STUDY BY INFRARED SPECTROSCOPY

AND THERMOGRAVIMETRIC ANALYSIS

OF TANNINS AND TANNIC ACID

Mayra A. Pantoja-Castroa*, Horacio González-Rodrígueza

(Received October 2011; Accepted February 2012)

ABSTRACT

Among the compounds in nature useful for people are tannins, which present
large molecular complexity and they had have an ancient use as tanning agents,
and nowadays some of them are used due their antioxidant properties for protect
metals of corrosion. Also elucidation, synthesis and purification represent a great
challenge to obtain them. Due this fact researches have tried to copy the synthesis
of less complex compounds similar to tannins. From a different point of view, the
use of tannins extracted from trees bark, considered in many places as a waste,
grant an extra value to the bark. In this work we have studied and analyzed through
gel permeation chromatography (GPC), infrared spectroscopy (FT-IR) and thermo-
gravimetric analysis (TGA) the average molecular weight, main functional groups
and thermal properties of tannins extracted from Schinopsis quebracho colorado.
The results of these analyses are compared with those obtained for the commercial
grade tannic acid. The comparison allowed to corroborate that is possible to use
tannins from the Schinopsis quebracho colorado bark, with functional groups and
thermal properties which tend to be similar to the tannic acid. www.relaquim.com

Keywords: coating, corrosion, Schinopsis quebracho colorado, tannic acid, tannins.

RESUMEN

Entre los compuestos que existen en la naturaleza útil para la población, se en-
cuentran los taninos, los cuales presentan una gran complejidad molecular y han
tenido un uso desde la antigüedad como agentes para curtido. Hoy en día algunos
de ellos se utilizan por sus propiedades antioxidantes para proteger los metales
de la corrosión. Además la elucidación, síntesis y purificación representa un gran

a
División de Estudios de Posgrado de la Facultad de Ingeniería Química, Universidad Michoacana de San
Nicolás de Hidalgo, Av. Francisco. J. Múgica s/n Col. Villa Universidad 58030, Morelia, Michoacán, México.
* Correspondence should be addressed to: [email protected] (M. A. Pantoja) Tel: +52 01 (443)
316-71-76 Fax: +52 01 (443) 316-71-76

107
108 M.A. Pantoja-Castro, H. González-Rodríguez

reto para su obtención y aplicación. Debido a lo anterior muchas investigaciones

han tratado de copiar la síntesis de compuestos menos complejos similares a los
taninos. Desde el punto de vista, el uso de taninos extraídos de la corteza de los
árboles, considerada en muchos lugares como un desecho, le otorga un valor agre-
gado a ésta. En este trabajo se estudió y analizó por cromatografía de permeación
en gel (GPC), espectroscopía infrarroja (IR) y análisis termogravimétrico (TGA), el
peso molecular medio, grupos funcionales y propiedades térmicas de los taninos
extraídos de Schinopsis quebracho colorado. Los resultados de estos análisis se
compararon con los obtenidos para el ácido tánico grado comercial. Esta compa-
ración permitió corroborar que es posible utilizar taninos de Schinopsis quebracho
colorado, con grupos funcionales y propiedades térmicas que tienden a parecerse
a las que presenta el ácido tánico. www.relaquim.com

Palabras clave: ácido tánico, corrosión, recubrimientos, Schinopsis quebracho

colorado, taninos.

INTRODUCTION 2004). The antioxidant property of tannins

has awaked special interest in the corrosion
Tannic acid and tannins are polyphenolic area, due to the fact that these compounds
compounds able to build very complex can inhibit corrosion in metals when they
chemical structures. The tannic acid, are incorporate in coatings. It can find in
which has an estimated chemical formula literature many researches about corrosion
C76H52O46, is a commercial form of tannins. inhibition using tannic acid or tannins
3 300 years ago Egyptians extracted the- extracted i.e. from pine, mimosa and aca-
se compounds and used them as tanning cia species (Jaén et al., 2003; Hernes et
agents. Due their tanning capacity these al., 2004). The antioxidant effect of these
compounds were very important at an polyphenols compounds is attributed at
industrial level and tanneries. Although their quelating action over transition metals
nowadays salts and synthetic tannins have and their capacity to attach free radicals
acquired more importance against tannins through the synthesis of less reactive struc-
extracted from natural sources (Matamala tures like show Iglesias et al. (2001). It is
et al., 1994; Haslam, 1996). worth to mention that tannins extraction
In the last two decades the isolation and from trees bark offer an extra value to the
structural determination of many types of barks, which is considered in many places
tannins, which also include hydrolysable as a waste. Even when tannins formula
and condensable tannins have been possi- varies among tree species, tannins present
ble using techniques as UV-visible, nuclear structures similar than the tannic acid, for
magnetic resonance (1H-NMR, 13C-NMR), this reason elucidation and comparison
mass spectroscopy (Isaza et al., 2004; between these compounds is important.
Meagher et al., 2004) and soon. According The aim of this work is to corroborate
to their structural differences between by gel permeation chromatography, infra-
many species of tannins, some researchers red spectroscopy and thermogravimetric
have been used these compounds for di- analysis that tannins extracted industrially
fferent applications within which are find (tannic acid), and tannins extracted from
as fungicide, antibiotic and antioxidant Schinopsis quebracho colorado have almost
(Schofield et al., 2001; Latté and Kolodziej, thermal, chemical and physicochemical si-
Study by infrared spectroscopy and thermogravimetric analysis of Tannins and Tannic Acid Rev. Latinoamer. Quím. 39/3(2011) 109

milar characteristics, and therefore tannins RESULT AND DISCUSSION

can be reliable compounds for used i.e in
anticorrosive coatings. The number average molecular weights
(Mw) obtained through GPC for tannins
from Schinopsis quebracho colorado and
MATERIALS AND METHODS tannic acid (Sigma-Aldrich) were of 6 485
and 1 701.23 respectively. The molecular
In this study it has used tannic acid supplied weight of tannins is approximately four ti-
by Sigma-Aldrich. Condensed tannins mes higher than acid tannic because a lot of
(98%) were provided by FITECMA-UMSNH hydroxyl benzene rings are connected with
(Facultad de Ingeniería en Tecnología de similar structures forming a big structure
la Madera de la Universidad Michoacana as is suggested by Grassino et al. (1999)
de San Nicolás de Hidalgo) and they were and Meagher et al. (2004).
extracted from Schinopsis quebracho colo- The Figure1 shows the spectrum of
rado bark based in the works of Isaza et tannins and tannic acid where it can find
al. (2004) and Sivakumaran et al. (2006). a strong absorption around 3700 and 3000
Tannins were milled to generate size sma- cm-1 with a wide and strong band cente-
ller particles (100 micrometers). red at 3381 and 3356 cm-1 respectively.
The molecular weight of tannins was These bands are assigned to the hydroxyl
obtained by high pressure liquid chroma- groups (OH) stretching vibrations and due
tography (HPLC) with a gel permeation to the wide variety of hydrogen bonding
chromatography system, 717 Plus Auto- between OH.
sample model using dimethylformamide In this spectrum it can notice a sharp
as solvent. Structural characteristics of peak at 2927 and a small shoulder at 2860
the compounds were analyzed with a FT-IR cm-1 associated with the symmetric and
spectrometer (Nicolet 5ZDA) in the absorp- antysimmetric -C-H- stretching vibrations
tion mode, ranging from 4000 to 400 cm-1. of CH2 and CH3 groups respectively. Also it
Thermogravimetric analyses were perfor- does not appear signals of free water mole-
med at a heating rate of 10°C/min under cules due there is no evidence of bands at
nitrogen flow by a differential scanning 2130 cm-1 and 1650 cm-1 (H-O-H bending
calorimetric (DSC) 822 Toledo Mettler. vibrations) and at about 700 cm-1; but in

-C-Carom
OH C=O C-O
3356 1191
1718 1328
1614
1452
Absorbance (a. u.)

2725
-CH-
3381 C=C
754
2927 Tannic acid
-CH-

1612
3356
1450

Tannins
758

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm-1)

Figure1. Infrared spectroscopy of tannins and tannic acid

110 M.A. Pantoja-Castro, H. González-Rodríguez

120 120
a) b)
11.47 % 8.66 %
100 100
1 %
33.24 % 35.62 %

80 80
Mass (%)

55.29 %

Mass (%)
60 60 26.41 %

40 40
255.49 °C 28.3 %

20 249.9 °C 20 306.36 °C
48.8 °C

37.7 °C 181.57 °C

0 0
0 100 200 300 400 500 600 0 100 200 300 400 500 600
Temperature (°C) Temperature (°C)

Figure 2. Thermogravimetric analysis of tannins (a) and tannic acid (b)

the tannic acid spectrum some of these Two distinct mass loss peaks can be
peaks appear due some hydrogen and seen in the Fig. 2(a): a weak peak centered
oxygen atoms in this molecule can be bon- at 48.8 °C where almost 11.47% of weight
ding and they are observed in the spectrum due the postcuring, thermal reforming,
as water signals. preliminary oxidation steps and elimina-
The deformation vibration of the car- tion of volatile fractions. The second peak,
bon-carbon bonds in the phenolic groups is sharper and more pronounced and it is
absorbs in the region of 1500-1400 cm-1. found at 249.9 °C where the degradation
At 754 cm-1 shows the result distortion tannins begins and it could be the result of
vibration of C=C in benzene rings (Socrates, the partial breakdown of the intermolecular
2004). Around 1452 cm-1 stretching vibra- bonding. Finally after at 500 °C remains a
tions of -C-Caromatic groups appear in both carbonized residue of 55.29% w.
spectrums respectively. TGA of tannic acid in Fig. 2 (b) shows
Spectrum of tannins compared with five thermal zones, the first one is appre-
tannic acid and tannins shows a decrea- ciated between 25 and 150°C with a mass
se in many peaks located at 1718, 1614, loss centered at 37.7 °C where preliminary
1452, 1328 and 1191 cm-1 which are not oxidation steps and elimination of volatile
sharp and strong as is observed in tannic fractions occurs.
acid. Also it can be observed that only the In the second zone (151 and 205 °C)
tannic acid contains some aromatic esters is carried out the first depolymerization of
due to the signal characteristics bands of tannic acid approximately 1.004%w. Bet-
carbonyl groups: C=O stretching vibration ween 206 and 295 °C is presented a second
at 1730-1705 cm-1 and C-O at 1100-1300
cm-1 (Silverstein et al.,1981; Stuart, 2005).
Table 1. Infrared positions of tannins and tannic
Detailed information is listed in Table
acid.
1; these results are similar to those re-
Group Vibration Approach fre-
ported in the literature for polyphenolic quency/experi-
compounds as tannic acid (Socrates, 2004). mentala (cm-1)
The TGA traces and mass spectra obtai- Arom-CH2-OH n OH 3400/3381
ned for the tannins and tannic acid heated Arom-CH2-OH 2920/2925
na CH2
at a rate of 5 °C cm-1 are shown in the Fi-
Arom-C-O- n C-O 1630/1614
gures 2(a)-(b), which show the dependence
Arom-CH2-OH d CH2 1420/1452
of the mass loss of the samples expressed
as a percentage of the initial mass and Arom-O- na C-O 1050/1165
temperature. Also the first derivative is Arom-O- n C-O 800/646
below of them. a
Socrates, 2004
Study by infrared spectroscopy and thermogravimetric analysis of Tannins and Tannic Acid Rev. Latinoamer. Quím. 39/3(2011) 111

depolymerization of the material (36.62%w) Aldrich®). Trough infrared spectroscopy it

with a pronounced peak at 255.49°C. Third was observed that tannins do not shows
degradation of tannic acid takes place after important signal from carbonyl groups (aro-
296 °C with a remarked peak at 306.39 matic esters) while they appears in tannic
°C; in this section is seen a mass loss of acid. Another important difference is in the
26.41%w. Finally after 500 °C remains hydroxyl group band, which in tannins is
28.3% w of carbon. less pronounced, because several hydroxyls
Comparing differences between tannic are interacting among them.
acid and tannins, we observe in the last Thermogravimetric analysis shows that
one, a difference of more than 27% weight tannins show a similar stability thermal
of carbon residues, due tannins contain that tannic acid, which also have more
impurity traces. Also, tannins contain depolymerization stages due to the easily
more atoms of carbon in their structure break in smaller structures than tannins
than tannic acid. Another important di- (compound con some monomer units simi-
fference between tannins and tannic acid lar to the tannic acid).
thermograms, is that in the first one we Even when results of GPC, FT-IR and
observe three thermal zones while in tan- TGA vary slightly, it can be observed that
nic acid it observe five zones, due tannic Schinopsis quebracho colorado tannins
acid has a less complex structure, and its present structures and functional groups
bonds can be easily broken forming sma- which tend to be similar to the tannic acid.
ller structures. The above makes tannins ideal candidates
to give them a good application, for example
as anticorrosive coatings.
CONCLUSIONS

In this work we have studied the molecu- ACKNOWLEDGEMENTS

lar weight, main functional groups and
thermal stability of a natural product, The authors acknowledge the economical sup-
tannins from Schinopsis quebracho colora- port provided by project 20.3-CIC-UMSNH.
do and it was compared with results of a Also we special thank to F. Bucio-P. and N.
similar synthetic compound (tannic acid, Flores-R. for supply us with tannins.

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