Thermochimica Acta 660 (2018) 94–100

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Thermochimica Acta
journal homepage: www.elsevier.com/locate/tca

Prediction of the properties of eutectic fatty acid phase change materials T

a a,b,⁎
Samer Kahwaji , Mary Anne White
a
Department of Chemistry, Dalhousie University, PO Box 15000, Halifax, Nova Scotia, B3H 4R2, Canada
b
Clean Technologies Research Institute, Dalhousie University, PO Box 15000, Halifax, Nova Scotia, B3H 4R2, Canada

A R T I C L E I N F O A B S T R A C T

Keywords: Phase equilibrium theory and the laws of thermodynamics provide valuable tools for predicting the composition
Phase change materials and the thermal properties of eutectic mixtures. In this work, we briefly review the predictions based on ideal
PCM mixtures. We evaluate the accuracy of the models by comparing the predicted values of the composition, the
Eutectic melting temperature (Tmpt) and the enthalpy change (ΔfusH) of binary mixtures of fatty acid phase change
Thermal properties
materials (PCMs), specifically as measured for decanoic – tetradecanoic acids, and dodecanoic – tetradecanoic
acids and with values reported in the literature for other fatty acid eutectics. Although the phase diagrams depart
from the ideal system (e.g., peritectic), there is, overall, reasonable agreement with the experimental data, i.e.,
the thermodynamic models can be a good starting point for the prediction of eutectic behaviour in binary or
higher order mixtures of organic PCMs. A computational tool based on these thermodynamic models was de-
veloped in Microsoft Excel® Kahwaji and White, [1] and used to calculate the composition, Tmpt and ΔfusH of a
total of 105 binary mixtures formed from 15 different fatty acid PCMs. The calculated properties show that
eutectics both extend the lower range of Tmpt and provide a wide range of new Tmpt values that are not otherwise
available from individual fatty acids, hence considerably expanding the scope of applications of fatty acids as
PCMs for thermal energy storage.

1. Introduction maintaining a large latent heat of fusion. A state-of-the-art study on

Phase change materials (PCMs) are useful for storing thermal energy
as latent heat due to their high heat-storage capacity and their avail-
ability over a range of transition temperatures. Their properties have
extended the use of PCMs to many thermal energy storage (TES) ap-
plications, including in the building environment to control the indoor
temperature fluctuations or to enhance the efficiency of domestic solar
water heating systems [2–12], and in consumer products such as por-
table electronics and temperature-regulated textiles [13–19]. An es-
sential criterion for optimal operation of a TES system is that the phase
transition temperature of the PCM matches the temperature at which
energy should be stored or released. A large number of organic and
inorganic PCMs with solid-liquid transitions are known and many of
their thermophysical properties, including the melting temperature,
Tmpt, and latent heat of fusion, ΔfusH, have been reported [3,4,20–23].
However, the transition temperature of a PCM is not significantly ad-
justable, and often a PCM with a specific required melting temperature
does not exist. In such a case, a eutectic mixture might yield the desired
transition temperature. Eutectics form a class of their own in terms of
PCMs [21,22], and offer the possibility of creating new PCMs with the
melting temperature tailored to match the temperature required, while
mixtures of PCMs was recently conducted [24]. This comprehensive
study reviews eutectic and other types of PCM mixtures, and demon-
strates that phase equilibrium characteristics, as derived from the phase
diagrams of the mixtures, can provide a valuable tool to assess the
suitability of mixtures as reliable PCMs for thermal energy storage [24].
Eutectic mixtures of fatty acids are particularly interesting because
fatty acids have many desirable properties as TES materials
[21,22,25–27], especially since they can be derived from sustainable
sources [28], they are non-toxic, and they have low commodity prices.
However, the transition temperatures of many of fatty acid PCMs are
outside the range required for some applications. For example, a PCM
with a melting temperature around 25 °C is typically required for in-
door comfort control applications, but an unbranched saturated fatty
acid PCM with such melting temperature does not exist. (Unsaturated
fatty acids have lower melting points, but undergo oxidative rancidity
in air so they are not suitable for PCM use. Undecanoic acid melts at
29 °C, but even-numbered-carbon fatty acids are preferable due to their
lower cost.) By forming a eutectic mixture of decanoic acid and hex-
adecanoic acid it is possible to achieve a PCM with a melting tem-
perature of 25 °C [29]. Eutectic PCMs are generally prepared by mixing
pure components, but a recent study has shown that eutectic mixtures

⁎
Corresponding author at: Department of Chemistry, Dalhousie University, PO Box 15000, Halifax, Nova Scotia, B3H 4R2, Canada.
E-mail address: mawhite@dal.ca (M.A. White).

https://doi.org/10.1016/j.tca.2017.12.024
Received 24 August 2017; Received in revised form 13 December 2017; Accepted 26 December 2017
Available online 28 December 2017
0040-6031/ © 2018 Elsevier B.V. All rights reserved.
S. Kahwaji, M.A. White
Nomenclature
C10 Decanoic acid (aka capric acid)
C12 Dodecanoic acid (aka lauric acid)
C14 Tetradecanoic acid (aka myristic acid)
C16 Hexadecanoic acid (aka palmitic acid)
C18 Octadecanoic acid (aka stearic acid)
Cp Heat capacity at constant pressure
Cp,l Heat capacity at constant pressure of liquid phase
Cp,s Heat capacity at constant pressure of solid phase
ΔfusH Latent heat of fusion
of fatty acids can be directly derived from non-edible animal fat waste
through a simple process of hydrolysis and crystallization [30]. The
latter work showed that a mixture of hexadecanoic acid and octade-
canoic acid derived from pig and chicken fat has a composition and
thermal properties similar to those of a eutectic composition obtained
by mixing pure hexadecanoic and octadecanoic acids [30]. Moreover,
fatty acids can be mixed with other organic PCMs such as fatty alcohols
[31,32] and esters [33,34] to prepare new eutectic PCMs, with different
melting temperatures.
The melting temperatures, latent heats of fusion and eutectic com-
positions of several binary, ternary or quaternary mixtures of fatty acids
and other organic PCMs have been reported in the literature [29,35–41].
In general, the eutectic point is found from the temperature-composition
phase diagram, which is established by measuring the melting tem-
peratures of different compositions of a given mixture by differential
scanning calorimetry (DSC). Peippo et al. [42] calculated and measured
the composition, Tmpt and ΔfusH of the ten possible eutectic mixtures of
five commonly used fatty acid PCMs: decanoic acid (CH3(CH2)8COOH;
abbrev. C10 hereafter), dodecanoic acid (CH3(CH2)10COOH; abbrev.
C12), tetradecanoic acid (CH3(CH2)12COOH; abbrev. C14), hex-
adecanoic acid (CH3(CH2)14COOH; abbrev. C16) and octadecanoic acid
(CH3(CH2)16COOH; abbrev. C18). The maximum deviation between
their calculated and measured values of Tmpt was 2.5 °C [42]. Studies of
binary and ternary eutectic mixtures of C12, C14, C16 and C18 were also
reported in [43]. The mixtures were prepared by heating-ultrasonic
method and their phase diagrams were determined from DSC measure-
ments [43]. For the five binary mixtures: C12-C14, C12-C18, C14-C16,
C14-C18 and C16-C18, the eutectic temperatures determined from the
phase diagrams were in good agreement with the calculated values, with
a maximum deviation of ∼ 1 °C. The maximum deviation between the
calculated and measured values of the mass ratio at the eutectic com-
position was 2.6% [43]. In another study, the phase diagrams of seven
binary mixtures of these five fatty acids were thoroughly determined
from DSC measurements [35]. The phase diagrams showed that some
mixtures exhibit peritectics [35]. Other studies also reported on the
measured properties of eutectic mixtures of the same fatty acids
[44–46,43], and on composites of these PCMs [47–49]. It appears that
most experimental studies on eutectic mixtures of fatty acids have fo-
cused on mixtures of even-carbon fatty acids, particularly with carbon
numbers between 10 and 18.
However, when a full determination of the phase diagram is not
needed, such experiments can be unduly time-consuming and ex-
pensive. It can be even more complicated for ternary or quaternary
mixtures. Alternatively, when Tmpt and ΔfusH of the components to be
mixed are known, it is possible to estimate the eutectic properties –
namely the composition, melting temperature and latent heat of fusion
– from the laws of thermodynamics and the rules of ideal mixtures,
without the need to determine the full phase diagram. In a recent study
[37], the phase diagrams (liquidus transitions only) of twenty-six
binary, ternary, quaternary and quinary mixtures of C10, C12, C14, C16
and C18 fatty acids were calculated using the Schröder–van Laar
equations in Matlab. The calculated compositions and thermal
95
Thermochimica Acta 660 (2018) 94–100
ΔfusHE Latent heat of fusion of the eutectic composition
ΔS Change in entropy
ΔfusSE Change in entropy on fusion of the eutectic composition
DSC Differential scanning calorimetry
PCM Phase change material
Tonset Onset of DSC thermal anomaly
TE Melting point temperature of the eutectic composition
TA Melting point temperature of component A
TB Melting point temperature of component B
Tmpt Melting point temperature
x Mole fraction
properties were then compared to experimental data of prepared eu-
tectic mixtures. The results showed that the properties of the binary
mixtures had the smallest deviations from the calculated values, when
compared to higher-order mixtures [37]. The theoretical prediction of
the eutectic compositions, melting temperatures and latent heats of
fusion of binary mixtures of the same fatty acids were also reported in
ref. [50]. A comparison between the calculated results of both studies
[37] and [50] shows that the deviations are within 4% for the predicted
eutectic composition (for decanoic-hexadecanoic eutectic mixture) and
around 3 °C for the melting temperature. Differences in the calculated
ΔfusH are not as favourable: close to 55 J g−1 in the case of decanoic-
dodecanoic eutectic mixture.
It can be concluded from the published works that mixtures of C10,
C12, C14, C16 and C18 fatty acids are the most commonly investigated,
both in experimental and numerical studies, while mixtures of other
fatty acid PCMs have not been significantly explored. Moreover, a
survey of the literature shows that the calculated and measured eutectic
composition and eutectic temperature of the same mixture can be dif-
ferent from different research groups, with differences of up to 10% for
the eutectic composition and close to 4 °C for the melting temperature
(see for example [20,35,42,49,51–53] for C10-C14 eutectic, and
[23,24] and references therein for other eutectic mixtures). This is
likely due to the use of chemicals with different purities and to different
measurement methods and handling of the samples and the data.
Therefore, to predict the properties of a eutectic mixture with a high
level of confidence, it is best to measure the grade of chemicals that will
be mixed and then use thermodynamic models to determine the li-
quidus transition of the phase diagram from the measured values and
estimate the eutectic point. The predicted values can then be verified by
measuring just a few samples with compositions around the predicted
eutectic point.
The main objective of the present work is to present a brief review
of the thermodynamic models that can be used to find the eutectic
composition, Tmpt and ΔfusH of eutectic mixtures, and then to evaluate
how well these models describe the properties of eutectic mixtures of
PCMs, especially when the phase diagram has more features than a
simple eutectic. This report also aims to provide the PCM research
community (and others interested in eutectics, as the present discussion
is not limited to PCMs use although that is the focus) with a compu-
tational tool that predicts the properties of eutectic mixtures. Here, we
use this tool to calculate the properties of 105 binary mixtures obtained
from the combinations of 15 different fatty acids. Most of these mix-
tures and their properties have not been explored before.
The calculations of eutectic composition and Tmpt are based on a
simple eutectic system of an ideal solution, i.e. ideal mixing of im-
miscible components in the solid state. The latent heat of fusion of the
eutectic, ΔfusHE, is estimated from the total change in entropy on fusion,
ΔfusSE. To evaluate the thermodynamic models, we compared the values
estimated by these models with experimental values reported in the
literature, and values obtained here for two eutectic mixtures of fatty
acids: a eutectic mixture of high-purity C10 and C14, and a eutectic
mixture of C12 and C14. We used DSC to establish the temperature-
S. Kahwaji, M.A. White Thermochimica Acta 660 (2018) 94–100

composition phase diagrams of these two mixtures and to determine

their eutectic properties. Although the two mixtures have peritectics
and, hence, do not obey the simple eutectic model, we show that the (2) (6) (5)
B
computational models give good approximations of the composition,
Tmpt and ΔfusH, and can be a reliable starting point for the prediction of
the thermal properties of eutectic mixtures of PCMs.
The computational tool consists of a workbook developed in (4)
Microsoft Excel® and available online [1]. The provided workbook T
contains a database with the properties of fifteen fatty acid PCMs (see (7)
the related Data in Brief article) along with the necessary formulae to (1) (3)
carry out calculations of the eutectic composition, Tmpt and ΔfusH of a
TE
xE
total of 105 binary mixtures of the fatty acids. This computational tool
is user-modifiable to allow addition of information for additional
compounds. Our aim is to provide an easily accessible and customizable
tool that allows researchers to quickly estimate the properties of a se-
0 0.2 0.4 0.6 0.8 1.0
lected mixture of two or more PCMs, or to identify which binary
composition of organic PCMs yields a specified melting temperature. x
Although the database contains only fatty acids (see Data in Brief ar-
Fig. 1. Schematic of an ideal binary temperature-composition phase diagram as a func-
ticle), it can be expanded by the user and PCM properties in the data-
tion of the mole fraction of component A, xA. The composition of the eutectic point, xE,
base can be modified. This is especially useful when different chemical and the eutectic temperature (dashed line, TE) are shown. The different steps used for the
grades of the same PCM have modified melting points or latent heats of calculation of total entropy change on fusion of the eutectic are numbered and indicated
fusion. by the green arrows. (For interpretation of the references to colour in this figure legend,
the reader is referred to the web version of this article.).

2. Thermodynamic models and experimental methods

where CP,l i and CP,s i are, respectively, the heat capacities of the liquid
2.1. Ideal eutectic model and entropy and enthalpy changes on fusion of and solid phases of component i. A more accurate value of ΔfusHE can be
eutectic determined from the total change in entropy of the eutectic mixture on
melting, ΔStotal, according to the equation:
For a binary mixture that forms a simple eutectic system, the li- Δfus HE = ΔStotal·TE (5)
quidus line in the temperature-composition phase diagram can be de-
termined from the second law of thermodynamics and phase equili- in which the entropy change for each step shown in Fig. 1, ΔSi
brium theory, and, for an ideal system, can be described by the (i = 1–7), is given by:
Schröder–van Laar equation [54,55]: TB
Cp, sB (T )
ΔS1 = xB, E ∫ dT
ln(x i ) = −
Δfus Hi
R ( 1
T
− Tmpt i
1
) (1)
TE
T
(6)
Δfus HB
where xi is the mole fraction of the compound i at temperature T, R is ΔS2 = xB, E TB (7)
the gas constant (8.3145 J K−1 mol−1), and ΔfusHi and Tmpt i are the
TA
molar enthalpy of fusion and the melting temperature of compound i, Cp, sA (T )
ΔS3 = xA, E ∫ dT
respectively. The details of the derivations can be found in the litera- TE
T
(8)
ture, e.g. ref. [56]. In the case of a binary mixture of two components A
and B, Eq. (1) can be rearranged so that the liquidus line is given by ΔS4 = xA, E
Δfus HA

either of the following two equations, depending on the range of the TA (9)
mole fraction with respect to the eutectic point, xE (Fig. 1): TB
Cp, lA (T )
ΔS5 = xA, E ∫ T
dT
T (xE ≤ xA ≤ 1) = ( TA·Δfus HA
Δfus HA − R·TA·ln(xA) ) (2)
TA (10)

ΔS6 = −R (xA, E ln xA, E + xB, E ln xB, E ) (11)

T (0 ≤ xA ≤ xE ) = ( TB·Δfus HB
Δfus HB − R·TB·ln(1 − xA) ) (3) TE
Cp, lE (T )
ΔS7 = ∫ T
dT
where xA is the mole fraction of component A, xE is the mole fraction of TB (12)
A at the eutectic, TA and ΔfusHA are the melting temperature and molar 7
enthalpy of fusion of component A, respectively, and TB and ΔfusHB are and ΔStotal = ∑ ΔSi . Note that Cp,l (T) and Cp,s (T) are now tempera-
those of component B. The two equations can be plotted as a function of i=1
xA and the intersection of the two curves determines xE and the eutectic ture-dependent, and represent the heat capacities of the liquid and solid
temperature, TE, as shown in Fig. 1. This determination requires the phases, respectively. (Eqs. (6)–(12) can be written correspondingly in
knowledge of the melting temperatures and latent heats of fusion of terms of enthalpy changes giving ΔfusHE directly, but the entropy ap-
each component. For PCMs, these parameters are often found in the proach is taken here to explicitly include the entropy of mixing [step
literature or can be measured by DSC. (6)].) The changes in enthalpy in steps (1) and (3) are associated with
Once the eutectic composition of this ideal system is known, i.e., the the heating of components B and A, respectively, from TE to the melting
proportions of the individual components at the eutectic point, xA,E and point of that component, TB or TA. Steps (2) and (4) correspond to the
xB,E, the latent heat of fusion of the eutectic mixture, ΔfusHE, can be melting of the components B and A, respectively, whereas step (5) is the
calculated from: heating of component A from TE to TB. The change in entropy due to
mixing is expressed by step (6) and treated as ideal because of the
Δfus HE = TE Σ xi
i = A, B
( Δfus Hi
Ti
+ (CP, l i − CP, s i ). ln
TE
Ti ) (4)
chemical similarity of the components under consideration. The last
step, (7), illustrates the change in entropy resulting from the cooling of

96
S. Kahwaji, M.A. White
the mixture from TB to TE. Although written more generally in Eq. (12),
here we also investigate whether the eutectic can be considered to be an
ideal mixture of the pure components such that its heat capacity in the
liquid state is given by the rule of mixtures.
For such an ideal mixture, knowledge of Tmpt and ΔfusH of each
component would give the eutectic composition xE and melting tem-
perature TE. The calculation of ΔfusHE further requires the measurement
of the temperature dependence of the heat capacities of each compo-
nent. All these properties can be measured by DSC or, for a quick es-
timation, values reported in the literature can be used.
2.2. Database and computational tool
A computational tool that predicts xE, TE and ΔfusHE of a eutectic
mixture based on the above for potential PCMs was developed in a
Microsoft Excel® workbook [1]. A worksheet that contains a database of
PCMs with their properties is included in the workbook. The properties
necessary to calculate the eutectic parameters are entered by the user
and include: the molar mass, Tmpt, ΔfusH and the heat capacities, Cp(T),
of the PCMs in the solid and liquid phases. A complete description of
the computational tool, along with the database and the calculated xE,
TE and ΔfusHE of 105 binary mixtures of fatty acid PCMs can be found in
the related Data in Brief article.
2.3. Experimental methods
DSC (TA Instruments Q200) was used to measure the onset of the
melting temperature, Tonset, and ΔfusH of five individual fatty acids:
C10, C12, C14, C16 and C18, and of two binary mixtures: a mixture of
decanoic and tetradecanoic acids (denoted by C10-C14) and a mixture
of dodecanoic and tetradecanoic acids (denoted by C12-C14) [53,57].
The DSC measurements were carried out as described in ref. [53]. Ty-
pical sample masses were between 5 and 10 mg. For optimal accuracy,
the heating and cooling rates were 10 K min−1 for ΔfusH determination
and 2 K min−1 for Tonset determination [58]. Five heat-cool cycles were
measured for each sample and ΔfusH was determined from the average
of the five melting (endothermic) peaks. Tonset was typically determined
after measuring ΔfusH, namely from the 6th heating cycle. We also used
DSC to measure Cp(T) of the fatty acids following the procedures de-
scribed in the standard test method ASTM E1269-11, using high-purity
sapphire as a reference sample [53,59]. The uncertainties for the DSC
system are typically ± 10% for ΔfusH and Cp(T), and ± 1.5 °C for Tonset.
To determine the temperature-composition phase diagrams of the
eutectic mixtures, we prepared samples with varying proportions of the
individual components and measured Tonset of each sample by DSC. The
mixtures were prepared in the solid phase by mixing appropriate
masses of pure fatty acids (Table 1), which were then heated on a hot
plate to above the melting point and stirred for about 15 min, then let
cool to ambient temperature [53]. The eutectic compositions and
thermal properties determined by DSC were then compared to those
obtained from the computational model.
3. Results and discussion
We compared the properties predicted by the computational model
of the two binary eutectic mixtures, C10-C14 [53] and C12-C14, with
their properties measured by DSC. The values we measured for Tonset,
ΔfusH and Cp(T) for C10, C12 and C14 (see Data in Brief article) were
used to calculate the thermal properties of the mixtures, and the tem-
perature-composition phase diagrams were determined by measuring
samples with wide composition ranges of C10, C12 and C14. To accu-
rately determine the eutectic composition, we investigated a higher
density of data points closer to the predicted eutectic point and mea-
sured the transition temperatures at a slow heating rate of 2 K min−1. A
slow rate is particularly necessary to confirm that a composition is the
eutectic, with a single endotherm and no shoulder [53]. For the DSC
97
Thermochimica Acta 660 (2018) 94–100
Table 1
Purity and suppliers of fatty acid PCMs used in this work.
PCM Purity Supplier
Decanoic acid (C10) 99% Alfa-Aesar
Dodecanoic acid (C12) 98% Sigma-Aldrich
Tetradecanoic acid (C14) 98% Alfa-Aesar
Hexadecanoic acid (C16) 95% Alfa-Aesar
Octadecanoic acid (C18) 97% ACROS Organics
thermograms where the liquidus transition has a broad endothermic
peak, the transition point is determined from the peak temperature and
not from Tonset [39,53,60].
The C12-C14 phase diagram is shown in Fig. 2 and the C10-C14
phase diagram is shown in our previous work [53]. Despite the ex-
istence of peritectics in both, as found previously [35], the observed
C10-C14 eutectic composition is close to that calculated (observed
xC10 = 0.82 ± 0.02 [53]; calculated xC10 = 0.80), and although the
C12-C14 eutectic is a little further off (observed xC12 = 0.71 ± 0.02;
calculated xC12 = 0.65), both are well within the range of published
compositions ([20,35,42,49,51,52,61,62,43]; see Table 2). The calcu-
lated eutectic melting point is not as well predicted for C10-C14 (ob-
served: 20.5 ± 1.5 °C [53]; calculated: 24.9 °C) as for C12-C14 (ob-
served: 33.6 ± 1.5 °C; calculated: 33.9 °C), but again the calculated
values are in the range of previous reports (Table 2). The latent heats of
fusion, determined from the average of five melt-freeze cycles measured
by DSC at a rate of 10 K min−1, agree with the calculated values, within
experimental error, for both C10-C14 (ΔfusH observed: 153 ± 15 J g−1
[53], calculated: 155 J g−1) and C12-C14 (ΔfusH observed:
160 ± 16 J g−1, calculated: 182 J g−1). The quoted values of ΔfusH
were calculated by assuming that the heat capacity of the eutectic
mixture in the liquid state, Cp,l E (T) in equation (12), is given by the
rule of ideal mixtures (i.e., the heat capacity of C10-C14 is given by
Cp,l = xC10 · Cp,l C10 + xC14 · Cp,l C14). However, for the two eutectic
mixtures, we also directly determined Cp (T) of the mixture by DSC [53]
and used these values of Cp in the liquid phase to calculate their ΔfusH.
For both cases, the deviations between both ΔfusH values are below
10%: using the measured Cp,l values, ΔfusH of the C10-C14 eutectic is
145 J g−1 (compared to 155 J g−1 as determined from the rule of
mixtures) and ΔfusH for the C12-C14 eutectic is 173 J g−1 (compared to
182 J g−1 as determined from the rule of mixtures). In both cases, the
values are in range (or close to the range) of experimental results
(Table 2).
Table 2 also includes a comparison between the values of xE, Tonset
and ΔfusH reported for other binary eutectic mixtures of fatty acids
[20,35,42,49,61,62,43] and our calculated values for the same mix-
tures, using the required heat capacities determined in [57] and [63].
For the sake of the comparison, the properties reported in the literature
are compared with the values calculated using Tonset and ΔfusH mea-
sured for the chemicals listed in Table 1. These values can be slightly
different for chemicals with different purities.
In general, for these pairs of fatty acids, despite the existence of
additional features in the phase diagram beyond the simple eutectic,
and the simplifications of the model used here (i.e., ideal mixtures,
which the existence of peritectics belies), and uncertainties in the ex-
perimental data on which the calculated eutectic properties rely, the
estimates of eutectic compositions and melting points are reasonable
starting points for prediction of eutectic behaviour in binary or higher
order mixtures of organic PCMs, or when starting a preliminary search
for a eutectic mixture that has a specific melting temperature.
Based on these results, we used the accompanying computational
tool, using the widely available computer software Microsoft Excel® and
based on the approach described above, to calculate eutectic properties
of more fatty acid mixtures. The computer file provided with this paper
[1] includes a database with the properties of 15 fatty acid PCMs with
melting points between −8 and 75 °C from which the composition, Tmpt
S. Kahwaji, M.A. White Thermochimica Acta 660 (2018) 94–100

Fig. 2. (a) Phase diagram of the binary mixture of dodecanoic

acid (C12) − tetradecanoic acid (C14) as a function of
60 45 C12 mol fraction, xC12. (b) A close-up of the onset tempera-
Liquidus transition
Eutectic tures in the eutectic region of the phase diagram. The dashed
Solidus transitions lines show the liquidus line calculated from the ideal com-

Temperature / °C
Peritectic
putational model discussed in the text. The solid lines are
50 Model
40 guides to the eye(For interpretation of the references to
colour in this figure legend, the reader is referred to the web
version of this article.).

40 35

30 30
0.0 0.2 0.4 0.6 0.8 1.0 0.5 0.6 0.7 0.8
x x

Table 2
Comparison between the properties of binary eutectic mixtures calculated using the model described in the text (xE calc., TE calc. and ΔfusHE calc.) and values obtained from experiments
and literature. Differences are from comparison with the calculated values. The composition of the eutectic, xE, is given in terms of the mole fraction of the first component in the mixture
(i.e. xE for C10-C14 is the mole fraction of C10). Present work in bold.

Mixtures xE calc. xE meas. Absolute TE calc. TE meas. (°C) Absolute difference ΔfusHE calc. ΔfusHE meas. Percent difference Refs.
difference (°C) (° C) (J g−1) (J g−1) (%)

C10-C14 0.80 0.82 0.02 24.9 20.5 ± 1.5 4.4 155 153 ± 15 1.3 this work and
[53]
0.80 0 23.6 1.3 – – [35]
0.78 0.02 21.4 3.5 152 2.0 [42]
0.72 0.08 24.0 0.9 148 4.5 [20]
0.79 0.01 21.7 3.2 155 0 [49]
C12-C14 0.65 0.71 0.06 33.9 33.6 ± 1.5 0.3 182 160 ± 16 12 this work
0.70 0.05 35.7 1.8 – – [35]
0.65 0 32.6 1.3 156 14 [61]
0.69 0.04 34.0 0.1 167 8.2 [62]
0.68 0.03 32.8 1.1 – – [43]
C10-C12 0.67 0.75 0.08 19.9 21.2 1.3 163 – – [35]
0.65 0.02 19.1 0.8 132 19 [61]
C10-C16 0.88 0.85 0.03 28.1 26.1 2 156 – – [35]
0.82 0.06 22.1 6.0 153 1.9 [61]
C12-C18 0.85 0.85 0 39.9 39.2 0.7 183 – – [35]
0.81 0.04 37.3 2.6 171 6.6 [61]

and ΔfusH of 105 binary eutectic and monotectic mixtures are generated PCM, especially for long-term thermal cycling. Also, a precise value of
(see Tables 2–5 in Data in Brief article). The computer file is also de- TE is required to ensure that the actual melting temperature of the
signed to find a binary mixture that yields a eutectic PCM with the eutectic mixture matches (or is within an acceptable value) the tem-
melting temperature specified by the user. The user can modify the perature of the desired application.
default properties and expand the database to include other classes of
PCMs. This computational tool provides a reasonable prediction of the 80 Eutectic mixtures
properties of eutectic mixtures and is intended to reduce the time and Individual fatty acid PCMs
the number of measurements needed to find the eutectic composition 61.7
60
52.5

when a complete phase-diagram is not necessary. The binary mixtures

extend the lower range of the melting point of fatty acid PCMs from the
41.8

original value of −8 to a reduced value of −22 °C (eutectic of hepta-

40
32.0

noic acid and nonanoic acid) and provide many values of Tmpt that are
28.4

not available from individual fatty acids, filling in gaps in Tmpt in ranges
mpt

of temperature that could be important for many thermal energy sto-

16.5

20
13.5
12.3

rage applications. Fig. 3 shows the vast range of Tmpt values obtained
from all binary eutectic mixtures considered here (Data in Brief and
[1]). As discussed above and shown in Table 2 for some of the known 0
eutectic mixtures, the properties predicted by the computational tool
-7.4

are generally well within the range of values reported in the literature
(see Table 2 and references therein).
Once a potential eutectic system has been identified using these
tools, more detailed experimental studies would be required. Precise
knowledge of the eutectic composition is required for consistent per-
formance of the eutectic mixture as a PCM for thermal energy storage:
in an off-eutectic mixture, ΔfusH is noticeably lower and the system is
inhomogeneous with different densities in different phases. A lower
ΔfusH and phase-separation due to density changes are detrimental for a
-20
Fig. 3. The melting points, Tmpt, of 15 pure fatty acid PCMs and the extended range of
Tmpt predicted for ideal binary eutectic mixtures of these fatty acids. The eutectic mix-
tures extend the range of Tmpt to −22 °C and provide values of Tmpt that are not otherwise
available from individual fatty acids. Some values of Tmpt of fatty acids are specified to
highlight the original gaps in Tmpt of the fatty acids (see Data in Brief article for the data)
(For interpretation of the references to colour in this figure legend, the reader is referred
to the web version of this article.).

98
S. Kahwaji, M.A. White
4. Conclusions
The calculations of the eutectic composition and eutectic tempera-
ture based on ideal interactions predict the eutectics of binary fatty acid
mixtures in reasonable agreement with experimental results, despite
features present in the phase diagram that indicate non-ideal interac-
tions. Although the results are not very highly accurate, from the
starting point of desired phase transition temperature or available
components, the online computational tool provided as a supplement to
the present work [1] can predict the properties of a eutectic mixture to
meet specific applications. Although the exact composition should be
determined more accurately by experiment, such a quick estimation can
reliably direct more detailed investigations, with considerable reduc-
tion in experimental time.
Acknowledgements
The authors acknowledge the financial support of NSERC (Discovery
grant to M.A.W., NSERC CREATE DREAMS postdoctoral fellowship to S.
K.) and assistance from Michel Johnson and John Noël. This study also
was supported by the Canada Foundation for Innovation, the Atlantic
Innovation Fund and other partners that fund the Facilities for
Materials Characterization at Dalhousie University.
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