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(DSC) is an alternative, being one of the most used Perkin Elmer DSC7 Differential Scanning Calorimeter.
techniques for studying thermal behaviour of various Nitrogen was the carrier gas and calibration was
foods components. Melting point obtained by DSC is done with indium, after checking the operation with
generally considered as the onset temperature, the distilled, deionized water. 10-15mg of sample were
inflection point of melting curve and solid line. enclosed in hermetically sealed aluminum pans and
Deman et al, (1991) consider melting point as the run against air (empty pan) as reference. DSC
peak temperature calculated from a DSC melting melting curves were obtained according to Dodd &
curve. In this referred study, temperature measured Tonge (1987). Samples were heated to 80C for 5
at the end of melting curve obtained by DSC was minutes, cooled at 10C/min to -50C, holding at this
considered as the real melting point, where the temperature for 5 minutes to crystallize the sample.
melting phenomenon finishes, when all crystals in After this procedure, melting curves were recorded
solid state became liquid. Slew et ai, (1982) concluded from initial temperature to 80C at a heating rate of
that melting point is essentially determined by the 10C/min. The resulting DSC data was analyzed by
hard fraction of stearins, indicated by the major peak. peak program and peak temperature, onset temperature
Chaisery & Dimick (1995), in a study of crystallization and melting temperature were recorded. Melting
of cocoa butter, measured melting point by DSC of temperature was considered as the temperature at
low and high melting fractions, considering onset the end of the curve, when melting has completed.
melting temperature. In a study of effect of cooling
and heating rates variation, Cebula & Smith (1991)
measured melting point of pure triglycerides, also 3. RESULTS AND DISCUSSION
considering the onset temperature.
In this study, final melting temperatures obtained Fatty acid composition of the samples can be
by DSC technique were compared with softening seen in table I. Values showed the great variability of
point (AOCS method Cc 3-25) (AOCS, 1988) values the samples, which influences melting point values
for various vegetable oils and fats. and the shape of DSC melting curves.
2. EXPERIMENTAL Table 1
Fatty acid composition of vegetable oils
2.1. Material
Sanle C8:0 C10:0 C12;0 C14:0 CI 6:0 C16:1 CI 8:0 CI 8:1 CI 8:2 CI 8:3 C20:0
14 different types of oils and fats were used:
soybean oil, cottonseed oil, palm oil, palm olein,
SON - 0.12 11.41 0.11 9.51 22.31
49.21(a)
2.05
4.84(b)
0.24 0.18
palm stearin, babassu oil and hydrogenated oils SOB ~ 0.12 11.16 0.11 13.04 35.02 0.91 0.25 0.44
36.28(a) 2.66(b)
(soybean, two types; palm oil, cottonseed oil and
babassu oil), palm kernel oil, palm kernel stearin and AGH 0.84 23.31 0.74 3.36 59.39 1.12
10.11(b)
0.01 0.25
0.86(c)
intersterified cottonseed oil. The samples were AGI 5.34 4.25 35.89 13.30 11.06 - 23.67 3.77 2.71 - -
gently supplied by Gessy Lever Ltda. (Valinhos, SP) PMD - 0.46 0.82 38.23 - 5.32 42.47 12.19 0.10 0.39
and Refinadora de leos Brasil (Sao Caetano do PME - 0.80 49.83 - 6.59 32.62 9.28 0.50 0.37
Sul, SP). PMO - 0.63 35.43 - 5.08 44.53 13.35 0.59 0.37
Figure 4 Figure 7
DSC melting curve for deodorized cottonseed oil DSC melting curve for deodorized palm oil
- - PALMA HIOROKNAOA
Figure 5 Figure 8
DSC melting curve for hydrogenated cottonseed oil DSC melting curve for hydrogenated palm oil
5 1.3
-hM -o.oo -laM 'M lo.oi S;; Sw 30fl A.K -30.08 -ao.oo -tO.OO 1.00 M.OS 20.00 30.00 40.00 SB. GO.OC
TsfipwMtuce dc] Teniwaturalcj
Figur 6 Figure 9
DSC melting curve for interesterified cottonseed oil DSC melting curve for palm oil
^'^v^
V.
Figure 10 Figure 13
DSC melting curve for palm stearin DSC melting curve for deodorized babassu oil
- - PALMISTE nCFINADQ
1.(10
TBperatura (C)
Figure 11
DSC melting curve for refined palm kernel oil Figure 15 shows a graphical comparison between
differences of melting points and other characteristic
temperatures obtained by DSC melting curves and
- - ESTEARINA DE PALMISTE
softening point values. If onset temperatures were
considered, differences between these temperatures
and softening point ones are bigger, because onset
temperatures were recorded when the fat began to
melt, while in softening point they had melt more
than this point recorded by DSC. When comparing
peak temperatures obtained by DSC with softening
points, we can observe that the former are higher
than those obtained by DSC, except for
hydrogenated palm sample. Big differences can be
seen between deodorized palm oil and palm olein.
This fact occurs because peak temperature is
recorded as the temperature of the main peak, when
-jo.eo 4).eQ -io.oo ol SIS l lw IM S U .O<
curve shows more than one. In this case, main peak
TaHppatur (C) of both samples was located in a region where
temperature was not sufficient to melt the sample in
Figure 12 the same point of that recorded by softening point.
DSC melting curve for palm kernel stearin
Table II ACKNOWLEDGEMENTS
Characteristic temperatures obtained by DSC
melting curves and AOCS softening point values The authors acknowledge the financial support
Onset Peak Melting Softening given by CNPq (Conselho Nacional de Desenvolvimento
Sample temperature temperature point point Cientfico e Tecnolgico, Brasilia, Brasil) and FAPESP
fC) (C) (C) (C) (Fundaao de Amparo Pesquisa do Estado de Sao
SOD -28.6 -26.1 -5.8 Paulo, Sao Paulo, Brasil).
SON 6.9 19.8 36.8 32.0
SOB 15.0 32.5 42.7 37.3
AGD -9.9 - -4.5 -0.5
AGH 10.9 27.8 38.4 32.7
REFERENCES
AGI 15.5 32.7 42.8 36.4
PMD -18.6 0.2 41.3 36.2
AOCS (1988).Official Methods and Recomnaended
PME 2.3 46.2 54.5
Practices of the American Oil Chenriists' Society. 3rd.
49.8
PMO -15.5 4.0 29.4
d., Champaign.
20.1
PMH 54.4 59.7
Cebula, D.J.; Smith, K.W. (1991).Differential Scanning
64.9 58.4
PKR 13.6 25.8
Calorimetry of Confectionery Fats. Pure triglycerides:
30.6 28.4
PKE 24.2
effects of cooling and heating rate variation.J. Am.
31.3 34.8 31.7
BBD 13.8
Oil Chem. Soc. 68: 591-595.
24.4 28.9 24.4
BBH
Chaiseri, S.; Dimick, P.S. (1995).Dynamic crystallization
12.3 27.3 40.4 35.5
of cocoa butter. II Morphological, thermal and chemical
SOD - deodorized soybean oil; SON - hydrogenated soybean oil characteristics during crystal growth..J. Am. Oil
type N; SOB - hydrogenated soybean oil type B; AGD - Chem. Soc. 82: 1497-1504.
deodorized cottonseed oil; AGH - hydrogenated cottonseed oil; Deman, J.M.; Deman, L; Blackman, B. (1983).
AGI - interesterified cottonseed oil; PMD - deodorized palm oil;
PME - palm stearin; PMO - palm olein; PMH - hydrogenated Melting-point determination of fat products.J. Am.
palm oil; PKR - refined palm kernel oil; PKE - palm kernel stearin; Oil Chem. Soc. 60:15-18
BBD - deodorized babassu oil; BBH - hydrogenated babassu oil. Deman, L; Deman, J.M.; Blackman, B. (1991). Physical
and textural characteristics of some North American
shortenings.xJ. Am. Oil Chem. Soc. 68: 63-69.
Dodd, J.W.; Tonge, K.H. (1987).Thermal methods.
John Wiley and Sons, London.
Hartman, L& Lago, R. C. (1973).Rapid determination
u 1 of fatty acid methyl esters from lipids.Lab. Practice
22(8): 475-476, 494.
" 1
UJ
Bdif. DSC onset temp, x S.P. Kaisersberger, E (1989).DSC investigations of the
If 20 4- 1 lodif. DSC peak temp, x S.P.
thermal characterization of edible fats and oils.
u.
a
A IIIy y
i
1
f^
11 A
Liill
Thermochim. Acta 151: 83-90.
Kanematsu, H.; Kinoshita, Y; Niiya, I.; Matsumoto, T.
(1979a).Automatic melting point determination of
SON SOB AGH AGI PMD Ptm PMO PMH PKR PKE BBO BBH
edible solid fats. IV. Mettler softening points of solid
fats.-^. Japan Oil Chem. Soc. (Yukagaku) 28:180-184
Kanematsu, H.; Kinoshita, Y; Niiya, I.; Matsumoto,
DSC - Differential Scanning Calorimetry; M.P. - melting point; S.P. T.(1979b).Automatic melting point determination of
- softening point. edible solid fats. V. Melting point of mixed fats and
SOD - deodorized soybean oil; SON - hydrogenated soybean oil plastic fat products.J. Japan Oil Chem. Soc.
type N; SOB - hydrogenated soybean oil type B>>; AGD - (Yukagaku) 28:344-347
deodorized cottonseed oil; AGH - hydrogenated cottonseed oil; Kanematsu, H.; Kinoshita, Y; Niiya, I.; Matsumoto, T.
AGI - interesterified cottonseed oil; PMD - deodorized palm oil; (1981).Automatic melting point determination of
PME - palm stearin; PMO - palm olein; PMH - hydrogenated edible solid fats. VI. Open-tubed melting point using
palm oil; PKR - refined palm kernel oil; PKE - palm kernel stearin; the Elex apparatus.J. Japan Oil Chem. Soc.
BBD - deodorized babassu oil; BBH - hydrogenated babassu oil. (Yukagaku) 30: 881-883.
Figure 15 Kawada-T; Suzuki-K; Yokomizo-K; Kanematsu-H;
Comparative graphic of differences between temperatures Hirata-Y; Shikama-T; Sakata-M; Mori-Hi Takeya-K;
obtained by DSC technique and AOCS softening point values Abeshima-T (1985).Softening point determination
by the ring and ball method.J. Japan Oil Chem.
4. CONCLUSIONS Soc. (Yukagaku) 34: 952-956.
Mertens, W.G. (1973).Fat melting point determinations:
These results show that DSC is a accurate a review.J. Am. Oil Chem. Soc. 50: 115-119
technique, which can measure the temperature when Siew, W.L; Ong, A.S.H.; Oh, FC.H.; Berger, K.G. (1982).
fat is completely in the liquid state. When measuring by Critical aspects of slip melting point measurements.
softening point technique, an empirical method, in the PORIMBull.4: 1-18.
point of measurement crystals are not melted Weiss, T.J. (1980).Food oils and their uses.2nd.
Ed.The AVI Publishinjg Company Inc., Westport,
completely, leading to lower values. Besides, by DSC
(Connecticut), p.27-28.
technique it is possible to determine melting point of
liquid oils such as soybean and cottonseed oils. DSC
melting curves are also obtained, which is very useful Recibido: Noviembre 1997
to observe the melting range of the sample. Aceptado: Abril 1998