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Thermochimica Acta
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A R T I C L E I N F O A B S T R A C T
Keywords: In this work, thermal characterization of centrifuged aromatic citrus oils was studied using thermal lens (TL) and
Thermal diusivity open photoacoustic cell (OPC). The thermal diusivity (D) was obtained by TL, tting the critical time parameter
Thermal eusivity of the experimental curves to the theoretical values. An experimental arrangement of non-matched mode lasers
Citrus essential oils with a probe and an excitation lasers was used. On the other hand, the thermal eusivity (e) of the samples was
Thermal lens
obtained by using OPC. The thermal conductivity (k) was calculated from the relationship between D and e. The
Open photoacoustic cell
thermal parameters obtained were compared with theoretical values in the literature. UVvis spectroscopy,
Attenuated Total Reectance-Fourier Transform Infrared spectroscopy (ATR-FTIR) and 1H Nuclear Magnetic
Resonance (NMR) were used to determine the absorption coecients and chemical structure of the citrus oils.
The importance of this research work was the determination of the thermal parameters of essential oils as an
alternative technique for quality control application.
Corresponding author.
E-mail address: jimenezp@s.cinvestav.mx (J.L. Jimnez-Prez).
http://dx.doi.org/10.1016/j.tca.2017.09.014
Received 11 June 2017; Received in revised form 3 September 2017; Accepted 13 September 2017
Available online 15 September 2017
0040-6031/ 2017 Elsevier B.V. All rights reserved.
R. Carbajal-Valdez et al. Thermochimica Acta 657 (2017) 6671
Table 1
Thermal lens experiment parameters.
2. Experimental
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frequency of the excitation beam in the sample, and IR is the slope of the
normalized photoacoustic signal, as a function of the square root of f.
The cell (Fig. 3) was calibrated with water to compare with the values
reported in the literature. The obtained value for distilled water was
(eH2O = 1487.05 47Ws1/2 /m2C) and the reported values are
eH2O = 1640Ws1/2 /m2C and eH2O = 1595Ws1/2 /m2C[14]). It can be
seen, that the obtained value was similar to the reported values. In the
case of the studied essential oils they contains, among others compo-
nents, ethanol and the reported thermal eusivity of ethanol is 0.0585
(Ws1/2/(cm2 C)) [15].
Measurements of absorption coecients and chemical structure
were determined by complementary techniques such as UVvis spec-
troscopy, ATR-FTIR and 1H NMR.
Dierent oil batches for the essential oils (lemon, orange, grapefruit Fig. 5. FTIR spectra of lemon, green mandarin, orange and grapefruit essential oil sam-
and green mandarin) were used (Chemical aromatic SA Mexico). ples. (For interpretation of the references to colour in this gure legend, the reader is
Essential oils were obtained from the pericarp of citrus peel by scrap- referred to the web version of this article.)
ping or breaking the oil cells near the fruits surface and using water to
drag the oil in the form of an emulsion, which was centrifuged to obtain approximately 95% and in other citrus oils at 5078%. Thus, the ATR-
the cold pressed oil [16]. Samples measurements were done at room FTIR spectra of these oils are mainly characterized by limonene vi-
temperature. A total of 10 measurements were made for each essential brational modes to be seen at 877 cm1 (out-of-plane bending of the
oil under the same conditions. terminal methylene group), at 1442 cm1 ( CH2) and at 1644 cm1
In Fig. 4, the UVvis spectra of centrifuged citrus oils of lemon, [20]. The individual (C]C) stretching vibrations of both mono-
orange, grapefruit, and green mandarin oils can be seen. An absorbance terpenes are found at 1658 cm1 ( pinene) and 1640 cm1 (-
peak is observed in the region of 300350 nm for the centrifuged citrus pinene), respectively. Also, pinene presents the characteristic signal
oils due to monoterpene alcohols (terpenes with OH). The bands at of the CH at 787 cm1, -pinene shows the absorption band of the
400450 nm and 660 nm are related to the presence of carotenoids and terminal methylene group at 873 cm1 and of the cyclohexane ring at
chlorophylls that give the characteristic color to oil and fruit. The 853 cm1. Finally, the bands at 800 and 950 cm1 are associated to the
spectra were recorded for essential oils extracted by centrifugation. wagging vibrations of CH and CH2 groups.
Changes were observed due to dierences in chemical composition of Among monoterpenes, numerous aldehyde derivatives can be well
the dierent oils [17,18]. recognized by ATR-FTIR spectroscopy where the intense IR band due to
In Fig. 5 the ATR-FTIR spectra for the dierent oils can be seen. Due the C]O stretching mode is seen between 1782 and 1569 cm1 (blue
to the similar chemical composition of the oils, these spectra showed circle), and the increased of the peak at 1158 cm1 (red circle) for
the typical characteristic absorption bands. The characteristic absorp- (C]C) in aromatics. These were observed only for lemon oil compared
tion bands for essential oils are present: the broad band between 3036 to the other essential oils.
and 2784 cm1 that corresponds to the asymmetrical and symmetrical Fig. 6 shows the 1H NMR spectrum of lemon essential oil. The
stretching vibration of the aliphatic eCH in CH2 and CH3 groups and spectrum shows the resonances of limonene (Table 2). The signal at
eOH stretching for alcohol and phenols. At 1743 cm1 the ester car- 0.66 ppm is attributed to a compound with a pinenic structure. Then,
bonyl functional groups of the triglycerides are assigned. The trigly- methylenic protons of all insaturated fatty chains were observed in the
cerides are the principal components in oils. The most relevant mono- 1.2 region. In 1.62 and 1.66 ppm there are the squalene and the li-
terpene components occurring in these oils are limonene and - monene signals, respectively. In the inset, the signals at 1.66 and 1.72
terpinene, but and pinene, myrcene, sabinene, octanal, de-
canal, citral, sinensal, and nootkatone can also be present [19]. In
lemon, orange and grapefruit essential oils, limonene occurs at levels of
Fig. 4. UVvis spectrum of centrifuged citrus oils: lemon, orange, grapefruit and green
mandarin. (For interpretation of the references to colour in this gure legend, the reader
is referred to the web version of this article.) Fig. 6. 1H NMR spectrum of the lemon essential oil (CDCl3, 750 MHz NMR).
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Table 3
Dependence of thermal diusivity (D), thermal eusivity (e), thermal conductivity (k) and tting parameters (tc and ) for the dierent citrus oils.
Essential Oils D(108m2/s) Literature [18,22,24] D(108m2/s) e(104Ws1/2/m2 C) Literature [25] e(104Ws1/2/m2 C) k(W/m C) Literature [25] k(W/m C)
Lemon 7.18 0.05 7.17 0.05 0.0532 0.0026 0.049 0.003 0.142 0.007 0.134 0.001
Orange 7.22 0.03 7.31 0.03 0.0508 0.0016 0.048 0.002 0.136 0.004 0.132 0.001
Grapefruit 7.33 0.03 7.37 0.02 0.0489 0.0011 0.049 0.003 0.133 0.003 0.137 0.002
Green mandarin 7.39 0.04 7.43 0.08 0.0478 0.0022 0.130 0.006
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