International Journal of Environment, Ecology,

Family and Urban Studies (IJEEFUS)

ISSN(P): 2250-0065; ISSN(E): 2321-0109
Vol. 6, Issue 5, Oct 2016, 27-36
TJPRC Pvt. Ltd.

AN INTEGRATED APPROCH FOR THE REMOVAL OF INDIGO CARMINE DYE

FROM ITS AQUEOUS SOLUTION AND THE SYNTHESIS OF NANO PIGMENT
NEERAJ KUMARI & MONIKA DATTA
Analytical Research Laboratory, Department of Chemistry, University of Delhi, Delhi, India
ABSTRACT
The purpose of present study was to develop a methodology for the removal of a Toxic dye, Indigo Carmine
(IC), from its aqueous solution without the formation of second generation waste material. Employing the batch
extraction method, interaction of Indigo Carmine with Montmorillonite (Mt) and organo Montmorillonite (OMt) was
investigated as a function of pH of the aqueous solution of the dye, time duration for batch extraction and the initial
concentration of the dye in aqueous solution. The results indicate adsorption kinetic in both the cases and could be best
described by the pseudo-second-order model and the isotherm model was best described by Langmuir equation. As
compared to Mt, OMt was observed to have higher adsorption capacity for IC dye.
The dye adsorbed beautiful bright blue colored nanometer size particles have been named as nano pigment and

material but also creating value added products.

KEYWORDS: Montmorillonite, Indigo Carmine, Value Added Products, Isotherms Models, Adsorptionkinetic

Received: Aug 18, 2016; Accepted: Sep 01, 2016; Published: Sep 08, 2016; Paper Id.: IJEEFUSOCT20162

Original Article

have been used to color various other substrates thereby not only preventing the formation of second generation waste

INTRODUCTION
Annual production of colorants in the world is about 0.7 Metric ton out of which 100,000 are dyes and
about 20,000 of these are indigo-derivatives [1]. Fifteen per cent of the total world production of dyes is lost
during the dyeing process and is released in the textile effluents. The release of those colored wastewaters in the
ecosystem is responsible for the aesthetic pollution, eutrophication, and perturbations in aquatic life. The content
of dyes in effluents are therefore, responsible for blocking the penetration of light in water bodies, thereby
inhibiting the biological processes based on photosynthesis; these effluents may contain chemicals that are toxic,
carcinogenic and mutagenic for multiple organisms and animals [2, 3].
Indigo carmine is the primary indigo derivative (sulfonated form is known as Acid Blue 74) found in
denim industry waste water [4]. Conventional treatments of dye wastes water mainly include biological oxidation
and adsorption. Although it is less expensive than other methods, biological treatment is relatively ineffective for
decolorization [5, 6]. Adsorption on activated carbon is very effective in sequestering many types of contaminants
onto the solid phase, but it is expensive and requires regeneration [5] also generates a second generation waste
material to be disposed separately.
The goal of this research work was to design an effective method for the removal of Indigo Carmine from
aqueous media using naturally occurring clay, Montmorillonite (Mt) and use these dye adsorbed colored materials
as a value added products instead of creating a second generation waste materials.

www.tjprc.org

editor@tjprc.org

28

Neeraj Kumari & Monika Datta

EXPERIMENTAL
Materials Used
The indigo Carmine (procured from Thomas Baker Chemicals Ltd. Mumbai, India), the Cetylpyridinium Chloride
(procured from E. Merck Pvt. Ltd., Mumbai, India)and other reagents used in present work were of analytical grade.
Montmorillonite clay was obtained from Sigma Aldrich, St. Louis, MO, U. S. A. and was used without any further
purification.
Synthesis of Organoclay
The organo Montmorillonite clay (OMt) was synthesized using cationic surfactant, Cetylpyridinium Chloride
(CPC)by the modification of the reported procedure [7]. The synthesized product was characterized by various appropriate
analytical techniques.
Effect of PH on the Stability of Indigo Carminein Aqueous Media

Figure 1: (A)Uv-Vis Spectrum of Aqueous Solution of IC (20 Mg L-1) at its Natural Ph (4.2),
(B) Uv-Vis Spectra of Aqueous Solution of IC (20 Mg L-1) as a Function of Ph,
(C)Absorbance as a Function of Concentration of Ic in Aqueous Solution (Ph 4)
The electronic absorption spectrum of Indigo Carmine (IC) dye in aqueous solution (at its natural pH of 4.2)
exhibits four main absorption bands located at 205, 253, 289 and 612 nm [Figure 1 (A)]. The effect of pH on the electronic
absorption spectrum of IC in aqueous solution was investigated, there seems to be no effect of pH (from 1 to 10) on the
electronic absorption spectrum of IC [Figure 1 (B)]. Therefore, pH 4 (close to its natural pH of the solution of IC) was
selected for the quantitative estimation of IC [Figure 1 (C)].
Batch Extraction of Indigo Carmine from Aqueous Media by Mt and OMt
Employing the batch extraction method, interaction of Indigo Carmine with Montmorillonite (Mt) and organo
Montmorillonite (OMt) was investigated as a function of pH of the aqueous solution of the dye, time duration for batch
extraction and the initial concentration of the dye in aqueous solution[Figure 2].

Impact Factor (JCC): 3.7216

NAAS Rating: 3.63

An Integrated Approch for the Removal of Indigo Carmine

Dye from its Aqueous Solution and the Synthesis of NANO Pigment

29

Figure 2: [A] Interaction of IC at different pH (Concentration = 50 mg L-1, Time = 30 Minutes)

[B] Interaction of IC as a Function of Contact Time (pH = 4, Concentration = 50 mg L-1)
[C] Interaction of IC as a Function of Initial Concentration (pH = 4,
Time = 40 Minutes for Mt and 80 Minutes for OMt)
Standard stock solution of 1000 mgL-1concentration of IC was prepared in double distilled water and was further
diluted with double distilled water to required concentrations for further experiments. Each experiment was performed
with0.10 g of adsorbent (Mt and OMt) in 25ml of dye solution of required concentration at room temperature. At the end of
each extraction, the solution was centrifuged and the concentration of the residual dye in the supernatant was determined
by spectrometric method.
Amount of dye retained on the Mt and OMt was calculated using following expression:

 =

(  )


(1)

Where: qe (mg g1) is the amount of IC adsorbed, Ci (mg L1) is the initial dye concentration, Ce (mg L1) is the
concentration of IC in solution at equilibrium, V (L) is the volume and m (g) is the amount of the adsorbent.
It is evident from the Figure 2 that, the IC was preferentially retained by the OMt and the condition for the
maximum uptake was observed at pH 4 with contact time of 100 minutes. Uptake of IC was further observed to be
dependent on the extent of surfactant loading on Mt. Maximum uptake of IC was found to be 171 mg/g when Mt was
treated with 0.5% CPC on increasing the concentration of CPC to 2% CPC the uptake of IC was substantially increased to
a value of 330 mg/g [Figure 3].

www.tjprc.org

editor@tjprc.org

30

Neeraj Kumari & Monika Datta

Figure 3: Interaction of IC with OMt, As A Function of Initial Concentration of IC (Ph = 4 and

Time = 80 Minutes) OMt Synthesized with 0.5% CPC OMt Synthesized with 2.0% CPC
Isotherm and Kinetic Studies
Two adsorption isotherm models, Freundlich and Langmuir, were used to explain the equilibrium phenomenon of
IC with Mt and OMt. The applicability of isotherm model is compared on the basis of R2 (correlation coefficient).
The linear form of Freundlich adsorption isotherm equation is expressed as:


(2)


 =  + 



The value of Kf and 1/n(adsorption isotherm constant related to bonding energy and degree of non-linearity) are
calculated from intercept and slop of linear plot of log Ce versus log qe [Figure 4]. The value of 1/n found to be <1 which
indicate that the adsorption isotherm is favorable.
The linear form of Langmuir adsorption isotherm is expressed by following equation:






(3)

 

The value of qmax (monolayer adsorption capacity (mg/g)) and KL (Langmuir adsorption constant (L/mg))are
determined from slope and intercept of linear plot of Ce/qe versus Ce [Figure 4]. The essential characteristics of Langmuir
isotherm equation can be expressed in terms of dimensionless constant, RL, also known as equilibrium parameter.
 =




(4)

The linear plot of Ce/qe versus Ce indicates that the adsorption of IC on Mt and OMt follows Langmuir isotherm
model since the R2 values are very close to the ideal value of 1.0 [Figure 4 and Table 1] [8]. The value of RL is less than
one for Mt and OMt [Table 1] indicating that the adsorption process is favorable.
Kinetic studies describe the rate of solute (IC) uptake on Mt and OMt. There are mainly two kinetic models,
Impact Factor (JCC): 3.7216

NAAS Rating: 3.63

An Integrated Approch for the Removal of Indigo Carmine

Dye from its Aqueous Solution and the Synthesis of NANO Pigment

31

pseudo first order and pseudo second order, suitable for describing the interaction of IC with Mt and OMt. Pseudo first
order kinetic of Lagergren is expressed by following equation:
log (

" ) = #$


% "

(5)

&.()(

The linear equation of pseudo second order kinetic order as given by Ho is expressed as:
"
*


+  +




(6)

Where, K1 (min-1) and K2 (g/mg/min) are rate constant of pseudo first order and second order adsorption process
which can be calculated from linear plot of log (qe qt) versus t for first order and t/qt versus t for second order [Figure 5].
On the basis of the higher value of R2 and qe, it can be concluded that the adsorption process follows a pseudo second order
reaction [Table 2, Figure 5].
Table 1: Parameters Fitted for Adsorption Isotherms
Adsorbent

Parameters for Freundlich Isotherm

2
K
1/n
--------R
F

Mt
OMt
Adsorbent

0.479
2.72
0.721
--------0.386
18.70
0.941
--------Parameters for Langmuir Isotherm
2
Q
R
K
R
max

Mt
OMt

14.30
182.10

0.029
0.036

0.292
0.041

0.993
0.966

Figure 4: Freundlich Adsorption Isotherm Mode Mt and OMt

Langmuir Adsorption Isotherm Model Mt and OMt
The plot of t/qt versus t follows the equation of a straight line and values of K2 (pseudo second order rate constant,
g/mg/min) and qe can be calculated from the intercept and the slop respectively [9]. On the basis of the higher value
ofR2and qe, it can be concluded that the adsorption process follows a pseudo second order reaction [Table 2, Figure 5].

www.tjprc.org

editor@tjprc.org

32

Neeraj Kumari & Monika Datta

Table 2: Parameters Fitted For Kinetic Models

Adsorbent

Parameters for Pseudo First

Order Reaction
2
q
K
R
e

Mt
OMt
Adsorbent

Mt
OMt

0.108
0.004
0.090
0.497
0.056
0.901
Parameters for Pseudo Second
Order Reaction
2
q
K
R
10.94
12.47

7.73
0.35

0.999
1.000

Figure 5: Pseudo First Order Reaction Mt and OMt

Pseudo Second Order Reaction Mt and OMt

RESULTS AND DISCUSSIONS

Characterization
X-Ray Diffraction Studies
XRD data indicates intercalation of CPC in the interlayer of Mt [Figure 6]. The characteristics diffraction peak of
001 plane of Mt at 2 value of 6.2 with basal spacing of 14.25 shifted towards lower angle of 5.1 after interaction with
CPC resulting in expansion of basal space to 17.50, suggesting intercalation of CPC in Mt gallery. However, on
interaction with IC there was no significant change in position of diffraction peaks of Mt and OMt, suggesting no further
intercalation. The diffraction peak at 8.7 had been attributed to the presence of small quantity of illite in the sample [10].
On interaction with of the IC there was no further expansion of the interlayer region in case of Mt as well as OMt,
suggesting surface interaction in both cases.

Impact Factor (JCC): 3.7216

NAAS Rating: 3.63

An Integrated Approch for the Removal of Indigo Carmine

Dye from its Aqueous Solution and the Synthesis of NANO Pigment

33

Figure 6: XRD Pattern of Mt, (IC +Mt), & Figure 7: UV-Vis. spectra of IC , (IC + CPC)1 ,
OMt, (IC +OMt)
(IC + CPC)2 and CPC
UV Visible Spectroscopic Studies
From Figure 7 it can be seen that there is interaction of aromatic ring of CPC with the IC in solution, the
interaction becomes more pronounced with increase in concentration of CPC. The bands at 205, 253 nm and 289 nm were
due to the * transition of the aromatic benzene ring present in IC. The transition involving the Chromophoric indigo
group was responsible for the band at and 612 nm and a shoulder at350 nm [11].These bands were unaffected by the
interaction of CPC with IC as a result of which the color of the IC on interaction with OMt remained unchanged. As the
concentration of CPC increased from 30% (IC + CPC)1 to 60% (IC + CPC)2 the CPC absorption bands became more
prominent and the interaction of negatively charged SO3 group of IC with the positively charged pyridinium group of the
CPC became evident, the absorption bands at 205 nm and 253 nm shifts to 215nm and 260 nm, the shoulder at 305 nm
disappeared.
Fourier Transform Infrared Spectroscopic Studies
In the FTIR spectrum of Mt, the vibration band at 3624 cm-1, 3410 cm-1, 3083 cm-1 has been assigned to the O-H
stretching vibration of structural water (OH group), H-O-H stretching vibration of interlayer water and a broad band
centered around 3083 cm-1 to the H-O-H stretching vibration of adsorbed water on the surface of Mt.

www.tjprc.org

editor@tjprc.org

34

Neeraj Kumari & Monika Datta

Figure 8: FT-IR spectra of Mt, (IC +Mt), OMt, (IC +OMt) and IC Dye
The band located at 2510 cm-1 is due to surface and/or interlayer water originating as a result of combination of
two vibrational frequencies of water. The vibrational band at 1648cm-1 is due to the H-O-H bending vibration of surface
and/or interlayer water [9]. The stretching vibration of Si-O in the silicates is observed as a very strong broad absorption
band at 1043cm-1[Figure 8]. In the FTIR spectrum of OMt, the vibrational bands at 2929 cm-1 and 2853cm-1 has been
assigned to the asymmetric and symmetric vibrations of methylene group of the CPC present on the surface of the OMt
[10]. The disappearance of the broad band centered around 3083 cm-1 and combination band at 2510 cm-1 confirms
replacement of surface adsorbed water by CPC and supports the formation of OMt. Substantial reduction in intensity of HO-H stretching vibration of interlayer water at 3410 cm-1 and at 1648cm-1further confirms the replacement of most of the
interlayer water by CPC and thus confirms the presence of CPC on the surface as well as in the interlayer region, also
supported by XRD data.
FT-IR spectrum of pure IC has several absorption bands in the mid IR region, the absorption bands at3457 cm-1 ,
1636 cm-1 and 1319 cm-1 have been assigned to the N-H, C=O and C-N stretching vibration belonging to the indigo group
present in the IC [Figure 1: (A)].The vibration bands at 2923 cm-1 and 2857 cm-1 are due to the C-H stretching and 1613
cm-1 is due to the C=C stretching vibration of the aromatic ring. The vibrational band at 1065 cm-1 has been assigned to the
sulphite group and at 733 cm-1 to C-S stretching vibration of IC.
Disappearance of 3083 cm-1 band (assigned to H-O-H stretching vibration of adsorbed water on the surface of
Mt.) and appearance of 2923 cm-1 and 2857 cm-1 band (assigned to C-H stretching vibrations belonging to the aromatic
ring of IC) are suggestive of surface interaction of IC with Mt. In case of IC treated OMt, the FT-IR spectrum practically
remains unchanged with respect to that of OMt in the frequency region of 4000 cm-1 to 2500 cm-1. However, appearance
Impact Factor (JCC): 3.7216

NAAS Rating: 3.63

An Integrated Approch for the Removal of Indigo Carmine

Dye from its Aqueous Solution and the Synthesis of NANO Pigment

35

of1741 cm-1 and 1639 cm-1 band indicates interaction of IC with OMt involving carbonyl group belonging to the indigo
group of IC. Interaction of sulphite group cannot clearly due to the presence of a broad Si-O stretching vibration band.

Mechanism of Indigo Carmine Adsorption on the Surface of OMt

Figure 9: Mechanism of Adsorption of IC Dye on the Surface of OMt

The surface of Mt was made positive by loading CPC, in excess of exchange capacity of Mt; this is further
confirmed by the + 29.3mV zeta potential value for synthesized OMt as compared to the - 17.6 mV of pristine Mt. There is
electrostatic interaction between the anionic IC dye and positively charged pyridinium ion of the OMt Figure 9. The
synthesized OMt therefore is able to act as an effective adsorbent for the anionic IC dye.
Application of Dye Adsorbed Clay as Value Added Product
The dye adsorbed intense colored nano sized Mt based material have the advantages of organic dyes and inorganic
pigments hence, they have been named as nano pigments. These nano pigments show enhanced thermal stability as
compared to the pure IC. The need to develop nano pigments was a result of the prospective inherent disadvantages of
organic dyes and inorganic pigments. They can also be used to form polymer composite material where they can act as a
reinforcement additive and improve the properties like thermal stability, UV stability and tensile strength. No significant
shift in the absorption maxima was seen in the nano pigments as compared to the pure dye. The demand of nano pigments
is rapidly growing because they offer variety of applications, such as optoelectronic functional materials, textiles, nanofiber
coloration, inkjet and medicinal applications.

CONCLUSIONS
The surface of Mt has net negative charge, as indicated by zeta value of -17.6mV.The IC is known to be anionic
in nature therefore, possibility of interaction of IC with Mt is through the edges of Mt layers, where positive charge centers
are located. The low uptake (14.5mg/g, 1.4%) of IC on Mt can be explained by the fact that the density of positive charge
is much less in comparison to the density of negative charge on the surface of the Mt. The edge interaction of IC is
supported by the XRD data, which indicate no change in the diffraction angle or interlayer spacing (001 plane) IC treated
Mt with respect to Mt.

www.tjprc.org

editor@tjprc.org

36

Neeraj Kumari & Monika Datta

Mt modified with 0.5% and 2% CPC is referred as OMt-1and OMt-2 respectively. The loading of CPC in case of
OMt-1and OMt-2 is 0.769 meq/100g and 2.65 meq/100g of Mt respectively. The amount of IC uptake is 171 mg/g and
330mg/g of Mt.
Since, the value of zeta potential for OMt-1is -17.2mV therefore, the possibility of interaction of IC is either
through the edges of OMt-1 or probably interact with intercalated CPC by removing CPC in solution. XRD studies indicate
the shifting of diffraction angle in 001 plane of OMt-1towards higher angle from 5.25 to 5.9 hence decrease in d value
from 17 to 14.9 suggesting the interaction of IC with OMt-1.
The surface of OMt-2 has positive charge, as indicated by zeta value of +29.3mV so; the possibility of interaction
of IC with OMt-2 is through the edges as well as on surface. The interaction of IC with OMt-2 is also supported by XRD
studies showing no significant change in diffraction angle or interlayer spacing of IC treated OMt-2 with respect to OMt-2.
The interaction of IC with Mt and OMt-2 is also supported by FT-IR spectra.
The experimental data was found to be best fitted to Langmuir adsorption isotherm model and pseudo second
order kinetic model hence, supporting the interaction of IC with Mt/OMt.

ACKNOWLEDGEMENTS
The authors are grateful to the Council of Scientific and Industrial Research, India for providing fellowship to one
of the authors, Ms. Neeraj Kumari. Authors express their sincere thanks to the Director, University Science
Instrumentation Centre, University of Delhi, India for providing some of the necessary instrumentation facilities. Authors
are also thankful to Professor R. Nagarajan, Department of Chemistry, University of Delhi, India for sharing XRD facility.
REFERENCES
1.

G. M. Marco et. al., (2013). An integrated electrocoagulation and ozonation process for removal of indigo carmine dye from
denim processing effluents. Sustainable Environmental resources, 23, 241-245.

2.

H. Zollinger, (1991). Color chemistry: synthesis, properties and applications of organic dyes and pigments. Second Edition.

3.

A.I., del Ro et. al., (2011). Electrochemical treatment of a synthetic wastewater containing a sulphonated azo dye.
Determination of naphthalenesulphonic compounds produced as main by-products, Desalination, 273, 428-435.

4.

M.Riera-Torres et. al., (2010). Combination of coagulation-flocculation and nanofiltration techniques for dye removal and
water reuse in textile effluents. Desalination, 252, 53-59. 5.

5.

A. Mittal et. al., (2006). Batch and bulk removal of hazardous dye, Indigo Carmine from wastewater through adsorption.
Journal of Hazardous Material, 137, 591-602.

6.

R. Khataeeet. al., (2009). Decolorization of CI Acid Blue 9 solution by UV/ Nano-TiO2, Fenton, Fenton-like, electro-Fenton
and electrocoagulation processes: A comparative study. Journal of Hazardous Material, 161, 1225-1233.

7.

H.

He,

et.

al.

(2007).

X-ray

photoelectron

spectroscopy

study

of

HDTMAB

distribution

within

organoclays.SpectrochimicaActa Part A: Molecular and Bimolecular Spectroscopy, 66, 1180-88.

8.

P. Baskaralingamet. al. (2006). Equilibrium studies for the adsorption of acid dye onto modified hectorite. Journal of
Hazardous Material, 136, 989-992.

9.

Y. S. Ho, et. al., (2005). Regression Analysis for the sorption isotherms of basic Dyes on sugarcane dust. Bioresource
Technology, 96, 1285-1291.

Impact Factor (JCC): 3.7216

NAAS Rating: 3.63

An Integrated Approch for the Removal of Indigo Carmine

Dye from its Aqueous Solution and the Synthesis of NANO Pigment

37

10. S. A. Shin, (2007). Ph. D. Thesis, In-situ polymerization and characterization of polyethylene clay nanocomposite. University
of Waterloo, Canada.
11. M. Vauteiret. al., (2001). Photocatalytic degradation of dyes in water: case study of Indigo and of Indigo Carmine. Journal of
catalysis, 201, 46-59.
12. M. Kaur and M. Datta (2013). Adsorption equilibrium and kinetics of toxic dye Erythrosine B adsorption onto
Montmorillonite. Separation Science & Technology, 48, 1370-1381.
13. M. Cano et. al., (2011). Biotransformation of indigo carmine to isatin sulphonic acid by lyophilized mycelia from
TrametesVersicolor. African Journal of Biotechnology, 10, 12224-12231.

www.tjprc.org

editor@tjprc.org