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Vibrational Spectroscopy 54 (2010) 118–122

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Vibrational Spectroscopy
journal homepage: www.elsevier.com/locate/vibspec

Pressure-induced phase transitions in stearic acid C form


F.F. de Sousa a,b , P.T.C. Freire a , G.D. Saraiva c,∗ , J.A. Lima Jr. a , P. Alcantara Jr. d ,
F.E.A. Melo a , J. Mendes Filho a
a
Departamento de Física, Universidade Federal do Ceará, 60.455-970 Fortaleza, CE, Brazil
b
Faculdade de Ciências Naturais, Universidade Federal do Pará, 68.505-080 Marabá, PA, Brazil
c
Faculdade de Educação Ciências e Letras do Sertão Central, Universidade Estadual do Ceará, 63.900-000 Quixadá, CE, Brazil
d
Faculdade de Física, Universidade Federal do Pará, 66.075-110 Belém, PA, Brazil

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

Article history: Pressure-dependent Raman scattering studies have been performed on stearic acid single crystal, C form.
Received 18 January 2010 The vibrational spectra have been recorded in the 20–1200 cm−1 and in the 2800–3100 cm−1 spectral
Received in revised form 21 June 2010 regions. The behavior of the Raman modes indicates that the crystal undergoes a series of structural
Accepted 22 June 2010
modifications. The change observed between 0.8 and 1.27 GPa was associated with a conformational
Available online 30 June 2010
modification or tilting of the dimer. A second modification was observed at ∼2.5 GPa accompanied by
jump of lattice mode frequencies, and the appearance and disappearance of bands. Finally, a third set
Keywords:
of changes in the Raman band profile was observed between 3.3 and 3.8 GPa and was associated with
Organic crystals
Phase transition
another structural phase transition.
Inelastic light scattering © 2010 Elsevier B.V. All rights reserved.

1. Introduction Many polymorphs of SA crystals are known: the A form crys-


tallizes in a triclinic structure; the B and C forms crystallize with a
Fatty acids have received much attention from the scientific monoclinic symmetry and the E form crystallizes in an orthorhom-
community due to their fundamental properties, with interest for bic structure [12–15]. Vogel-Weill and Corset [16] have reported a
science and technology [1–3]. They are significantly important in comparative study of the infrared and the Raman spectra of fatty
the field of food, pharmaceuticals and cosmetics, as well as, in acids of long chains in the C form with an even number of carbon
medicine. They also play fundamental roles in human nutrition atoms (C12 –C26 ) varying the temperature from 300 to 90 K. An arti-
because they are the main source of energy for the body. The cle in the literature reports a study of the vibrational properties of
functional activity of biological membranes, for example, depends SA crystals in the C form with calculations and experimental results
on the amount and the type of fatty acids in phospholipids, and [17].
the major part of them contains both one saturated and one cis- Here we report a Raman investigation of SA in the C form under
unsaturated fatty acid at the first and second positions of the high-pressure conditions 0.0–9.0 and 0.0–10.4 GPa in the spec-
glycerol skeleton [4–6]. tral regions from 20 to 1200 cm−1 (the region 1200–1400 cm−1
Many experimental techniques such as differential scanning was not investigated due the C–C stretching mode of diamond
calorimetry (DSC), Fourier-transform (FT) Raman spectroscopy and of the anvil cell [18]) and 2800–3100 cm−1 , respectively. To the
infrared spectroscopy, have been used in the last years to charac- best of our knowledge, Raman spectroscopy has never been used
terize the composition of substances found in fatty acids, to search for pressure-dependent studies of stearic acid substances. So, we
for polymorphism and phase transitions in crystals obtained from investigate the influence of high hydrostatic pressure on a sin-
these substances [7–9] and to furnish quantitative data about the gle crystal of SA, by analyzing the low and the high-frequency
constituents of the fatty acids, among others. From the point of regions of the Raman spectra in order to extend our understanding
view of vibrational spectroscopy some works focused on studying about the vibrational properties of SA. Special attention to both
mixtures of ceramide, palmitic and stearic acids (SA) and choles- the pressure-induced phase transitions and the conformational
terol [10] and recently, the infrared absorption technique was used changes of the molecules in the unit cell is given in the present
to identify the constitution of each majority fatty acid in buriti oil work.
(Mauritia flexuosa L.) [11].
2. Experimental

∗ Corresponding author. Tel.: +55 88 34451036; fax: +55 85 33669450. Stearic acid was purchased from Merck (USA) and used with-
E-mail address: gilberto@fisica.ufc.br (G.D. Saraiva). out further purification. The single crystals of SA in the C form

0924-2031/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.vibspec.2010.06.008
F.F. de Sousa et al. / Vibrational Spectroscopy 54 (2010) 118–122 119

investigated in this paper were crystallized by slow evaporation


of chloroform solution at controlled temperature (16 ◦ C); samples
were obtained as transparent tiny platelets in the lozenge shape.
The high-pressure Raman spectra were recorded with a Jobin Yvon
T64000 spectrometer, equipped with a N2 -cooled Charge Coupled
Device (CCD) detection system. The laser excitation was supplied
by the line 514.5 nm of an Argon ion laser. An Olympus microscope
lens with a focal length of 20.5 mm and a numeric aperture of 0.35
was used to focus the laser on the sample surface. High-pressure
Raman experiments from 20 to 1200 cm−1 were performed using
a diamond anvil cell (DAC) with mineral oil as transmitting fluid
and the high-pressure Raman experiments from 2800 to 3100 cm−1
were performed using a membrane diamond anvil cell (MDAC) [19]
with argon [20] as pressure-transmitting medium in order to avoid
the Raman bands of nujol in the high-frequency region. A stainless-
steel gasket (200 ␮m of thickness preindented to 40 ␮m and with
a 150 ␮m-diameter hole) was filled with a small sample and a ruby
chip, in order to calculate the pressure [21,22]. Raman spectra were
measured with increasing pressures from atmospheric pressure up Fig. 2. Raman spectra of SA in the C form in the spectral range 20–230 cm−1 at room
temperature with deconvolution of the modes.
to 9.0 GPa and then decreasing from 9.0 GPa to atmospheric pres-
sure. The X-ray diffraction (XRD) patterns were obtained using a
Rigaku powder diffractometer with a Bragg–Brentano geometry. A frequency region the bands are associated to the lattice modes or
Cu–K␣ radiation source was used and operated at 40 kV and 25 mA. described as intermolecular vibrations related to the vibrations of
The XRD measurements were taken in the 2 range of 3–45◦ using the chain and some contributions of the hydrogen bonds [16,17].
step scan procedure (0.02◦ ) for counting times of 5 s. For the intermediate frequency region, De Gelder et al. [25] assigned
the band at approximately 890 cm−1 as originated from the rocking
3. Results and discussion vibration of CH2 and bands between 1050 and 1150 cm−1 as being
originated from stretching of CC bond. Therefore we assigned the
Stearic acid (C 18:0, octadecanoic acid) is a fatty saturated acid band 894 cm−1 as rocking of CH2 and the peaks observed at 1064,
with molecular structure (CH3 –(CH2 )16 –COOH) constituted of car- 1105, and 1132 cm−1 as stretching of CC.
bon atoms linked to each other through single bonds (Fig. 1). In Fig. 2 shows the pressure–Raman spectra of SA for the low-
order to characterize the phase of the material, XRD measurements frequency region from 20 to 230 cm−1 spectral range. The spectrum
at room temperature were performed. The crystal structure was of the lattice mode of the stearic acid was decomposed into eight
found to belong to the P21 /a (C2h 5 ) space group of monoclinic sym- Lorentzian peaks. The choice of eight peaks resulted in a very good
metry with four formula units with trans conformation per unit cell. fitting and the resulting frequencies are listed in Table 1. The exper-
The unit cell parameters a, b and c are nearly equal to 9.51, 4.95, and imental lattice frequencies obtained for the stearic acid are plotted
51.40 Å and ˇ = 129.6 ◦ C confirming the occurrence of the C form in Fig. 3(b) as solid dots and the fits as dotted lines; the error bars are
[23]. The dimers are arranged so as to exhibit terminal methyl and also shown in Fig. 3(b). The experimental frequencies are closer to
terminal carboxyl group monolayers parallel to the (0 0 1) plane the calculated frequencies. Many changes in the mode frequencies
[15]. are observed as well as appearance, disappearance and splitting
The optical modes are distributed among the irreducible rep- of modes. These very clear changes can be associated with phase
resentations of the C2h factor group as  op = 168Ag + 168Bg [24]. transitions. The bands located at 47, 53, 66 and 72 cm−1 change
We have performed Raman experiments on stearic acid crystal at slopes at 1.3 GPa, and show a discontinuity near 2.4 GPa. The first
room temperature and varying the pressure up to 9.0 GPa. In this two modes overlap in a new mode at about 3.8 GPa, the third mode
range, several strong modifications were observed in the spectra disappears above 3.3 GPa and the fourth mode presents a new
with increasing pressure. At room temperature and atmospheric discontinuity between 3.3 and 3.8 GPa. The modes located at 94
pressure only twelve peaks were observed for the spectral range and 148 cm−1 disappear for pressures higher than 0.8 and 1.3 GPa,
from 20 to 1200 cm−1 (see Figs. 3 and 4a) and seven peaks appear respectively. The mode at 164 cm−1 shows a discontinuity around
between 2800 and 3200 cm−1 . 1.2 GPa and disappears for pressures above 2.0 GPa. Finally, a new
The discussion of the vibrational properties of SA at atmospheric mode with frequency at 145 cm−1 appears at about 0.8 GPa and
pressure is based on the analysis of the modes for the low, inter- takes a slight discontinuity at 2.0 GPa. The frequency (ω) vs. pres-
mediate and high-frequency regions, from 20 to 230 cm−1 , 1000 sure (P) plots in Fig. 3b present a series of discontinuities during
to 1200 cm−1 and 2800 to 3100 cm−1 , respectively. For the low- the high-pressure experiment for all lattice modes. These discon-
tinuities are remarkable once these peaks are associated with the
lattice modes; such a feature suggests some kind of modification
in the crystal structure of SA. In fact, as it is well known for several
organic crystals, the modification of lattice modes (frequency jump,
change of dω/dP or modification in the number of bands) can be
only explained (if the material does not have ferroelastic domains)
as phase transition undergone by crystal [26,27]. For adjusting the
experimental frequency values a linear fitting (ω = ω0 + ˛P) in the
pressure regions before and after these discontinuities was used.
Information on ω0 and ˛ for several modes is given in Table 1.
The dashed lines in Fig. 3b delimited the range of pressure where
structural changes occurred. We can note that the pressure depen-
Fig. 1. Molecular structure of stearic acid. dence of frequency in phase I from 0 up to 1.27 GPa is strong for
120 F.F. de Sousa et al. / Vibrational Spectroscopy 54 (2010) 118–122

Table 1
Experimental values (ωexp ) of the frequency of the modes of SA in the C form at 0, 0.5, 1.2, 2.0, 2.4, 3.1, 3.82, 4.2, 5.0, 6.8 and 7.9 GPa (in cm−1 ), and coefficients of the linear,
˛ (cm−1 /GPa) and quadratic equation (ω0 in cm−1 , ˛ in cm−1 /GPa, and ˇ in cm−1 /GPa2 ) fittings.

Assignments ωexp ω0 ˛ ωexp ω0 ˛ ωexp ω0 ˛ ωexp ω0 ˛


(0 GPa) (0 ≤ P ≤ 1.27) (1.27 GPa) (1.27 ≤ P ≤ 2.07) (2.47 GPa) (2.47 ≤ P ≤ 3.26) (3.82 GPa) (3.82 ≤ P ≤ 8.8)

ω = ωo + ˛P
Lattice 47 47 13.5 63 56 5.8 61 50 4.5 70 66 1.30
Lattice 53 52 14.3 71 64 5.3 74 70 1.5
Lattice 66 64 26.3 98 85 9.6 112 88 9.4
Lattice 72 71 28 107 96 8.3 122 98 9.6

Lattice 94 92 21.6 138 136 0.87


145 133 15.1 161 154 3.7 168 154 3.77

Lattice 148 148 10.0


Lattice 164 164 17.8 178 168 7.9
Assignments ωexp (0 GPa) ω0 ˛ (0 < P ≤ 8.8) ωexp (1.27 GPa) ω0 ˛ (1.27 ≤ P ≤ 8.8)

ω = ω0 + ˛P
(CC) 1064 1067 3.57
1084 1073 5.05
(CC) 1105 1107 3.17
(CC) 1132 1134 3.47
1176 1176 0.38
Assignments ωexp (0 GPa) ω = ω0 + ˛P + ˇP2 ω = ω0 + ˛P

ω0 ˛ ˇ ωexp (3.82 GPa) ω0 ˛ (3.82 ≤ P ≤ 8.8)

ı(CH2 ) 894 893 11.25 -1.128 920 906 3.49


Assignments ωexp (0.5 GPa) ω0 ˛ (0.5 < P ≤ 4.2) ωexp (5.0 GPa) ω0 ˛ (5.0 ≤ P ≤ 10.4)

ω = ω0 + ˛P
Stretching of CH, CH2 , CH3 region 2855 2852 7.34
2881 2872 2.07
2878 2874 8.31
2913 2890 4.62
2888 2884 11.20
2937 2899 7.80
2905 2900 11.39
2973 2918 8.1
Assignments ωexp (0.5 GPa) ω0 ˛ (0.5 < P ≤ 1.4)

ω = ω0 + ˛P
Stretching of CH, CH2 , CH3 region 2910 2901 19.35
Assignments ωexp (2.0 GPa) ω0 ˛ (2.0 < P ≤ 5.6)

ω = ω0 + ˛P
Stretching of CH, CH2 , CH3 region 2934 2911 10.65
Assignments ωexp (7.9 GPa) ω0 ˛ (7.9 < P ≤ 10.4)

ω = ω0 + ˛P
Stretching of CH, CH2 , CH3 region 2997 2942 7.05
Assignments ωexp (3.1 GPa) ω0 ˛ (3.1 < P ≤ 5.6)

ω = ω0 + ˛P
Stretching of CH, CH2 , CH3 region 2964 2924 12.43
Assignments ωexp (0.5 GPa) ω0 ˛ (0.5 < P ≤ 1.4) ωexp (6.8 GPa) ω0 ˛ (6.8 < P ≤ 10.4)

ω = ω0 + ˛P
Stretching of CH, CH2 , CH3 region 2935 2929 13.55 3006 2937 10.00
Assignments ωexp (0.5 GPa) ω0 ˛ (0.5 < P ≤ 1.4) ωexp (5.0 GPa) ω0 ˛ (5.0 ≤ P ≤ 10.4)

ω = ω0 + ˛P
Stretching of CH, CH2 , CH3 region 2995 2943 10.53
2951 2944 14.57
3015 2961 10.79

all lattice modes described above. The large pressure shifts of the transition as discussed before. The shift of the Raman modes to
mode energies in the low-frequency region are due to the fact that higher frequencies (for stretching vibration of CC) indicates that the
the pressure should greatly decrease the intermolecular distances increase of pressure results in an increase of interactions between
while the interatomic separations of each molecule are only slightly CC atoms and in a decrease of some CC bond lengths. In fact, if the
decreased. structure is greatly modified due to the application of pressure and
The effects of hydrostatic pressure on the vibrational properties if a strong change occurs in the intermolecular distances, the crystal
of this compound in the intermediate frequency region are shown must adapt itself to a new configuration and its symmetry must be
in the Fig. 4. Also, on applying pressure the bands located at 1064 changed. Associated with these changes, drastic modifications in
and 1132 cm−1 change intensities. This behavior could be related the external mode region of the Raman spectra will be observed in
with a partial rotation of the molecule with increasing pressure and most cases, as have been verified for some organic crystals, such as
the split of the mode could be associated with a first-order phase amino acid [26,27]. The peak located at 894 cm−1 is related with the
F.F. de Sousa et al. / Vibrational Spectroscopy 54 (2010) 118–122 121

Fig. 3. (a) Raman spectra of SA in the C form in the spectral range 20–230 cm−1 at several pressures values. (b) Wavenumber vs. pressure plot in the same region of (a).

Fig. 4. (a) Raman spectra of SA in the C form in the spectral range 1000–1200 cm−1 at several pressures values. (b) Wavenumber vs. pressure plot in the same region of (a).

bending mode ı(CH2 ) and the experimental frequency was fit to a Because this region gives information about the conformation
second order polynomial (ω = ω0 + ˛P + ˇP2 ) in the pressure region of molecules in the unit cell we observe that a slight conforma-
before discontinuity. tional change occurs for pressures between 4 and 4.5 GPa. This
Fig. 5 presents the Raman spectra of stearic acid crystal in the is understood due the change of dω/dP for some peaks in this
spectral region between 2800 and 3100 cm−1 . The bands appearing spectral region. Such a conformational change, however, is not
in this region are associated with CH, CH2 and CH3 groups. associated with any structural phase transition because no mod-

Fig. 5. (a) Raman spectra of SA in the C form in the spectral range 2800–3100 cm−1 at several pressures values. (b) Wavenumber vs. pressure plot in the same region of (a).
122 F.F. de Sousa et al. / Vibrational Spectroscopy 54 (2010) 118–122

ification is observed for lattice vibration modes in this pressure Acknowledgments


range.
So, there are three pressure ranges (values) where the frequen- G.D.S. and J.A.L. thank support from MCT/CNPq Edital 14/2008
cies of the modes, mainly in the low-frequency region, change (process 480364/2008-7) and FUNCAP/Edital 05/2009 (process
behavior. The first modification, occurred between 0.8 and 1.2 GPa, 186.01.00/09). The authors also thank the Brazilian institutions
can be understood as due to a rotation or twisting of the molecule CAPES and FUNCAP.
in the unit cell altering dimer configuration. For pressures higher
than 2.47 GPa the crystal undergoes a first-order phase transition. References
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