Fuel 212 (2018) 309–314

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Fuel
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Full Length Article

Determination of the biodiesel content in diesel/biodiesel blends by using MARK

the near-near-infrared thermal lens spectroscopy
⁎
M. Venturaa, W.B. Deusa, J.R. Silvaa, L.H.C. Andradea, T. Catundab, S.M. Limaa,
a
Grupo de Espectroscopia Óptica e Fototérmica, Programa de Pós-Graduação em Recursos Naturais, Universidade Estadual de Mato Grosso do Sul, CP 351 Dourados, MS,
Brazil
b
Instituto de Física de São Carlos, Universidade de São Paulo, São Carlos, SP, Brazil

G RA P H I C A L AB S T R A C T

A R T I C L E I N F O A B S T R A C T

Keywords: A dual-beam mode-mismatched configuration of the Thermal Lens (TL) technique was applied to characterize
Near-near infrared biodiesel, diesel and diesel/biodiesel blends. The excitation was performed using a tunable laser in the near-near
Thermal Lens Spectroscopy infrared region in order to assess overtones and combination bands of the vibration modes. The thermo-optical
Diesel/biodiesel blends properties of the fuels were also determined. The results showed that the biodiesel contents in diesel/biodiesel
Thermal diffusivity
blends can be monitored with this technique, by excitation the third overtone of the C–H (4ν(C–H)) bond
stretching vibration at 916 nm. Both the amplitude of the photothermal signal and thermal diffusivity are im-
portant parameters to quantify the biodiesel content in diesel/biodiesel blends.

1. Introduction
The use of alternative fuels is growing on the world in the last few
years. The biodiesel produced from vegetal or animal fats have being
the main substitute for petroleum-derived diesel fuel due to some fac-
tors, such as high combustion efficiency, lower sulfur content, excellent
lubricity and high cetane number [1,2]. In addition, its economic and
environmental advantages can be highlighted [1–3]. Since biodiesel is
completely miscible in diesel fuel and have similar properties, the use of
diesel/biodiesel blends in different proportions is increasing, mainly in
Brazil. Currently, the National Energy Policy Council has approved the
addition of 8% (v/v) of biodiesel in diesel oil for commercial use [4]. In
this context, it becomes necessary to develop or improve methods able
to provide fast and efficient results on the biodiesel content in diesel/
biodiesel blends, in order to control the quality of the commercialized
product.

⁎
Corresponding author at: Universidade Estadual de Mato Grosso do Sul – UEMS, Programa de Pós-Graduação em Recursos Naturais – PGRN, Grupo de Espectroscopia Óptica e
Fototérmica – GEOF, CEP 79804-970 – C.P. 351, Dourados, MS, Brazil.
E-mail address: smlima@uems.br (S.M. Lima).

http://dx.doi.org/10.1016/j.fuel.2017.10.069
Received 6 September 2017; Accepted 12 October 2017
0016-2361/ © 2017 Elsevier Ltd. All rights reserved.
M. Ventura et al. Fuel 212 (2018) 309–314

A variety of analytical techniques have been developed for the
quantification of biodiesel content in diesel/biodiesel blends [5–8],
among them, spectroscopic methods involving absorption [9–11] and
fluorescence [12]. Infrared (IR) spectroscopy is a reliable and non-de-
structive analytical technique appropriate for these applications.
However, in the NIR spectral range (780–2500 nm) the absorptions of
the overtones and combination bands of biofuels are broad, with low
absorption coefficients, becoming hardly selective. In addition, differ-
ences among samples may cause very subtle spectral differences that
are difficult to distinguish without a statistical interpretation [13].
Thus, chemometric methods need to be applied to extract information
from NIR spectra obtained with transmittance technique, in order to
determine some quality parameters in biodiesel and diesel/biodiesel
blends [11].
The Thermal Lens (TL) spectrometry is a time-resolved photo-
thermal technique that has been applied in the characterization of oil,
biodiesel, biodiesel/oil and diesel/biodiesel blends [14–17]. Castro
et al. were the first to use TL in the study of physico-chemical properties
of biodiesel and certification purposes [18]. As an ultra-sensitivity
technique, TL enable the study of samples with very small optical ab-
sorptions (< 10−8 cm−1 in liquids) [19–23]. It is also attractive be-
cause it is neither destructive nor invasive, so it could be used at gas
stations to monitor the quality of oils and biofuels. Besides, the thermo-
optical properties can be directly determined, without the requirement
of any statistical analysis. In 1976, Long et al. [19], firstly demonstrated
the application of TL as a spectroscopic technique, using a tunable dye
laser in the visible range (637–575 nm). Swofford et al. obtained the
absorption spectra of benzene, naphthalene and anthracene corre-
sponding to the fifth overtone of the CeH stretching vibrations, with
absorptions coefficients as small as 10−6 cm−1 [20]. More recently, the
absorption of overtones and combination bands of sulfentrazone pes-
ticide in the near-near infrared (N-NIR) region were evaluated by the TL
spectroscopy, using a Ti3+:Sapphire laser [21]. In this paper, a marker
for the pesticide in methanol was identified, enabling the determination
of very low concentrations (∼2 ng/μL).
The goal of this work is to apply the TL technique, in both spec-
troscopic and spectrometric forms, in biodiesel, diesel and diesel/bio-
diesel blends in order to obtain their absorption spectra and thermo-
optical properties. The dual-beam mode-mismatched TL configuration
was set with excitation in the N-NIR region (860–980 nm). The ab-
sorptions bands were assigned to vibrations of overtones and combi-
nation bands of CeH stretching bonds. This electromagnetic region is
interesting comparable to the visible one, due to be absence of laser-
induced of photochemical reactions or Soret effect (mass diffusion) that
can affect the TL signal [22].
2. Materials and methods
The samples of methyl biodiesel (B100), S-10 and S-500 diesel types
(B0) used in this research are commercially available in Brazil. The
diesel/biodiesel blends were prepared by us according to the con-
centrations indicated in Table 1. The Brazilian National Agency of
Table 1
Concentrations of biodiesel (B100), diesel oil (B0) and diesel/biodiesel blends used in the
Petroleum, Natural Gas and Biofuels [24] has the following classifica-
tion: types A (without biodiesel) and B (diesel/biodiesel blends). Both
diesel types can be S-10 or S-500, according to the sulfur content in the
fuel, 10 or 500 mg/kg, respectively.
The mid-infrared (MIR) absorption spectra, in the range from 4000
to 400 cm−1, were obtained with a Fourier transform infrared (FTIR)
spectrophotometer Nexus 670 from Thermo Nicolet, coupled to an at-
tenuated total reflectance accessory (ATR – Nexus Smart ARK). The
spectrophotometer was purged with dry air to remove any water vapor
and the detector was cooled with liquid Nitrogen. The measurements
were performed using 0.5 cm−1 of resolution and 16 scans.
Absorption measurements in the NIR spectral region (780–2500 nm)
were performed using transmittance spectrometer (NIRQUEST by
Ocean Optics), with a tungsten lamp and an of 300 μm diameter optical
fiber (TP300-VIS-NIR). The absorption spectra were collected with
500 ms integration time and average of 5 spectra per collection.
The TL experimental setup in the dual-beam mode-mismatched
configuration is shown in Fig. 1. In this configuration, the sample was
inserted in a quartz cuvette with L = 1 mm thickness, placed in the
position of minimum waist (woe) of the excitation beam, a
Ti3+:Sapphire laser pumped by a 532 nm semiconductor. The TL effect
was probed by a 632.8 nm HeNe laser, which passes through the sample
almost collinear through the excitation beam. Both beams are nearly
TEMoo Gaussian.
In the TL experiment the excitation induces a refractive index pro-
file which results in a lens like effect. In most liquids, dn/dT is negative,
so sample behaves like a divergent lens. The theoretical model for the
mode-mismatched TL experiment was developed by Shen et al. [25].
According to this model, the on-axis transient intensity of the probe
beam, I(t), can be expressed by:
2
⎧⎡
⎪ ⎛ ⎞⎤⎪⎫
θ 2mV
I (t ) = I (0) ⎢1− tan−1 ⎜ ⎟⎥
⎨⎢ 2
⎪
⎩⎣
⎜ [(1 + 2m) + V ]
⎝
2 2 t
( )
2t
c
+ [1 + 2m + V ] ⎟ ⎬
2 ⎥
⎠⎦⎪⎭
(1)
in which I(0) is the intensity when t = 0 or θ = 0, m and V are intrinsic
geometric parameters from the probe and excitation lasers (see Ref.
[26] for details). In Eq. (1) tc = woe2 /4D is the TL characteristic time
constant; woe (cm) is the waist of the excitation beam in the sample
position and D (cm2 s−1) is the thermal diffusivity. The amplitude of the
TL signal is proportional to the parameter θ, which is approximately to
the probe beam thermally induced phase difference and is given by
[25,26]:
PAL ⎛ dn ⎞
θ=−
λp K ⎝ dT ⎠ (2)
−1
in which P (W) is the excitation power, A (cm ) is the absorption
coefficient at the excitation wavelength, λp (cm) is the probe wave-
length, L (cm) is the cuvette thickness, dn/dT (K−1) is the thermo-op-
tical coefficient at the probe beam wavelength and K = ρCD is the
thermal conductivity (Wcm−1K−1), ρ (gcm−3) is the volumetric density
of the sample and C (Jg−1K−1) is the specific heat. With these defini-
tions it is possible to rewrite Eq. (2) as:
PAL ⎛ dn ⎞
θ=− ⎜ ⎟

study. Two sets of samples were prepared with both S-10 and S-500 diesel types. λp D ⎝ dQ ⎠ (3)
dn 1 dn
Biodiesel mL (%) Diesel mL (%) Diesel/Biodiesel Blends with dQ
= ρC dT
defines how the refractive index changes with the heat
deposited per unit volume in the sample.
0 (0) 20 (100) B0 (diesel)
1 (5) 19 (95) B5
Fig. 2 presents a typical normalized TL transient signal, I(t)/I(0),
2 (10) 18 (90) B10 obtained for the S-10 diesel with P = 4 mW and λexc = 916 nm. The
3 (15) 17 (85) B15 experimental data were fitted with Eq. (1) from which two parameters
4 (20) 16 (80) B20 were determined: tc = (40 ± 2) ms and θ = (0.151 ± 0.003) rad.
6 (30) 14 (70) B30
From tc and woe = 119 µm, the thermal diffusivity DB0(S-
10 (50) 10 (50) B50 −3
20 (100) 0 (0) B100 (biodiesel) 10) = (0.89 ± 0.01) × 10 cm2 s−1 was calculated. The value dn/
−4 3 −1
dQ = −2.45 × 10 cm J was obtained using the following

310
M. Ventura et al. Fuel 212 (2018) 309–314

Fig. 1. Dual-beam mode-mismatched TL experi-

mental configuration: L’s are lenses, M’s are mir-
rors and Ph’sare photodetectors.

1.00 The measurements were performed scanning the Ti3+:Sapphire laser in

Sample: S-10 diesel
the range 860–970 nm (N-NIR), in steps of ∼3 nm. The MIR (Fig. 3.a)
Experimental data spectra shows absorption peaks due the fundamental vibrations of
Theoretical fit symmetrical and asymmetric stretching of CeH bonds of methylene and
0.96 methyl groups, characteristic of normal alkanes. In the NIR and N-NIR
I(t)/Io

spectral regions, the absorption peaks are attributed to 1st(2ν), 2nd(3ν)

0.92
0.88
0.0 0.3 0.6 0.9
Time ( s )
Fig. 2. Characteristic thermal lens transient signal for S-10 diesel sample (open balls) and
the theoretical fit curve with Eq. (1) (solid line). The used experimental parameters were:
m = 13; V = 3.88; P = 4 mW; λexc = 916 nm; λp = 632.8 nm; and L = 1 mm.
literature values for S-10 diesel fuel: ρ = 0.830 g cm−3 [27], C = 2.0 J/
g K [28] and dn/dT = -4.1 × 10−4 K−1 [29]. Them, inserting our θ and
D data in Eq. (2) we obtained A = 0.87 × 10−3 cm−1 at 916 mn. As
observed before [19,20], the absorptions of the overtones in N-NIR are
very small, difficult to be detected by standard transmission experi-
ments.
Alternatively, the absorption spectrum can be obtained using TL
steady-state procedure. In this case, only the initial and final time signal
are registered, I (t = 0) and I (t = ∞) , so that by Eq. (1), θ can be ob-
tained by:
2
θ 2mV
I (∞) = I (0) ⎡1− tan−1 ⎛ ⎞⎤
⎢ 2
⎣ ⎝ 1 + 2m + V 2 ⎠ ⎦
⎥ (4)
In fact, very good agreement was obtained in the θ values de-
termined by both procedure (steady-state or time-resolved). However,
the steady-state procedure is faster and more convenient in spectro-
scopic measurements aimed to achieve the absorption spectrum in a
wide excitation range.
3. Results and discussion
Fig. 3 presents the MIR (a), NIR (b and c) absorbance spectra of
biodiesel (B100), S-10 and S-500 diesels (B0). Fig. 3.d presents TL
spectra in the steady-state regime with P ∼ 10 mW of excitation power.
and 3rd(4ν) overtones of the CeH stretching vibration. As expected, the
absorption peaks of overtones are broader than the fundamental ones
(MIR), so their peak absorptions are lower by one order of magnitude
[13,30].
From the average CeH vibrational frequencies of first (2ν) and
second (3ν) overtones, the anharmonicity constant (χ) was determined
according to the Groh’s model [31]:
v1 m−v1 χm (m + 1)
vm =
1−2χ (5)
In this equation, vm is the frequency of the mth overtone (m = 2,3,4,
…) andv1 is the position of the fundamental vibration. For instance, in
the case of B100 the first overtone (m = 2) is observed at
v2 = 5711 cm−1 and the second (m = 3) at v3 = 8390 cm−1 (Fig. 3.b
and 3.c, respectively). Inserting v2 and v3 in Eq. (5) and solving the
equation system, χ = (1.9 ± 0.1) × 10−2 and the fundamental fre-
quency v1c = 2914 cm−1 were calculated. These values are in very good
agreement with the literature value (χ = 1.9 × 10−2) [31] and
v1exp = 2910 cm−1, observed in the MIR spectrum (Fig. 3.a). From this
result is possible to obtain all overtones up to the dissociation energy
(De) of the CeH bond. This procedure was adopted for all samples, as
shown in Table 2. It can be observed that the χ values of diesel and
biodiesel are very similar, and De are higher than ∼34,000 cm−1,
correspond to the ultraviolet spectral region (291–266 nm). The accu-
racy of our experimental procedure can be inferred from the excellent
agreement between v1c and v1exp (within 0.4%).
Using χ and v1 obtained above in Eq. (5) with m = 4, we calculated
v4c (the third overtone) in good agreement with the experimental line
center value, v4exp , form the TL spectra (Fig. 3.d) as shown in Table 2.
The absorption bands around 11,200 and 11,360 cm−1 could be as-
signed as a combination band between the third overtone of the CeH
stretching vibration and the fundamental vibration of the symmetric
angular deformation of the methylene group CeH:
4ν(CeH) + 1δ(CeH).
Fig. 4 shows the N-NIR TL spectra (θ/P) for the B0, B5, B10 and
B100 samples, prepared with S-10 (Fig. 4.a) and S-500 (Fig. 4.b) die-
sels. The assignments of all bands are the same as discussed for Fig. 3.d.

311
M. Ventura et al. Fuel 212 (2018) 309–314

B100

νas (CH2)
B100 2ν (C-H)
B0 (S-10) (a) MIR B0 (S-10) (b) NIR
0.6
2 B0 (S-500) B0 (S-500)

νs (CH2)
Absorbance

νas (CH3)

Absorbance
νs (CH3)
0.4

1
0.2

0 0.0
2800 2900 3000 5200 5600 6000 6400
-1 -1
Wavenumber ( c m ) Wavenumber ( cm )

0.12 B100 B100

(c) NIR 0.012 4ν (C-H) (d) N-NIR (TL) 50
B0 (S-10) 3ν (C-H) B0 (S-10)
B0 (S-500) B0 (S-500)
40
0.08
Absorbance

Αbsorbance
0.008

θ /P ( W )
30
4ν (C-H) + 1δ (C-H)

0.04 20
0.004

-1
10

0.00 0.000 0
8000 8400 8800 10400 10800 11200 11600
-1 -1
Wavenumber ( cm ) Wavenumber ( cm )
Fig. 3. Absorbance spectra of biodiesel (B100), S-10 and S-500 diesel (B0) in the MIR region (a), obtained with FTIR-ATR; in the NIRregion (1st overtone(b) and 2nd overtone (c)),
acquired with conventional transmittance spectroscopy; and in the N-NIR region (3rd overtone(d)) obtained by TL technique in the steady-state. ν corresponds to the stretching
vibrational mode and δ corresponds to the symmetric angular deformation vibrational mode.

Table 2 In Fig. 4 it is observed that θ/P parameter decreases strongly with the
Anharmonicity constant (χ) and the dissociation energy (De) of the CeH functional group increase of biodiesel content in diesel. In order to clarify this behavior,
for each sample obtained by Eq. (5). time-resolved TL measurements were performed as a function of bio-
Sample χ v1c v1exp v4c v4exp De
diesel content, with excitation wavelength fixed at λexc = 916 nm, as
shown in Fig. 5. Each data point resulted from an average of eight
(10−2) (cm−1) (cm−1) (cm−1) (cm−1) transient signals, similar to the one shown in Fig. 2, with different ex-
citation powers. The linear dependence of θ with the excitation power
B100 1.9 ± 0.1 2914 2910 10,950 10,790 37,622 266
B0 (S-10) 2.1 ± 0.1 2918 2906 10,898 10,830 34,410 291
(P) was verified in all samples. The determined values for diesel and
B0 (S-500) 2.1 ± 0.1 2919 2907 10,902 10,870 34,532 290 biodiesel were: DB0(S-10) ] (0.89 ± 0.01), DB0(S-500) ] (0.90 ± 0.01),
DB100 ] (1.07 ± 0.01) × 10−3 cm2 s−1. The biodiesel value (DB100) is
in agreement with previous measurements in different vegetable oils

Wavelength ( nm ) Wavelength ( nm )
960 930 900 870 960 930 900 870

50 (a)
B0 (S-10) 50 B0 (S-500)
B5 (S-10) (b) B5 (S-500)
B10 (S-10) B10 (S-500)
40 B100 40 B100
θ /P ( W )
θ /P ( W )

-1
-1

30 30

20 20

10 10

0 0
10400 10800 11200 11600 10400 10800 11200 11600
-1 -1
Wavenumber ( cm ) Wavenumber ( cm )
Fig. 4. θ/P spectra (proportional to the absorbance) in the N-NIRregion obtained with the TL technique in the steady-state for diesel, biodiesel and diesel/biodiesel blends. In (a) are the
spectra obtained with S-10 diesel and in (b) with S-500 diesel.

312
M. Ventura et al.
% Diesel S-10
100 80 60 40 20
40
35
θ /P ( W-1 )
(a)
30 λe = 916 nm
25
20
0 20 40 60 80
% Biodiesel
Fig. 5. θ/P and thermal diffusivity values obtained for diesel, biodiesel and diesel/biodiesel blends with S-10 (a) and S-500 (b) diesel.
[18], within the range (1.03 – 1.17) × 10−3cm2s−1. The D values of S-
10 and S-5 diesels are very similar but ∼15% smaller than the biodiesel
value. This difference can be related to the chain size and viscosity. It is
well known that biodiesel has a viscosity ∼20% higher compared to
diesel, mainly because it is slightly more polar due to the presence of
oxygen in its chemical structure [32]. Thus, the increase in D value with
biodiesel content of the blends, shown in Fig. 5, could be related to the
viscosity of biodiesel.
Fig. 5 (a) and (b) show the dependence of θ/P and D values for
biodiesel content in S-10 and S-500 diesels, respectively. Independently
of the diesel type, a similar reduction in θ/P and an increase in D values
with the addition of biodiesel in the blends is observed. Both para-
meters (θ/P and D) exhibit a strong variation for concentrations lower
than 20% of biodiesel in diesel and a slight variation between B20 and
B100. From B0 to B20, the thermal diffusivity increases ∼10% for both
S-10 and S-500 blends. However, θ/P decreases 26% for S-10 and 21%
for S-500 blends. The observed reduction in θ/P value can be caused
mainly by a decrease in the absorbance at 916 nm, which may be af-
fected by the red shift observed for the B100 sample (see Fig. 4).
However, according to Eq.3, θ/P also depends on D and dn/dQ or dn/
dT. From literature we obtained for methyl biodiesel dn/
dT = −(3.2 ± 0.3) × 10−4 K−1 [18], and for diesel dn/
dT = −(4.1 ± 0.3) × 10−4 K−1 [29]. According to Shen et al. [29],
dn/dT and viscosity are inversely related. So, the increase of biodiesel
content in blends would increase the viscosities, decrease dn/dT and,
consequently, decrease θ/P values.
The TL technique was previously applied in the study of in inedible
oils [33], oil/biodiesel [17] and biodiesel/diesel [16] blends using
visible excitation. In all these experiments, mass diffusion (Soret effect)
and/or photochemical reactions affected the TL signal, and conse-
quently the reliability of θ and tc measurements. In the present study,
long time transients were performed and no mass diffusion or photo-
chemical effects were observed, indicating that N-NIR excitation is
preferable to the visible one.
4. Conclusions
In this study, the TL method was successfully applied in the N-NIR
spectral region to assign the low absorption of the third overtone of the
CeH bond stretching vibration (4ν (CeH)) and the combination band of
4ν(CeH) + 1δ(CeH). The TL results indicate that the third overtone 4ν
(CeH) centered at 916 nm (10,917 cm−1) is appropriate to the char-
acterization of biodiesel, diesel and diesel/biodiesel blends. The
thermal diffusivity (D) and θ/P photothermal parameters are suitable
for the determination of biodiesel content in blends. Moreover, the high
sensitivity of the TL method enables the use of N-NIR region, where the
blends are not affected by undesirable effects such as photochemical
reactions and/or mass diffusion.
Fuel 212 (2018) 309–314
% Diesel S-500
0 100 80 60 40 20 0
1.10 1.10
40
1.05 1.05
35
D ( 10-3cm²s-1 )
D ( 10-3cm²s-1 )
θ /P ( W -1 )
1.00 (b) 1.00
30 λe = 916 nm
0.95 0.95
25
0.90 0.90
20
0.85 0.85
100 0 20 40 60 80 100
% Biodiesel
Acknowledgements
The authors thank Coordenação de Aperfeiçoamento de Pessoal de
Nível Superior (CAPES) for an undergraduate fellowship awarded to the
first author, Fundação de Apoio ao Desenvolvimento do Ensino, Ciência e
Tecnologia do Estado de Mato Grosso do Sul (FUNDECT) and Conselho
Nacional de Desenvolvimento Científico e Tecnológico (CNPq), (SML, grant
number 304029/2015-7), (LHCA, grant number 305412/2014-0).
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