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High Pressure Solid−Liquid Equilibrium of Fatty Alcohols Binary


Systems from 1‑Dodecanol, 1‑Tetradecanol, 1‑Hexadecanol, and 1-
Octadecanol
Natália Daniele Dorighello Carareto,†,‡ Mariana Conceiçaõ Costa,§ Antonio José Almeida Meirelles,†
and Jérôme Pauly*,‡

Laboratory of Extraction, Applied Thermodynamics and Equilibrium, School of Food Engineering, University of Campinas, R.
Monteiro Lobato 80, 13083-862 Campinas, São Paulo, Brazil

Laboratoire des Fluides Complexes et leurs Réservoirs, UMR 5150, BP1155, 64013 Pau Cedex, France
§
School of Applied Sciences, University of Campinas, R. Pedro Zaccaria, 1300, 13484-350 Limeira, São Paulo, Brazil
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ABSTRACT: The melting temperatures of four fatty alcohols, 1-


Publication Date (Web): September 9, 2015 | doi: 10.1021/acs.jced.5b00330

dodecanol, 1-tetradecanol, 1-hexadecanol, and 1-octadecanol,


were measured at atmospheric pressure using a μDSC calorimeter
and at higher pressures (up to 80 MPa) thanks to a dedicated
microscope. The solid−liquid phase diagrams of six binary
mixtures formed by these fatty alcohols, namely, 1-dodecanol + 1-
tetradecanol, 1-dodecanol + 1-hexadecanol, 1-dodecanol + 1-
octadecanol, 1-tetradecanol + 1-hexadecanol, 1-tetradecanol + 1-
octadecanol, and 1-hexadecanol + 1-octadecanol systems, were
also measured using high pressure microscopy within the range of
0.1 MPa to 80 MPa. In addition, the phase diagrams of the 1-
dodecanol + 1-tetradecanol, 1-tetradecanol + 1-hexadecanol, and
1-hexadecanol + 1-octadecanol systems were also measured by DSC in order to compare the results obtained from the
microscopy. On the basis of the experimental data, it could be concluded that the behavior of the phase diagrams is slightly
affected by the pressure, even within very large pressure ranges such as the ones studied in this work.

1. INTRODUCTION alcohols, and triacylglycerols, under high pressure are important


Fatty alcohols have a potential of usage in the pharmaceutical, to allow the development of high pressure processes without
food, and chemical industries. They are natural derivatives of neglecting the quality of the final product. The modeling
plants or animal oils and fats and are considered as a class of approach for the SLE of fatty substances commonly used in the
compounds that can be used as structurants in the lipid phase literature does not take into account the influence of pressure.
present in a wide range of products.1−3 The solid−liquid However, we recently have found an increasing interest for
boundaries and behavior of simple fatty systems can be helpful experimental data and development of models for solid−liquid
to understand the physical properties of complex lipids and equilibrium under high pressure.4,7−13
their mixtures. They are also important for developing Important aspects to be investigated in the melting of
purification and fractionation processes of lipid mixtures. For mixtures under high pressure are the modification to higher
example, the controlled precipitation of solid phases is widely temperatures of the liquidus line due to the pressure increase,
applied in pharmaceutical, cosmetic, and food industries as a the potential changes of the eutectic (defined as an isothermal
separation process. In other areas like petroleum engineering, reversible reaction of a liquid phase transformed into two
the wax crystallization is a problem for the storage, exploitation, different solid phases when cooling a binary system)14 or
and transportations of fossil oils.4 peritectic (defined as an isothermal, reversible reaction between
It is a trend in the food industry for searching new two phases, a liquid and a solid ones, that results during the
esterilization methods with less adverse effects on product cooling of a binary system into one new solid phases)14
quality. One of the solutions may be high pressure processing compositions and of the structure of different solid phases.
that is actually been applied on the pasteurization of products Solid−liquid equilibrium data of systems containing fatty
like fruit juices, oysters, and ham.5 Additionally, high pressure alcohols were investigated by different research groups.
conditions are used in a range of 400 MPa to 600 MPa to Yamamoto et al.15 measured the phase diagram of a binary
inactivate microorganisms and enzymes.6
In the case of fatty mixtures, solid−liquid equilibrium (SLE) Received: April 9, 2015
data measured under high pressure are very rare; nevertheless, Accepted: August 31, 2015
the properties of fatty compounds, such as fatty acids, fatty

© XXXX American Chemical Society A DOI: 10.1021/acs.jced.5b00330


J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

system formed by 1-heptadecanol + 1-octadecanol, with a melting temperature because the onset temperature can be
detailed description of the solid−solid transitions. Ventolà et incorrectly determinated due to the presence of polymorphic
al.16−19 presented the phase behavior of fatty alcohol systems transitions close to the melting point.9,23,27 The uncertainty of
showing different polymorphic behaviors. Domańska and the temperature is equal to 0.2 K.
Gonzalez20−22 studied the solid−liquid equilibrium of a series The advantage of a μDSC is that it combines the power of
of fatty alcohol binary mixtures, using a dynamic method with DSC and the precision of Calvet calorimetry, leading to a
visual detection of the melting temperatures. suitable method for precise results over a wide temperature
This work is part of a series of studies regarding the SLE of range. Nevertheless, the rates usually used are lower than a
binary systems composed of saturated fatty alcohols. In a DSC which increase the total time of each analysis. So, we
previous work, we have reported the phase diagrams of fatty applied the DSC analyses (that also provides accurate results)
alcohols mixtures measured by DSC in which the systems to describe the SLE for the binary system.
present either a simple eutectic behavior23 or, in the case of 2.2. Differential Scanning Calorimetry (DSC). The DSC
more complex mixtures, peritectic and metatectic reactions.24 tecnique was applied in order to evaluate the solid−liquid phase
The aim of the present work was to investigate the liquidus line diagrams at atmospheric pressure for the folowing binary
of six binary mixtures, namely, 1-dodecanol (abbreviated systems: C12OH + C14OH, C14OH + C16OH, and C16OH
C12OH) + 1-tetradecanol (abbreviated C14OH), C12OH + + C18OH. A TA Instruments calorimeter (model MDSC
1-hexadecanol (abbreviated C16OH), C12OH + 1-octadecanol 2920) equipped with a refrigerated cooling system was used.
(abbreviated C18OH), C14OH + C16OH, C14OH + C18OH,
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Samples of a selected mixture (3 to 5 mg) were weighed in a


and C16OH + C18OH, by means of a cross polar microscope microanalytical balance (PerkinElmer AD6) with a 0.005 mg
device that allows the study of phase equilibrium up to 80 MPa. accuracy and put in sealed aluminum pans. An empty pan was
Publication Date (Web): September 9, 2015 | doi: 10.1021/acs.jced.5b00330

In addition, DSC was used in order to improve the used as reference in the analyses. A pretreatment was applied as
understanding of the SLE of the following systems: C12OH follows: the samples were kept isothermally for 20 min at 15 K
+ C14OH, C14OH + C16OH, and C16OH + C18OH. As far above the melting temperature of the heavier component of the
as we know, the systems C12OH + C14OH and C14OH + mixture and subsequently cooled to 45 K below the melting
C16OH have not been previously reported in the literature, point of the lightest component at a cooling rate of 1.0 K·min−1
even at ambient pressure, and none of them has been
and kept in isothermal state during 30 min. After this
investigated at higher pressures.
pretreatment, the samples were then analyzed by a heating
run with a rate of 1.0 K·min−1. As well as for μDSC analyses,
2. EXPERIMENTAL SECTION
peak temperatures were selected to represent the melting and
High purity reactants (Sigma-Aldrich) with no further other transitions temperatures of the mixtures. The uncertainty
purification process were used to prepare the samples (Table of the phase equilibrium data is estimated to be less than 0.3 K,
1). All of the binary mixtures were prepared gravimetrically as reported in preceding works.23,24
using a high precision balance with an accuracy of (± 0.2 mg). 2.3. High Pressure Microscopy. The melting temperature
of the pure fatty alcohols and the SLE of their binary mixtures
Table 1. Melting Temperature, Tmelt, at 0.1 MPa for the Pure were studied in a high pressure microscope. The apparatus has
Fatty Alcohols, and Absolute Deviation, AD = |Tmelt,DSC − been successfully used in previous works for measuring the
Tmelt,i |, between Tmelt,DSC at Atmospheric Pressure and liquidus line for waxes, alkanes, fatty acids, and methylic or
Microscope, AD1, or Literature, AD2a ethylic esters.4,7−10 The samples were injected in a stainless
Tmelt at 0.1 MPa AD steel autoclave cell that has two sapphire windows, which allows
us to observe the changes in the samples. A polarized light
reactant (CAS
number) Purityc Tmelt,HPb Tmelt,DSC Tmelt,lit AD1 AD2 microscope coupled to a video camera was used to observe and
w/w K K K K K
registrate the transitions. The cell has an end closed with a
moving piston that is able to produce a pressure up to 100 MPa
C12OH (112- 0.98 296.9 297.1 297.2,d 0.2 0.1,
53-8) 297.15e 0.05 (as described in Figure 1). The temperature of the sample can
C14OH (112- 0.97 310.6 310.9 311.05,e 0.3 0.15, be controlled by flowing a heat-transducing fluid in flow lines of
72-1) 311.4f 0.5 the metallic thermostat block, and it was carried out by a
C16OH 0.99 322.2 322.8 322.50,e 0.6 0.3, 1.2 thermostat bath (Huber, Germany) with a temperature stability
(36653-82-4) 321.6g
C18OH (112- 0.99 330.9 331.3 331.15,e 0.4 0.15,
92-5) 330.3g 1.0
a
Standard uncertainties u are u(P) = 0.1 MPa, u(AD) = 0.2 K,
u(Tmelt,HP) = 0.2 K, u(Tmelt,DSC) = 0.2 K. bTmelt,HP: melting temperature
at atmospheric pressure using the high pressure cell, Tmelt,DSC: melting
temperature at atmospheric pressure using μDSC. caccording to the
supplier. dFrom ref 25. eFrom ref 20. fFrom ref 26. gFrom ref 18.

2.1. Microdifferential Scanning Calorimetry (μDSC).


The μDSC analyses were used to measure the fatty alcohols
melting temperatures and carried out using a SETARAM Micro
DSC 7 evo calorimeter with nitrogen as purge gas (from Linde
group with purity ≥ 99.995%), as described in previous
works.8,9 Each sample was analyzed with a heating rate of 0.01
K·min−1. Peak top temperatures were selected to represent the Figure 1. Scheme of the high pressure microscopy apparatus.

B DOI: 10.1021/acs.jced.5b00330
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

of 0.01 K working in a range between 253 K and 353 K. The


sample temperature could be measured with a calibrated
platinum resistance inserted inside the cell and connected to a
high-precision thermometer (AOIP). The temperature un-
certainty was estimated not large than 0.2 K.4 The pressure
inside the cell was measured by a piezoresistive silicon pressure
transducer (Kulite), placed inside the cell in order to reduce the
dead volume, with a precision of 0.2%.
The samples were inserted into the high pressure cell at a
temperature higher than the melting temperature of the fatty
alcohols to avoid a precrystallization. At a pressure of 0.1 MPa,
the temperature was decreased 10 K to 15 K below the melting
Figure 2. Fatty alcohols melting temperature at different pressures: ■,
temperature and kept isothermally for 20 min to 30 min. The C12OH (R2 = 0.9988); □, C14OH (R2 = 0.9978); ●, C16OH (R2 =
temperature was increased in small steps (0.1 K to 0.5 K) and 0.9999); ○, C18OH (R2 = 0.9998).
allowed to stay isothermally about 1 min to 3 min at each step.
The temperature was increased until the disappearance of the The coefficients of determination (R2) for the (T, P) curves
last crystal, which was annotated as the melting temperature of varied from 0.9978 to 0.9999. The (T, P) dependence can be
the sample. Then, the pressure of the system was increased to
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calculated by means of the average slope of each curve as


20 MPa and a new experience was started respecting the same follows (see Table 2):
aforementioned steps. All of the samples had the melting
Publication Date (Web): September 9, 2015 | doi: 10.1021/acs.jced.5b00330

temperature measured in pressures of 0.1 MPa, 20 MPa, 40 ΔT T (P ) − Tmelt(P0)


MPa, 60 MPa, and 80 MPa. = melt max
ΔP Pmax − P0 (1)

3. RESULTS AND DISCUSSION For comparison purposes and in order to reduce the
uncertainty of the calculated slopes, Pmax was set as 80 MPa and
3.1. Effect of Pressure on the Melting Temperature of P0 corresponds to atmospheric pressure for all compositions.
Pure Fatty Alcohols. The melting temperature of pure fatty The uncertainty of the (T, P) slope was calculated by error
alcohols was measured at atmospheric pressure using the propagation and is equal to 0.004 K·MPa−1, the same value
mycroscopy and μDSC, and the results are presented in Table calculated by ref 4 for n-alkanes and by ref 9 for methyl esters.
1. The absolute deviations between these melting temperatures 3.2. High Pressure Solid−Liquid Equilibrium for Fatty-
(AD1) ranged from 0.2 K to 0.6 K. When the uncertainty of Alcohols Binary Mixtures. The effect of pressure on the
each experimental technique is considered, both sets of data solid−liquid phase equilibrium was measured for each binary
showed a good agreement. A comparison between the melting system at various constant compositions. The melting temper-
temperatures from the μDSC and from literature was made and atures were measured for different pressures at various
the absolute deviations (AD2) ranged from 0.1 K to 1.2 K, also compositions. The experimental results are summarized in
showing a good agreement between the set of data. The Tables 3 to 8.
relatively high deviations (1.0 K and 1.2 K) for the 1-
hexadecanol and 1-octadecanol are probably related to the Table 3. SLE Data for the System C12OH + C18OH from
interpretation of the results. In this study, we use the peak top Microscope Device in Function of Pressurea
temperature of the thermograms to represent the melting
temperature for the pure fatty alcohols and, usually, the onset Tmelt
temperature of the thermograms is considered as the melting K
temperature by others authors. xC12OH 0.1 MPa 20 MPa 40 MPa 60 MPa 80 MPa
The effect of pressure on the melting temperatures of pure
0.0000 330.9 335.8 340.9 345.9 350.6
fatty alcohols are presented in Table 2. The corresponding
0.2987 326.1 330.9 335.4 340.0 344.5
curves are shown in Figure 2, and they indicate that the melting
0.5043 321.7 326.5 331.8 336.8 341.4
temperatures have a quasilinear dependence of the pressure.
0.7034 315.4 320.4 325.6 330.1 334.4
0.8000 310.0 314.9 319.7 323.2 327.3
Table 2. Melting Temperature, Tmelt, as a Function of 0.8530 304.6 309.8 314.0 318.1 322.1
Pressure and the Average Slope of the Melting Temperature, 0.9007 297.5 302.3 307.3 311.1 315.4
as calculated from Equation 1, for the Pure Fatty Alcoholsa 0.9533 295.9 300.4 304.5 308.5 312.2
Average 1.0000 296.9 300.5 304.6 308.4 311.7
Tmelt slope a
Standard uncertainties u are u(xC12OH) = 0.0001, u(P) = 0.1 MPa,
−1 u(Tmelt) = 0.2 K.
K K·MPa
fatty
alcohol 0.1 MPa 20 MPa 40 MPa 60 MPa 80 MPa The SLE data for the systems C12OH + C18OH, C12OH +
C12OH 296.9 300.5 304.6 308.4 311.7 0.1852 C16OH, and C14OH + C18OH were already reported at
C14OH 310.6 314.2 319.0 323.8 327.8 0.2153 atmospheric pressure and were obtained by using the DSC
C16OH 322.2 327.3 332.4 337.6 342.7 0.2566 technique at a heating rate of 1.0 K min−1.23,24 In general, the
C18OH 330.9 335.8 340.9 345.9 350.6 0.2466 systems measured by the different techniques presented a good
agreement with an average absolute deviation (AAD = (1/
a
Standard uncertainties u are u(average slope) = 0.004 K·MPa−1, n)∑i n= 1[|Tmelt,lit − Tmelt,exp|]) of 0.8 K, 0.5 K, and 0.5 K for the
u(Tmelt) = 0.2 K, u(P) = 0.1 MPa. systems C12OH + C18OH, C12OH + C16OH, and C14OH +
C DOI: 10.1021/acs.jced.5b00330
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 4. SLE Data for the System C12OH + C16OH from Table 7. SLE Data for the System C14OH + C16OH from
Microscope Device in Function of Pressurea Microscope Device in Function of Pressurea
Tmelt Tmelt
K K
xC12OH 0.1 MPa 20 MPa 40 MPa 60 MPa 80 MPa xC14OH 0.1 MPa 20 MPa 40 MPa 60 MPa 80 MPa
0.0000 322.2 327.3 332.4 337.6 342.7 0.0000 322.2 327.3 332.4 337.6 342.7
0.2033 319.5 324.0 328.4 333.3 337.5 0.2691 317.9 322.9 327.7 332.5 337.7
0.3995 315.2 320.0 324.5 328.3 332.7 0.4023 315.3 320.2 325.1 329.9 334.2
0.6002 308.3 313.0 317.8 322.0 326.7 0.6046 312.2 317.1 321.7 326.0 330.3
0.6986 304.0 308.5 313.2 317.7 321.9 0.7045 311.0 315.9 320.5 324.9 329.2
0.7501 299.8 304.2 308.7 313.0 316.9 0.8031 310.1 315.2 320.0 324.7 328.4
0.7997 296.5 300.6 305.0 309.1 312.5 0.9033 310.0 315.1 319.8 324.5 328.8
0.8494 293.7 298.0 301.9 306.1 309.4 1.0000 310.6 314.2 319.0 323.8 327.8
0.8992 293.9 298.2 302.5 306.7 310.2 a
Standard uncertainties u are u(xC14OH) = 0.0001, u(P) = 0.1 MPa,
1.0000 296.9 300.5 304.6 308.4 311.7 u(Tmelt) = 0.2 K.
a
Standard uncertainties u are u(xC12OH) = 0.0001, u(P) = 0.1 MPa,
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u(Tmelt) = 0.2 K. Table 8. SLE Data for the System C16OH + C18OH from
Microscope Device in Function of Pressurea
Table 5. SLE Data for the System C14OH + C18OH from
Publication Date (Web): September 9, 2015 | doi: 10.1021/acs.jced.5b00330

Microscope Device in Function of Pressurea


Tmelt
K
Tmelt
xC16OH 0.1 MPa 20 MPa 40 MPa 60 MPa 80 MPa
K
0.0000 330.9 335.8 340.9 345.9 350.6
xC14OH 0.1 MPa 20 MPa 40 MPa 60 MPa 80 MPa 0.1996 328.0 333.2 338.0 343.0 347.5
0.0000 330.9 335.8 340.9 345.9 350.6 0.3981 325.6 330.4 335.3 340.1 344.4
0.1994 327.2 331.8 336.2 340.8 345.3 0.5987 323.3 328.3 333.0 337.2 341.7
0.3951 324.5 329.2 333.9 338.0 342.6 0.7952 321.3 326.3 331.2 335.6 339.9
0.5981 318.2 323.0 327.6 333.3 337.6 0.8848 321.3 326.3 331.2 335.8 340.2
0.6992 311.7 316.6 321.5 325.9 329.8 1.0000 322.2 327.3 332.4 337.6 342.7
0.8008 308.3 313.1 317.8 322.6 326.7 a
Standard uncertainties u are u(xC16OH) = 0.0001, u(P) = 0.1 MPa,
0.8500 307.4 312.3 316.9 321.3 325.8 u(Tmelt) = 0.2 K.
0.8994 308.2 312.8 317.4 321.4 325.9
1.0000 310.6 314.2 319.0 323.8 327.8
a
Standard uncertainties u are u(xC14OH) = 0.0001, u(P) = 0.1 MPa,
u(Tmelt) = 0.2 K.

Table 6. SLE Data for the System C12OH + C14OH from


Microscope Device in Function of Pressurea
Tmelt
K
xC12OH 0.1 MPa 20 MPa 40 MPa 60 MPa 80 MPa
0.0000 310.6 314.2 319.0 323.8 327.8
0.2021 306.5 311.3 316.3 320.8 325.0
0.3992 301.3 306.5 311.7 316.2 320.3 Figure 3. Liquidus line deviation between melting temperature from
0.5346 298.1 303.0 308.0 312.8 316.6 literature which was measured by DSC (Tmelt,lit) and experimental
0.7004 294.8 299.6 304.2 308.4 312.4 melting temperature measured by the microscope device (Tmelt,HP): □,
0.8003 293.4 298.1 302.6 306.9 311.2 C12OH + C18OH from ref 23; ■, C12OH + C16OH; ○, C14OH +
0.9003 294.7 298.9 302.7 306.5 310.8 C18OH from ref 24.
1.0000 296.9 300.5 304.6 308.4 311.7
a
Standard uncertainties u are u(xC12OH) = 0.0001, u(P) = 0.1 MPa, temperatures measured in the microscope are higher than the
u(Tmelt) = 0.2 K. values from the DSC, as already observed when comparing data
from both experimental tecniques for fatty acids or n-alkanes
C18OH, respectively. A comparison of the liquidus lines binary systems.4,7
between the different sets of data is presented as deviations in In previous work,23 the C12OH + C18OH system was
Figure 3. As can be noted, the higher deviations occur in the classified as a simple eutectic one, with the eutectic point
regions close to the eutectic and peritectic points. The occurring at atmospheric pressure around xC12OH = 0.93. The
deviations may be explained by the appearance of a metastable same behavior was observed in the set of data obtained by
phase close to the melting of the samples and by kinetic means of the high pressure microscope as can be noted in
considerations, because the heating rates are different. In Figure 4. It is possible to note that the general behavior of the
general, the deviations were negative, meaning that the liquidus line, including the eutectic point, is not affected by the
D DOI: 10.1021/acs.jced.5b00330
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

liquid transitions can not be easily determined by the


microscopy analyses, but still the inflection point related to
the peritectic reaction can be noted in the Figures 5 and 6 (the
line representing the trend of the liquidus line makes easier the
identification of the peritectic inflection point in Figures 5 and
6). By comparing the liquidus line for the different pressures, it
is possible to note that the increasing of pressure did not affect
the eutectic and peritectic points for both binary systems.
The DSC results for the C12OH + C14OH, C14OH +
C16OH, and C16OH + C18OH systems are summarized in
Tables 9 to 11 and shown in Figures 7a, 8a, and 9a, respectively.

Table 9. SLE Data for the System C12OH + C14OH from


Figure 4. Liquidus line of the C12OH + C18OH binary system in DSC at Atmospheric Pressurea
function of pressure: □, 0.1 MPa; ●, 20 MPa; ○, 40 MPa; ▲, 60 MPa;
△, 80 MPa; , a guide to the eye. xC12OH Ttrans,solb Ttrans,sol Ttrans,sol Tmelt
K K K K
pressure, although the melting temperature values increase in a
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0.0000 310.9c
quasilinear way as already observed for the pure components. 0.1010 306.0 309.0
Both C12OH + C16OH and C14OH + C18OH systems 0.1956 287.3 301.5 307.3
Publication Date (Web): September 9, 2015 | doi: 10.1021/acs.jced.5b00330

presented a eutectic point close to the 0.85 molar concentration 0.3102 288.6 294.2 304.9
of the ligher component, as can be noted in Figures 5 and 6. In 0.3984 289.0 291.7 296.2 302.4
0.4983 288.4 289.1 296.8 300.6
0.5939 286.1 289.8 296.6 297.9
0.6955 285.2 288.8 295.6 297.3
0.8028 286.6 295.5
0.8982 288.1 296.3
1.0000 297.1c
a
Standard uncertainties u are u(xC12OH) = 0.0001, u(T) = 0.3 K.
b
Ttrans,sol: represents a solid−solid transition. cMeasured by μDSC with
a standard uncertainty of u(T) = 0.2 K.

Table 10. SLE Data for the System C14OH + C16OH from
DSC at Atmospheric Pressurea
xC14OH Ttrans,solb Ttrans,sol Ttrans,sol Tmelt
Figure 5. Liquidus line for the C12OH + C16OH system in function K K K K
of pressure: □, 0.1 MPa; ●, 20 MPa; ○, 40 MPa; ▲, 60 MPa; △, 80
0.0000 322.8c
MPa; , a guide to the eye.
0.1017 316.0 321.2
0.2047 310.6 319.8
0.2967 295.6 299.2 305.1 318.6
0.3991 295.6 317.5
0.5024 294.3 298.2 315.8
0.5990 296.8 314.5
0.7014 294.0 297.4 312.2
0.7988 293.3 297.8 311.0
0.9019 299.8 311.6
1.0000 310.9c
a
Standard uncertainties u are u(xC12OH) = 0.0001, u(T) = 0.3 K.
b
Ttrans,sol: represents a solid−solid transition. cMeasured by μDSC with
a standard uncertainty of u(T) = 0.2 K.

Figure 6. Liquidus line for the C14OH + C18OH system in function For these three systems, a point of minimum temperature is
of pressure: □, 0.1 MPa; ●, 20 MPa; ○, 40 MPa; ▲, 60 MPa; △, 80 observed around a molar fraction of 0.8 of the lower melting
MPa; , a guide to the eye. point component. Nevertheless, this point can not be
associated with a eutectic transition because the compounds
a previous work, the solid−liquid phase diagrams were have a large miscibility region on the solid state and solid−
presented as having more complex behavior,24 with an liquid domains is very narrow in comparison with others fatty
inflection in the liquidus line related to the peritectic point. alcohol systems, as already reported by Smith28 and Ventolà et
Because the microscopy is a visual method of measuring phase al.18 for the C16OH + C18OH system. A similar behavior was
diagrams, it is only possible to determine the liquidus line with reported in the literature for binary mixtures formed by n-
this technique. The solidus lines, which is the line that separates alkanes,29,30 where these n-alkane systems were also charac-
the SLE region from the solid state region, and other solid− terized by a high miscibility on the solid phase. So, the
E DOI: 10.1021/acs.jced.5b00330
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Table 11. SLE Data for the System C16OH + C18OH from the C12OH + C14OH, C14OH + C16OH, and C16OH +
DSC at Atmospheric Pressurea C18OH systems, a small SLE range of temperatures was
observed for all analyzed samples along the entire concen-
xC16OH Ttrans,solb Ttrans,sol Ttrans,sol Tmelt
tration range.
K K K K Concerning the pressure effect, the progress of the melting
0.0000 331.3c temperature for all samples displayed a quasilinear function of
0.0996 324.0 325.8 330.0 the increasing pressure (see Figures 7b, 8b, and 9b). Plotting
0.1977 301.9 319.0 328.5 these slope values as a function of composition for the three
0.2989 304.0 309.8 313.1 327.2 systems, C12OH + C14OH, C14OH + C16OH and C16OH +
0.4003 304.8 310.4 326.1 C18OH (Figure 10), it is shown that the average slope of the
0.5004 304.2 310.0 324.7 liquidus lines in the (T, P) diagram is similar for the three
0.6004 304.6 310.1 323.9 different systems. In fact, in the case of the C12OH + C14OH,
0.7003 302.1 307.9 323.0 the average slope is equal to (0.22 ± 0.01) K MPa−1, for
0.7998 300.7 308.0 322.4 C14OH + C16OH it is equal to (0.234 ± 0.008) K MPa−1 and
0.9008 305.9 308.4 322.2 for C16OH + C18OH the average slope is equal to (0.240 ±
1.0000 322.8c 0.009) K·MPa−1 excluding the slope values for the pure fatty
a alcohols. Comparing this with the average slope of the pure
Standard uncertainties u are u(xC12OH) = 0.0001, u(T) = 0.3 K.
b
Ttrans,sol: represents a solid−solid transition. cmeasured by μDSC with reactants, the values are slightly different, which may imply that
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a standard uncertainty of u(T) = 0.2 K. the mixtures have some differences in the crystal forms when
compared with the original compounds. This difference on the
Publication Date (Web): September 9, 2015 | doi: 10.1021/acs.jced.5b00330

slope values may give an additional support to the hypothesis


minimum point on the liquidus line of these binary systems that these systems have miscibility in the solid state. A better
corresponds to a transition of a liquid phase l in equilibrium characterization of the transitions observed under the liquidus
with a single solid phase associated with the formed solid line can be performed using X-ray analysis.
solution. In contrast, the definition of the eutectic point is an When compared with the data obtained by using DSC, the
invariant point in which a liquid phase l is in equilibrium with microscope results shows a relatively good agreement
two different solid phases α and β at the eutectic temperature (deviations ranging from 0.1 to 2.6 K). The visual microscopy
and composition.14 is known to give different temperatures in comparison to other
The events detected by the DSC under the liquidus line for techniques.34,35 The onset temperature measured by DSC for
the three systems, C12OH + C14OH, C14OH + C16OH, and mixtures that crystallize in a rotator form seem to give a
C16OH + C18OH, were investigated; nevertheless, the underestimated result for some compositions and should
enthalpy of these events does not allow us to identify a correspond to the melting point of the metastable phase.
thermodynamic event on the solid state as, for example, a Because the kinetics of transformation for the stable form for
eutectoid reaction.14 In fact, probably, these DSC events reflect some compositions is very slow, the stable phase can take many
another kind of transition, as unstable polymorphic forms, hours to be formed after the rotator one and might be easily
associated with one of the components of the mixture or with missed.4 However, the experimental apparatus used in this work
the mixture itself (they are identified in Tables 9, 10, and 11 as for the microscope analyses allows increasing the system’s
Ttrans,sol). A better characterization of these solid−solid pressure by a fast rising, and then the phase change is almost
transitions depends on the use of supplementary methods instantaneous. In the work of Milhet et al.,4 it was verified that
such as X-ray, which is out of the scope of this study. this fast rising in the pressure can induce the crystallization of
On the basis of the results for other fatty systems,23,24,31−33 it the stable form and may be the reason for the temperatures
is possible to conclude that mixtures with eutectic or even deviations between the two analytical techniques.
peritectic transitions exihibit a relatively large range of
temperatures in the solid liquid equilibrium region, that is,
the temperature difference between the solidus and liquidus 4. CONCLUSIONS
line is large, making easier to separate the beginning and end of The SLE of six saturated fatty alcohol binary systems was
the mixturés melting by the microscopy analysis. However, for studied with a high pressure microscope device up to 80 MPa.

Figure 7. SLE lines for the C12OH + C14OH system. (a) Data from DSC and (b) data from high pressure microscopy. Melting temperature at: □,
0.1 MPa; ■, 20 MPa; ○, 40 MPa; ●, 60 MPa; △, 80 MPa; ▲, a solid−solid transition; , a guide to the eye.

F DOI: 10.1021/acs.jced.5b00330
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

Figure 8. SLE lines for the C14OH + C16OH system. (a) Data from DSC and (b) data from high pressure microscopy. Melting temperature at: □,
0.1 MPa; ■, 20 MPa; ○, 40 MPa; ●, 60 MPa; △, 80 MPa; ▲, a solid−solid transition; , a guide to the eye.
Downloaded by UNIV OF NEBRASKA-LINCOLN on September 9, 2015 | http://pubs.acs.org
Publication Date (Web): September 9, 2015 | doi: 10.1021/acs.jced.5b00330

Figure 9. SLE lines for the C16OH + C18OH system. (a) Data from DSC and (b) data from high pressure microscopy. Melting temperature at: □,
0.1 MPa; ■, 20 MPa; ○, 40 MPa; ●, 60 MPa; △, 80 MPa; ▲, a solid−solid transition; , a guide to the eye.

they exist, or the solubility of the fatty alcohols in the solid


domain, when they are soluble, even with the increase of system
pressure.

■ AUTHOR INFORMATION
Corresponding Author
*E-mail: jerome.pauly@univ-pau.fr. Tel.:+33 5 59 40 76 91.
Fax:+33 5 59 40 76 95.
Funding
The authors are grateful to CNPq (304495/2010-7, 552280/
2010-0, 142193/2010-0, 201896/2011-7, 483340/2012-0,
305870/2014-9, 479533/2013-0, 308616/2014-6), FAPESP
Figure 10. Average slopes ΔT/ΔP of the liquidus curves in the (T, P) (2012/05027-1), CAPES, and FAEPEX/UNICAMP for their
diagram calculated for each solid phase as a function of composition financial support and assistantships.
for C12OH + C14OH (■), C14OH + C16OH (△), and C16OH + Notes
C18OH (○) systems.
The authors declare no competing financial interest.
As this technique allows visual monitoring of the samples, it
was possible to measure their melting point as a function of
pressure. The liquidus lines for the binary systems measured by
■ REFERENCES
(1) Gandolfo, F.; Bot, A.; Flöter, E. Structuring of Edible Oils by
the microscope device at atmospheric pressure were compared Long-Chain FA, Fatty Alcohols, and Their Mixtures. J. Am. Oil Chem.
with the DSC results, showing good agreement between both Soc. 2004, 81, 1−6.
sets of data, despite of the fact that the two techniques are (2) Daniel, J.; Rajasekharan, R. Organogelation of Plant Oils and
Hydrocarbons by Long-Chain Saturated FA, Fatty Alcohols, Wax
probably measuring the melting temperature of different Esters, and Dicarboxylic Acids. J. Am. Oil Chem. Soc. 2003, 80, 417−
polymorphic forms for the pure fatty alcohols and their 421.
mixtures. It is also shown that the behavior of the liquidus line (3) Schaink, H. M.; van Malssen, K. F.; Morgado-Alves, S.; Kalnin,
is only slightly affected by the pressure, that is, the SLE lines D.; van der Linden, E. Crystal Network for Edible Oil Organogels:
preserve the same tendency for all measured pressures, Possibilities and Limitations of the Fatty Acid and Fatty Alcohol
confirming the presence of eutectic and peritectic points, if Systems. Food Res. Int. 2007, 40, 1185−1193.

G DOI: 10.1021/acs.jced.5b00330
J. Chem. Eng. Data XXXX, XXX, XXX−XXX
Journal of Chemical & Engineering Data Article

(4) Milhet, M.; Pauly, J.; Coutinho, J. A. P.; Dirand, M.; Daridon, J. L. ization in Terms of DISQUAC. Fluid Phase Equilib. 1997, 129, 139−
Liquid−solid Equilibria under High Pressure of Tetradecane + 163.
Pentadecane and Tetradecane + Hexadecane Binary Systems. Fluid (23) Carareto, N. D. D.; Costa, M. C.; Rolemberg, M. P.;
Phase Equilib. 2005, 235, 173−181. Krähenbühl, M. A.; Meirelles, A. J. A. The Solid-Liquid Phase
(5) Matser, A. M.; Krebbers, B.; van den Berg, R. W.; Bartels, P. V. Diagrams of Binary Mixtures of Even Saturated Fatty Alcohols. Fluid
Advantages of high pressure sterilisation on quality of food products. Phase Equilib. 2011, 303, 191.e1−191.e8.
Trends Food Sci. Technol. 2004, 15, 79−85. (24) Carareto, N. D. D.; dos Santos, A. O.; Rolemberg, M. P.;
(6) Cheftel, J. C. Review: High-pressure, microbial inactivation and Cardoso, L. P.; Costa, M. C.; Meirelles, A. J. A. On the Solid−liquid
food preservation. Food Sci. Technol. Int. (London, U. K.) 1995, 1, 75− Phase Diagrams of Binary Mixtures of Even Saturated Fatty Alcohols:
90. Systems Exhibiting Peritectic Reaction. Thermochim. Acta 2014, 589,
(7) Costa, M. C.; Krahenbuhl, M. A.; Meirelles, A. J. A.; Daridon, J. 137−147.
L.; Pauly, J.; Coutinho, J. A. P. High Pressure Solid-Liquid Equilibria of (25) Domańska, U.; Morawski, P.; Piekarska, M. Solid−Liquid Phase
Fatty Acids. Fluid Phase Equilib. 2007, 253, 118−123. Equilibria of 1-Decanol and 1-Dodecanol with Fragrance Raw
(8) Carareto, N. D. D.; Costa, M. C.; Meirelles, A. J. A.; Pauly, J. Materials Based on Cyclohexane. J. Chem. Eng. Data 2009, 54,
High Pressure Solid−liquid Equilibrium of Fatty Acid Ethyl Esters 1271−1276.
Binary Systems. Fluid Phase Equilib. 2014, 382, 158−163. (26) Widmer, D. R.; Calhoun, D. F.; Thurston, D.; Edwards, A. M.
(9) Kouakou, A. C.; Mapihan, K. L.; Pauly, J. Solid-Liquid Equilibria Water diffusivity in a mixed phase binary system: Effective water
under High Pressure of Pure Fatty Acid Methyl Esters. Fuel 2013, 109, diffusion coefficients in tetradecanol−eicosanol mixtures. Fluid Phase
297−302. Equilib. 2014, 379, 157−166.
Downloaded by UNIV OF NEBRASKA-LINCOLN on September 9, 2015 | http://pubs.acs.org

(10) Daridon, J. L.; Pauly, J.; Milhet, M. High Pressure Solid-Liquid (27) Costa, M. C.; Rolemberg, M. P.; Boros, L. A. D.; Krahenbuhl,
M. A.; de Oliveira, M. G.; Meirelles, A. J. A. Solid-Liquid Equilibrium
Phase Equilibria in Synthetic Waxes. Phys. Chem. Chem. Phys. 2002, 4,
of Binary Fatty Acid Mixtures. J. Chem. Eng. Data 2007, 52, 30−36.
4458−4461.
Publication Date (Web): September 9, 2015 | doi: 10.1021/acs.jced.5b00330

(28) Smith, J. C. Higher Aliphatic Compounds Part I The Systems


(11) Morawski, P.; Coutinho, J. A. P.; Domańska, U. High Pressure
Ethyl Palmitate-Ethyl Stearate and Hexadecyl Alcohol-Octadecyl
(solid-Liquid) Equilibria of N-Alkane Mixtures: Experimental Results,
Alcohol. J. Chem. Soc. 1931, 802−807.
Correlation and Prediction. Fluid Phase Equilib. 2005, 230, 72−80. (29) Coutinho, J. A. P.; Knudsen, K.; Andersen, S. I.; Stenby, E. H. A
(12) Pauly, J.; Daridon, J. L.; Coutinho, J. A. P.; Dirand, M. Local Composition Model For Paraffinic Solid Solutions. Chem. Eng.
Crystallisation of a Multiparaffinic Wax in Normal Tetradecane under Sci. 1996, 51, 3273−3282.
High Pressure. Fuel 2005, 84, 453−459. (30) He, B.; Martin, V.; Setterwall, F. Liquid−solid Phase
(13) Yang, M.; Terakawa, E.; Tanaka, Y.; Sotani, T.; Matsuo, S. Solid- Equilibrium Study of Tetradecane and Hexadecane Binary Mixtures
Liquid Phase Equilibria in Binary (1-Octanol plus N-Alkane) Mixtures as Phase Change Materials (PCMs) for Comfort Cooling Storage.
under High Pressure - Part 1. (1-Octanol plus N-Tetradecane or N- Fluid Phase Equilib. 2003, 212, 97−109.
Hexadecane) Systems. Fluid Phase Equilib. 2002, 194, 1119−1129. (31) Costa, M. C.; Rolemberg, M. P.; Meirelles, A. J. A.; Coutinho, J.
(14) Gamsjager, H.; Lorimer, J. W.; Scharlin, P.; Shaw, D. G. A. P.; Krähenbühl, M. A. The Solid-Liquid Phase Diagrams of Binary
Glossary of Terms Related to Solubility. Pure Appl. Chem. 2008, 80, Mixtures of Even Saturated Fatty Acids Differing by Six Carbon
233−276. Atoms. Thermochim. Acta 2009, 496, 30−37.
(15) Yamamoto, T.; Nozaki, K.; Hara, T. X-Ray and Thermal Studies (32) Costa, M. C.; Sardo, M.; Rolemberg, M. P.; Coutinho, J. A. P.;
on the Rotator Phases of Normal Higher Alcohols C17H35OH, Meirelles, A. J. A.; Ribeiro-Claro, P.; Krahenbuhl, M. A. The Solid-
C18H37OH, and Their Mixtures. J. Chem. Phys. 1990, 92, 631−641. Liquid Phase Diagrams of Binary Mixtures of Consecutive, Even
(16) Ventolà, L.; Calvet, T.; Cuevas-Diarte, M. A.; Mondieig, D.; Saturated Fatty Acids. Chem. Phys. Lipids 2009, 160, 85−97.
Oonk, H. A. J. The C19H39OH-C20H41OH System: Experimental (33) Costa, M. C.; Sardo, M.; Rolemberg, M. P.; Ribeiro-Claro, P.;
Phase Diagram and Thermodynamic Modelling. Phys. Chem. Chem. Meirelles, A. J. A.; Coutinho, J. A. P.; Krahenbuhl, M. A. The Solid-
Phys. 2002, 4, 1953−1956. Liquid Phase Diagrams of Binary Mixtures of Consecutive, Even
(17) Ventolà, L.; Calvet, T.; Cuevas-Diarte, M. A.; Oonk, H. A. J.; Saturated Fatty Acids: Differing by Four Carbon Atoms. Chem. Phys.
Mondieig, D. Solid-Solid and Solid-Liquid Equilibria in the N-Alkanols Lipids 2009, 157, 40−50.
Family: C18H37OH-C20H41OH System. Phys. Chem. Chem. Phys. (34) Roenningsen, H. P.; Bjoerndal, B.; Baltzer Hansen, A.; Batsberg
2004, 6, 3726−3731. Pedersen, W. Wax Precipitation from North Sea Crude Oils: 1.
(18) Ventolà, L.; Calvet, T.; Cuevas-Diarte, M. A.; Ramirez, M.; Crystallization and Dissolution Temperatures, and Newtonian and
Oonk, H. A. J.; Mondieig, D.; Negrier, P. Melting Behaviour in the N- Non-Newtonian Flow Properties. Energy Fuels 1991, 5, 895−908.
Alkanol Family. Enthalpy-Entropy Compensation. Phys. Chem. Chem. (35) Ji, H.-Y.; Tohidi, B.; Danesh, A.; Todd, A. C. Wax Phase
Phys. 2004, 6, 1786−1791. Equilibria: Developing a Thermodynamic Model Using a Systematic
(19) Ventolà, L.; Calvet, T.; Cuevas-Diarte, M. A.; Solans, X.; Approach. Fluid Phase Equilib. 2004, 216, 201−217.
Mondieig, D.; Negrier, P.; van Miltenburg, J. C. Solid State
Equilibrium in the N-Alkanols Family: The Stability of Binary Mixed
Samples. Phys. Chem. Chem. Phys. 2003, 5, 947−952.
(20) Domańska, U.; Gonzalez, J. A. Solid-Liquid Equilibria for
Systems Containing Long-Chain 1-Alkanols 0.1. Experimental Data for
1-Dodecanol, 1-Tetradecanol, 1-Hexadecanol, 1-Octadecanol or 1-
Icosanol-Benzene or -Toluene Mixtures. Characterization in Terms of
DISQUAC. Fluid Phase Equilib. 1996, 119, 131−151.
(21) Domańska, U.; Gonzalez, J. A. Solid-Liquid Equilibria for
Systems Containing Long-Chain 1-Alkanols 0.2. Experimental Data for
1-Dodecanol, 1-Tetradecanol, 1-Hexadecanol, 1-Octadecanol or 1-
Eicosanol plus CCl4 or plus Cyclohexane Mixtures. Characterization
in Terms of DISQUAC. Fluid Phase Equilib. 1996, 123, 167−187.
(22) Domańska, U.; Gonzalez, J. A. Solid-Liquid Equilibria for
Systems Containing Long-Chain 1-Alkanols 0.3. Experimental Data for
1-Tetradecanol, 1-Hexadecanol, 1-Octadecanol or 1-Icosanol plus 1-
Butanol, 1-Hexanol, 1-Octanol or 1-Decanol Mixtures, Character-

H DOI: 10.1021/acs.jced.5b00330
J. Chem. Eng. Data XXXX, XXX, XXX−XXX