Chemical Engineering Journal 195196 (2012) 173179

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Ternary adsorption of acid dyes onto activated carbon from amboyant pods
(Delonix regia): Analysis by derivative spectrophotometry and response surface
methodology
Alexandro M.M. Vargas, Alessandro C. Martins, Vitor C. Almeida
Department of Chemistry, State University of Maring, Av. Colombo 5790, CEP 87020-900, Maring, State of Paran, Brazil

h i g h l i g h t s

" Ternary adsorption of food dyes on activated carbon obtained from amboyant pods.
" Determination of dyes by derivative spectrophotometry.
" Studies of the adsorption factors by response surface methodology.

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

Article history: Ternary adsorption of food dyes Acid Yellow 6 (AY-6), Acid Yellow 23 (AY-23), and Acid Red 18 (AR-18)
Received 19 March 2012 onto activated carbon ACop produced from amboyant pods (Delonix regia) was performed in this work.
Received in revised form 24 April 2012 Derivative spectrophotometry was used for simultaneous determination of the dyes, and the response
Accepted 25 April 2012
surface methodology (RSM) was applied to analyze the adsorption behavior of the three dyes onto ACop.
Available online 5 May 2012
The RSM revealed the parameters that inuence the ternary adsorption of each dye: pH for AY-23,
adsorption time for AR-18, and initial concentration for AY-6 and AR-18. The best experimental condition
Keywords:
showed Qe,AY-6, Qe,AY-23, and Qe,AR-18 values equal to 254.493, 199.584, and 164.438 mg g1, respectively.
Activated carbon
Ternary adsorption
ACop was shown to be a fast and effective adsorbent for the ternary adsorption of AY-6, AY-23, and AR-18
Response surface methodology from aqueous solutions.
Derivative spectrophotometry 2012 Elsevier B.V. All rights reserved.
Flamboyant pods (Delonix regia)
Food dyes

1. Introduction
Synthetic dyes are widely used by food and pharmaceutical
industries in the fabrication of their products [14]. Many studies
have shown that the use of these dyes may cause allergic reactions
and diseases in human beings, for which reason, their use is much
debated [14]. Particularly the dyes Sunset yellow (Acid Yellow 6),
Tartrazine (Acid Yellow 23), and Ponceau 4R (Acid Red 18), either
alone or in combination, are responsible for the coloration of many
products for human consumption. Therefore, an adequate treat-
ment of wastewaters containing these dyes it is necessary before
they are disposed to the environmental [5].
Among the proposed treatment methods for the removal of
dyes from aqueous efuents, the adsorption process using
activated carbons (ACs) has been reported by several researchers
[614]. However, there are few adsorption studies in the literature
that use, specically, the dyes Acid Yellow 6, Acid Yellow 23, and
Corresponding author. Tel.: +55 44 3261 3678; fax: +55 3261 4334.
E-mail address: vcalmeida@uem.br (V.C. Almeida).
Acid Red 18 [4,5]. In addition, most of these studies report the
individual adsorption of dyes; however, industrial wastewaters
and residual waters usually have many dyes in their chemical com-
position. Therefore, it is necessary to study how the adsorption
process occurs when a group of dyes is present in an aqueous
solution and what the inuencing factors.
On the other hand, the determination of dyes concentrations by
spectrophotometry it is limited when both binary and ternary
mixtures are analyzed, due to overlap of absorption spectra, which
difcult the simultaneous determination [15,16]. The overlap of
absorption spectra of the analytes makes their simultaneous
determination difcult. To solve this problem, derivative spectro-
photometry (DS) can be used. The DS is dened as a modern
advanced spectrophotometric technique, which is based on the
analysis of derivative spectra generated from the UVVis absorp-
tion spectra of zero order [15,16]. This technique has the advantage
of separate the overlapping signals, eliminating the background
signals, in turn, allowing to quantify one or more analytes without
prior separation and purication [17]. Several researches have re-
ported the use of DS in determination of drugs from pharmaceutical

1385-8947/$ - see front matter 2012 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.cej.2012.04.090
174 A.M.M. Vargas et al. / Chemical Engineering Journal 195196 (2012) 173179

-1
zero order derivative for AY-6 (10 mg L )
To the best of our knowledge, there are no studies in the litera-
0.9 -1
zero order derivative for AY-23 (10 mg L ) ture involving the adsorption of dye ternary mixtures. Therefore,
-1
zero order derivative for AR-18 (10 mg L )
0.8 zero order derivative for mixture
the aim of this paper was to study the simultaneous adsorption
of food dyes Acid Yellow 6 (AY-6), Acid Yellow 23 (AY-23), and Acid
0.7 Red 18 (AR-18) onto activated carbon from amboyant pods
(ACop), and assess the effects of pH, adsorption time, and initial
0.6
dye concentration applying DS and RSM.
Absorbance

0.5
431 nm 483 nm 2. Methods
0.4 510 nm

0.3 2.1. Adsorbent and adsorbates

0.2 The adsorbent used in this study, ACop, was obtained using
chemiometric tools and also was characterized for many analytical
0.1 techniques. The details of this adsorbent have been previously
0.0 published by our group [32,33]. The structures and details for food
300 400 500 600 700 dyes Acid Yellow 6 (AY-6), Acid Yellow 23 (AY-23), and Acid Red 18
Wavelength (nm) (AR-18) can be found in Ref. [5], where a study of individual
adsorption of these three dyes was done applying many isotherms
Fig. 1. Zero order derivative spectra for AY-6, AY-23, AR-18, and ternary mixture. and kinetic models.

2.2. Procedure of derivative spectrophotometric method

0.0006 -1
second derivative for AY-6 (10 mg L )
-1
second derivative for AY-23 (10 mg L )
-1
Standard solutions of ternary mixtures were prepared from
second derivative for AR-18 (10 mg L )
0.0004 second derivative for mixture stock solutions (1.0 g L1), which were prepared by dissolving
appropriate amounts of AY-6, AY-23, and AR-18. The pH of the ter-
552 nm nary mixtures was adjusted from HCl and NaOH solutions. The zero
0.0002 order spectra were obtained between 350 and 770 nm with Dk and
444 nm 584 nm
scan speed equal to 1 nm and 400 nm s1, respectively; using a
2
d A / d

UVVis spectrophotometer (Varian Cary 50 UV/Vis). The derivative

0.0000 spectra were generated using the software Origin 6.0 from Sav-
2

itzkyGolay procedure, applying the smoothing function (20

-0.0002 points). The k values from the second order derivative spectra for
the determination of the individual dyes were selected from the
zero-crossing technique [15].
-0.0004
2.3. Batch adsorption studies

-0.0006
400 450 500 550
Wavelength (nm)
Fig. 2. Second order derivative spectra for AY-6, AY-23, AR-18, and ternary mixture.
formulations [18,19], pesticides [20], heavy metals [21], textile
dyes [22] and food dyes [23,24].
In addition, it is necessary knows what factors inuencing the
adsorption process, synergism effects, anti-synergism effects, etc.
Thus, many authors have applied the response surface methodol-
ogy (RSM) as analyses tool [2527]. Chemiometric models such
as central composite rotatable design (CCRD) are widely used both
for production and application of ACs [2832], presenting the re-
sults from an analysis of the linear, interaction, and quadratic
parameters. Based on these models it is possible to study factors
simultaneously without needing to maintain none of them con-
stant, which allow know their true inuence in the process.
Batch adsorption was performed in plastic asks containing
600 650
25 mL of the ternary solutions with various initial concentrations,
and an amount of 0.025 g of ACop on a shaker (25 C). All samples
were ltered prior to analysis using 0.45-lm membrane lters.
The amounts of AY-6, AY-23, and AR-18 in the ternary mixture ad-
sorbed onto ACop, qe (mg g1) were calculated by:
C o  C e V
qe 1
W
where Co and Ce (mg L1) are the initial and equilibrium liquid-
phase concentrations of the dyes, respectively; V (l) is the volume
of the solution, and W (g) is the mass of ACop used.
2.4. Experimental design for the response surface procedure
RSM and CCRD were applied to determine the best combination
of activation process factors: pH, adsorption time (min), and initial

Table 1
Second order derivative equations for the dyes.

Dye k (nm) Regression equation Correlation coefcient (R)

AY-6 552 d2A/dk2 = 1.77715  105 C + 4.81037  107 0.99996
AY-6 444 d2A/dk2 = 1.3173  105 C  1.0961  106 0.99995
AR-18 584 d2A/dk2 = 1.51751  105 C  1.06344  106 0.99996
AR-18 444 d2A/dk2 = 1.25204  105 C + 2.36904  107 0.99993
AY-23 444 d2A/dk2 = 2.45889  105 C  2.68106  106 0.99989
 A.M.M. Vargas et al. / Chemical Engineering Journal 195196 (2012) 173179 175

Table 2
Coded and actual levels for independent factors used in the experimental design.

Factors Coded values

a(1.68) 1 0 +1 +a(+1.68)

Actual values
pH (X1) 2.30 4 6.5 9 10.70
Adsorption time (min) (X2) 26.36 40 60 80 93.64
Initial dye concentration (mg L1) (X3) 181.82 250 350 450 518.18

Table 3
Central composite rotatable design of three factors and ve levels.

Order X1a (x1)b X2a (x2) b

X3a (x3) b
Qe,AY-6 (mg g-1) Qe,AY-23 (mg g-1) Qe,AR-18 (mg g-1)
15 4 (1) 40 (1) 250 (1) 215.932 49.205 139.886
12 9 (+1) 40 (1) 250 (1) 213.224 39.185 135.512
17 4 (1) 80 (+1) 250 (1) 217.564 42.217 150.455
1 9 (+1) 80 (+1) 250 (1) 216.564 40.896 144.635
19 4 (1) 40 (1) 450 (+1) 315.672 42.048 151.359
7 9 (+1) 40 (1) 450 (+1) 314.592 44.531 141.962
5 4 (1) 80 (+1) 450 (+1) 319.695 42.041 149.283
14 9 (+1) 80 (+1) 450 (+1) 325.315 46.069 159.207
18 2.3 (1.68) 60 (0) 350 (0) 254.493 199.584 164.438
13 10.7 (+1.68) 60 (0) 350 (0) 283.625 42.074 179.088
6 6.5 (0) 26 (1.68) 350 (0) 264.816 35.419 132.075
4 6.5 (0) 94 (+1.68) 350 (0) 284.903 40.679 152.297
16 6.5 (0) 60 (0) 182 (1.68) 163.909 52.033 125.789
11 6.5 (0) 60 (0) 518 (+1.68) 325.08 35.503 136.72
10 6.5 (0) 60 (0) 350 (0) 278.292 44.104 152.187
2 6.5 (0) 60 (0) 350 (0) 275.999 42.574 148.913
3 6.5 (0) 60 (0) 350 (0) 279.253 44.921 145.951
9 6.5 (0) 60 (0) 350 (0) 280.353 41.218 143.406
20 6.5 (0) 60 (0) 350 (0) 279.88 47.568 157.262
8 6.5 (0) 60 (0) 350 (0) 278.627 49.342 155.902

Qe,AY-6 = amount adsorbed of AY-6, Qe,AY-23 = amount adsorbed of AY-23, and Qe,AR-18 = amount adsorbed of AR-18.
a
Actual values.
b
Coded values

Table 4
Variance analyses (ANOVA) for three factors (x1, x2, x3) and Qe,AY-6, Qe,AY-23, and Qe,AR-18.

Parameter Sum of squares Mean square F ratio p Value

Qe,AY-6 Qe,AY-23 Qe,AR-18 Qe,AY-6 Qe,AY-23 Qe,AR-18 Qe,AY-6 Qe,AY-23 Qe,AR-18 Qe,AY-6 Qe,AY-23 Qe,AR-18
x1 181.79 5327.28 16.41 181.79 5327.28 16.41 4.16 5.70 0.50 0.0687 0.0381 0.4954
x2 209.58 1.90 347.31 209.58 1.90 347.31 4.80 2.04  103 10.59 0.0533 0.9649 0.0086
x3 34162.49 44.36 180.92 34162.49 44.36 180.92 781.94 0.047 5.52 <0.0001 0.8319 0.0407
(x1)2 73.86 6608.39 729.73 73.86 6608.39 729.73 1.69 7.07 22.26 0.2227 0.0239 0.0008
(x2)2 0.65 888.79 160.88 0.65 888.79 160.88 0.015 0.95 4.91 0.9050 0.3523 0.0511
(x3)2 1727.55 490.03 748.33 1727.55 490.03 748.33 39.54 0.52 22.83 <0.0001 0.4855 0.0007
x1x2 8.84 13.12 39.94 8.84 13.12 39.94 0.20 0.014 1.22 0.6625 0.9080 0.2955
x1x3 8.50 39.84 14.37 8.50 39.84 14.37 0.19 0.043 0.44 0.6685 0.8405 0.5229
x2x3 11.94 5.79 2.56 11.94 5.79 2.56 0.27 6.20  103 0.078 0.6125 0.9388 0.7857

Qe,AY-6 = amount adsorbed of AY-6, Qe,AY-23 = amount adsorbed of AY-23, Qe,AR-18 = amount adsorbed of AR-18, degree of freedom = 1 for all parameters
(x1 ; x2 ; x3 ; x21 ; x22 ; x23 ; x1 x2 ; x1 x3 ; x2 x3 ).

dye concentration (mg L1). The experimental planning responses
were the amount adsorbed of AY-6 (Qe,AY-6), amount adsorbed of
AY-23 (Qe,AY-23), and amount adsorbed of AR-18 (Qe,AR-18). The
coded values of each factor level were obtained by Eqs. (2) and
(3) shows the second-order polynomial regression model used:
xi X i  X 0 =DX i
the constant term, bi is the linear effect term, bii is the quadratic ef-
fect term, and bij is the interaction effect term), and Y is the re-
sponse value predicted by the model.
The statistical signicance was evaluated by variance analysis
(ANOVA) and also by the determination coefcient (R2). The pro-
grams Design Expert (Version 6.0.5) and STATISTICA 7.0 (StatSoft)
2 were used to study all the parameters and experiment data.

X
3 X
3 X
2 X
3
Y b0 bi xi bii x2i bij xi xj 3 3. Results and discussion
i1 i1 i1 ji1
3.1. Simultaneous analysis of AY-6, AY-23, and AR-18 in ternary
where for Eq. (2), xi is the coded value for each factor, Xi is the real mixtures
value for each factor, X0 is the real value for each factor at the cen-
tral point, and DXi is the difference between the levels of each fac- Fig. 1 shows the zero order spectra for AY-6, AY-23, AR-18, and
tor. For Eq. (3), b0, bi, bii, and bij are the regression coefcients (b0 is ternary mixture. The maximum wavelengths (kmax) appear at
176 A.M.M. Vargas et al. / Chemical Engineering Journal 195196 (2012) 173179

Table 5
Variance analyses (ANOVA) of the quadratic models adjusted to the Qe,AY-6, Qe,AY-23,
and Qe,AR-18 results.

Source Sum of DF Mean F ratio p Value R2

squares square
Qe,AY-6
Model 36344.95 9 4038.33 92.43 <0.0001 0.9881
Residual 436.90 10 43.69
Lack of t 425.00 5 85.00 35.74 0.0006
Pure error 11.89 5 2.38
Total 36781.84 19
Qe,AY-23
Model 14220.83 9 1580.09 1.69 0.2122 0.6036
Residual 9340.83 10 934.08
Lack of t 9294.39 5 1858.88 200.17 <0.0001
Pure error 46.43 5 9.29
Total 23561.65 19
Qe,AR-18
Model 2405.51 9 267.28 8.15 0.0015 0.8801
Residual 327.81 10 32.78
Lack of t 176.59 5 35.32 1.17 0.4345
Pure error 151.22 5 30.24
Total 2733.32 19

Qe,AY-6 = amount adsorbed of AY-6, Qe,AY-23 = amount adsorbed of AY-23, Qe,AR-

18= amount adsorbed of AR-18, DF = degree of freedom, R2 = determination
coefcient.

AR-18 because their absorbance in this wavelength is equal to zero.

At 584 nm, AR-18 can be determined, whereas the absorbances of
AY-6 and AY-23 are equal to zero. However, AY-23 does not have a
point at which the absorbances of AY-6 and AR-18 are zero and AY-
23 shows a signal. Thus, the concentration of this dye was deter-
mined using the additive law of absorbance [15]. The wavelength
(k) of 444 nm was selected for the determination of AY-23
(Fig. 2), considering that at this point, the derivative signal value
is higher (in module) than the signals for AY-6 and AR-18. The cal-
culations involved are based on the fact that the molar absorptivity
values for AY-6 and AR-18 are known at k = 444 nm and that their
concentrations were previously determined at 552 nm and
584 nm, respectively. Therefore, subtracting the absorbance values
of AY-6 and AR-18 from the total absorbance value of the mixture,
the absorbance of AY-23, and consequently, its concentration, can
be determined. According to the aforementioned, the following
equation can be written as:

AT444 nm AAY-6444 nm AAY-23444 nm AAR-18444 nm 4

where AT(444 nm), AAY-6(444 nm), AAY-23(444 nm), and AAR-18(444 nm) cor-
respond to the total absorbance for the mixture, AY-6, AY-23, and
AR-18, respectively, at 444 nm. The calibration equations used for
determinations by second order derivative spectrophotometry are
given in Table 1.

3.2. Inuence of the factors on Qe,AY-6, Qe,AY-23, and Qe,AR-18 responses

Fig. 3. Inuence of some factors over Qe,AY-6, Qe,AY-23, and Qe,AR-18 responses.
483 nm, 431 nm and 510 nm for AY-6, AY-23, and AR-18, respec-
tively. The individual spectra for the three dyes show kmax very
close to each other with a large overlap among them, not being
possible to determine their concentrations in the ternary mixture.
To solve this overlap problem and determine the dyes simulta-
neously, the second order derivates of the spectra were obtained
as shown in Fig. 2. The second order derivative spectra shows that
AY-6 can be determined at 552 nm in the presence of AY-23 and
The real and codied values of the three factors of each exper-
iment are shown in Table 2. The development of the experiments,
as well as the experimental response values of Qe,AY-6, Qe,AY-23, and
Qe,AR-18 are shown in Table 3. Table 4 presents the variance analysis
of all of the linear, quadratic, and interaction effects of the three
planning factors with regard to Qe,AY-6, Qe,AY-23, and Qe,AR-18. Fig. 3
shows the inuence of some of these factors over the responses.
The x3, and (x3)2 effects were signicant for Qe,AY-6, and the x1, x2,
(x1)2, (x2)2, x1x2, x1x3, and x2x3 effects were not signicant. For
Qe,AY-23, the x1, and (x1)2 effects were signicant and the x2, x3,
(x2)2, (x3)2, x1x2, x1x3, and x2x3 effects were not signicant. On the
other hand, the x2, x3, (x1)2, and (x3)2 effects were signicant for
Qe,AR-18 and the x1, (x2)2, x1x2, x1x3, and x2x3 effects were not signif-
icant. A quadratic regression model was obtained for the three re-
 A.M.M. Vargas et al. / Chemical Engineering Journal 195196 (2012) 173179
(a)
350
Predicted Qe,AY-6 values (mg/g)
315
280
245
210
175
150 180 210 240 270 300
Experimental Qe,AY-6 values (mg/g)
(c)
Predicted Qe,AR-18 values (mg/g)
Fig. 4. Relation between values predicted by the models and experimental values for the three responses.
sponses. The codied values for the quadratic equations after
excluding the insignicant terms are shown in Eqs. (5)(7):
Q e;AY-6 278:56 50:01x3  10:9x3 2
Q e;AY-23 45:78  19:75x1 21:41x1 2
Q e;AR-18 150:66 5:04x2 3:64x3 7:12x1 2  7:21x3 2
Positive values in these equations indicate that these terms in-
crease the response and the negative values decrease the response.
According to Fig. 3a, the increase of initial concentration values in-
creases the Qe,AY-6 values indicating that the linear effect x3 was the
factor most important for the adsorption of AY-6. For AY-23
(Fig. 3b), the response (Qe,AY-23) increases when the pH decreases,
which means that the linear effect x1 was the most important fac-
tor. For AR-18, the linear effects x2 and x3 were important because,
as shown in Fig. 3c, the initial concentration increase and adsorp-
tion time caused a increase of the Qe,AR-18 values. The Qe,AR-18 de-
crease at high values of x3 could be attributed to the saturation
of AR-18 (Fig. 3c). The F ratio values, shown in Table 4, also conrm
the behavior of these effects (to be signicant, the effects must
have an F ratio > F = 0.05(1,10) = 4.96 and a p value < 0.05). The
interaction terms did not show any inuence over the responses
and the quadratic terms were not considered because they indi-
cated behaviors that occurred outside the studied value ranges.
3.2.1. Variance analyses (ANOVA) of the models
Table 5 shows the variance analysis (ANOVA) of the quadratic
model adjusted to Qe,AY-6, Qe,AY-23, and Qe,AR-18. For a model to be
signicant and have a good t, the F ratio value for the regression
177
(b)
150
Predicted Qe,AY-23 values (mg/g)
125
100
75
50
25
330 30 60 90 120 150 180 210
Experimental Qe,AY-23 values (mg/g)
180
170
160
150
140
130
120
120 130 140 150 160 170 180
Experimental Qe,AR-18 values (mg/g)
must be higher than F = 0.05(9,10) = 3.02, and for lack of t, lower
than F = 0.05(5,5) = 5.05. In addition, the p value for the regression
must be lower than 0.05 and the p value for lack of t, higher than
5 0.05. Thus, the regression model for Qe,AY-6 was signicant; how-
ever, it shows a lack of t. For Qe,AY-23, the regression model was
6 not signicant, consequently showing a lack of t. On the other
hand, Qe,AR-18 shows a signicant regression model without lack
7 of t. The p values, shown in Table 5, also support the aforemen-
tioned behavior. The determination coefcient (R2) for the models
indicates that they explain 98.81, 60.36, and 88.01% of the varia-
tions around the average for Qe,AY-6, Qe,AY-23, and Qe,AR-18, respec-
tively. For residuals, 1.19, 39.64, and 11.99% for Qe,AY-6, Qe,AY-23,
and Qe,AR-18, respectively, remain. Fig. 4ac shows the relation be-
tween values predicted by the models and the experimental values
for the three responses.
3.2.2. Behavior of the ternary adsorption of the dyes onto ACop
The study of the inuence of the individual effects (Section 3.2)
and the variance analysis (Section 3.2.1) for each model allow
understanding the adsorption behavior of each dye in the ternary
mixture. Due to competition and interference, each dye adsorbs
under favorable and specic conditions. For AY-6, only the initial
concentration inuenced the adsorption process, while the process
was independent on the pH and adsorption time. According to Ref.
[5], the length of the AY-6 molecule is equal to that of AR-18, and
shorter than that of AY-23. Additionally, it has the lowest molecu-
lar weight (452.36 g mol1), and its kinetic models showed that the
equilibrium is attained rapidly [5]. Therefore, the facility of AY-6 to
enter the ACop pores and its fast adsorption allows this dye to be
the most adsorbed onto the ACop, showing Qe.AY-6 values from
163.909 to 325.315 mg g1 (Table 3). The regression model for
178 A.M.M. Vargas et al. / Chemical Engineering Journal 195196 (2012) 173179
Fig. 5. Behavior of AY-6 (red), AY-23 (black), and AR-18 (blue) in simultaneously adsorption onto ACop. (For interpretation of the references to color in this gure legend, the
reader is referred to the web version of this article.)
AY-6 (Table 5) shows a lack of t, indicating that the levels of the
factors studied can be changed to obtain a better t.
For the adsorption of AY-23, only the pH showed to be signi-
cant. This was conrmed in the experiment with pH equal to 2.3
(Table 3), which showed the highest value of Qe.AY-23
(199.584 mg g1). Excluding this experiment, the Qe.AY-23 values
ranged just between 35.419 and 52.033 mg g1 (Table 3 and
Fig. 4b). The small variation of these values means that the regres-
sion model was not adjusted to the experimental data (Table 5).
On the other hand, the regression model for AR-18 was signi-
cant and without lack of t (Table 5). Adsorption time and initial
dye concentration were the most important factors in the adsorp-
tion process of AR-18 onto ACop. The values of Qe.AR-18 ranged be-
tween 132.075 and 179.088 mg g1 (Table 3).
Based on the behavior of the factors studied (pH, adsorption
time, and initial dye concentration), structural dimensions, molec-
ular weights, and adsorbed amount (Qe); an adsorption sequence of
the dyes onto ACop can be proposed. The rst dye to enter the ACop
pores is AY-6, since it has the smallest molecular weight and a
structure that facilitates its adsorption. Despite the competition
of the other dyes for adsorption sites, AY-6 is adsorbed preferen-
tially and, for this reason, it is more adsorbed than AY-23 and
AR-18. At the same time that the adsorption of AY-6 occurred,
probably a small quantity of AR-18 was adsorbed onto ACop, since
this dye also showed higher Qe values. After AY-6 reached equilib-
rium, the adsorption of AR-18 increased gradually. It is important
to point out that AY-6 and AR-18 were inuenced by the initial
dye concentration alone, while AR-18 was also inuenced by the
adsorption time. This indicates that the AR-18 in solution needs
a longer adsorption time to attain equilibrium, being the second
dye to enter the pores of ACop. Furthermore, the molecular weight
of AR-18 (604.46 g mol1) is higher than that of AY-6
(452.36 g mol1), which supports this hypothesis. On the other
hand, a different behavior was observed for AY-23. This dye was
little adsorbed in comparison to the other dyes, and the data indi-
cates that it probably does not enter the ACop pores because its
adsorption was only due to the chemical interactions with func-
tional groups present on the surface of ACop, such as carboxylic
and phenolic groups [9]. Obviously, these groups participate in
the adsorption of the three dyes; however, for AY-23, these inter-
actions play a major role. Unlike AY-6 and AR-18, AY-23 is inu-
enced by the solution pH. Furthermore, a previous study showed
that the three dyes adsorbed preferentially in acid solution [5].
Thus, both electrostatic and non-electrostatic interactions help
AY-23 to stay adsorbed on the outer surface of ACop without need-
ing to enter the pores. The fact that the structure of AY-23 has the
largest steric impediment in relation to the other dyes supports
this hypothesis [5]. Thus, after AY-6 and AR-18 have attained equi-
librium, a small quantity of AY-23 attains the adsorption equilib-
rium on the surface of ACop, mainly in acid solution. Fig. 5 allows
understanding the adsorption behavior of the three dyes onto ACop.
According to this gure, dyes AY-6 and AR-18 enter the ACop pores,
while AY-23 does not, staying on the surface of ACop. Ultimately,
the best adsorption condition of three dyes was chosen according
to the results in Table 3. Thus, the experimental pH, adsorption
time, and initial dye concentration values of 2.3, 60 min, and
350 mg L1, respectively, were the best conditions, giving Qe,AY-6,
Qe,AY-23, and Qe,AR-18 values equal to 254.493, 199.584, and
164.438 mg g1, respectively. In addition, the Qe values for the ter-
nary solution were higher or close to those of some studies in
 A.M.M. Vargas et al. / Chemical Engineering Journal 195196 (2012) 173179
which these dyes were individually adsorbed, indicating that even
in the presence of the three dyes in solution, ACop had a high
adsorption capacity [4,5,34].
4. Conclusion
ACop, an activated carbon produced from amboyant pods
(Delonix regia), was used to remove a ternary mixture of the food
dyes Acid Yellow 6 (AY-6), Acid Yellow 23 (AY-23), and Acid Red
18 (AR-18). The second order derivative spectra showed that AY-
6, AY-23, and AR-18 can be determined at 552, 584, and 444 nm,
respectively. For AY-23, the additivity law was applied to the spec-
tra. The response surface methodology was applied for under-
standing the factors that inuenced the adsorption process of the
three dyes onto ACop. For AY-6, AY-23, and AR-18, the central com-
posite rotatable design showed that the initial dye concentration,
pH, and adsorption time and initial dye concentration, respectively,
were the most important factors in the simultaneous adsorption
process. The inuence of molecular weight, structural dimensions,
and accessibility to the ACop pores were also discussed. The dyes
AY-6 and AR-18 entered the pores, while the AY-23 did not, staying
on the surface of ACop. The best condition among those of all exper-
iments gave Qe,AY-6, Qe,AY-23, and Qe,AR-18 values equal to 254.493,
199.584, and 164.438 mg g1, respectively. This result indicates
that high quantities of dyes AY-6, AY-23, and AR-18 can be re-
moved from aqueous solutions using ACop as an adsorbent in a ter-
nary solution of these dyes.
Acknowledgements
The authors acknowledge Fundao Araucria and CAPES for
the nancial support.
References
[1] R. Jain, M. Bhargava, N. Sharma, Electrochemical studies on a pharmaceutical
azo dye: tartrazine, Ind. Eng. Chem. Res. 42 (2003) 243247.
[2] M.A. Prado, H.T. Godoy, Corantes articiais em alimentos, Alim. Nutr. 14 (2003)
237250.
[3] X. Pan, P. Qin, R. Liu, J. Wang, Characterizing the interaction between tartrazine
and two serum albumins by a hybrid spectroscopic approach, J. Agric. Food
Chem. 59 (2011) 66506656.
[4] R. Shokoohi, V. Vatanpoor, M. Zarrabi, A. Vatani, Adsorption of Acid Red 18
(AR18) by activated carbon from poplar wood a kinetic and equilibrium
study, E-J. Chem. 7 (2010) 6572.
[5] A.M.M. Vargas, A.L. Cazetta, A.C. Martins, J.C.G. Moraes, E.E. Garcia, G.F. Gauze,
W.F. Costa, V.C. Almeida, Kinetic and equilibrium studies: adsorption of food
dyes Acid Yellow 6, Acid Yellow 23, and Acid Red 18 on activated carbon from
amboyant pods, Chem. Eng. J. 181182 (2012) 243250. [31] I.A.W. Tan, A.L. Ahmad, B.H. Hameed, Optimization of preparation conditions
[6] B.H. Hameed, F.B.M. Daud, Adsorption studies of basic dye on activated carbon
derived from agricultural waste: Hevea brasiliensis seed coat, Chem. Eng. J. 139
(2008) 4855.
[7] M. Hadi, M.R. Samarghandi, G. McKay, Equilibrium two-parameter isotherms
of acid dyes sorption by activated carbons: study of residual errors, Chem. Eng.
J. 160 (2010) 408416.
[8] V. Gmez, M.S. Larrechi, M.P. Callao, Kinetic and adsorption study of acid dye
removal using activated carbon, Chemosphere 69 (2007) 11511158.
[9] A.M.M. Vargas, A.L. Cazetta, M.H. Kunita, T.L. Silva, V.C. Almeida, Adsorption of
methylene blue on activated carbon produced from amboyant pods (Delonix
regia): study of adsorption isotherms and kinetic models, Chem. Eng. J. 168
(2011) 722730.
[10] E.N. El Qada, S.J. Allen, G.M. Walker, Adsorption of basic dyes from aqueous
solution onto activated carbons, Chem. Eng. J. 135 (2008) 174184.
179
[11] Y.S. Al-Degs, M.I. El-Barghouthi, A.H. El-Sheikh, G.M. Walker, Effect of solution
pH, ionic strength, and temperature on adsorption behavior of reactive dyes on
activated carbon, Dyes Pigments 77 (2008) 1623.
[12] S. Azizian, M. Haerifar, H. Bashiri, Adsorption of methyl violet onto granular
activated carbon: equilibrium, kinetics and modeling, Chem. Eng. J. 146 (2009)
3641.
[13] Z.-H. Zhong, Q. Yang, X.-M. Li, K. Luo, Y. Liu, G.-M. Zeng, Preparation of peanut
hull-based activated carbon by microwave-induced phosphoric acid activation
and its application in Remazol Brilliant Blue R adsorption, Ind. Crop. Prod. 37
(2012) 178185.
[14] A.L. Cazetta, A.M.M. Vargas, E.M. Nogami, M.H. Kunita, M.R. Guilherme, A.C.
Martins, T.L. Silva, J.C. Moraes, V.C. Almeida, NaOH-activated carbon of high
surface area produced from coconut shell: kinetics and equilibrium studies
from the methylene blue adsorption, Chem. Eng. J. 174 (2011) 117125.
[15] J. Karpinska, Review derivative spectrophotometry recent applications and
directions of developments, Talanta 64 (2004) 801822.
[16] F.S. Rojas, C.B. Ojeda, Review recent development in derivative ultraviolet/
visible absorption spectrophotometry: 20042008, a review, Anal. Chim. Acta
635 (2009) 2244.
[17] G. Talsky, Derivative Spectrophotometry, rst ed., VCH, Weinheim, 1994.
[18] M.I. Toral, S. Pope, S. Quintanilla, P. Richter, Simultaneous determination of
amiloride and furosemide in pharmaceutical formulations by rst digital
derivative spectrophotometry, Int. J. Pharm. 249 (2002) 117126.
[19] B. Morelli, Derivative spectrophotometry in the analysis of mixtures of
cefotaxime sodium and cefadroxil monohydrate, J. Pharmaceut. Biomed. 32
(2003) 257267.
[20] A. Espinosa-Mansilla, A.M. de la Pea, F. Salinas, A. Zamoro, Simultaneous
determination of pesticides by multivariate spectral analysis and derivative
spectrophotometry, Anal. Chim. Acta 258 (1992) 4753.
[21] A. Varghese, A.M.A. Khadar, B. Kalluraya, Simultaneous determination of
titanium and molybdenum in steel samples using derivative
spectrophotometry in neutral micellar medium, Spectrochim. Acta A 64
(2006) 383390.
[22] V.C. Almeida, A.M.M. Vargas, J.C. Garcia, E. Lenzi, C.C. Oliveira, J. Nozaki,
Simultaneous determination of the Textile Dyes in industrial efuents by rst-
order derivative spectrophotometry, Anal. Sci. 25 (2009) 487492.
[23] S. Altnz, S. Toptan, Simultaneous determination of Indigotin and Ponceau-4R
in food samples by using Vierordts method, ratio spectra rst order derivative
and derivative UV spectrophotometry, J. Food Comp. Anal. 16 (2003) 517530.
[24] E.C. Vidotti, J.C. Cancino, C.C. Oliveira, M.C.E. Rollemberg, Simultaneous
determination of food dyes by rst derivative spectrophotometry with
sorption onto polyurethane foam, Anal. Sci. 21 (2005) 149153.
[25] D.C. Montgomery, Design and Analysis of Experiments, fth ed., John Wiley &
Sons, New York, 2001.
[26] M.A. Bezerra, R.E. Santelli, E.P. Oliveira, L.S. Villar, L.A. Escaleira, Response
surface methodology (RSM) as a tool for optimization in analytical, Talanta 76
(2008) 965977.
[27] R.H. Myers, D.C. Montgomery, Response Surface Methodology Process and
Product Optimization Using Designed Experiments, rst ed., John Wiley &
Sons, New York, 1995.
[28] B.H. Hameed, I.A.W. Tan, A.L. Ahmad, Preparation of oil palm empty fruit
bunch-based activated carbon for removal of 2,4,6-trichlorophenol:
optimization using response surface methodology, J. Hazard. Mater. 164
(2009) 13161324.
[29] B.H. Hameed, I.A.W. Tan, A.L. Ahmad, Optimization of basic dye removal by oil
palm bre-based activated carbon using response surface methodology, J.
Hazard. Mater. 158 (2008) 324332.
[30] I.A.W. Tan, A.L. Ahmad, B.H. Hameed, Preparation of activated carbon from
coconut husk: optimization study on removal of 2,4,6-trichlorophenol using
response surface methodology, J. Hazard. Mater. 153 (2008) 709717.
for activated carbons from coconut husk using response surface methodology,
Chem. Eng. J. 137 (2008) 462470.
[32] A.M.M. Vargas, C.A. Garcia, E.M. Reis, E. Lenzi, W.F. Costa, V.C. Almeida, NaOH-
activated carbon from amboyant (Delonix regia) pods: optimization of
preparation conditions using central composite rotatable design, Chem. Eng.
J. 162 (2010) 4350.
[33] A.M.M. Vargas, A.L. Cazetta, C.A. Garcia, J.C.G. Moraes, E.M. Nogami, E. Lenzi,
W.F. Costa, V.C. Almeida, Preparation and characterization of activated carbon
from a new raw lignocellulosic material: amboyant (Delonix regia) pods, J.
Environ. Manage. 92 (2011) 178184.
[34] G.L. Dotto, L.A.A. Pinto, Adsorption of food dyes acid blue 9 and food yellow 3
onto chitosan: stirring rate effect in kinetics and mechanism, J. Hazard. Mater.
187 (2011) 164170.