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Thermal Diffusivity of Palm

Olein and Compounds
Containing -carotene
ARTICLE in INTERNATIONAL JOURNAL OF THERMOPHYSICS SEPTEMBER
2011
Impact Factor: 0.96 DOI: 10.1007/s10765-011-1059-y

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Universidade Federal da Par
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Int J Thermophys (2011) 32:19661972

DOI 10.1007/s10765-011-1059-y

Thermal Diffusivity of Palm Olein and Compounds

Containing -carotene
A. J. de Freitas Cabral P. C. de Oliveira
S. G. C. Moreira P. Alcantara Jr.

Received: 17 June 2010 / Accepted: 25 July 2011 / Published online: 6 August 2011
Springer Science+Business Media, LLC 2011

Abstract The effect of dissolving -carotene into palm olein was experimentally
investigated using time-resolved thermal lens spectroscopy. The thermal diffusivity of
palm olein was measured, and the dependence on the concentration of the compounds
was studied. The results show an enhancement in the thermal diffusivity by increasing
the quantity of -carotene in the compounds. This behavior was interpreted on the
basis of the electronic structure of the -carotene molecule.
Keywords

-Carotene Palm olein Thermal diffusivity Thermal lens

1 Introduction
Time-resolved thermal lens (TL) spectroscopy is a high-sensitivity and nondestructive optical technique used to study samples with very small optical absorption, by
measuring the thermal properties of the materials. In recent years, the TL technique
has been used to measure optical and thermal properties of transparent samples with
an enhanced accuracy, for solid samples, liquids, as well as other complex systems
[15]. In the TL experiments, the sample is exposed to an excitation laser beam with
a TEM00 Gaussian intensity profile. A fraction of the absorbed energy is converted
into heat, generating a radial temperature profile. As a result of this local temperature
increase, a lens-like optical element in the heated region is created. The presence of

A. J. de Freitas Cabral S. G. C. Moreira P. Alcantara Jr. (B)

Grupo de Fsica de Materiais da Amaznia, Instituto de Cincias Exatas e Naturais,
Universidade Federal do Par, 66075-110 Belm, PA, Brazil
e-mail: [email protected]
P. C. de Oliveira
Departamento de Fsica, Universidade Federal da Paraba, 58051-970 Joo Pessoa, PB, Brazil

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1967

such a thermal lens is detected by the convergence or divergence of the propagation

of a probing beam passing through the sample. The temporal evolution of the on-axis
probe beam intensity is measured in the far field using a circular aperture in front of a
photodiode. The TL technique has also been used successfully to measure the thermal
diffusivity of organic solvents [6], edible commercial oils [7], and biodiesel oils [8].
Palm olein is the liquid fraction obtained by fractionation of palm oil after crystallization at controlled temperatures. Rich in oleic acid (42.7 % to 43.9 %), -carotene,
and vitamin E (tocopherols and tocotrienols), palm oil, obtained from the fruit of the
tropical palm tree Elaeis guineensis, is the second major edible oil used worldwide [9].
In health applications, palm olein has been demonstrated to play an important nutritional role with regard to ischemic heart disease [10]. On the other hand, -carotene
is an important source of vitamin A for the human organism; its chemical structure
has a centrosymmetrical principal conjugated chain and two alcenic cycles at their
ends. In order to elucidate the physical processes governing the functions of carotenoids in biological complexes, a fundamental knowledge concerning the influence of
the surrounding environment on the properties of carotenoids is very important. For
that purpose, a number of studies have been performed, and the physical properties
of carotenoids have been intensively investigated by systematically changing environmental parameters such as the amount of applied pressure [11], the types of solvents
[12,13], and the types of amino-acid residues [14].
In this work, the thermal diffusivities of palm olein (PO) and -carotene dissolved
in palm olein (POBC) were measured by time-resolved thermal lens spectroscopy. In
spite of the importance of these compounds in food and medicine industries, little is
known about their physicochemical properties and this study represents an effort to
provide additional knowledge about these materials.
2 Theory
In this work, a theoretical model for mode-mismatched dual-beam TL spectroscopy
[15,16] that takes into account the Fresnel diffraction theory to the imaging of the
probe beam is used. By this model, the intensity of the TL signal in the plane of the
detector is given by
2

2mV
1




I (t) = I (0) 1 tan
2
(1 + 2m)2 + V 2 2t + 1 + 2m + V 2


(1)

where

m=

p
e

Z1
Pe Ae L
,V =
, =
Zc
p k

n
T

.
p

In Eq. 1, I (t) is the temporal dependence of the probe laser beam intensity at the
detector, I (0) is the initial value of I (t), is the thermally induced phase shift of
the beam after it passes through the sample, Z c is the confocal distance of the probe
beam, and Z 1 is the distance of the probe beam waist from the sample; p is the probe

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beam waist, e is the minimum excitation beam waist at the sample position, p is
the probe beam wavelength, Pe is the power of the excitation laser, k is the thermal
conductivity, (n/ T )p is the temperature coefficient of the refractive index at the
probe beam wavelength, Ae is the optical absorption coefficient at the excitation beam
wavelength, and L is the sample thickness. Finally, is the characteristic TL time
constant defined as
=

e2
4D

(2)

where D is the thermal diffusivity.

Equation 1 will be used to fit the experimental data of the TL transient signal giving
the values of both and parameters. The latter will be used to find D.
3 Materials and Methods
Palm olein (PO) was supplied by Agropalma (Par, Brazil) and used without modification.
-Carotene (BC, Fluka, 97 %) was purchased and used directly in the preparation of the compounds PO + BC at different concentrations. The TL measurements
were performed in the dual-beam mode-mismatched configuration. A solid-state laser,
532 nm wavelength and adjustable power from 3 mW to 6 mW in the position of the
samples, was used as the excitation beam, focused onto the sample with a waist radius
of 65 m. The probe beam was a HeNe laser, 632.8 nm wavelength and 2 mW power,
with a waist radius of 128.4 m on the sample. Measurements of the beam waist
were performed using a pinhole with a diameter of 30 m, and it was observed that
the excitation and probe lasers operate in the TEM00 mode. This procedure enables
determination of the spatial parameters m and V used in Eq. 1 to fit the experimental
data [16].
An electronic circuit controls a shutter, which consists of a mechanical diaphragm
that was used for limiting the exposure time of the sample to the light; when it is open,
the sample is illuminated, and the shutter driver sends a signal to initialize the data
acquisition. The maximum intensity of the probe beam is centered on the photodiode
detector, and its time variation, in the form of a voltage, is registered by a digital
oscilloscope (Hewlett-Packard 54522A), recorded as a function of time and sent to
the PC through a GPIB interface bus. Optical absorption spectra were obtained using
an Acton Research (300i) spectrometer with 0.1 nm in resolution. Additional details
of the experimental procedure can be found elsewhere [17].
4 Results and Discussion
Figure 1 shows the optical absorption spectrum for palm olein (a) and for compounds
PO + BC (b to e) at different concentrations. This set of spectra shows two features
of interest: the strong absorption from PO around 398 nm, and the crescent bands
around 430 nm, 460 nm, and 488 nm due to -carotene. In fact, the maximum optical

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1969

0.9
0.04

0.8

e = 532 nm

Absorbance, a.u.

0.7
0.6

(e)

0.5

(d)

0.4

(c)

530

532

534

536

538

540

0.3
(b)
0.2

(a)

0.1
0.0
250

300

350

400

450

500

550

600

Wavelength, nm
Fig. 1 Absorption spectra for: (a) palm olein, (b) PO + BC; concentration of BC, 5.96 106 mol L1 ,
(c) PO + BC, 1.49 105 mol L1 , (d) PO + BC, 2.23 105 mol L1 , and (e) PO + BC, 3.35
105 mol L1
Table 1 Thermal diffusivities
of oleic acid (OA) and olive oil
(OO) compared with literature
values

Samples (ms)

(rad) Thermal diffusivity (104 cm2 s1 )

This work Literature [2022]

OA

10.3 0.2 0.22

10.2

10.3

OO

12.0 0.1 0.26

8.7

8.8

absorption of -carotene has been reported between 425 nm and 490 nm, depending
on the type of solvent used [18,19]. The influence of -carotene on the compound
is evident from the figure. The inset in the figure shows the low absorption of the
compounds around the wavelength of the excitation laser in the experiment. One can
see that there is a very small enhancement in the absorption near 532 nm.
To check the reliability of the experimental setup, measurements of the thermal
diffusivity of oleic acid (OA) and pure olive oil (OO) were performed. The results are
reported in Table 1 and compared with values previously reported. One can see that the
thermal diffusivities measured in this work are in very good agreement with literature
values. It is important to note the values of < 0.3 in Table 1, a necessary condition for the application of the approximate theoretical model for mode-mismatched
dual-beam TL spectroscopy [16].
The TL signal from palm olein (PO) at room temperature is shown in Fig. 2. The
signal decreases in time indicating that the thermal lens defocuses the probe beam
on the detector, and the sample behaves like a divergent lens. The symbols represent the experimental data, and the solid line is the result of the best fit by Eq. 1
with m = 3.91 and V = 1.73 given by the experimental measurements of the beam

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Int J Thermophys (2011) 32:19661972

1.02
1.00

= 0.23 rad

0.98

= 8.9 0.1 ms

TL signal, a.u.

0.96
0.94
0.92
0.90
0.88
0.86
0.84
0.82
0

20

40

60

80

100

120

140

160

Time, ms
Fig. 2 Thermal lens signal for palm olein

12.8

D, 10 cm s

-1

12.6

-4

12.4

12.2

12.0

11.8
0.0

0.5

1.0

1.5

2.0

2.5

-5

-1

3.0

3.5

Concentration, 10 molL

Fig. 3 Thermal diffusivity as a function of the concentration of BC in the solutions PO + BC

waist, and and as adjustable parameters. The values for these parameters were
= 0.23 rad and = 8.9 ms. Using Eq. 2 with e = 65 m, a thermal diffusivity
D = 11.9 104 cm2 s1 for PO was obtained.
The same procedure was repeated to measure the thermal diffusivities of the compounds PO + BC, and the results are summarized in Table 2. The experimental values
for the parameter < 0.3 are emphasized. The thermal diffusivities measured in
this work have the same order of magnitude as many other vegetable oils previously
measured [7,8,17]. Figure 3 shows the thermal diffusivities as a function of the concentration of -carotene in the solution with palm olein. The solid line is an exponential

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Table 2 Thermal lens parameters and thermal diffusivities for palm olein (PO) and compounds PO + BC
Concentration (mol L1 )

(ms)

D (104 cm2 s1 )

0.0a

8.9 0.1

0.23

11.9

0.59 105

8.9 0.1

0.17

11.9

1.49 105

8.8 0.1

0.23

12.0

2.23 105

8.7 0.1

0.20

12.1

3.35 105

8.2 0.1

0.26

12.9

a PO

function fitting the experimental points. This fit was made using least squares with
2 minimization. Some important features can be observed in the figure: firstly, the
curve fits very well the value of the thermal diffusivity of the pure palm olein when
no -carotene was dissolved, in total agreement with the value found through Fig. 2.
Another feature is that the exponential function has the form,
D(c) = D(0)ec/

(3)

where D(0) is the thermal diffusivity at zero concentration, c is the concentration of

the solutions, and inverse is a constant of exponential growth.
Analyzing the dependence of the thermal diffusivity of edible vegetable oils on
temperature, Lima et al. [23] pointed out that both the composition and microstructure
of the oils affect the value of this thermal property. So, the addition of -carotene in
palm oil diminishes the time of formation of the thermal lens. This can be observed
in Table 2, where the characteristic time diminishes with an increase of the concentration. One assumes here that the enhancement of the observed thermal diffusivity is
due to the delocalized -electrons in the principal chain of the -carotene molecules.
These electrons could be excited by the laser at 532 nm without strong absorption, and
they should be responsible to transfer some energy to the other molecular specimens
in their neighborhood. Nonradiative decay of these excited molecules is responsible
for the rise in temperature and, consequently, for the enhancement of the thermal
diffusivity. A saturation of the exponential growth behavior would be expected but
could not be observed due to limitations of the experimental conditions imposed by
the theoretical model. For high concentrations, -carotene absorbs too much energy
from the pumping laser and the theoretical model loses its validity.
5 Conclusions
The thermal diffusivity of palm olein, one of the more important vegetable oils used
worldwide, and compounds of palm olein and -carotene were measured. The best
fit of the theoretical function for the LT signal of the laser probe in the photodetector
results in a thermal diffusivity D = 11.9 104 cm2 s1 , which is the same order as
other vegetable oils reported in the literature [7,8,17]. An exponential enhancement
in the thermal diffusivity was observed when the concentration of -carotene in the

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Int J Thermophys (2011) 32:19661972

samples was increased. This behavior can be attributed to the number of delocalized
-electrons in the principal chain of the -carotene molecules that could be excited
by the laser excitation at 532 nm without strong absorption, but should be responsible
to transfer energy to the other molecular species in their neighborhood. Nonradiative decay of these excited molecules will be responsible for the enhancement in the
temperature and, consequently, for the increase of the thermal diffusivity.
Acknowledgments The authors thank Agropalma (PA, Brazil) for supplying palm olein. A.J.F.C. thanks
the CAPES Agency for a grant for this work. The financial support from CAPES (Proequip 1074/2007),
CNPq, and FAPESPA (Projeto 112/08) is gratefully acknowledged.

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