tmp59EC TMP
tmp59EC TMP
tmp59EC TMP
Cao Xiaoling,
and Bai Li
School of Energy and Power Engineering, Xi'an Jiaotong University, Xi'an, 710049, P. R. China
H
A
T
A
T
m
T
A
RT
m
ln1 X
A
G
A, ex
0
H
B
T
B
T
m
T
B
RT
m
ln1 X
B
G
A, ex
0
8
>
>
>
<
>
>
>
:
1
For the fatty acids, G
A,ex
= G
B,ex
= 0. The eutectic point is an
intersection point at which the liquid phase lines A and B
intersect. So the phase diagram can be plotted by the following
formula.
T
m
1
T
i
R ln X
i
=H
i
i A, B 2
wherein T
m
is the melting temperature of mixture, K, T
i
is the
melting temperature of the i-st substance, K, X
i
is mole fraction of
Received: January 21, 2011
Accepted: April 29, 2011
2890 dx.doi.org/10.1021/je200057j |J. Chem. Eng. Data 2011, 56, 28892891
Journal of Chemical & Engineering Data
ARTICLE
the i-st substance, H
i
is the latent heat of the i-st substance,
J
3
mol
1
, and R is gas constant, 8.315 J
3
mol
1
3
K
1
.
On the basis of the calculation formula, the phase diagram can
be plotted, and the eutectic point of the binary eutectic system
can be determined. The formula on the latent heat of the
multiplex eutectic system is as follows.
H
m
T
m
n
i 1
X
i
H
i
T
i
X
i
C
PLi
C
PSi
ln
T
m
T
i
3
wherein H
m
is the latent heat of the mixture, J
3
mol
1
, C
PLi
is the
specic heat at constant pressure of the i-st substance at liquid
state, and C
PSi
is the specic heat at constant pressure of the i-st
substance at solid state.
If the molecular weight of every component is big enough, the
error of the formula for latent heat is rather small due to ignoring
the sensible heat. As for the long-chain organic compounds, the
error is less than 4 %.
H
m
T
m
n
i 1
X
i
H
i
T
i
4
To verify the accuracy of the formula, its results have been
compared with experiment data from ref 8. The literature
investigated the eutectic mixture of MA and PA by experiment,
including the proportion, melting temperature, and the latent
heat. In the experiment, a General V4.1C DuPont 2000DSC
instrument was used to measure the melting temperature and
latent heat. Samples were measured in a sealed aluminum pan
with a mass of 6.5 mg. The DSC thermal analyses were per-
formed in the temperature range of (0 to 80) C with a heating
rate of 5 C
3
min
1
and under a constant stream of nitrogen at
atmospheric pressure. The molecular weight, melting tempera-
ture, and latent heat of MA are 228.37, 52.2 C, and 182.6 J
3
g
1
,
respectively, and the corresponding parameters of PAare 256.42,
58.9 C, and 189.6 J
3
g
1
, respectively. Table 2 shows the
comparison between the calculated result by formula 2 and 4
and experimental data.
Figure 1 is the calculation diagramof the proportion of MA-PA
eutectic mixture, while Table 2 shows the comparison of proper-
ties of the MA-PA eutectic mixture. From Table 2, the calculated
value is in good agreement with the experimental value; thus, the
formula can be used to calculate the thermal properties of the
fatty acid eutectic mixtures.
3.2. Calculation of Melting Temperature and Latent Heat.
With Table 2, formula 2 and 4, the proportion, melting temperature,
Table 1. Basic Calculation Parameters on Fatty Acids as
PCMs
BS (methyl
stearate) PA MA SA LA CA
melting point (C) 19 58.9 52.2 69.1 42.4 31.6
latent heat
of fusion (J
3
g
1
)
140 189.6 182.6 201.8 186.4 152.6
molecular weight 340.57 256.42 228.37 284.48 200.32 172.27
Table 2. Comparison on Properties of the MA-PA Eutectic
Mixture
a
MA-PA melting temperature latent heat
wt % C J
3
g
1
experimental data 58.0:42.0 42.6 169.7
calculated value 58.2:41.8 42.1 178.2
absolute error 0.2 0.5 0.3
relative error 0.3 %/0.5 % 1.2 % 5.0 %
a
0.3 %/0.5 %, 0.3 % is the computing result relative to 58.0, while 0.8 %
is relative to 42.0.
Figure 1. Calculation sketch of the ratio of MA-PA eutectic mixtures.
Table 3. Theoretical Value of the Ratio (wt %), Melting Point
(C), and Latent Heat of Eutectic Mixtures (J
3
g
1
)
a
BS PA MA SA LA
PA 17.7/141.6
8.2/91.8
MA 16.6/142.4 42.1/178.2
15.0/85.0 61.0/39.0
SA 18.6/140.6 51.5/187.5 46.5/182.0
2.9/97.1 33.3/66.7 23.9/76.1
LA 14.7/146.1 35.7/180.8 32.5/177.2 39.0/184.4
25.4/74.6 73.4/26.6 63.0/37.0 85.7/14.3
CA 10.2/138.6 26.8/153.4 24.0/153.0 29.5/154.6 20.0/155.7
45.6/54.4 84.8/15.2 76.8/23.2 92.9/7.1 66.3/33.7
a
Take the rst group data; for example, 17.7/141.6, 8.2/91.8 in the table
denotes that the melting point, latent heat, and mole ratio of the PA-BS
eutectic mixtures are 17.7 C, 141.6 J
3
g
1
, and 8.2:91.8, respectively.
Figure 2. Distribution of melting temperature of the fatty acid eutectic
mixtures.
2891 dx.doi.org/10.1021/je200057j |J. Chem. Eng. Data 2011, 56, 28892891
Journal of Chemical & Engineering Data
ARTICLE
and latent heat of the fatty acid eutectic mixture were calculated and
listed in Table 3.
Figure 2 shows the distribution of melting temperature of the
fatty acid eutectic mixtures. It can be drawn a conclusion that,
within the temperature range of (10.2 and 48.5) C, there is at
least one eutectic mixture at intervals of 5 C, and among the 15
calculated fatty acid eutectic mixtures, the lowest latent heat is
138.6 J
3
g
1
, while the highest is 185.5 J
3
g
1
. In terms of practical
application of PCMs, materials with the thermal properties are
applicable to low temperature heating, hot water supply system,
temperature-control concrete, and phase change clothing.
4. CONCLUSION
From the calculated results, the calculation is in good agree-
ment with the previous experiment; thus, the formula can be used
to calculate the thermal properties of the fatty acid eutectic
mixtures.
Among the 15 calculated fatty acid eutectic mixtures, the
lowest latent heat is 138.6 J
3
g
1
, and the highest is 185.5 J
3
g
1
.
In terms of practical application of PCMs, fatty acid eutectic
mixtures are applicable to low temperature heating, hot water
supply system, temperature-control concrete, and phase change
clothing.
AUTHOR INFORMATION
Corresponding Author
*Tel.: 86 13880871068; fax: 86 28 87634937. E-mail address:
[email protected].
REFERENCES
(1) Avery, H. E.; Shaw, D. J. Basic Physical Chemistry Calculations;
Butterworths: London, 1971.
(2) Zalba, B.; Marn, J. M.; Cabeza, L. F.; Mehling, H. Review on
thermal energy, storage with phase change: materials, heat transfer
analysis and applications. Appl. Therm. Eng. 2003, 23 (3), 251283.
(3) Atul, S.; Tyagi, V. V.; Chen, C. R.; Buddhi, D. Review on thermal
energy storage with phase change materials and applications. Renewable
Sustainable Energy Rev. 2009, 13 (2), 318345.
(4) Abhat, A. Low temperature latent heat thermal energy storage:
heat storage materials. J. Sol. Energy Eng. 1983, 30 (4), 313332.
(5) Ahmet, S.; Kamil, K. Thermal performance of mystiric acid as a
phase change material for energy storage application. Renewable Energy
2001, 24 (3), 303317.
(6) Ahmet, S.; Kamil, K. Thermal performance of palmitic acid as a
phase change energy storage material. Energy Convers. Manage. 2002, 43
(6), 863876.
(7) Ahmet, S.; Kamil, K. Thermal energy storage systemusing stearic
acid as a phase change material. Solar Energy 2001, 71 (6), 365376.
(8) Ahmet, S.; Hayati, S.; Adem, O. Thermal properties and thermal
reliability of eutectic mixtures of some fatty acids as latent heat storage
materials. Energy Convers. Manage. 2004, 45 (3), 365376.
(9) Lv, S.; Zhu, N.; Feng, G. Eutectic mixtures of capric acid and
lauric acid applied in building wallboards for heat energy storage. Energy
Bldg. 2006, 38 (6), 708711.
(10) Lv, S.; Feng, N.; Zhu, N.; Li, D. Experimental study and
evaluation of latent heat storage in phase change materials wallboards.
Energy Bldg. 2007, 39 (10), 10881091.
(11) Lv, S.; Feng, G.; Zhu, N. Impact of phase change wall room on
indoor thermal environment in winter. Energy Bldg. 2006, 38 (1), 1824.
(12) Costa, M. C.; Rolemberg, M. P.; Laslo, A. D. B. SolidLiquid
Equilibrium of Binary Fatty Acid Mixtures. J. Chem. Eng. Data 2007, 52
(1), 3036.
(13) Zhang, Y.; Su, Y.; Ge, X. Prediction of the Melting Temperature
and the Fusion Heat of (Quasi-) Eutectic PCM. J. China Univ. Sci.
Technol. 1995, 25 (4), 474478.