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Thermochimica Acta 630 (2016) 50–63

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

Solid liquid phase diagrams of binary fatty acid


mixtures—Palmitic/stearic with oleic/linoleic/linolenic acid mixture
Karl-Andreas Eckert, Sunanda Dasgupta ∗ , Benjamin Selge, Peter Ay
BTU Cottbus-Senftenberg, Chair of Mineral Processing, Siemens-Halske-Ring 8, 03046 Cottbus, Germany

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

Article history: The solid liquid phase diagrams of binary mixtures of the five main saturated and unsaturated fatty acids
Received 18 August 2015 present in most edible plant oils have been determined in this paper. These binary mixtures comprise
Received in revised form 4 February 2016 of a saturated fatty acid, either palmitic (C16:0) or stearic (C18:0) and an unsaturated one, oleic (C18:1),
Accepted 20 February 2016
linoleic (C18:2) or linolenic (C18:3) acid. Differential scanning calorimetry (DSC) was used to obtain
Available online 5 March 2016
an overview of the solid liquid transition behaviour including the metastable ranges of these mixtures.
In order to describe all the phase transformations in these systems, the boundary functions have been
Keywords:
determined and compared. Phase diagrams determined, illustrate characteristic behaviour in accordance
Binary mixtures
Solid liquid equilibrium
to literature. This work specifically focuses on to describe the solid liquid transitions of the mixtures and
Saturated and unsaturated fatty acids not on every single transition or reaction. This paper contributes to the elucidation of the phase behaviour
Phase diagram of these important mixtures which are applied in diverse industries.
DSC © 2016 Elsevier B.V. All rights reserved.

1. Introduction temperature. Generally, the metastable range of a mixture


describes how far that mixture can be cooled below the equilib-
Fats and fatty acids based on edible plant oils are important rium temperature before spontaneous nucleation and eventually
renewable resources which are applied to substitute industrial crystal growth starts [2].
mineral oil based raw materials. Fatty acids are used in many dif- Differential scanning calorimetry was used to analyse the ther-
ferent fields, such that of biodiesel, textile, lubricant, cosmetics and mal properties and phase transformations of these mixtures. As
nutritional additives. Fatty acids derived from edible plants oils mentioned before, these binary mixtures comprise of a saturated
are usually a mixture of five main components, namely, palmitic, fatty acid, either palmitic (P, C16:0) or stearic (S, C18:0) and an
stearic, oleic, linoleic and linolenic acid. There is a wide variety unsaturated one, oleic (O, C18:1), linoleic (L, C18:2) or linolenic
in the distribution of these acids depending on the species of the (Ll, C18:3) acid. This information was used to construct the phase
plant. Naturally occurring mixtures typically show a distribution diagrams as well as the enthalpy plots with respect to the molar
of around 10% saturated acids and 90% unsaturated acids. There fraction of the saturated fatty acid in the mixture. Phase bound-
are mixtures with a high oleic acid content, as for example in sun- aries and metastable range functions were fitted with high accuracy
flower oil based mixtures, as well as high linoleic or high linolenic using a mathematical program named ‘fityk’.
mixtures, such as those based on linseed or soybean. In order to
technically optimize melt crystallization purification processes, a
deep and fundamental understanding of the underlying kinetics is 2. Experimental
indispensable.
Previous investigations on such systems have shown that as in 2.1. Materials
the liquidus line, the solidus line also has a metastable range [1].
Therefore, a second metastable range of solidification is present Samples used were supplied by Sigma–Aldrich, the purities of
and these temperatures are significantly lower than the eutectic which are shown in Table 1 alongside with the corresponding
product numbers for further information. There was no further
purification of the studied samples.
∗ Corresponding author.
Thermal analyses of the samples were carried out using a DSC
E-mail addresses: Karl-Andreas.Eckert@b-tu.de (K.-A. Eckert),
1 (HP DSC827e , Mettler Toledo Ltd.) equipped with a cryostat
sunanda.dasgupta@b-tu.de (S. Dasgupta), Benjamin.Selge@b-tu.de (B. Selge), (TC100MT-NR, Peter Huber Kältemaschinenbau GmbH). The DSC
Peter.Ay@b-tu.de (P. Ay). was calibrated with an indium and zinc standard (<0.9999% molar

http://dx.doi.org/10.1016/j.tca.2016.02.008
0040-6031/© 2016 Elsevier B.V. All rights reserved.
K.-A. Eckert et al. / Thermochimica Acta 630 (2016) 50–63 51

Table 1 for binary systems [3,7]. Solidus and solid phase transformation
Overview of the samples.
lines were fitted with a constant value, whereas liquidus lines were
Fatty acid Purity Product-number fitted to the thermodynamic model as in Eq. (1) [8,9].
≥98% (GC)
 
Palmitic acid 27734 Aldrich TA HA + ω(1 − xA )2
Stearic acid ≥98.5% (GC) S4751 Sigma T= (1)
Oleic acid ≥99% (GC) O1008 Sigma–Aldrich HA − RTA lnxA
Linoleic acid ≥99% (GC) 62230 Fluka
This equation can describe the equilibrium temperature for eutec-
Linolenic acid ≥98.5% (GC) 62160 Fluka
tic systems which are assumed to be ideally mixed in the liquid
state and completely immiscible in the solid phase. In the equation
fraction, Mettler Toledo Ltd.) and deionized water. All weighing above, xA represents the mole fraction of compound A in the mix-
was carried out using a precision scale (XS105 Dual Range, Mettler ture, HA is the molar heat of fusion and TA the melting point of the
Toledo Ltd.) with an accuracy of ±0.1 mg. pure component A. Additionally, there is an interaction parameter
ω that describes the non-ideality of mixing for a binary system. It
is defined by Eq. (2), where uAA , uBB , and uAB are the interaction
2.2. Methods
energies for A–A, B–B, and A–B pairs formed in the mixture.
 1

2.2.1. Differential scanning calorimetry (DSC)
ω = z uAB − (uAA + UBB ) (2)
The mixtures were weighed in a standard 40 ␮l aluminium cru- 2
cible from Mettler Toledo and immediately put into the DSC oven. Factor z is the coordination number, which stands for the num-
To overcome problems due to local concentration gradients and to ber of nearest neighbour molecules of one single molecule. From
obtain clear signals, large sample sizes of around 25–30 mg were the physical point of view, ω is the energy difference between
chosen. It is known from literature [3] that larger sample masses that of a pair of different molecules (A–B) and the average of
shift the peak temperatures to higher values. This reproducible the energy between pairs of the similar molecules (A–A, B–B). In
effect can be described by the law of Illers [3]. To minimize that case of ideal mixing, there is no energy difference between the
shift, a slow cooling rate of 1 K min−1 was chosen. The tempera- molecules and hence ω becomes zero. If ω is a negative value, the
ture profiles were started immediately after closing the DSC oven. energy of the same pair molecules is higher than that of the mixed
The profile started with a hold level of 90 ◦ C for 10 min. The samples molecules, meaning that attractive interactions occur between dis-
were then cooled down with a rate of 1 K min−1 until a temperature, similar molecules. If ω is positive, the energy of the mixed molecule
that was at least 15 K below the smallest detectable exothermic pair is higher, that is, there are repulsive interactions between dif-
event of the pure sample, was reached. After a short steady state ferent species molecules.
of 5 min, the sample was reheated to 90 ◦ C with a heating rate of In the case of fatty acids, there is a special feature regarding the
1 K min−1 . The obtained curves were then normalized to the sam- interactions between molecules. In case of binary systems where
ple size and evaluated using the Mettler Toledo StarE Software with the components are completely immiscible in the solid phase,
spline shaped baseline interpolation and exported as plain text for which is the true for all investigated systems, fatty acids form
later evaluation. dimers of similar fatty acids. Hence, they are aggregating to form
Fig. 1 illustrates a thermogram obtained by the DSC for a binary clusters of a smectic liquid crystal like structure [10–12]. There-
mixture with 1:1 ratio of oleic and stearic acid. For better visu- fore, interaction occurs between the dimer form of same species
alization, the baseline is removed. By cooling the sample, three molecules (AA–AA, AA–BB, BB–BB).
well separated exothermic peaks appear, denoted as Peak A–C.
By applying the tangential method, the onset of the peaks could 2.2.4. Metastable range modelling
be determined [1] which are clearly showing the beginning of an Metastable zone boundaries for complete solidification and
exothermal event and therefore the point of spontaneous nucle- solid phase transformation of oleic acid were fitted using a constant
ation (Peak A), solidification (Peak B) or solid phase transition (Peak value. The metastable curve for the two phase region, meaning the
C). During reheating of the sample, again three well separated temperature of spontaneous nucleation for the given cooling rate,
endothermic peaks appear, denoted as Peak A to C . The endother- was fitted using Eq. (3).
mic peaks are naturally shifted to higher temperatures compared to
their respective cooling peaks. By determining the local maximum T = TA(Onset) + aln (xA ) + bln(xA )2 (3)
value of each peak, the peak top temperatures are obtained. All sig- This equation depicts the same trend as those of the liquidus
nificant temperatures used are denoted in Fig. 1. Furthermore, the lines obtained from experimental values, although it does not use
peak intensity is determined by integration of the marked regions, enthalpy or any other variants apart from the onset temperature
that is normalized to sample size for better comparability. TA(Onset) of the pure compound A. Therefore, Eq. (3) is practical and
easy for modelling the metastable range.
2.2.2. Curve fitting
Mathematical modelling and curve fitting was performed using 3. Results and discussion
the software ‘fityk 1.3.0’ [4]. It was used to fit the known and
expected functions on the obtained experimental values. Published 3.1. DSC curves
values available from literature have been re-evaluated for compar-
ison. Fig. 2 depicts the heating curves obtained by DSC for the six
Curve fitting within fityk was performed using the nonlinear binary systems. The significant peaks are denoted as A to C ,
least squares routine of Levenberg and Marquardt, which delivers wherein  indicates the heating process and therefore the endother-
the best fitting function parameters by optimizing the coefficient mic behaviour of the melting peaks [1,13].
of determination, R2 [5,6]. Regarding the pure samples, peak A can directly be associated
with the melting of the saturated fatty acid, whereas peak B refers
2.2.3. Phase change boundary modelling to the melting of the unsaturated acid. For binary mixtures, peak B
Peak top temperatures from DSC thermograms have been taken is shifted to lower temperatures and then refers to the melting of
to form the phase boundaries so as to construct the phase diagrams the eutectic crystalline phase. In the systems containing oleic acid,
52 K.-A. Eckert et al. / Thermochimica Acta 630 (2016) 50–63

Table 2
Experimental metastable range temperatures T and mole fractions xSat for crystallization, solidification and transformation on the solid phase of oleic acid, obtained from
peak onsets of the cooling curves at pressure p = 101.7 kPa.

xSat Crystallization Solidification Solid phase transformation

T [◦ C] Solid phase T [◦ C] Solid phase T [◦ C] Transformation

S–O 0.000 3.6 Oleic Acid (cr) −6.0 Oleic Acid ␣ (cr) to ␥ (cr)
0.099 24.2 Stearic Acid (cr) 11.5 Eutectic S–O (cr) −6.4 Oleic Acid ␣ (cr) to ␥ (cr)
0.194 36.6 Stearic Acid (cr) 11.3 Eutectic S–O (cr) −6.6 Oleic Acid ␣ (cr) to ␥ (cr)
0.297 45.2 Stearic Acid (cr) 11.1 Eutectic S–O (cr) −6.8 Oleic Acid ␣ (cr) to ␥ (cr)
0.403 52.7 Stearic Acid (cr) 11.1 Eutectic S–O (cr) −6.7 Oleic Acid ␣ (cr) to ␥ (cr)
0.500 58.0 Stearic Acid (cr) 11.1 Eutectic S–O (cr) −6.8 Oleic Acid ␣ (cr) to ␥ (cr)
0.602 59.1 Stearic Acid (cr) 10.9 Eutectic S–O (cr) −7.1 Oleic Acid ␣ (cr) to ␥ (cr)
0.698 59.7 Stearic Acid (cr) 11.0 Eutectic S–O (cr) −7.1 Oleic Acid ␣ (cr) to ␥ (cr)
0.807 62.1 Stearic Acid (cr) 11.0 Eutectic S–O (cr) −7.2 Oleic Acid ␣ (cr) to ␥ (cr)
0.917 64.2 Stearic Acid (cr) 10.7 Eutectic S–O (cr) −8.1 Oleic Acid ␣ (cr) to ␥ (cr)
1.000 67.3 Stearic Acid (cr)

S–L 0.000 −26.1 Linoleic Acid (cr)


0.098 30.0 Stearic Acid (cr) −12.6 Eutectic S–L (cr)
0.198 44.3 Stearic Acid (cr) −11.9 Eutectic S–L (cr)
0.298 51.2 Stearic Acid (cr) −12.4 Eutectic S–L (cr)
0.394 56.5 Stearic Acid (cr) −12.5 Eutectic S–L (cr)
0.498 59.7 Stearic Acid (cr) −12.0 Eutectic S–L (cr)
0.594 59.1 Stearic Acid (cr) −12.5 Eutectic S–L (cr)
0.696 60.9 Stearic Acid (cr) −13.6 Eutectic S–L (cr)
0.806 63.0 Stearic Acid (cr) −14.2 Eutectic S–L (cr)
0.899 64.3 Stearic Acid (cr) −16.0 Eutectic S–L (cr)
1.000 67.3 Stearic Acid (cr)

S–Ll 0.000 −19.2 Linolenic Acid (cr)


0.100 29.9 Stearic Acid (cr) −14.1 Eutectic S–Ll (cr)
0.201 42.6 Stearic Acid (cr) −13.7 Eutectic S–Ll (cr)
0.294 48.6 Stearic Acid (cr) −13.9 Eutectic S–Ll (cr)
0.395 54.2 Stearic Acid (cr) −13.7 Eutectic S–Ll (cr)
0.493 56.7 Stearic Acid (cr) −13.9 Eutectic S–Ll (cr)
0.593 60.3 Stearic Acid (cr) −14.0 Eutectic S–Ll (cr)
0.701 62.2 Stearic Acid (cr) −13.3 Eutectic S–Ll (cr)
0.792 63.0 Stearic Acid (cr) −15.0 Eutectic S–Ll (cr)
0.900 64.7 Stearic Acid (cr) −15.1 Eutectic S–Ll (cr)
1.000 67.3 Stearic Acid (cr)

P–O 0.000 3.6 Oleic Acid (cr) −6.0 Oleic Acid ␣ (cr) to ␥ (cr)
0.113 / Palmitic Acid (cr) 8.3 Eutectic P–O (cr) −10.9 Oleic Acid ␣ (cr) to ␥ (cr)
0.225 29.7 Palmitic Acid (cr) 9.8 Eutectic P–O (cr) −9.1 Oleic Acid ␣ (cr) to ␥ (cr)
0.329 36.9 Palmitic Acid (cr) 9.5 Eutectic P–O (cr) −9.9 Oleic Acid ␣ (cr) to ␥ (cr)
0.450 44.4 Palmitic Acid (cr) 9.2 Eutectic P–O (cr) −10.4 Oleic Acid ␣ (cr) to ␥ (cr)
0.532 50.0 Palmitic Acid (cr) 9.1 Eutectic P–O (cr) −10.7 Oleic Acid ␣ (cr) to ␥ (cr)
0.638 52.7 Palmitic Acid (cr) 9.1 Eutectic P–O (cr) −10.6 Oleic Acid ␣ (cr) to ␥ (cr)
0.721 53.4 Palmitic Acid (cr) 8.4 EutecticP–O (cr) −11.6 Oleic Acid ␣ (cr) to ␥ (cr)
0.818 55.6 Palmitic Acid (cr) 8.3 Eutectic P–O (cr) −11.3 Oleic Acid ␣ (cr) to ␥ (cr)
0.923 58.6 Palmitic Acid (cr) 7.2 Eutectic P–O (cr) −13.2 Oleic Acid ␣ (cr) to ␥ (cr)
1.000 60.6 Palmitic Acid (cr)

P–L 0.000 −26.1 Linoleic Acid (cr)


0.110 14.8 Palmitic Acid (cr) −10.5 Eutectic P–L (cr)
0.213 32.2 Palmitic Acid (cr) −11.0 Eutectic P–L (cr)
0.307 40.9 Palmitic Acid (cr) −11.1 Eutectic P–L (cr)
0.432 45.0 Palmitic Acid (cr) −11.4 Eutectic P–L (cr)
0.514 50.8 Palmitic Acid (cr) −12.0 Eutectic P–L (cr)
0.636 53.9 Palmitic Acid (cr) −13.7 Eutectic P–L (cr)
0.712 55.7 Palmitic Acid (cr) −12.1 Eutectic P–L (cr)
0.807 55.8 Palmitic Acid (cr) −13.8 Eutectic P–L (cr)
0.893 57.6 Palmitic Acid (cr) −15.0 Eutectic P–L (cr)
1.000 60.6 Palmitic Acid (cr)

P–Ll 0.000 −19.2 Linolenic Acid (cr)


0.109 15.9 Palmitic Acid (cr) −14.1 Eutectic P–Ll (cr)
0.216 32.3 Palmitic Acid (cr) −14.5 Eutectic P–Ll (cr)
0.317 39.1 Palmitic Acid (cr) −14.5 Eutectic P–Ll (cr)
0.417 44.8 Palmitic Acid (cr) −14.5 Eutectic P–Ll (cr)
0.520 50.4 Palmitic Acid (cr) −14.5 Eutectic P–Ll (cr)
0.623 52.1 Palmitic Acid (cr) −15.4 Eutectic P–Ll (cr)
0.709 54.7 Palmitic Acid (cr) −15.7 Eutectic P–Ll (cr)
0.805 56.6 Palmitic Acid (cr) −15.6 Eutectic P–Ll (cr)
0.895 57.3 Palmitic Acid (cr) −19.2 Eutectic P–Ll (cr)
1.000 60.6 Palmitic Acid (cr)

Standard uncertainties u are u(T) = 0.1 K, u(x) = 0.001 and u(p) = 1.0 kPa.
K.-A. Eckert et al. / Thermochimica Acta 630 (2016) 50–63 53

Table 3
Experimental melting, eutectic melting and solid phase transition temperatures T, enthalpies H and mole fractions xSat for the binary systems, obtained from peak top
temperatures of the heating curves at pressure p = 101.7 kPa.

xSat Melting Eutectic melting Solid phase transformation

T [◦ C] H [J g−1 ] Solid phase T [◦ C] H [J g−1 ] Solid phase T [◦ C] H [J g−1 ] Transformation

S–O 0.000 13.7 133.1 Oleic Acid (cr) −4.2 27.7 Oleic Acid ␥ (cr) to ␣ (cr)
0.099 36.4 13.5 Stearic Acid (cr) 13.8 112.1 Eutectic S–O (cr) −3.8 24.4 Oleic Acid ␥ (cr) to ␣ (cr)
0.194 45.1 32.5 Stearic Acid (cr) 13.7 100.0 Eutectic S–O (cr) −4.0 21.6 Oleic Acid ␥ (cr) to ␣ (cr)
0.297 51.1 55.9 Stearic Acid (cr) 13.6 86.6 Eutectic S–O (cr) −4.3 18.7 Oleic Acid ␥ (cr) to ␣ (cr)
0.403 55.4 78.6 Stearic Acid (cr) 13.4 73.9 Eutectic S–O (cr) −4.3 15.9 Oleic Acid ␥ (cr) to ␣ (cr)
0.500 58.5 97.0 Stearic Acid (cr) 13.4 61.0 Eutectic S–O (cr) −4.4 13.1 Oleic Acid ␥ (cr) to ␣ (cr)
0.602 61.9 125.1 Stearic Acid (cr) 13.3 50.1 Eutectic S–O (cr) −4.6 10.7 Oleic Acid ␥ (cr) to ␣ (cr)
0.698 64.2 148.6 Stearic Acid (cr) 13.3 38.1 Eutectic S–O (cr) −4.6 8.1 Oleic Acid ␥ (cr) to ␣ (cr)
0.807 66.7 174.4 Stearic Acid (cr) 13.2 24.4 Eutectic S–O (cr) −4.8 5.2 Oleic Acid ␥ (cr) to ␣ (cr)
0.917 69.0 204.8 Stearic Acid (cr) 12.9 10.4 Eutectic S–O (cr) −5.4 2.1 Oleic Acid ␥ (cr) to ␣ (cr)
1.000 70.6 221.7 Stearic Acid (cr)

S–L 0.000 −5.4 111.3 Linoleic Acid (cr)


0.098 37.6 17.5 Stearic Acid (cr) −7.2 64.2 Eutectic S–L (cr)
0.198 46.3 38.9 Stearic Acid (cr) −7.2 58.3 Eutectic S–L (cr)
0.298 51.8 58.4 Stearic Acid (cr) −7.1 51.1 Eutectic S–L (cr)
0.394 55.7 79.6 Stearic Acid (cr) −7.2 44.2 Eutectic S–L (cr)
0.498 59.0 100.7 Stearic Acid (cr) −7.2 37.4 Eutectic S–L (cr)
0.594 62.0 124.3 Stearic Acid (cr) −7.3 29.6 Eutectic S–L (cr)
0.696 64.4 147.3 Stearic Acid (cr) −7.6 21.5 Eutectic S–L (cr)
0.806 66.8 170.5 Stearic Acid (cr) −7.6 14.3 Eutectic S–L (cr)
0.899 68.8 189.6 Stearic Acid (cr) −8.0 7.0 Eutectic S–L (cr)
1.000 70.6 221.7 Stearic Acid (cr)

S–Ll 0.000 −10.9 105.1 Linolenic Acid (cr)


0.100 37.7 19.8 Stearic Acid (cr) −12.2 73.7 Eutectic S–Ll (cr)
0.201 47.8 40.5 Stearic Acid (cr) −12.2 67.2 Eutectic S–Ll (cr)
0.294 52.9 60.9 Stearic Acid (cr) −12.2 57.9 Eutectic S–Ll (cr)
0.395 56.6 84.2 Stearic Acid (cr) −12.1 50.4 Eutectic S–Ll (cr)
0.493 59.8 102.5 Stearic Acid (cr) −12.2 41.6 Eutectic S–Ll (cr)
0.593 62.3 127.9 Stearic Acid (cr) −12.2 33.3 Eutectic S–Ll (cr)
0.701 64.5 148.6 Stearic Acid (cr) −11.7 26.5 Eutectic S–Ll (cr)
0.792 66.6 167.5 Stearic Acid (cr) −12.7 16.2 Eutectic S–Ll (cr)
0.900 68.8 192.9 Stearic Acid (cr) −12.6 8.0 Eutectic S–Ll (cr)
1.000 70.6 221.7 Stearic Acid (cr)

P–O 0.000 13.7 133.1 Oleic Acid (cr) −4.2 27.7 Oleic Acid ␥ (cr) to ␣ (cr)
0.113 27.3 5.0 Palmitic Acid (cr) 12.7 115.3 Eutectic P–O (cr) −9.1 23.4 Oleic Acid ␥ (cr) to ␣ (cr)
0.225 36.3 22.3 Palmitic Acid (cr) 12.7 100.5 Eutectic P–O (cr) −6.8 21.3 Oleic Acid ␥ (cr) to ␣ (cr)
0.329 43.3 43.6 Palmitic Acid (cr) 12.6 87.9 Eutectic P–O (cr) −9.5 18.3 Oleic Acid ␥ (cr) to ␣ (cr)
0.450 48.8 69.0 Palmitic Acid (cr) 12.5 71.8 Eutectic P–O (cr) −8.3 14.4 Oleic Acid ␥ (cr) to ␣ (cr)
0.532 51.1 91.1 Palmitic Acid (cr) 12.4 60.8 Eutectic P–O (cr) −8.3 12.3 Oleic Acid ␥ (cr) to ␣ (cr)
0.638 54.6 112.5 Palmitic Acid (cr) 12.4 46.5 Eutectic P–O (cr) −8.4 9.4 Oleic Acid ␥ (cr) to ␣ (cr)
0.721 57.1 131.9 Palmitic Acid (cr) 12.3 35.8 Eutectic P–O (cr) −9.8 7.0 Oleic Acid ␥ (cr) to ␣ (cr)
0.818 59.3 156.9 Palmitic Acid (cr) 11.8 22.9 Eutectic P–O (cr) −10.0 4.1 Oleic Acid ␥ (cr) to ␣ (cr)
0.923 61.9 184.9 Palmitic Acid (cr) 11.0 9.3 Eutectic P–O (cr) −12.0 1.1 Oleic Acid ␥ (cr) to ␣ (cr)
1.000 63.1 210.5 Palmitic Acid (cr)

P–L 0.000 −5.4 111.3 Linoleic Acid (cr)


0.110 28.7 15.1 Palmitic Acid (cr) −6.7 80.2 Eutectic P–L (cr)
0.213 36.1 33.3 Palmitic Acid (cr) −6.7 67.9 Eutectic P–L (cr)
0.307 42.4 52.5 Palmitic Acid (cr) −6.9 61.1 Eutectic P–L (cr)
0.432 48.5 77.5 Palmitic Acid (cr) −7.0 51.0 Eutectic P–L (cr)
0.514 50.9 94.5 Palmitic Acid (cr) −7.2 41.9 Eutectic P–L (cr)
0.636 55.0 122.3 Palmitic Acid (cr) −8.4 27.2 Eutectic P–L (cr)
0.712 56.2 139.1 Palmitic Acid (cr) −7.2 26.4 Eutectic P–L (cr)
0.807 58.9 162.0 Palmitic Acid (cr) −7.7 17.9 Eutectic P–L (cr)
0.893 60.9 180.5 Palmitic Acid (cr) −8.4 9.0 Eutectic P–L (cr)
1.000 63.1 210.5 Palmitic Acid (cr)

P–Ll 0.000 −10.9 105.1 Linolenic Acid (cr)


0.109 29.1 15.0 Palmitic Acid (cr) −11.7 75.8 Eutectic P–Ll (cr)
0.216 38.9 35.5 Palmitic Acid (cr) −11.9 69.3 Eutectic P–Ll (cr)
0.317 43.5 54.2 Palmitic Acid (cr) −11.9 62.6 Eutectic P–Ll (cr)
0.417 48.1 76.8 Palmitic Acid (cr) −11.9 53.8 Eutectic P–Ll (cr)
0.520 51.9 91.2 Palmitic Acid (cr) −11.7 42.5 Eutectic P–Ll (cr)
0.623 55.1 115.0 Palmitic Acid (cr) −12.2 32.7 Eutectic P–Ll (cr)
0.709 57.0 139.5 Palmitic Acid (cr) −12.5 26.8 Eutectic P–Ll (cr)
0.805 59.0 159.2 Palmitic Acid (cr) −12.4 18.6 Eutectic P–Ll (cr)
0.895 61.0 183.8 Palmitic Acid (cr) −13.8 9.1 Eutectic P–Ll (cr)
1.000 63.1 210.5 Palmitic Acid (cr)

Standard uncertainties u are u(T) = 0.1 K, u(x) = 0.001, u(H) = 2.3% and u(p) = 1.0 kPa.
54 K.-A. Eckert et al. / Thermochimica Acta 630 (2016) 50–63

Fig. 1. A typical thermogram and its evaluation.

Fig. 2. DSC thermograms of the binary systems (a) S–O, (b) S–L, (c) S–Ll, (d) P–O, (e) P–L and (f) P–Ll.

a third peak C appears owing to the polymorphic transformation shape, position and shift over all systems shows that peak A is very
of oleic acid from ␥ to ␣ form, which has been previously discussed similar for systems with the same saturated acid and peak B and C
in literature [14,15]. With increasing ratio of saturated acid in the are very similar for systems containing the same unsaturated acid.
mixture, the intensity of peak B decreases, although the peak tem- All experimental values obtained are given with in Tables 2 and 3.
peratures remain in the same region. On the other hand, peak A Figs. 3 and 4 show the data of melting and transformation
that is corresponding to the saturated acids, shows an increase in temperatures and enthalpies, respectively, obtained from the DSC
both the peak intensity and temperature. Direct comparison of peak measurements of the pure fatty acids compared to available
K.-A. Eckert et al. / Thermochimica Acta 630 (2016) 50–63 55

Fig. 3. comparison of available literature data for the melting and solid phase transition temperatures of the pure fatty acids;  this work,  literature data,  literature data
with comparable experimental conditions.

Fig. 4. comparison of available literature data for the melting and solid phase transition enthalpies of the pure fatty acids;  this work,  literature data,  literature data
with comparable experimental conditions.
56 K.-A. Eckert et al. / Thermochimica Acta 630 (2016) 50–63

Table 4
References and literature values for melting and solid phase transition temperatures.

Refs. Year of publication Melting and solid phase transition temperatures [◦ C]

P S O (␣) O (␤) O (␥ → ␣) L Ll

[21] 1898 62.0 69.2


[22] 1925 61.7
[23] 1926 62.7 70.6
[24] 1926 64.0 71.0
[24] 1926 63.5
[25] 1930 63.1 70.1
[26] 1933 61.8 68.8
[27] 1934 62.3 69.1
[28] 1938 −6.8
[29] 1939 62.9 69.6
[18] 1939 62.8 69.6 13.4 16.3
[30] 1941 13.4 16.2 −6.5 −12.8
[31] 1950 69.7
[32] 1952 62.5
[33] 1953 62.9 69.7
[34] 1954 62.5 69.0
[35] 1957 63.5 69.0
[36] 1960 69.3 13.5 16.3
[37] 1962 62.5 69.3 16.3
[38] 1962 62.0 68.2
[39] 1963 63.1 69.7
[39] 1963 62.7 69.4
[39] 1963 63.0 69.7
[40] 1963 62.8 69.3
[40] 1963 63.1 69.6
[41] 1964 62.7 69.4
[42] 1967 62.9 69.9 13.3
[43] 1967 63.0
[44] 1968 62.5 69.5 13.3 16.2
[45] 1968 13.5 16.3
[46] 1968 62.5 69.5
[47] 1969 62.4 69.5 13.3 16.2
[48] 1970 64.0
[49] 1970 69.5
[50] 1974 68.9
[51] 1975 61.5
[52] 1979 63.0 69.7 13.3
[53] 1979 63.0 69.7 16.4
[54] 1982 62.5 69.3
[55] 1983 63.1 71.3 16.4
[56] 1984 62.6 70.5
[14] 1985 69.6 13.3 16.2 −2.2
[57] 1986 63.0 69.7 13.4
[58] 1986 62.9 69.6
[59] 1989 61.5 67.9
[60] 1991 61.9 68.9
[55] 1991 61.8 68.8
[61] 1999 8.1
[62] 2000 13.8
[63] 2000 −7.2 −13.0
[20] 2001 64.4 70.8 5.4
[64] 2002 61.0
[65] 2003 58.9 69.1
[66] 2003 59.9 53.8
[67] 2003 61.3 54.7
[19] 2004 69.8 13.6 −2.6
[19] 2004 62.6 13.6 −2.6
[68] 2004 58.9 69.1
[69] 2005 64.0 69.0
[70] 2005 64.5 67.8
[71] 2006 60.4 66.8
[72] 2007 59.4
[73] 2007 68.8
[74] 2008 63.9 70.0 15.2 −4.1 −10.4
[75] 2008 60.5 66.9
[76] 2009 64.5
[77] 2009 62.3 70.8
[78] 2010 58.2
[79] 2010 62.4
[80] 2010 56.9
[16] 2011 63.6 13.6 −4.9
[81] 2011 62.3 8.8 −25.5 −5.3
[17] 2011 69.9 13.2 14.2 −3.3 −5.2
[82] 2011 63.0 69.9
K.-A. Eckert et al. / Thermochimica Acta 630 (2016) 50–63 57

Table 4 (Continued)

Refs. Year of publication Melting and solid phase transition temperatures [◦ C]

P S O (␣) O (␤) O (␥ → ␣) L Ll

[83] 2011 65.5


[84] 2011 59.9
[85] 2012 62.1 69.0
[86] 2013 62.6
[87] 2014 62.0 68.5
This work 2016 63.1 70.6 13.7 −4.2 −5.4 −10.9

literature data. The values and referenced literature sources are transformation of oleic acid, are generally above the mean value of
given in Tables 4 and 5. The measurements are in good agreement all data. This is due to the larger sample masses used in our exper-
with the majority of the published values. It was found that our iments, as described before. The offset within the values for the
values for characteristic temperatures, but that for the solid phase solid phase transformation of oleic acid cannot be explained, but it

Table 5
References and literature values for melting and solid phase transition enthalpies.

Refs. Year of publication Enthalpy of fusion/solid phase transition [J mol−1 ]

P S O (␣) O (␤) O (␥→␣) L Ll

[22] 1925 57740


[23] 1926 54310
[31] 1950 68443
[32] 1952 54830
[88] 1954 54325 68486
[41] 1964 53400 63000
[42] 1967 54350 63180
[45] 1968 46442 49790
[51] 1975 46020
[51] 1975 51460
[52] 1979 54402 63200
[53] 1979 54325 62412
[54] 1982 53711 61209
[54] 1982 54832 63180
[55] 1983 42037 56586
[56] 1984 53712 61209
[89] 1984 62600
[14] 1985 61300 39600 51900 8760
[57] 1986 53886 68497
[58] 1986 63100
[59] 1989 44875 52060
[60] 1991 42042 56592
[55] 1991 42040 56590
[90] 1993 62600
[63] 2000 33600 27800
[20] 2001 53389 59968 21326
[91] 2001 52030
[64] 2002 52158
[65] 2003 48619 57408
[66] 2003 50747 49670
[67] 2003 50747 45318
[12] 2004 59500 39000 8700
[19] 2004 52300 39000 8700
[68] 2004 48619 57408
[69] 2005 47542 57607
[70] 2005 53389 56583
[71] 2006 59810 73675
[72] 2007 56038
[73] 2007 56555
[74] 2008 54568 64378 42990 33402 32019
[75] 2008 56779 68887
[76] 2009 51373
[77] 2009 55850 67560
[78] 2010 51366
[79] 2010 53337
[80] 2010 51886
[16] 2011 53500
[82] 2011 54389 63211
[83] 2011 53081
[84] 2011 50592
[85] 2012 54389 63382
[86] 2013 53773
[87] 2014 50883 57417
This work 2016 53973 63081 37598 7830 31200 29252
58 K.-A. Eckert et al. / Thermochimica Acta 630 (2016) 50–63

Fig. 5. comparison of available literature data for the melting and solid phase transformation temperatures of the binary systems (a) P–O; (b) S–O; (c) P–L; 䊉 this work; 
[17]; ♦ [18]; 䊐 [12], [19];  [20]; 夽 [16].

Fig. 6. comparison of available literature data for the melting and solid phase transition enthalpies of the binary systems (a) P–O; (b) S–O; 䊉  this work;  [20].

showed a good reproducibility within our experimental measure- latter, very high heating rates of 10 K min−1 were used leading to
ments. overlapping peaks. Therefore, in this literature, the peak for solid
Regarding the values for enthalpies, the measurements are phase transformation of oleic acid and the melting of the eutectic
again in good agreement with the majority of the published val- crystalline phase were evaluated together. Furthermore, the base-
ues, eventual deviations mainly caused by the peak integration or line was also always chosen to be linear [20]. However, these values
experimental method that was used for determination. In case of then should be significantly higher than those obtained in our work,
DSC measurement, even small deviations within the chosen base- which is not the case. This directly shows that the experimental
line model and integration range might cause large differences conditions are not comparable and hence no further comparison
within the results. Due to the higher sample masses used in our was performed.
work, these values should be more accurate. However, regarding
the absolute values of the deviations, all differences are small and
3.2. Phase diagrams
in acceptable ranges.
Comparison of our values with those from literature, as given in
As described before, plotting the peak top temperatures of
Fig. 5, for the binary mixtures shows good agreement. The values for
the heating curves and onset temperatures of the cooling curves
P–L, although, depict significant offsets for the compositions xP of
together as a function of the molar fraction of the saturated fatty
0.5 and 0.7, which might be caused by the method used in that work
acid gives the phase diagram with metastable ranges (Fig. 7).
[16]. In the mentioned literature, higher heating rates of 3 K min−1
As expected from the DSC curves, there are horizontal phase
were used, which is known to cause shifting of peak temperatures
boundary lines, two for the oleic acid systems and one for linoleic
to higher values. Regarding the peak for the eutectic temperature all
and linolenic acid systems. All phase boundaries that are based on
literature values are lower, which cannot be explained because no
the melting peak B represent the point of solidification and there-
further information about sample preparation or sample masses
fore the solidus line. The higher the degree of unsaturation of the
are given. The overall offset is low and our values are showing a
fatty acid, the lower is the temperature of solidification. In case of
good agreement for the P–L and S–L system.
the oleic acid systems, the horizontal line based on peak C stands
Fig. 6 shows the literature data for enthalpies, either of melt-
for the polymorphic transformation in the solid phase, as explained
ing or solid phase transformation, available for the P–O and S–O
before. The phase boundary that is based on peak A is caused
system [20]. There is a big error in the values owing to the experi-
by the melting of the saturated fatty acid and therefore denotes
mental conditions and evaluation method used in that work. In the
the point of complete melting, that is in other words, the liquidus
K.-A. Eckert et al. / Thermochimica Acta 630 (2016) 50–63 59

Fig. 7. Phase diagrams obtained from Peak A (䊉), Peak B () and Peak C (䊏) with the metastable ranges for nucleation (Peak A ()), solidification (Peak B (♦)) and polymorphic
transformation (Peak C (䊐)) of the binary systems (a) S–O, (b) S–L, (c) S–Ll, (d) P–O, (e) P–L and (f) P–Ll.

line of a mixture. The presented curves were obtained by fitting Regarding the metastable range curves, it can be observed that
the experimental values with the described model. Regarding the there is a local minimum of supercooling in the range of 0.5 M
metastable ranges, the same phenomena is noted. The metastable fraction of the saturated acid. Due to the logarithmic trend of the
ranges of solidification and polymorphic transformation show hor- functions the metastable range becomes wider with lower molar
izontal trends, whereas the metastable range in the two phase area fraction of saturated acid. The metastable range functions in the two
is showing the same logarithmic trend as the liquidus lines. phase area intersects with the metastable range in the solid phase
All determined functions and values such as the interaction fac- below the solidus line in a region of low molar fraction of saturated
tor ω, are depicted in Tables 6–8 together with re-evaluated results acid. This intersecting point signifies that systems below this molar
from literature [12,16–19]. It can be observed that the liquidus fraction of saturated acid which is treated with the given experi-
lines for the same saturated acid are just differing minimally and mental conditions, is solidifying immediately without spontaneous
the solidus lines are also nearly the same for the same unsatu- nucleation as it reaches the metastable temperature in the solid
rated acid. In addition, the metastable ranges are very similar for range. Furthermore, it can be seen that the oleic and linolenic acid
systems of the same unsaturated acid. All fitted functions are in systems are showing relatively wide metastable ranges of sponta-
accordance with experimental values. The results furthermore are neous nucleation and small metastable ranges for solidification. The
in good agreement with data from literature. linoleic systems are showing the opposite behaviour, with small
It can be noted with respect to the interaction factor ω that its metastable ranges of spontaneous nucleation and wider metastable
values are in a similar range for systems containing the same unsat- ranges for solidification.
urated acid with a linear rise with increasing number of double The obtained results are in good agreement with those from
bonds of the unsaturated acid. That means the general preference literature, the only big difference being the fact that the solid phase
of these mixtures is the formation of mixed molecule pairs. The transformation line and its metastable range for the P–O system is
palmitic and linolenic acid system depict a small positive value with around 9 K significantly lower than reported in literature [19].
showing the affinity of this system to form similar molecule pairs. This difference is due to the fact, that the literature values [19]
The results obtained are fitting the values obtained from literature are based on samples that were undergoing a different thermal
in most cases [12,16–19]. Reasons for deviations were previously treatment. In this work values were obtained for samples which
discussed. were immediately reheated after solidification.
Eutectic compositions for the systems containing oleic acid
could be determined by the intersecting point of the obtained func-
3.3. Enthalpy plots
tions with xstearic acid = 0.0155 and xpalmitic acid = 0.041. The
eutectic composition is nearly that of the pure unsaturated acid
The peak areas were also determined besides the characteristic
for the systems with linoleic and linolenic acid.
peak temperatures from the thermograms. By plotting these values
60 K.-A. Eckert et al. / Thermochimica Acta 630 (2016) 50–63

Table 6
Function parameters for the liquidus line functions.

Our evaluations Literature (reevaluated)

S–O S–L S–Ll P–O P–L P–Ll S–O [12] S–O [17] S–O [18] P–O [19] P–O [18] P–O [16] P–L [16]

Heat of Fusion (Pure 63081 53973 59500 63100 63000 52300 53000 53500 53500
Saturated Acid)
[Jmol−1 ]
Melting Temperature 70.6 63.1 69.8 69.9 69.6 62.6 62.8 63.6 63.6
(Pure Saturated Acid)
[◦ C]
␻ −542 −236 −18 −540 −258 56 −323 −611 338 43 −148 −740 124
R2 0.998 0.998 0.999 0.998 0.996 0.999 0.988 0.993 0.999 0.995 0.997 0.999 0.990

Table 7
Function parameters for the metastable range functions for crystallization.

Our evaluations Literature (reevaluated)

S–O S–L S–Ll P–O P–L P–Ll S–O [12] S–O [17] S–O [18] P–O [19] P–O [18] P–O [16] P–L [16]

Tsolidus [◦ C] 13.6 −7.1 −12.2 12.6 −6.7 −11.8 12.9 13.0 13.1 12.0 12.1 10.3 −8.5
R2 −0.491 −0.540 −0.027 −0.469 −0.902 −0.414 0.000 0.000 0.000 −0.001 0.000 0.000 −0.225
Tmetasolidus [◦ C] 11.1 −12.3 −13.8 8.7 −11.0 −14.4
R2 0.000 −0.366 −0.244 −0.009 −0.785 −0.393
Ttransformation [◦ C] −4.2 −8.4 −3.33 −3.91 −3.75
R2 −0.482 −0.287 0.000 0.000 0.000
Tmetatransformation [◦ C] −6.7 −10.8
R2 −0.470 0.000

Table 8
Function parameters for the solidus line and solid phase transformation functions with its metastable ranges.

TA (Onset) [◦ C] S–O S–L S–Ll P–O P–L P–Ll

67.3 60.6

b 16.49 11.16 13.84 18.83 13.86 16.12


c −0.98 −2.07 −1.05 −1.39 −3.10 −1.81
R2 0.989 0.984 0.997 0.991 0.995 0.997

Fig. 8. Enthalpy of fusion derived from Peak A (䊉), Peak B () and Peak C (䊏) in the binary systems (a) S–O, (b) S–L, (c) S–Ll, (d) P–O, (e) P–L and (f) P–Ll.
K.-A. Eckert et al. / Thermochimica Acta 630 (2016) 50–63 61

Table 9
Function parameters of enthalpy functions.

S–O S–L S–Ll

Peak A Peak B Peak C Peak A Peak B Peak A Peak B

a −10.48 123.88 26.79 −4.02 72.65 −2.08 82.93


b 227.63 −123.61 −27.00 214.84 −72.85 215.57 −83.20
R2 0.997 1.000 1.000 0.999 0.999 1.000 0.998

P–O P–L P–Ll


    
Peak A Peak B Peak C Peak A Peak B Peak A Peak B

a −21.09 131.17 27.42 −10.10 87.55 −9.45 88.55


b 214.55 −132.20 −28.48 211.04 −87.92 209.06 −88.13
R2 0.989 1.000 0.998 0.996 0.993 0.993 0.995

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