.3 [8]
45

40

35 The differences were 0.30 °C and 0.55 °C, which were slight and
acceptable.
30 Applying the equation of Schröeder-Van Laar to the pseudo-
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 binary fatty acid system, we obtained the eutectic temperatures
Proportion (%) and the corresponding mixing proportions of LA–(MA&SA) and
SA–(LA&MA). Table 4 shows the comparison between the experi-
Fig. 3. The curves of melting points corresponding to the different proportions of
mental and theoretical results. To pseudo-binary system of LA
binary fatty acid.
and MA–SA, the experimental mass ratio in the eutectic point
was 55:45, which was equivalent to saying that the mass ratio of
pseudo-binary system of SA and LA–MA. The thermal properties of LA:MA:SA was 55:22.5:22.5; to pseudo-binary system of SA and
these mixtures were measured by DSC, and the results are shown LA–MA, the experimental mass ratio in the eutectic point was
as Fig. 5. The melting point and latent heat of phase change of the 15:85, which corresponding to LA:MA:SA was 42.5:42.5:15 (mass
pseudo-single component of LA and MA in ratio of 1:1 were ratio). The disparity between theoretical and practical value was
35.90 °C and 142.954 J/g, respectively; while the melting point ignorable. The differences of eutectic temperature in LA–(MA&SA)
and latent heat of phase change of the pseudo-single component and SA–(LA&MA) were 0.09 °C and 1.13 °C, respectively; while the
of MA and SA in ratio of 1:1 was 51.29 °C and 175.260 J/g, respec- disparities of mass ratio in the eutectic point were 0.0632 and
tively. The melting points measured by DSC were very close to 0.0489, respectively. It can be inferred that the empirical formula
those measured by Binocular microscope melting point apparatus. can be applied in pseudo-binary fatty acid system.

Table 2
The theoretical and experimental eutectic points of binary fatty acid system.

Binary fatty acid Theoretical mass ratio Experimental mass ratio Theoretical eutectic point (°C) Experimental eutectic point (°C)
LA:MA 62.4:37.6 65:35 32.37 32.85
LA:SA 85.3:14.7 85:15 39.06 37.93
MA:SA 74.1:25.9 75:25 48.2 48.04
MA:PA 59.9:40.1 60:40 44.88 44.65
SA:PA 37.5:65.5 35:65 54.29 54.00
 P. Zhao et al. / Applied Energy 115 (2014) 483–490 487

100%LA
A
100(0) 41.12
90 10
38.20 Y 38.80
Q
80 20
35.65 34.62 I 38.55

70 30
34.88
K 33.75 32.97 G 39.95

n%
P 40

Ma
60

itio
31.75 32.67 37.03 Z 42.60
J H

ss
po
33.75

com
com
50 50
F 35.75 32.87 34.53 39.05 43.90 L 44.75

po
ss

sit
Ma

ion
40 60
33.86 36.69 38.02 44.83 47.36

%
38.25 48.25
30 70
41.35 38.15 37.72 38.45 43.20 49.40 50.70 51.95
20 80
44.85 40.85 41.85 40.82 45.82 51.71 52.43 54.23 55.90

10 90
48.35 45.78 42.92 43.53 46.48 47.37 55.40 57.96 59.82 60.70
66.07
52.08 49.45 48.35 48.30 50.00 52.40 54.78 57.10 59.80 62.30
100%MA B S
0(100) 90 W T
70 60 50 E 40 30 20 10 100(0)C 100%SA
80
Mass composition %

Fig. 4. Phase diagram of ternary fatty acid & the scope of the ternary eutectic point (LA–MA–SA).

of phase change (DH) was approximately 220 J/g with the location
14 of LA:(MA&SA) being 0.6:0.4 (mass ratio) as presented in Table 5.
LA-MA The point of LA:(MA&SA) being 0.6:0.4 (mass ratio) possessed the
12 MA-SA lowest melting point (about 30 °C) as well as a relatively high la-
tent heat (220 J/g) in this system, which indicated that the mixture
Heat FlowEndo up (mW)

10 curve (a) of LA:(MA&SA) being 0.6:0.4 (mass ratio) is the excellent candidate
Area=671.885mJ curve (b) in the application of building construction to moderate the indoor
8 temperature. The differences of latent heat of phase change (DH)
Deta H=142.954J/g
Area=771.146mJ between pseudo-binary and ternary system was below 3.3 J/g
6 Deta H=175.260J/g and was negligible.
Nine ternary mixtures of LA–SA–MA were prepared in the same
4
combination proportions with the corresponding pseudo-binary
fatty acid systems (SA–(LA&MA)). The melting point and latent
2
onset=51.95 C
o heat of phase change (DH) were measured by DSC as presented
0 onset=36.00 C
o in Fig. 7 and Table 6, respectively. To the melting point of ternary
system (LA–SA–MA) and pseudo-binary system (SA–(LA&MA)),
24 28 32 36 40 44 48 52 56 60 the biggest difference was 0.6 which were three points of SA:
Temperature ( oC) (LA&MA) being 0.5:0.5 (mass ratio), SA:(LA&MA) being 0.3:0.7
(mass ratio) and SA:(LA&MA) being 0.1:0.9 (mass ratio). The small-
Fig. 5. DSC curve of (a) pseudo-single component of LA and MA in ratio of 1:1 and
est one was located at the points of SA:(LA&MA) being 0.9:0.1
(b) pseudo-single component of MA and SA in ratio of 1:1.
(mass ratio). The disparity of the latent heat of phase change
3.3.2. Comparison between ternary and pseudo-binary fatty acid (DH) between the two systems was acceptable as well as the
systems melting point. The maximum disparity was 4.194. As same as the
The ternary systems of LA–SA–MA in the same combination LA:(MA&SA) system, the point of SA:(LA&MA) being 0.15:0.85
proportions with the corresponding pseudo-binary fatty acid sys- (mass ratio) possessed the lowest melting point (about 31 °C) as
tems (LA–(MA&SA)) were prepared by the above synthetic method. well as the highest latent heat (186 J/g) among this system.
The thermal properties of eutectic mixtures were measured by The properties of ternary mixture were similar to these of pseu-
DSC. The melting point is shown in Fig. 6. It can be seen that the do-binary mixture through the above analysis, so the equation of
difference of melting points between the two systems was small. Schröeder-Van Laar was suitable to ternary fatty acid system.
The disparities were within the range of 0.08–0.7 °C, in which
the largest one was in the point of LA:(MA&SA) being 0.3:0.7 (mass 3.3.3. Ternary fatty acid system
ratio) and the minimal one was in the lowest melting point with A succession of ternary fatty acid eutectic mixtures (LA–MA–
LA:(MA&SA) being 0.6:0.4 (mass ratio). The greatest latent heat SA) in different mixing proportions was prepared through the same

Table 4
The theoretical and experimental eutectic points of pseudo-binary fatty acid system.

Pseudo-binary fatty acid Theoretical mass ratio Experimental mass ratio Theoretical eutectic point (°C) Experimental eutectic point (°C)
LA:(MA&SA) 56.2:43.7 55:45 31.26 31.17
SA:(LA&MA) 18.4:81.6 15:85 32.88 31.75
488 P. Zhao et al. / Applied Energy 115 (2014) 483–490

70
50
65
Pseudo-binary system
ternary system 60
45
Melting points ( C)

Melting points ( o C)
55
o

40 50

45

35 40

35 pseudo-binary system
30 ternary system
30

0.0 0.2 0.4 0.6 0.8 1.0 25

0.0 0.2 0.4 0.6 0.8 1.0
100% MA&SA Mass composition (%) 100% LA 100% LA&MA Mass composition (%) 100% SA

Fig. 6. The curves of melting points corresponding to the different proportions in Fig. 7. The curves of melting points corresponding to the different proportions in
ternary and pseudo-binary fatty acid systems (SA–(LA&MA)). ternary and pseudo-binary fatty acid systems (SA-(LA&MA)).

combination process. The thermal properties of eutectic mixtures was formed by the three connections between the point A and T,
were measured by Binocular microscope melting point apparatus the point B and Q, the point C and P, as shown in Fig. 4. This triangle
as Fig. 4 shown. The points in the edge were the mixtures of binary was within the range encircled by the line AB, IW, KG and FL.
fatty acid, whose melting points decreased from both sides to the Through analysis of the test data trends, it can be seen that ternary
eutectic point. The points inside the triangle were the mixtures eutectic point in the vicinity of the small triangle. The theoretical
of ternary fatty acids whose melting points change regularly to ternary eutectic point obtained by applying the equation of
the points of the parallels to the edges, melting points changed Schröeder-Van Laar was orientated in the point H as presented in
similarly to the ones of corresponding edges. The eutectic points Fig. 4. The location of H can verify the above conclusion.
and the corresponding mixing proportions of ternary fatty acids Ternary fatty acid eutectic mixtures (MA–SA–PA) were pre-
were shown in Table 7. The experimental mass ratio was located pared to validate the above conclusion. As shown in Fig. 8, the
at the lowest melting temperature presented in Fig. 4. To the ter- points of M, Q and N are eutectic points of the binary mixtures
nary fatty acid system (LA–MA–SA), the eutectic point was valued PA&MA, PA&SA and MA&SA, respectively. To the point M, Q and
according to the theory that the eutectic point of ternary systems N, the mass ratio of PA to MA, PA to SA and MA to SA was 40–
was lower than those of corresponding pseudo-binary systems. 60%, 65–35% and 75–25%, respectively. The small triangle was
In the line of KG, the melting point of the mixtures formed by the three connections AN, BQ and CM. The theoretical
(LA:MA = 70:30, LA:MA:SA = 70:20:10, LA:MA:SA = 70:10:20 and ternary eutectic point was received by using the equation of
LA:SA = 70:30) are 33.75 °C, 32.97 °C, 34.88 °C and 39.95 °C, Schröeder-Van Laar, and then it was located in the point H as pre-
respectively. It can be inferred that the lowest melting point in this sented in Fig. 8. It can be clearly seen that the point H is very close
line was located the position between the point (LA:MA = 70:30) to the scope of small triangle. Several ternary fatty acid mixtures
and the point (LA:MA:SA = 70:20:10). To the line of JZ, the lowest were chosen to be measured by Binocular microscope melting
phase change temperature was fixed the location near the point point apparatus, aiming to determine the melting points.
(LA:MA:SA = 60:30:10). In the direction parallel to the line AB, In the line of 1–2–3–4, the melting point of the mixtures (PA:
the phase change temperature in the line JZ was lower than the MA:SA = 35:55:10, PA:MA:SA = 35:50:15, PA:MA:SA = 35:45:20
corresponding one in the line KG as well as the line FL. The lowest and PA:MA:SA = 35:40:25) were 42.85 °C, 41.19 °C, 42.17 °C and
melting point of the ternary fatty acid system was within the range 42.60 °C, respectively. The lowest melting point in this line was lo-
between the line KG and FL. The same to the line AB, YS and IW, the cated the position close to the point 3; To the line of 5–6–7–8, the
location of the lowest melting point of the ternary system was be- melting point of the mixtures were 42.07 °C, 40.93 °C, 41.85 °C and
tween the line AB and IW. So we found that the lowest melting 42.45 °C, respectively. The lowest phase change temperature in
point of the ternary system was in the extent surrounded by the this line was fixed the location nearby the point 6; while to the line
line AB, IW, KG and FL. of 9–10–11–12, the melting point of the mixtures were 43.01 °C,
The points of P, Q and T are eutectic points of the binary mix- 41.05 °C, 42.35 °C and 42.98 °C, respectively. In the direction
tures LA&MA, LA&SA and MA&SA, respectively. A small triangle parallel to the line DB, the phase change temperature in the line

Table 5
The comparison of latent heat of phase change between ternary system and pseudo-binary fatty acid system.

Proportion of MA & SA (%) Proportion of LA (%) DH (J/g) in pseudo-binary system DH (J/g)in ternary system Difference of DH pseudo-binary
and ternary system (J/g)
0.1 0.9 127.761 129.652 1.891
0.2 0.8 193.537 194.541 1.004
0.3 0.7 206.845 208.348 1.503
0.4 0.6 142.592 139.687 2.905
0.5 0.5 107.072 110.369 3.297
0.6 0.4 219.373 221.546 2.173
0.7 0.3 122.437 120.345 2.092
0.8 0.2 100.571 101.682 1.111
0.9 0.1 159.278 157.364 1.914
 P. Zhao et al. / Applied Energy 115 (2014) 483–490 489

Table 6
The comparison of latent heat of phase change between ternary system and pseudo-binary fatty acid system (SA–(LA&MA)).

Proportion of LA & MA (%) Proportion of SA (%) DH in pseudo-binary system (J/g) DH in ternary system (J/g) Difference of DH pseudo-binary
and ternary system (J/g)
0.1 0.9 75.952 73.564 2.388
0.2 0.8 102.99 105.341 2.351
0.3 0.7 94.261 98.369 4.108
0.4 0.6 105.771 102.322 3.449
0.5 0.5 121.361 118.241 3.12
0.6 0.4 139.777 139.373 0.404
0.7 0.3 158.205 155.543 2.662
0.8 0.2 174.122 178.316 4.194
0.85 0.15 185.466 186.541 1.075
0.9 0.1 112.838 112.046 0.792

Table 7
The eutectic points and the corresponding mixing proportions in ternary fatty acid system.

Ternary fatty acid Theoretical mass ratio Experimental mass ratio Theoretic eutectic point (°C) Experimental eutectic point (°C)
LA:MA:SA 57.5:34.3:8.2 60:30:10 31.03 29.35
MA:SA:PA 52.5:17.2:30.3 50:20:30 41.94 40.93

100%PA
D
0 61.35

90 90
57.00 58.39
80 80
53.70 55.92

70 70
50.75 54.05
%

Q
ion

60 60
Ma
sit

48.87 54.28
po

ss
com

com

50 50
55.37
po

47.01
ss
Ma

sit
ion

40 40
M 45.55 57.15
%

1 2 3 4
30 5 30
45.20 6 H 7 8 59.52
20 9 10 11 12 20
48.01 61.27

10 10
50.70 63.83
66.79
0 52.89 50.89 48.50 48.30 50.02 51.96 54.78 57.01 60.19 63.93
B N C
10 20 30 40 50 60 70 80 90 100(0)
100%MA Mass composition % 100%SA

Fig. 8. Phase diagram of ternary fatty acid & the scope of the ternary eutectic point (MA–SA–PA).

of 5–6–7–8 was lower than the corresponding one in the line of 1– mixtures of MA–SA–PA had the same result as the ternary mix-
2–3–4 as well as the line 9–10–11–12. The lowest melting point of tures of LA–MA–SA.
the ternary fatty acid system was within the range between the The scope to find the ternary eutectic point can be narrowed
line of 1–2–3–4 and 9–10–11–12. The same to the line 1–5–9, greatly, which makes the location quicker and easier. This finding
3–7–10 and 4–8–11, the location of the lowest melting point of provides theoretical support for the analysis of the ternary system
the ternary system was between the line of 1–5–9 and 4–8–11. in the future.
So we found that the lowest melting point of the ternary system
was in the extent surrounded by the line of 1–2–3–4, 9–10–11–12, 4. Conclusion
1–5–9 and 4–8–11, where contained the small triangle as
presented in Fig. 8. The theoretical ternary eutectic point was ori- The eutectic mixtures in binary, pseudo-binary and ternary sys-
entated in the point H. Through the above analysis, the ternary tem were prepared by blending LA, MA, SA and PA in different
490 P. Zhao et al. / Applied Energy 115 (2014) 483–490

combination proportions and then were characterized to [3] Inoue T, Hisatsugu Y, Ishikawa R, Suzuki M. Solid–liquid phase behavior of
binary fatty acid mixtures: 2. Mixtures of oleic acid with lauric acid, myristic
investigate the effects of mixture ratio on the thermal properties
acid, and palmitic acid. Chem Phys Lipids 2004;127:161–73.
of fatty acids eutectic mixtures, especially the phase change tem- [4] Zalba B, Marı´n JM, Cabeza LF, Mehling H. Free-cooling of buildings with phase
perature. The eutectic points of binary, pseudo-binary and ternary change materials. Int J Refrig 2004;27:839–49.
system were determined by drawing and analyzing binary and ter- [5] Zhou D, Zhao C-Y, Tian Y. Review on thermal energy storage with phase change
materials (PCMs) in building applications. Appl Energy 2012;92:593–605.
nary phase diagrams. [6] Oró E, De Gracia A, Castell A, Farid M, Cabeza L. Review on phase change
The results extracted from Binocular microscope melting point materials (PCMs) for cold thermal energy storage applications. Appl Energy
apparatus and DSC measurements indicated that the phase transi- 2012;99:513–33.
[7] Baetens R, Jelle BP, Gustavsen A. Phase change materials for building
tion temperatures of ternary fatty acid eutectics were lower than applications: a state-of-the-art review. Energy Build 2010;42:1361–8.
those of binary fatty acids, while the phase transition temperatures [8] Baran G, Sari A. Phase change and heat transfer characteristics of a eutectic
of binary fatty acid eutectics were lower than those of individual mixture of palmitic and stearic acids as PCM in a latent heat storage system.
Energy Convers Manage 2003;44:3227–46.
fatty acids. Consequently, ternary and pseudo-binary mixtures [9] Sarı A, Kaygusuz K. Some fatty acids used for latent heat storage: thermal
had advantage in energy conservation applications in which the stability and corrosion of metals with respect to thermal cycling. Renew
temperature was low, to satisfy the comfortability of the residen- Energy 2003;28:939–48.
[10] Sarı A. Eutectic mixtures of some fatty acids for latent heat storage: thermal
tial surroundings. properties and thermal reliability with respect to thermal cycling. Energy
It can be concluded that: Convers Manage 2006;47:1207–21.
[11] Suppes G, Goff M, Lopes S. Latent heat characteristics of fatty acid derivatives
pursuant phase change material applications. Chem Eng Sci 2003;58:1751–63.
(1) The equation of Schröeder-Van Laar was applicable to the
[12] Khoo I-C, Wu S-T. Optics and nonlinear optics of liquid crystals. World
pseudo-binary fatty acid LA–(MA&SA) and SA–(LA&MA) Scientific; 1993.
systems; [13] Cai Y, Ke H, Lin L, Fei X, Wei Q, Song L, et al. Preparation, morphology and
(2) The thermal properties of ternary mixture were similar to thermal properties of electrospun fatty acid eutectics/polyethylene
terephthalate form-stable phase change ultrafine composite fibers for
these of pseudo-binary mixture in both melting temperature thermal energy storage. Energy Convers Manage 2012;64:245–55.
and latent heat of phase change. The Schröeder-Van Laar [14] Li M, Wu Z, Kao H. Study on preparation and thermal properties of binary fatty
equation was suitable to ternary fatty acid system as well; acid/diatomite shape-stabilized phase change materials. Sol Energy Mater Sol
Cells 2011;95:2412–6.
(3) Both of the melting points in vicinity of the point [15] Tuncbilek K, Sari A, Tarhan S, Ergünesß G, Kaygusuz K. Lauric and palmitic acids
(LA:(MA&SA) = 65:35) in the pseudo-binary system and the eutectic mixture as latent heat storage material for low temperature heating
point (LA:MA:SA = 60:30:10) in the ternary system were applications. Energy 2005;30:677–92.
[16] Tyagi VV, Buddhi D. PCM thermal storage in buildings: a state of art. Renew
about 30 °C. These mixtures would be applied in the build- Sustain Energy Rev 2007;11:1146–66.
ing construction to better meet the need of comfortability [17] Shilei L, Neng Z, Guohui F. Eutectic mixtures of capric acid and lauric acid
in the residential surroundings; applied in building wallboards for heat energy storage. Energy Build
2006;38:708–11.
(4) To the phase diagram of eutectic ternary system, the eutectic [18] Sarı A. Eutectic mixtures of some fatty acids for low temperature solar heating
point was in the vicinity of a small triangle which was applications: thermal properties and thermal reliability. Appl Therm Eng
formed by the connection between the three vertices and 2005;25:2100–7.
[19] Feldman D, Banu D, Hawes D. Low chain esters of stearic acid as phase change
the three eutectic points of binary fatty acid in the corre-
materials for thermal energy storage in buildings. Sol Energy Mater Sol Cells
sponding across flats; 1995;36:311–22.
(5) The method to find ternary eutectic point in this study is [20] Lu SS. Phase diagram & phase transformation. Anhui, China: Press of University
successful, viable and meaningful. of Science and Technology of China; 1990.
[21] Kukushkin S, Grigoriev D. Theory of the late-stage crystallization of eutectic
composition melts. J Phys Chem Solids 2000;61:1337–43.
[22] Costa MC, Rolemberg MP, Meirelles AJ, Coutinho JA, Krähenbühl M. The solid–
References liquid phase diagrams of binary mixtures of even saturated fatty acids
differing by six carbon atoms. Thermochim Acta 2009;496:30–7.
[23] Costa MC, Rolemberg MP, Boros LA, Krähenbühl MA, de Oliveira MG, Meirelles
[1] Wang L, Meng D. Fatty acid eutectic/polymethyl methacrylate composite as
AJ. Solid–liquid equilibrium of binary fatty acid mixtures. J Chem Eng Data
form-stable phase change material for thermal energy storage. Appl Energy 2007;52:30–6.
2010;87:2660–5. [24] Sarı A, Sarı H, Önal A. Thermal properties and thermal reliability of eutectic
[2] Li M, Kao H, Wu Z, Tan J. Study on preparation and thermal property of binary mixtures of some fatty acids as latent heat storage materials. Energy Convers
fatty acid and the binary fatty acids/diatomite composite phase change Manage 2004;45:365–76.
materials. Appl Energy 2011;88:1606–12.