J. Chem.

Thermodynamics 128 (2019) 127–133

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Heat capacities of potential organic phase change materials

John A. Noël a, Mary Anne White a,b,⇑
a
Department of Chemistry, Dalhousie University, Halifax, Nova Scotia B3H 4R2, Canada
b
Clean Technologies Research Institute, Dalhousie University, 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

Article history: The heat capacity of a material is an important factor for many applications, including phase change
Received 11 April 2018 material (PCM) selection for thermal energy storage. Aside from storing energy via the latent heat of a
Received in revised form 7 August 2018 phase transition, significant sensible heat can be stored using the material’s heat capacity outside the
Accepted 10 August 2018
transition temperature region. Furthermore, accurate heat capacity values are required to model and
Available online 12 August 2018
thereby optimize PCM heat storage systems. Various group additivity models can be used to estimate
the heat capacity of organic liquids. However, these methods do not distinguish isomers built of the same
Keywords:
base units. In the present study the liquid phase heat capacities of five isomeric, 12-carbon, linear,
Heat capacity
Phase change material
saturated fatty esters (potential PCMs) have been measured experimentally, and the results are compared
Ester to calculations from several group additivity methods. It was found that the heat capacities of the liquid
Group additivity esters are well described by the group additivity models, and that each of the esters had approximately
the same heat capacity at a given temperature, despite their structural differences. The heat capacity of
another isomer, dodecanoic acid, was also compared to the ester isomers, and found to be significantly
different. The group additivity methods also were able to accurately represent the heat capacity of the
acid isomer.
Ó 2018 Elsevier Ltd.

1. Introduction the enthalpy change of the phase transition is not accessed, and
much of the thermal storage capacity is lost [1]. Among potential
Phase change materials (PCMs) offer considerable promise for PCMs with suitable transition temperatures, the best material
storage of renewable energy via thermal energy storage and tem- can then be selected to maximize the volumetric or gravimetric
perature moderation [1]. PCMs store thermal energy isothermally thermal storage. Usually this means choosing a material with a
by utilizing the latent heat of a phase transition, typically melting high latent heat of fusion. The thermal energy, Q, stored over the
[1–3], but solid-solid transitions are also possible [4]. Coupled with temperature range of the application is given by:
a solar thermal collector, PCMs can store heat for use when the sun
Z T fus Z T2
is not available, for applications such as heating hot water or build-
Q¼ mcp;s ðT ÞdT þ mDfus H þ mcp;l ðT ÞdT ð1Þ
ings [1,5]. Alternatively, PCMs can be encapsulated within walls,
floors, or ceilings to increase the ‘thermal inertia’ of a room. In such T1 T fus

a situation, the PCM absorbs heat during the day and keeps the
room cooler for longer, thus acting as a thermal buffer and reduc-
ing cooling energy requirements. The PCM then releases its stored
energy at night when the temperature has dropped, with the over-
all effect of reducing temperature swings [1,6].
While cost, safety, and long-term stability of PCMs are impor-
tant concerns in material selection, the paramount consideration
is the transition temperature. If the PCM does not undergo its
phase transition within the temperature range of its application,
⇑ Corresponding author at: Department of Chemistry, Dalhousie University,
Halifax, Nova Scotia B3H 4R2, Canada.
E-mail address: mawhite@dal.ca (M.A. White).
where T1 is the minimum temperature of the application, T2 is the
maximum temperature of the application, Tfus is the melting tem-
perature (T1 < Tfus < T2) , m is the mass of the PCM, DfusH is the melt-
ing enthalpy change, and cp,s and cp,l are the specific heat capacities
of the solid and liquid phases. From Eq. (1), it can be seen that over a
sufficiently broad temperature range, the heat capacity of the PCM
can contribute significantly to the total energy stored [1]. As such,
the selection of a PCM with a high heat capacity, as well as a high
DfusH, can maximize the storage capacity of the system.
For good PCM selection, there must be accurate thermodynamic
data on which the choice can be based. Accurate simulations of
PCM systems to optimize performance also rely on accurate ther-
modynamic property inputs. There are many PCMs for which the

https://doi.org/10.1016/j.jct.2018.08.014
0021-9614/Ó 2018 Elsevier Ltd.
128 J.A. Noël, M.A. White / J. Chem. Thermodynamics 128 (2019) 127–133
melting temperature and the melting enthalpy change are avail-
able. However, there can be considerable variation in values pub-
lished for the same compound [7–9]. Care must be taken to
consult the original literature to check the veracity of the data,
and the expected accuracy of the methods. Considerably less infor-
mation is available regarding the heat capacity of PCMs, making it
difficult to fully model, and thereby optimize, thermal storage sys-
tems that utilize PCMs [10]. Various calorimetric methods can be
used to determine heat capacity experimentally, but these require
access to suitable instrumentation and a sample. For example, Jia
et al. have measured the heat capacities of six sugar alcohol PCMs,
including three stereoisomers, by relaxation calorimetry [11].
Chieruzzi et al. determined the heat capacity of a molten nitrate
salt-based nanofluid PCM [12]. Lu et al. measured the heat capacity
of a solid-to-solid PCM, bis(1-octylammonium) tetrachlorocuprate
by adiabatic calorimetry [13]. In situations where experimental
data are insufficient or difficult to obtain, or a quick assessment
of the PCM would be helpful to decide whether to proceed with
detailed investigations, it would be especially useful to have simple
methods to provide reasonable estimates of the thermodynamic
properties of PCMs, including the heat capacity.
The heat capacities of elemental solids at room-temperature are
well-approximated by the Dulong-Petit law [14]. The Dulong-Petit
law states that all atoms of simple bodies have equal heat capacity,
and in elemental solids at room temperature, a molar heat capacity
of 3R, where R is the gas constant, is a good estimate. The
Neumann-Kopp law extends the Dulong-Petit model to com-
pounds: the Neumann-Kopp law states that the heat capacity of
a solid compound is equal to the sum of the heat capacities of its
constituent elements [14]. The Neumann-Kopp law works well
for estimating the heat capacities of simple materials such as bin-
ary compounds or alloys, but often deviates from experimental
results for more complex compounds in which chemical interac-
tions influence the physical properties. In such cases, methods of
group additivity can be used with considerable success.
While the Neumann-Kopp law is based on the sum of contribu-
tions from the individual elements, group additivity treats the heat
capacity as the sum of contributions from the constituent chemical
groups of the compound. In inorganic compounds, the constituent
groups are often the base minerals. For example, the heat capacity
of sodalite (Na8Al6Si6O24Cl2) is well modelled from 100 to 1000 K
by summing the contributions of Na2O, Al2O3, a-SiO2, and NaCl
[14]. This method works well for many mineral species.
Inorganic PCMs have high volumetric enthalpies of fusion, but
also have a number of drawbacks including potential for incongru-
ent melting, corrosiveness, and supercooling [1]. Organic PCMs lar-
gely avoid these issues, while maintaining high enthalpies of
fusion. As such, much interest has been focused on developing
organic PCMs. In organic compounds, the constituent groups are
the functional groups of the molecule, and several methods for
determining the contributions of individual functional groups to
the heat capacity have been developed. Růžička and Domalski
[15,16], Zábranský and Růžička [17], and Kolská et al. [18], have
published extensive tables of temperature-dependent contribu-
tions for numerous organic functional groups, to calculate the heat
capacities of organic liquids with high accuracy. Chickos et al. have
developed a similar method for estimating heat capacities of both
solid and liquid organic compounds at room temperature [19].
Their method works well for both simple and more complex
organic molecules such as sucrose. Su et al. have extensively
reviewed a large number of group additivity methods useful for
modeling working fluids used in thermodynamic cycles, such as
refrigeration [20]. Valderrama and coworkers [21] and Soriano
et al. [22] have developed accurate models to determine the heat
capacities of ionic liquids. Valderrama’s model uses group additiv-
ity in conjunction with a structural parameter called the mass
connectivity index which takes into account the masses of adjacent
groups in the molecules. Ceriani et al. have put forth a group addi-
tivity method for determining heat capacities of hydrocarbons
commonly found in biodiesel and edible oils [23]. Their method
has been found to accurately predict cp in many fatty compounds.
Pilar et al. measured the heat capacities of 24 solid explosives by
DSC and compared their results to several group additivity estima-
tions [24]. They found that the group additivity estimations could
match some experiments within 1%, but had an average deviation
of 11% at T = 298 K.
Group additivity can be used to estimate a range of thermody-
namic properties in addition to the heat capacity. Much of the early
work on the estimation of thermodynamic properties by group
additivity was initiated by Benson, particularly the calculation of
transition temperatures, enthalpy changes and entropy changes
[25,26]. Benson also showed it to be possible to estimate the heat
capacity from vaporization enthalpy and entropy changes deter-
mined by group additivity [27]. Similar to the tables of functional
group contributions to the heat capacity of organic compounds,
Chickos et al. have provided tables of constituent contributions to
melting/fusion entropy and enthalpy changes for organic com-
pounds, derived from 1858 compounds and tested on 260 more
[28].
An attractive feature of group additivity estimations is that they
are quick, usually simple, and provide results of reasonable accu-
racy. There are, nonetheless, more advanced methods for predicting
heat capacities. For example, vibrational frequencies calculated via
ab initio methods can be used to estimate ideal gas heat capacities
of organic compounds using the harmonic oscillator model with
high accuracy [29]. These estimates out-performed group additivity
methods for rigid molecules containing heteroatoms.
When heat capacity additivity models do not represent the
experimental data well, new insights also can arise. An example
is the heat capacity of clathrates (binary materials with structures
in which one component forms a lattice in which the other compo-
nent is trapped). Sometimes the heat capacity of the guest mole-
cules and host lattice can be additive; an example is the hexakis
(phenylthiol)benzene (HPTB) clathrate containing CBr4 [30]. How-
ever, the non-additivity of the guest and host heat capacity contri-
butions in the case of the THF guest species in the corresponding
clathrate hydrate indicates additional degrees of freedom for the
THF guest molecules, making them ‘‘fluid-like” [31], and account-
ing for its exceptionally low thermal conductivity [32] as the
heat-carrying phonons are perturbed by the motions of the THF
guests. These insights into a novel mechanism to reduce thermal
conductivity opened an important new approach to more efficient
thermoelectric materials [33], again contributing to capture of
renewable energy.
One promising class of PCMs for low-temperature (near or just
above ambient temperature) applications is linear, saturated fatty
esters [1]. Fatty esters have relatively high enthalpies of fusion
[34], and melting temperatures suitable for a variety of cooling
and refrigeration applications [1]. Linear esters have better packing
efficiency in the crystalline phase than branched esters, which
gives them higher values of DfusH. PCM interest is focussed on sat-
urated fats, as unsaturated fats are prone to oxidation at the double
bond, which leads to poor long-term stability of the material.
In a recent study, we examined the influence of the distribution
of methylene units between the two alkyl chains of isomeric linear
esters on the melting temperature and on the melting enthalpy
and entropy changes of the esters [34]. As isomers, the compounds
were equal in molecular mass, all were linear, and all contained the
same number of the same organic units: from a group additivity
perspective, they were identical. It was found that esters with
longer uninterrupted alkyl chains had higher melting temperatures
and associated enthalpy changes than those with two shorter
 J.A. Noël, M.A. White / J. Chem. Thermodynamics 128 (2019) 127–133
chains. For example, consider two 12-carbon isomers: ethyl decan-
oate, with its 2-carbon and 10-carbon chain, has Tfus = 252 K and
DfusH = 143 J mol1, while hexyl hexanoate, with two 6-carbon
chains, has Tfus = 217 K and DfusH = 108 J mol1 [34]. The melting
entropy change, however, was largely independent of the alkyl
chain distribution.
The above example highlights one of the shortcomings of group
additivity methods: they fail to distinguish isomers containing the
same elementary constituents. In the present work, we determine
experimentally the heat capacity of five 12-carbon, isomeric, liquid
esters. The values from experiment are compared to values esti-
mated by various group additivity methods [15–19,23]. With the
exception of methyl esters [35,36], which are used in biodiesel,
there are few fatty ester liquids for which experimental heat capac-
ity data are available, and therefore there is a need for heat capac-
ity information for other esters as PCMs.
Fatty acids have been well-studied as PCMs for heat storage and
load-levelling applications [1]. They offer high enthalpies of fusion,
cycle well [37], are non-toxic, and can be produced sustainably
[38]. Dodecanoic acid, a promising PCM [37,39] and isomer of
the five 12-carbon esters for which experimental heat capacity
information is available [40] is also compared. The fatty acid has
the same elemental composition as the esters, but differs in its con-
stituent chemical groups.
The goals of this work are thus twofold. First, we wish to deter-
mine whether the distribution of methylene units between the two
alkyl chains of the esters influences the heat capacity, as it does
change the melting temperature and melting enthalpy of fusion
[34]. Secondly, we wish to know if the group additivity methods
describe the heat capacity of some isomers better than others,
based on the distribution of the constituents. The importance of
esters and saturated fatty acids for phase change materials provide
the focus for this investigation. The information revealed will allow
better modelling and optimization of PCM thermal energy storage
systems, based on better prediction of PCM properties.
2. Materials and methods
The heat capacities of methyl undecanoate (Alfa Aesar, 99%),
ethyl decanoate (Sigma-Aldrich, >98%), butyl octanoate (Aldrich),
hexyl hexanoate (Sigma-Aldrich, >97%), and octyl butyrate
(Sigma-Aldrich > 98%) (Table 1) were measured according to the
ASTM standard test method designation E1269-11 [41]. All of the
esters were used without further purification. Measurements were
made using a TA Instruments DSC Q200 under a 25 mL min1 flow
of helium gas. The instrument was calibrated for temperature with
mercury and indium melting points as standards prior to the start
Table 1
Sample Sources and Purities.
Chemical Name Source
Test Materials
Octyl Butyrate Sigma-Aldrich
Hexyl Hexanoate Sigma-Aldrich
Butyl Octanoate Aldrich
Ethyl Decanoate Sigma-Aldrich
Methyl Undecanoate Alfa Aesar
Calibration and Standard Materials
Indium TA Instruments
Mercury TA Instruments
Sapphire Calorimetry Conference [NBS-49]
a
Based on the manufacturer’s certificate of analysis indicating purity of 1.0.
b
As stated on the manufacturer’s product specification sheet.
c
Based on melting point relative to literature value; note that manufacturer does not record analytical data on this product.
d
As stated by the supplier.
e
Gas-chromatography
129
of the tests. The samples were measured in crimped aluminum
pans, and had masses of 6–9 mg. Melting points were determined
using onset temperatures and a scanning rate of 2 K min1. The
ASTM standard heat capacity determination method [41] is com-
parative, in which the sample data is compared to a reference
material with known Cp; in this case 6.5 mg of high-purity sapphire
crystallites (Calorimetry Conference [NBS-49]) was used. Each Cp
measurement consisted of three temperature scans performed
under identical conditions. The heat flow to the empty sample
pan was measured first. Secondly, the heat flow to the reference
material in a sample pan was measured. Finally, the heat flow to
the sample in a sample pan was measured. While it is recom-
mended that the same sample pan be used for all three tempera-
ture scans, we used three separate pans with well-matched
masses (<2% difference), and applied a correction factor as recom-
mended in the standard method [41], to account for Al mass differ-
ences. For each temperature scan, the DSC was held isothermally
for 5 min at 203 K, ramped at 10 K min1 to 303 K, thus defining
the temperature range of the experiment, and then held isother-
mally at 303 K for 5 min. The isothermal steps were included to
ensure that the samples had reached thermal equilibrium before
and after heating.
The heat flow to the empty sample pan was subtracted from the
heat flow to the reference material, and also to the sample, as back-
ground corrections. The differences between the heat flow signals
to the sample pan and the sapphire, Dst, and between the heat flow
signals to the sample pan and the sample, Ds, were then calculated
as a function of temperature and used to calculate Cp. At any tem-
perature, the heat capacity of the sample, Cp(s), was found from [41]
Ds W st
C pðsÞ ¼ C pðstÞ
Dst W s
 
Ds ðW st  W pan Þ ðW s  W pan Þ
þ C pðpanÞ  ð2Þ
Dst Ws Ws
where Cp(st) and Cp(pan) are the heat capacities of the sapphire refer-
ence [41] and the empty sample pan, respectively, Wpan is the mass
of the empty sample pan used for the background subtraction, and
Ws and Wst are the masses of the sample pans containing the sample
and sapphire reference material, respectively. The Cp(pan) term is
included to account for the minor mass differences between the
sample pans used. The method was validated with indium, magne-
sium, and benzoic standards, compared to literature values, the rel-
ative standard uncertainty was <10% [42]. For the purposes of
assessment of PCMs, and to see if additivity models accurately rep-
resent experimental heat capacities, this information is sufficiently
accurate. More accurate results could be obtained by other meth-
ods, including by of use relaxation calorimetry which, with the heat
Mass Fraction Purity (as received) Purification Method Method of Analysis
>0.99a None GCe
0.97b None GC
>0.98c None MPt
0.998a None GC
0.986a None GC
0.99999d None –
0.9999d None –
0.999d None –
130 J.A. Noël, M.A. White / J. Chem. Thermodynamics 128 (2019) 127–133

capacity option of the Quantum Design Physical Properties Mea-
surement System (PPMS), can give relative standard uncertainty
of 2% for volatile samples [43,44]. Initial trials were run in a PPMS
but, with the very high volatility of the liquid esters, proved futile.
The need for a sealed pan to prevent the esters from volatilizing
when placed under high vacuum would have required such a mas-
sive seal that the container heat capacity would have dwarfed the
sample’s contribution to the total heat capacity. For further details,
see Supplemental Information.
3. Results and discussion
The heat capacities of liquid octyl butyrate, hexyl hexanoate,
butyl octanoate, ethyl decanoate, and methyl undecanoate were
measured from 203 K to 303 K. The heat capacities of the esters
from their individual melting points to 303 K are plotted in
Fig. 1. All heat capacity values are given in units of the gas constant,
R, where R = 8.314 J K1 mol1. The experimentally determined
values are compared with values determined using five different
Fig. 1. Heat capacities, Cp, in units of the gas constant, R, as a function of
temperature, T, of five 12-carbon esters in the liquid phase determined here by
experiment [octyl butyrate ( ), hexyl hexanoate (d), butyl octanoate ( ), ethyl
decanoate ( ), methyl undecanoate ( )], and by the group additivity methods of
Ceriani (–––)[23], Kolská ( ) [18], Chickos ( ) [19], Růžička ( ) [15,16], and
Zábranský (. . .)[17]. A representative relative standard uncertainty (error bar of
±10%) is shown. Note that the method used here gives >50 data points per kelvin
and only selected data are shown here.
group additivity methods for organic liquids. Table 2 presents the
measured and calculated heat capacities at T = 298 K, along with
the deviations between experiment and calculation. The
temperature-dependent values of the heat capacities of the five
esters in the liquid phase are presented in the Supplemental
Information.
Despite the differences in the distribution of methylene units
between the five isomers, each of the esters has the same heat
capacity, within the standard uncertainty of the measurement,
over the temperature range examined. Isomeric esters exhibit dif-
ferences in melting temperature and in melting enthalpy change
[34], but similar results are not observed when it comes to heat
capacity. The melting point and enthalpy change differences stem
from increased stabilization of the crystalline phase, relative to the
liquid, by chain-chain interactions by isomers with longer alkyl
chains. Here, rather unsurprisingly, the relative thermodynamic
stabilities of the solid and liquid phases have little bearing on the
heat capacity of the liquid.
Fig. 2 compares the values of Cp for methyl undecanoate and
ethyl decanoate to previously published values [35,45,46]. Dzida
et al. [46] made their measurements using micro-DSC, while van
Bommel et al. [35] and Zaitsau et al. [46] used adiabatic calorime-
try. The results acquired in the present work by DSC underestimate
the heat capacity of the esters in both cases, but are still well
within the anticipated 10% uncertainty of the values from the other
methods. The results presented in this work share the same gen-
eral trend as the previously reported data, and accuracy within
10% is suitable for most PCM modelling applications. The deviation
likely arises due to low relative mass of the sample compared to
the mass of the sample pan used here.
The data from the adiabatic calorimetry and micro-calorimetry
studies are well-estimated by group additivity. The group additiv-
ity estimate for the heat capacity of a 12-carbon ester using the
method of Zábranský [17] also is plotted in Fig. 2, and describes
methyl undecanoate and ethyl decanoate equally well, with all
experimental data points within 1% of the estimate.
The heat capacity of linear esters in the liquid phase does
increase with increasing number of carbon atoms, and thereby
molar mass, as has been shown for series of methyl esters
[35,36]. Comparing our results, group additivity estimates for
esters[23], and heat capacity results for other esters [47–50] to
those for the methyl esters (Fig. 3), it appears that all linear, satu-
rated, fatty esters of the same molecular mass (i.e., number of car-
bons) have essentially equivalent heat capacity in the liquid phase.
Each of the five group additivity methods tested predicts the
measured heat capacities of the five liquid 12-carbon esters with
reasonable accuracy. At T = 298 K, no group additivity estimate
was further than 10% away from experiment, which is sufficient
accuracy for PCM modelling. Depending on the method, the esti-
mates are on average 2–8% higher than the experiment at
T = 298 K. Note that at T = 298 K, all five group additivity methods
appear to over-estimate the heat capacity, compared to our

Table 2
Measured and calculated heat capacities, Cp, of several 12-carbon esters at temperature T = 298 K and pressure p = 0.10 MPa, where heat capacities are expressed in units of the
gas constant, R. Note that the calculated values from the group additivity methods are independent of structure.a

Ester Experimental Ceriani 2009 Kolská 2008 Chickos 1993 Růžička 1993 Zábranský 2004 Average Difference (%)
Calculated 48.4 47.8 50.5 48.6 49.0
Octyl Butyrate 46.1 Difference 2.3 1.7 4.4 2.5 2.9 6
Hexyl Hexanoate 47.5 0.9 0.3 3.0 1.1 1.5 3
Butyl Octanoate 47.8 0.6 0 2.7 0.8 1.2 2
Ethyl Decanoate 46.1 2.3 1.7 4.4 2.5 2.9 6
Methyl Undecanoate 46.8 1.6 1.0 3.7 1.8 2.2 5
Average Difference (%) 3 2 8 4 5
a
Standard uncertainties, u, are ur(Cp) = 10%, u(T) = 0.1 K, u(p) = 10 kPa.
 J.A. Noël, M.A. White / J. Chem. Thermodynamics 128 (2019) 127–133
Fig. 2. (a) Heat capacity, Cp, of methyl undecanoate as a function of temperature, T, determined in this work (d) and by van Bommel et al. ( ) [35] and compared to the group
additivity estimate of Zábranský (–––) [17] (b) Heat capacity of ethyl decanoate as a function of temperature determined in this work (d) and Zaitsau et al. ( ) [45] and Dzida
et al. ( ) [46] and compared to the group additivity estimate of Zábranský (–––) [17]. Note that the method used here gives >50 data points per kelvin and only selected data
are shown in these figures.
experimental values. In terms of the group additive methods’ abil-
ity to distinguish isomers, all of the ester isomers are predicted
well, within 6% of experiment on average.
With regard to PCM selection and modelling: as all linear satu-
rated esters of equal molar mass have approximately equal liquid
Fig. 3. Heat capacities, Cp, in units of the gas constant, R, of linear saturated fatty
esters in the liquid phase (at T = 300 K, unless otherwise stated) from this work (j),
methyl esters from van Bommel ( ) [35], Pauly ( ) [36], Liu ( ) [47] (305.4 K), van
Miltenburg ( ) [48], Agafonova (s) [49] (350 K), and Dzida (x)(298.13 K) [50], and
group additivity estimates by the method of Ceriani ( ) [23]. The 20-carbon esters
(open circles) are given at T = 350 K as they are solid at T = 300 K. Error bar
represents the relative standard uncertainty of the measurements ur(Cp) = 10%.
131
phase heat capacities, the heat capacity of the methyl ester of equal
molar mass to the desired ester for the PCM application can be
used a reasonably accurate surrogate. The heat capacities for many
fatty acid methyl esters are known [35,36]. In the absence of exper-
imental information, group additivity methods provide estimates
of reasonably accuracy (<10% deviation at 298 K) for PCM use for
fatty esters.
Dodecanoic acid is an isomer of the five 12-carbon esters exam-
ined. It, however, is different from a group additivity perspective.
Comparison of the heat capacity of liquid dodecanoic acid deter-
mined by adiabatic calorimetry [40] to the group additivity estima-
tions shows that the acid is well described by the estimations as an
acid, whereas comparable ester estimates are lower (Fig. 4). Thus,
although dodecanoic acid is isomeric to the 12-carbon esters,
dodecanoic acid behaves differently with respect to heat capacity.
In addition, using group additivity, it is possible to distinguish
isomers when the constituent groups are altered, even when the
alteration is relatively minor (ester to acid).
Heat capacities of liquid saturated, n-fatty acids of even num-
bers of carbons in the range 8 to 20 carbons are, in general, mod-
elled well using group additivity. Comparing the experimental
results of Schaake [40] to four group additivity estimates
[15–18,23], there is little difference (within about 2%; see Fig. 5).
Saturated fatty acids are useful PCMs [39] and the present results
suggest that group additivity estimations provide acceptable heat
capacity estimates for liquid fatty acids as PCMs. Such estimates
can be used in modelling PCM systems at temperatures for which
experimental data are not available (e.g., Schaake gives heat capac-
ities at only two temperatures for liquid hexadecanoic acid,
octadecanoic acid and eicosanoic acid [40]).
In conclusion, we have determined experimentally the heat
capacity of five saturated 12-carbon linear ester isomers in the liq-
uid phase from just above their melting points to T = 303 K, by DSC.
The ASTM method used provided data of reasonable accuracy
without requiring high vacuum, which is detrimental for such
highly volatile liquid samples. In this temperature range, values
of Cp of the five isomers are equal within the standard uncertainty
132 J.A. Noël, M.A. White / J. Chem. Thermodynamics 128 (2019) 127–133
Fig. 4. Heat capacity, Cp, in units of the gas constant, R, of liquid dodecanoic acid ( )
[40] as a function of temperature, T, compared to values estimated by group
additivity for dodecanoic acid [Ceriani (–––), Kolská (  ), Růžička (-  -),
Zábranský (-  -)] and for 12-carbon esters [Ceriani ( ), Kolská (   ), Růžička
(-  -), Zábranský (-  -)] [15–18,23].
Fig. 5. Experimental heat capacities, Cp, ( ) [40] and group additivity estimates
using the methods of Růžička ( ), Ceriani ( ), Kolská (▲), and Zábranský ( ) [15–
18,23] for saturated n-fatty acids of general formula CnH2n+1OOH, n = even, at
temperature, T = 300 K (C8), T = 345 K (C10 to C16), or T = 355 K (C18 to C20) in units of
the gas constant, R. Vertical dashed lines separate different temperatures.
of the measurement, despite the variation in the distribution of
carbon atoms between the two alkyl chains. It is proposed that
the heat capacities of liquid linear esters depend only on molar
mass, not alkyl chain distribution. The Cp values of the liquid esters
are well described by group additivity, and as such, group additiv-
ity estimates provide a reasonable Cp value in circumstances when
experimental data are not available. Using group additivity, the Cp
of liquid fatty acids also can be accurately predicted and distin-
guished from their isomeric esters. Group additivity has been
shown to provide Cp values for potential organic phase change
materials that are of acceptable accuracy to be used in modelling
of heat storage systems for their optimization, in the absence of
experimental data.
Acknowledgements
J. A. N. acknowledges support from Dalhousie Research in
Energy, Advanced Materials and Sustainability (DREAMS), an
NSERC CREATE program, and an NSERC and a Nova Scotia scholar-
ship. M. A. W. acknowledges support from NSERC and the Clean
Technologies Research Institute at Dalhousie University. We also
acknowledge S. Kahwaji for assistance. The authors thank and
commend Professor Trevor Letcher on his abiding interest in chem-
ical thermodynamics and sustainable energy, and dedicate this
paper to him on the occasion of his 80th birthday.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.jct.2018.08.014.
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JCT 2018-189