Arabian Journal of Chemistry (2019) 12, 1322–1337

King Saud University

Arabian Journal of Chemistry

www.ksu.edu.sa
www.sciencedirect.com

SPECIAL ISSUE: ENVIRONMENTAL CHEMISTRY

Adsorption of Basic Magenta II onto H2SO4

activated immature Gossypium hirsutum seeds:
Kinetics, isotherms, mass transfer, thermodynamics
and process design
N. Sivarajasekar *, R. Baskar *

Department of Chemical Engineering, Kongu Engineering College, Perundurai, Erode 638052, Tamil Nadu, India

Received 6 June 2013; accepted 29 October 2014

Available online 18 November 2014

KEYWORDS Abstract The adsorption of Basic Magenta II onto H2SO4 activated immature Gossypium hirsutum
Gossypium hirsutum seeds; seeds was analysed using Ho, modified Freundlich, Sobkowsk–Czerwi, Blanchard, Elovich, Avram-
Isotherms; i, and modified Ritchie kinetic models by nonlinear regression-sum of normalized errors analysis.
Kinetics; The goodness of fit was evaluated with coefficient of determination and root mean square error.
Mass transfer; The good agreement of experimental data to Avrami second-order model indicated that the mech-
Thermodynamics; anism of adsorption followed multiple kinetic orders. The Avrami second-order mechanism was
Process design applied to predict the rate constant of sorption and the equilibrium capacity and subsequently
the obtained equilibrium adsorption capacities were utilized to find the equilibrium concentrations.
Langmuir, Freundlich, Temkin, Sips and Hill isotherms were investigated to understand the nature
of adsorption with the help of nonlinear regression analysis. Both Sips and Hill isotherms were best
fit to the adsorption equilibrium data showing the homogeneous adsorption on the heterogeneous
surface of carbon and the positive co-operative manifestations of the Basic Magenta II molecules.
The mass transfer study depicted the details such as mass transfer coefficient, intra-particle diffusion
rate, pore diffusion coefficient, and film diffusion coefficient. The adsorption process was found to
be controlled by film diffusion. The thermodynamic parameters like, Gibbs free energy change,

* Corresponding authors. Tel.: +91 4294 226600; fax: +91 4294

220087 (N. Sivarajasekar). Tel.: +91 4294 226602; fax: +91 4294
220087 (R. Baskar).
E-mail addresses: sivarajasekar@gmail.com (N. Sivarajasekar),
naturebaskar@yahoo.co.in (R. Baskar).
Peer review under responsibility of King Saud University.

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http://dx.doi.org/10.1016/j.arabjc.2014.10.040
1878-5352 ª 2014 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University.
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Adsorption of Basic Magenta II onto H2SO4 activated immature Gossypium hirsutum seeds 1323

enthalpy change, entropy change and isosteric heat of adsorption confirmed the endothermic, fea-
sible and spontaneous nature of adsorption. A single stage batch adsorber was designed using Sips
isotherm constants to estimate the amount of carbon required for desired purification.
ª 2014 The Authors. Production and hosting by Elsevier B.V. on behalf of King Saud University. This is
an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/3.0/).

1. Introduction Adsorption process design demands the insight into the

equilibrium adsorption capacity, the mass transfer rate, the
Industries such as textile, plastic, tannery, packed food, pulp and rate controlling step and the thermodynamics of the adsorp-
paper, paint and electroplating are extensively using more than tion process. Therefore, it is important to have information
10,000 synthetic dyes in their processes (Fu and Viraragvahan, relating to the rate of dye removal, the liquid phase diffusion
2002; Radha et al., 2005; Bayramoglu and Yakup Arica, coefficients, Gibbs free energy, enthalpy and entropy of the
2007). Since many of the organic dyestuffs are harmful to plant system (Ofomaja, 2011; Sivarajasekar and Baskar, 2014).
and animal biota, removal of dyestuffs from wastewater has Even though many agricultural and waste materials were
received considerable attention over the past decades. Textile used as adsorbents for the removal of colour, adsorbent
industries are responsible for the discharge of large quantities derived from immature Gossypium hirsutum seeds were never
of dyes into natural water bodies due to the inefficiencies in dye- reported yet to the best of our knowledge. Therefore an
ing techniques (Forgacs et al., 2004). Cationic dyes are exten- attempt was made to prepare adsorbent from immature G.
sively used in the textile industry because of their favourable hirsutum seeds via chemical activation and to examine its abil-
characteristics of bright colour, high solubility in water, simple ity of up-taking BM2 from aqueous solution. The experimen-
application technique, and low-energy consumption (Heiss tal data resulting from batch adsorption experiments were
et al., 1992). Among them, Basic Magenta II (BM2) is widely analysed by using two-parameter (Ho, modified Freundlich,
employed in acrylic, wool, nylon and silk dyeing. It may decom- and Sobkowsk–Czerwi) and three-parameter (Blanchard, Elo-
pose into carcinogenic aromatic amines under anaerobic condi- vich, Avrami, and modified Ritchie) kinetic models. The equi-
tions, so discharge of this dye bearing effluent into water bodies librium data pertained to the well-fitting kinetic models were
can cause harmful effects such as allergic dermatitis, skin irrita- adopted for examine the suitability of five different isotherms
tion, mutations and cancer (Nawar and Doma, 1989; (Langmuir, Freundlich, Temkin, Sips and Hill). Sum of nor-
Roderiguez-Reininoso and Molino Sabio, 1992; Pollard et al., malized errors and statistical comparison values were applied
1992; Srinivasan and Viraraghavan, 2010). Keeping the toxicity to find a best fitting isotherm. The feasibility of the adsorption
of the dye in view there is an urgent need to develop effective process under various temperatures was studied and a single
methods for its removal from the waste water. Different physico- stage batch adsorber was designed.
chemical methods like coagulation, ozonation, chemical oxida-
2. Materials and methods
tion, solvent extraction, ion exchange, photo-catalytic
degradation, and adsorption have been tried by many research-
ers for the treatment of dye bearing water. Amid all the methods 2.1. Chemicals
mentioned, adsorption is an effective and eco-friendly process
for colour removal from wastewaters due to its simple design, Basic Magenta II (also called Basic red 9, molecular
easy operation and its efficacy to remove a wide range of com- weight = 337.86, chemical formula C20H20ClN3 and kmax =
pounds (Nawar and Doma, 1989; Roderiguez-Reininoso and 550 nm) was obtained from Hi Media Laboratories Ltd, Mum-
Molino Sabio, 1992; Pollard et al., 1992). Activated carbon bai. All other chemicals used were obtained from Merck India
has been extensively utilized as adsorbent in the recent past Ltd, Mumbai. The structure of BM2 is shown in Fig. 1.
due to the presence of various oxygenated functional surface
groups and its pore structure. Recognizing the high cost of acti- 2.2. Preparation of dye solution
vated carbon, many investigators have attempted for replacing it
by cheap, commercially available and renewable bio-based The stock solution of BM2 was prepared by dissolving 1 g of
materials (Pollard et al., 1992; Rafatullah et al., 2010; Amran dye in 1 l of doubly distilled water. All working solutions were
et al., 2011). Some among them include: apricot stones (Philip,
1996), Spirogyra (Sivarajasekar et al., 2008), white oak
(Jagtoyen and Derbyshire, 1998), deoiled soya (Gupta et al.,
2008), Acacia (Sivarajasekar et al., 2009), date pits (Girgis and
Abdel-Nasser, 2002), palm shell (Jia-Guo et al., 2005), cellulose
(Zhou et al., 2012), sunflower stalks (Shi et al., 1999), sewage
sludge (Martin et al., 2003), olive mill waste (Moreno-
Castillaa et al., 2001), Zizania latifolia (Huang et al., 2012),
coconut shell (Hu and Srinivasan, 1999), peanut hull (Girgis
et al., 2002), lignin (Hayashi et al., 2000), coir pith
(Namasivayam and Sangeetha, 2004), corn cob (Tsai et al.,
2001), rice husk (Daifullah et al., 2004), walnut shell (Jin-Wha
et al., 2001), coffee bean husk (Baquero et al., 2003) and etc.
Figure 1 Structure of BM2.
1324 N. Sivarajasekar, R. Baskar

prepared by diluting the stock solution with doubly distilled (Remi R-24 Centrifuge, India) to remove the suspended solids.
water to the desirable concentration. The initial pH of working The clear supernatants were analysed for the residual dye con-
solution was adjusted to the required value by adding 0.1 N centration using double beam UV–Vis spectrophotometer
HCl or 0.1 N NaOH solutions before mixing the adsorbent (ELICO-SL244, India). The dye adsorption capacity qt
with the dye solution. The concentration of dye in the sample (mg g1) was determined as
was analysed using a double beam UV–Vis spectrophotometer
(ELICO-SL244, India) at a maximum wavelength of 550 nm. V
qt ¼ ðC0  Ct Þ  ð1Þ
M
2.3. Activated carbon preparation where C0 (mg l1) and Ct (mg l1) are initial and final concen-
tration of BM2, V (l) is volume of dye solution, and M (g) is
Immature G. hirsutum seeds were collected from G. hirsutum amount of IGHSAC.
seed producers near Attur, Tamil Nadu, India. The collected
seeds were washed thoroughly with distilled water to remove
dirt and dried at 40 C in a temperature controlled oven for 2.6. Nonlinear error analysis
3 days. The dried biomass was soaked with 98% concentrated
sulphuric acid in the weight ratio of 1:4 (1 g G. hirsutum seed: Frequently, by linear regression magnitude of the coefficient of
4 g H2SO4). In order to achieve effective activation the acid determination (R2) is the index to measure the quality of the fit
soaked biomass was stirred periodically and kept for 12 h. to the batch adsorption data. However, transformation of
The resultant slurry was carefully washed with doubly distilled non-linear equations into linear ones utterly upset their error
water. Further, the traces of acid were removed by washing the structure and may defy the error variance of normality
material twice with 0.1 N sodium bicarbonate solution. The assumptions of standard least squares (Myers, 1990;
resultant material, immature G. hirsutum seed activated carbon Ratkowski, 1990). Additionally linear regression is not always
(IGHSAC) was dried, finely ground sieved with 170 mesh and a good choice to apply for equations with more than two
stored in an air tight container to subsequently use it in the parameters and therefore the non-linear regression analysis is
batch adsorption experiments. preferable to determine isotherm and kinetic parameters (Ho,
2006; Kumar and Sivanesan, 2007; Ncibi, 2008). Generally,
2.4. The characterization of IGHSAC the optimization procedure required an error function to be
able to evaluate the fit of the equation to the experimental data
The iodine number and methylene blue number of IGHSAC and the parameters derived can be affected by the choice of the
was calculated based on the ASTM 4607-86 standards at error function (Hanna and Sandall, 1995; Ho, 2004;
298 K (Moreno-Castillaa et al., 2001). To measure iodine num- Sivarajasekar and Baskar, 2013). Various error functions
ber, 0.1 g of carbon was washed initially by 5% HCl solution employed are:
and agitated with 100 ml of 0.1 N iodine solution until equilib- X
p

rium reached. The residual iodine concentration in the aque- Sum of the square error ðERRSQÞ : ðqt;meas  qt;calc Þ2i ð2Þ
i¼1
ous phase was determined by titrating with 0.1 N sodium
thiosulphate solution taking starch as an indicator. Methylene
blue number was determined by agitating 0.1 g of carbon with Derivative of hybrid fractional error function ðHYBRIDÞ
" #
10 ml of 150 mg l1 methylene blue solution. The concentra- Xp
ðqt;meas  qt;calc Þ2
tion of methylene blue was analysed using a double beam :
i¼1
qt;meas
UV–Vis spectrophotometer (ELICO-SL244, India) at i

665 nm. The specific surface area of IGHSAC was determined ð3Þ
from the adsorption–desorption isotherm of nitrogen 77 K
using a surface analyser (Micromeritics ASAP 2020). 1 g of Derivative of Marquardt’s percentage standardright
carbon was added to 100 ml of deionized water and agitated !2
for 2 h and the pH of the slurry was noted subsequently as Xp
qt;meas  qt;calc
deviation ðMPSDÞ : ð4Þ
the pH of carbon. The bulk density of the carbon was mea- i¼1
qt;meas
i
sured using a pycnometer.
p 
X 
qt;meas  qt;calc 
2.5. Batch adsorption Average relative error ðAREÞ :   ð5Þ
 q 
i¼1 t;meas i

Batch adsorption studies were conducted for the selected con- X

p
 
centration range (50–250 mg l1), at the pH of 12, IGHSAC The sum of absolute errors ðEABSÞ : qt;meas  qt;calc  ð6Þ
i
dosage of 5 g and contact time of 3 h. The thermodynamic i¼1

studies were carried at four different temperatures (20– where qt,meas is adsorption capacity from experiment
40 C). Each experiment were carried out by agitating 5 g of (mg g1), qt,calc is adsorption capacity calculated from mod-
adsorbent with 200 ml of dye solution taken in Erlenmeyer els (mg g1), qt;calc is mean adsorption capacity calculated
flasks and agitating them using a thermo-regulated shaker from models (mg g1), n is number of data points, p is num-
(GeNei SLM-IN-OS-16, India) operating at 100 rpm. The ber of variables in the models. The statistical comparison
samples were withdrawn from the flasks at predetermined time values such as coefficient of determination (R2) and root
intervals for kinetic studies and at equilibrium time for iso- mean square error (RMSE) can also be utilized to gauge
therm studies. Obtained samples were centrifuged for 2 min the goodness of the fit.
Adsorption of Basic Magenta II onto H2SO4 activated immature Gossypium hirsutum seeds 1325

Coefficient of determination ðR2 Þ q2e kHo t

qt ¼ ð9Þ
ðqt;meas  qt;calc Þ2i 1 þ kHo qe t
: Pp ð7Þ
 qt;calc Þ2 þ ðqt;meas  qt;calc Þ2 where kHo (g mol1 min1) is the rate constant of pseudo-sec-
i¼1 ðqt;meas
ond-order model which can be useful to calculate the initial
Root mean square errorðRMSEÞ sorption rate h (mg g1 min1), as follows:
sffiffiffiffiffiffiffiffiffiffiffi
h ¼ kHo q2e ð10Þ
1 X
p
: ðq  qt;calc Þ2 ð8Þ
p  2 i¼1 t;meas The modified Freundlich equation was authored by Kuo
and Lotse (Yeddou et al., 2010):
These error functions and statistical comparison values can
be evaluated using the tools like solver add-in with Microsoft’s qt ¼ kmF Ci t1=mmF ð11Þ
spread sheet, Excel (Microsoft, 1995) through any of the iter- 1 1
where kmF (l g min ) is the apparent adsorption rate con-
ation methods. The application of these five different error stant, and m is the Kuo–Lotse constant. The values of kmF
methods will produce different parameter sets; therefore, it is and mmF were used empirically to evaluate the effect of solute
hard to recognize an overall optimum parameter set. In order surface loading and ionic strength on the adsorption process.
to facilitate a meaningful comparison between the isotherms Blanchard et al. (1984) postulated a second order kinetic
parameter sets, the procedure of ‘sum of the normalized errors’ model assuming that the solute adsorption on the adsorbent
(SNE) is usually adopted (Ho et al., 2002; Foo and Hameed, follows ion exchange mechanism. Blanchard model is given as
2010). This approach allows a direct comparison of the scaled
errors and thus identifies the parameter set that would provide kBla qe t þ aBla qe  1
qt ¼ ð12Þ
the closest fit to the measured data. The parameter set derived kBla t þ aBla
based on the smallest SNE will be an optimal one providing where kBla (min1) is Blanchard kinetic rate constant and aBla
that there is no bias in the data sampling and type of error is Blanchard model constant. This model reduces to Ho model
functions selected. when aBla is equal to 1/qe.
Elovich equation is also used successfully to describe sec-
3. Result and discussion ond-order kinetic assuming that the actual solid surfaces are
energetically heterogeneous (Sparks, 1989). It can be expressed
3.1. Characterization of IGHSAC in the following form:
qt ¼ bE lnðrE bE Þ þ bE t ð13Þ
Iodine number is an index of pores with diameter ranging from 1 1
10 to 28 Å usually falls in the microporous range (<20 Å) where rE (mg g min ) is the initial adsorption rate, and the
which is 510 mg g1 in our case. The development of micro bE (g mg1) is related to the extent of surface coverage and
pores on the IGHSAC was depicted by methylene blue number activation energy for chemisorption.
since the molecular diameters of its molecules were 15 Å The Avrami kinetic equation determines some kinetic
(Kasaoka et al., 1981; Rajgopal et al., 2006) and was measured parameters as possible changes of the adsorption rates in terms
to be 42 mg g1. These results demonstrated that good amount of the initial concentration and the adsorption time in addition
of meso and micro-pores were developed on the surface of to the determination of fractional kinetic orders (Ho and
IGHSAC. The larger BET surface area (496.5 m2 g1) also McKay, 2003). Avrami kinetic equation can be written as
indicated the suitability of the carbon for dye adsorption. follows:
The pH and bulk density of IGHSAC were found to be 6.5 qt ¼ qe ½1  exp ðkAv tÞnAv  ð14Þ
and 0.56 g ml1 respectively. 1
where kAv (min ) is Avrami rate constant and nAv is Avrami
model exponent of time which is related to the adsorption
3.2. Kinetics
mechanism changes.
Ritchie Cheung et al. (2000) proposed a method for the sec-
The kinetics of solute sorption is required for selecting opti- ond-order kinetic adsorption of gases on solids. He assumed
mum operating conditions for the full-scale batch process. that the rate of adsorption of solute onto adsorbent depends
The kinetic parameter, which is supportive for the prediction solely on the fraction of surface sites (h), which are occupied
of adsorption rate and equilibrium time, gives important infor- by adsorbed gas. It is in the following form:
mation for designing and modelling the processes   
(Sivarajasekar and Baskar, 2014). Therefore various kinetic q 1
h¼ t ¼ 1 ð15Þ
equations including two-parameter kinetic models: Ho, modi- qe b R þ kR t
fied Freundlich, and Sobkowsk–Czerwi, and three-parameter where kR (min1) is the Ritchie rate constant and bR is Ritchie
kinetic models: Blanchard, Elovich, Avrami and modified model constant that represents initial particle loading.
Ritchie were employed for testing the experimental batch data. A second order kinetic model proposed by Sobkowsk and
The pseudo-second order model proposed by Ho and Czerwi (1974) similar to Ritchie model based on the maximum
McKay Ho (1995) describes that adsorption process is con- adsorption capacity of adsorbents. Modified form of this
trolled by chemisorption which involve valence forces through model is expressed as:
sharing or exchange of electron between the solute and the
adsorbent. The Ho pseudo-second order model can be repre- qe kSC t
qt ¼ ð16Þ
sented in the following form: kSC þ 1
1326 N. Sivarajasekar, R. Baskar

Table 1 Error functions and sum of normalized errors for two-parameter kinetic models.
Model mg l1 Error ERRSQ HYBRID MPSD ARE EABS SNE
Ho 50 ERRSQ 22.3468 4.7342 1.0093 308.5801 6.6829 3.5667
HYBRID 22.3634 4.7311 1.0078 322.0540 6.7026 3.6085
MPSD 22.3931 4.7325 1.0075 331.2050 6.7183 3.6386
ARE 30.9312 7.0483 1.6816 1.2106 10.4308 4.0037
EABS 22.3611 4.7419 1.0115 299.6484 6.6662 3.5410
100 ERRSQ 74.9121 8.7297 1.0246 1480.1194 12.5231 2.7544
HYBRID 75.1613 8.7050 1.0165 1605.5157 12.5883 2.8275
MPSD 75.8342 8.7249 1.0143 1729.8864 12.8883 2.9175
ARE 134.1080 19.0450 2.9461 1.4763 23.4501 4.0009
EABS 75.6107 8.7793 1.0285 1409.0183 12.1714 2.7074
150 ERRSQ 140.4267 12.0263 1.0489 3534.2949 19.3342 2.2254
HYBRID 141.4099 11.9574 1.0333 3917.6051 19.7431 2.3230
MPSD 143.8280 12.0054 1.0294 4281.3157 20.2839 2.4287
ARE 371.8521 39.7576 4.6940 1.6532 38.9594 4.0004
EABS 141.1182 12.0878 1.0552 3360.3023 19.0288 2.1816
200 ERRSQ 201.3342 14.5810 1.0909 6242.1883 25.8244 1.9433
HYBRID 204.2498 14.4172 1.0612 7112.2548 26.9882 2.0715
MPSD 211.0993 14.5234 1.0541 7930.3395 28.1096 2.2056
ARE 705.3114 63.9697 6.5253 1.8133 54.2971 4.0002
EABS 201.9511 14.7051 1.1048 6110.7429 25.6104 1.9277
250 ERRSQ 250.2930 16.6285 1.1708 8638.5911 31.6771 1.7171
HYBRID 258.3165 16.2356 1.1015 10308.1780 33.6771 1.8801
MPSD 280.4568 16.5536 1.0826 12164.3708 36.1812 2.0919
ARE 1097.8707 94.3783 9.3008 1.8550 66.4301 4.0002
EABS 259.3445 17.9343 1.3079 7069.6256 29.5030 1.5922
Modified Freundlich 50 ERRSQ 7.5164 1.2471 0.2343 1.0839 7.3385 4.2252
HYBRID 8.0940 1.1439 0.1804 1.1447 7.8032 4.0816
MPSD 9.5161 1.2183 0.1662 1.2182 8.4023 4.3229
ARE 11.7261 1.5187 0.2199 1.0664 8.2778 4.7990
EABS 11.7261 1.5187 0.2199 1.0664 8.2778 4.7990
100 ERRSQ 30.1599 3.0995 0.3872 1.1777 14.5730 3.8198
HYBRID 33.9540 2.7181 0.2655 1.3119 16.3713 3.7207
MPSD 44.1554 3.0253 0.2314 1.4286 18.2035 4.0967
ARE 51.5664 4.2151 0.4427 1.0989 16.0071 4.6486
EABS 51.5664 4.2151 0.4427 1.0989 16.0071 4.6486
150 ERRSQ 77.9923 5.6361 0.5222 1.3547 23.4823 3.8234
HYBRID 89.2511 4.8068 0.3293 1.4211 25.0174 3.5039
MPSD 117.8740 5.4120 0.2792 1.5668 28.2596 3.8481
ARE 180.1224 7.7414 0.3955 1.3260 29.4367 4.6036
EABS 180.1224 7.7414 0.3955 1.3260 29.4367 4.6036
200 ERRSQ 150.9835 8.9024 0.6963 1.5750 33.5465 3.8179
HYBRID 176.1100 7.3643 0.4016 1.6200 35.0094 3.3962
MPSD 235.8934 8.3648 0.3314 1.7318 38.6744 3.6865
ARE 373.5733 12.2453 0.4776 1.5545 43.1610 4.5836
EABS 373.5733 12.2453 0.4776 1.5545 43.1610 4.5836
250 ERRSQ 250.1842 13.8550 1.0556 1.7469 42.8212 3.9884
HYBRID 303.2859 10.9561 0.5463 1.8300 45.1907 3.5925
MPSD 427.2599 12.7589 0.4297 2.0641 52.0711 4.1398
ARE 329.9922 16.4088 1.1863 1.7114 47.4313 4.5124
EABS 329.9922 16.4088 1.1863 1.7114 47.4313 4.5124
Sobkowsk–Czerwi 50 ERRSQ 1.7346 0.2735 0.0471 0.4635 3.1787 4.5144
HYBRID 1.7686 0.2672 0.0444 0.4916 3.3176 4.5566
MPSD 1.8213 0.2696 0.0439 0.5085 3.3951 4.6392
ARE 1.7862 0.2979 0.0538 0.4316 3.0287 4.6375
EABS 1.9275 0.3071 0.0532 0.4404 3.0045 4.7395
100 ERRSQ 4.4363 0.3796 0.0370 0.4337 5.3676 4.7356
HYBRID 4.7084 0.3525 0.0293 0.4319 5.6819 4.5562
MPSD 5.2904 0.3679 0.0276 0.4329 5.9839 4.7134
ARE 4.4465 0.3759 0.0361 0.4319 5.3480 4.6969
EABS 4.4478 0.3765 0.0362 0.4322 5.3456 4.7018
(continued on next page)
Adsorption of Basic Magenta II onto H2SO4 activated immature Gossypium hirsutum seeds 1327

Table 1 (continued)
Model mg l1 Error ERRSQ HYBRID MPSD ARE EABS SNE
150 ERRSQ 15.5782 0.8948 0.0604 0.5884 10.1711 3.1047
HYBRID 16.6689 0.8172 0.0447 0.5520 10.2837 2.8146
MPSD 18.6960 0.8811 0.0443 0.5420 10.1183 2.8630
ARE 48.8244 1.7840 0.0699 0.7088 17.2444 5.0000
EABS 18.2662 0.9307 0.0533 0.5762 9.9353 3.0484
200 ERRSQ 38.7241 1.8840 0.1089 0.7758 16.3030 4.6795
HYBRID 42.1379 1.6867 0.0763 0.7379 16.7572 4.3208
MPSD 48.8244 1.7840 0.0699 0.7088 17.2444 4.4320
ARE 51.8429 1.9084 0.0738 0.7138 16.7120 4.5668
EABS 42.9718 1.8741 0.0950 0.7701 15.9875 4.6032
250 ERRSQ 74.8624 3.4933 0.2067 0.9776 22.8631 1.4751
HYBRID 84.7954 2.9916 0.1278 0.9371 23.6881 1.3974
MPSD 106.9245 3.2886 0.1101 0.9072 24.9595 1.4623
ARE 124.8696 3.8435 0.1229 0.8932 23.4636 1.5135
EABS 80.7063 3.3892 0.1805 0.9570 21.7202 1.4283

where kSC (min1) is Sobkowsk–Czerwi second order kinetic (<30 min) was most likely due to certain active surface sites
rate constant. on IGHSAC; and quickly adsorption becoming dependent on
Batch experiments were carried out for differential concen- the diffusion controlling process which had good agreement
trations (50–250 mg l1) with pH 12, temperature 40 C, and with the conclusion arrived by Sobkowsk–Czerwi kinetic
contact time 3 h. The resulting experimental data was analysed model. The poor R2 and high RMSE values of Elovich and
on the basis of the nonlinear curve fitting SNE procedure by modified Freundlich kinetic models were shown that these
minimizing one error function and calculating all other error models failed to explain the experimental data. According to
values. The determined SNE values for the two-parameter the R2 and RMSE values the best-fitted kinetic models were
and three parameter kinetic models are displayed in Tables 1 found in the order: Avrami > Sobkowsk–Czerwi > modified
and 2 respectively. Error functions which contribute minimum Ritchie > Blanchard > Elovich > modified Freundlich >
SNE value were selected to calculate the optimum parameter Ho. Therefore the qe values predicted by the Avrami kinetic
set for that kinetic model. From Table 1, it was inferred that model were considered for the isotherm calculations.
the HYBRID error function produced the best fit giving the
lowest SNE value for the 14 cases out of the 35 cases studied
3.3. Isotherms
followed by the MPSD error function for 9 cases and EABS
error function for 7 cases. Additionally, the ERRSQ error
function selected to measure optimum parameter set for 4 To optimize the design of an adsorption system for the
cases and ARE error function provided optimum parameter removal of solutes by adsorbents, it is important to establish
set for only one case. The values of optimum parameter sets the most appropriate correlation for the equilibrium curves.
calculated based on minimum SNE procedure and their coeffi- Adsorption isotherm provides valuable information such as
cient of determination (R2) and root mean square error equilibrium sorption capacity and certain constants whose val-
(RMSE) values are presented in Tables 3 and 4 in order to ues express the surface properties and affinity of the adsorbent
assess the fitness of the kinetic models. (Sivarajasekar and Baskar, 2013). In many cases, the equilib-
Among the two-parameter kinetic models, the Sobkowsk– rium sorption capacity is unknown, chemisorption tends to
Czerwi model provided a better fit to the experimental data become immeasurably slow, and the amount sorbed is still sig-
with high R2 (0.9996–0.95596) and low RMSE (0.9313– nificantly smaller than the equilibrium amount (Ungarish and
6.51135) values than Ho and modified Freundlich models at Aharoni, 1981). This problem can be easily rectified if the equi-
studied concentration range. This conveyed an idea that the librium adsorption capacity (qe) and equilibrium concentration
adsorption may be followed first order kinetics at low concen- (Ce) values owing to the well-fitting kinetic models are adopted
trations and second order kinetics at high concentrations (Ho, for isotherm fitting (Ho, 2004; Ho and Wang, 2004). Therefore
2006). As for as three-parameter kinetic models concerned, the the amount of dye adsorbed at equilibrium predicted from the
Avrami kinetic model followed by modified Ritchie kinetic Avrami kinetic model was considered for isotherm studies. The
model had a good agreement with the experimental batch data equilibrium solute phase concentration in liquid can be calcu-
which was known from their high R2 and low RMSE values lated from the Eq. (1) as follows:
(Table 4). The applicability of Avrami kinetic model (R2: qe M
0.9997–0.9789, RMSE: 0.7388–4.5028) indicated that the mech- Ce ¼ C0  ð17Þ
V
anism of adsorption certainly followed multiple kinetic orders
which may change during the contact of the dye with IGHSAC The predicted equilibrium data from Avrami kinetics were
(Lopes et al., 2003). The modified Ritchie kinetic model also fitted to the five isotherm models to understand the nature of
reasonably explained the experimental data (R2: 0.9996– adsorption process. The most widely used two-parameter iso-
0.9537, RMSE: 0.9299–6.6785) which conveyed the idea that therm models (Langmuir, Freundlich and Temkin) and
dye molecules were adsorbed onto two different surface sites. three-parameter isotherm models (Sips and Hill) isotherms
The higher initial dye uptake at small time duration were used to describe the equilibrium nature of adsorption.
1328 N. Sivarajasekar, R. Baskar

Table 2 Error functions and sum of normalized errors for three-parameter kinetic models.
Model mg l1 Error ERRSQ HYBRID MPSD ARE EABS SNE
Blanchard 50 ERRSQ 1.7294 0.2727 0.0471 1.4653 3.2469 3.4819
HYBRID 1.8246 0.2659 0.0453 1.4971 3.6140 3.5630
MPSD 2.1831 0.2787 0.0433 1.5059 3.9503 3.7267
ARE 4.7498 0.3675 0.0710 1.4062 4.3927 4.9338
EABS 1.9274 0.3070 0.0531 1.4402 3.0041 3.6298
100 ERRSQ 4.3284 0.3584 0.0343 1.4172 5.5263 3.8209
HYBRID 12.1444 0.2748 0.0258 1.3729 7.6204 4.1163
MPSD 6.5332 0.2911 0.0243 1.3820 6.6580 3.6455
ARE 15.8644 0.3336 0.0324 1.3087 7.4013 4.6035
EABS 4.4846 0.3863 0.0378 1.4352 5.3141 3.9800
150 ERRSQ 15.0981 0.8269 0.0538 1.5559 10.3938 4.1137
HYBRID 28.6658 0.6496 0.0401 1.5014 12.8107 4.2774
MPSD 18.5863 0.6953 0.0370 1.5023 11.4678 3.8399
ARE 30.7659 0.7545 0.0488 1.4354 12.0114 4.5072
EABS 17.7611 0.9384 0.0568 1.5849 9.9385 4.3531
200 ERRSQ 37.2914 1.7157 0.0949 1.7225 16.5662 4.0454
HYBRID 55.7791 1.3858 0.0716 1.6860 19.3906 4.0088
MPSD 43.4845 1.5097 0.0647 1.6949 18.0008 3.7938
ARE 82.2779 1.8045 0.1085 1.5561 18.9616 4.7939
EABS 42.0898 1.9181 0.1029 1.7778 15.9470 4.2820
250 ERRSQ 71.0119 3.0311 0.1673 1.9069 23.4122 3.1197
HYBRID 120.0957 2.1843 0.1046 1.8240 27.7817 3.0601
MPSD 89.2053 2.4365 0.0922 1.8267 25.7124 2.8884
ARE 260.6857 3.3831 0.2009 1.6309 29.6347 4.0874
EABS 84.9210 4.9311 0.3450 1.9915 21.3419 4.0459
Elovich 50 ERRSQ 5.2231 0.7757 0.1290 0.8910 6.1417 4.3843
HYBRID 5.5004 0.7211 0.1019 0.8781 6.2510 4.1527
MPSD 5.9943 0.7450 0.0968 0.8688 6.3769 4.2077
ARE 8.1326 0.9546 0.1168 0.7898 6.6073 4.7913
EABS 8.1326 0.9546 0.1168 0.7898 6.6073 4.7913
100 ERRSQ 17.8296 1.5163 0.1574 0.9363 11.7461 3.3747
HYBRID 19.4156 1.3359 0.1034 0.9222 12.1978 3.0851
MPSD 22.2886 1.4124 0.0939 0.8878 12.4445 3.0874
ARE 59.2559 3.3537 0.1938 0.7505 14.5141 4.8016
EABS 59.2559 3.3537 0.1938 0.7505 14.5141 4.8016
150 ERRSQ 44.4300 2.5024 0.1775 1.0206 18.0873 4.5687
HYBRID 48.0622 2.1867 0.1105 0.9155 17.5873 3.9993
MPSD 53.2981 2.2790 0.1015 0.8641 17.7674 4.0188
ARE 67.7654 2.7407 0.1149 0.7678 17.8257 4.3854
EABS 67.7654 2.7407 0.1149 0.7678 17.8257 4.3854
200 ERRSQ 83.8736 3.7261 0.2084 1.1587 25.3543 4.6983
HYBRID 90.0337 3.2574 0.1300 1.0321 24.6666 4.1174
MPSD 96.2185 3.3368 0.1228 0.9709 24.4774 4.0968
ARE 115.1053 3.8430 0.1405 0.9187 25.2402 4.4625
EABS 115.1053 3.8430 0.1405 0.9187 25.2402 4.4625
250 ERRSQ 137.4871 5.5355 0.2957 1.2868 32.0210 4.8294
HYBRID 149.6143 4.6755 0.1665 1.1230 31.0469 4.1526
MPSD 159.4578 4.7819 0.1571 1.0922 31.1064 4.1773
ARE 165.7731 4.9110 0.1647 1.0365 31.3582 4.2291
EABS 165.7731 4.9110 0.1647 1.0365 31.3582 4.2291
Avrami 50 ERRSQ 1.0799 0.2385 0.0558 0.4810 2.3240 4.7632
HYBRID 1.0937 0.2364 0.0543 0.4799 2.3738 4.7568
MPSD 1.1807 0.2421 0.0534 0.4935 2.5922 4.9497
ARE 1.0917 0.2385 0.0555 0.4701 2.2404 4.7141
EABS 1.0968 0.2405 0.0562 0.4704 2.2210 4.7323
100 ERRSQ 1.2452 0.1440 0.0191 0.2991 2.8811 4.6309
HYBRID 1.2676 0.1421 0.0183 0.2879 2.7922 4.5205
MPSD 1.4230 0.1481 0.0177 0.2818 2.8610 4.6255
ARE 1.6350 0.1657 0.0187 0.2704 2.8119 4.8603
EABS 1.3120 0.1434 0.0179 0.2787 2.7228 4.4814
150 ERRSQ 4.2171 0.2596 0.0195 0.3426 5.3723 4.9405
HYBRID 4.2287 0.2589 0.0195 0.3419 5.3300 4.9322
MPSD 4.2558 0.2606 0.0194 0.3406 5.3272 4.9357
ARE 4.3776 0.2634 0.0196 0.3383 5.2260 4.9602
EABS 4.3702 0.2632 0.0196 0.3384 5.2313 4.9575
(continued on next page)
Adsorption of Basic Magenta II onto H2SO4 activated immature Gossypium hirsutum seeds 1329

Table 2 (continued)
Model mg l1 Error ERRSQ HYBRID MPSD ARE EABS SNE
200 ERRSQ 15.4295 0.7430 0.0406 0.4748 10.0595 4.4188
HYBRID 15.8842 0.7187 0.0377 0.5000 10.4413 4.4477
MPSD 16.3989 0.7241 0.0374 0.5119 10.6113 4.5175
ARE 16.4741 0.8729 0.0509 0.4382 9.4878 4.7008
EABS 16.7287 0.8876 0.0518 0.4364 9.4451 4.7426
250 ERRSQ 37.7549 1.6084 0.0814 0.6407 16.1939 3.8527
HYBRID 40.5510 1.4787 0.0627 0.6046 16.2903 3.6848
MPSD 46.7315 1.5579 0.0583 0.6360 16.9567 3.8980
ARE 41.5862 1.4862 0.0615 0.5974 16.3152 3.6922
EABS 49.1227 2.5013 0.1484 0.6832 16.1157 4.9504
Modified Ritchie 50 ERRSQ 1.7294 0.2727 0.0471 0.4653 3.2469 3.3499
HYBRID 1.8246 0.2659 0.0453 0.4971 3.6140 3.4696
MPSD 2.1831 0.2787 0.0433 0.5059 3.9503 3.6361
ARE 5.2202 0.3742 0.0725 0.4046 4.5083 4.7997
EABS 1.7842 0.2975 0.0537 0.4318 3.0281 3.4028
100 ERRSQ 4.3284 0.3584 0.0343 0.4172 5.5263 3.3381
HYBRID 12.1444 0.2748 0.0258 0.3729 7.6204 3.6686
MPSD 6.5332 0.2911 0.0243 0.3820 6.6580 3.2119
ARE 15.8268 0.3334 0.0323 0.3086 7.3942 3.9796
EABS 5.3605 0.4864 0.0504 0.4522 5.1642 4.0164
150 ERRSQ 15.0981 0.8269 0.0538 0.5559 10.3938 4.0634
HYBRID 28.6658 0.6496 0.0401 0.5014 12.8107 4.1276
MPSD 18.5863 0.6953 0.0370 0.5023 11.4678 3.7184
ARE 33.5572 0.7659 0.0506 0.4312 12.2375 4.4195
EABS 17.5334 0.9289 0.0564 0.5810 9.9767 4.3013
200 ERRSQ 37.2914 1.7157 0.0949 0.7225 16.5662 4.0079
HYBRID 37.2914 1.7157 0.0949 0.7225 16.5662 4.0079
MPSD 43.4845 1.5097 0.0647 0.6949 18.0008 3.7396
ARE 82.4417 1.8057 0.1086 0.5560 18.9683 4.6417
EABS 41.8344 1.9422 0.1065 0.7810 15.9325 4.3284
250 ERRSQ 71.0119 3.0310 0.1673 0.9069 23.4123 3.7203
HYBRID 71.0119 3.0310 0.1673 0.9069 23.4123 3.7203
MPSD 89.2052 2.4366 0.0922 0.8267 25.7124 3.5946
ARE 71.0119 3.0310 0.1673 0.9069 23.4123 3.7203
EABS 84.9422 4.9337 0.3452 0.9916 21.3418 4.7822

Table 3 Kinetic parameters and statistical comparison values for two-parameter models at various initial concentrations.
Model Parameters 50 mg l1 100 mg l1 150 mg l1 200 mg l1 250 mg l1
Ho kHo (g mol1 min1) 0.0147 0.0057 0.0031 0.0019 0.0019
qe (mg g1) 9.8533 19.1758 28.9351 39.1651 45.3490
h (mg g1 min1) 1.4243 2.1137 2.6297 2.9427 3.8318
R2 0.9944 0.9669 0.9054 0.8613 0.8653
RMSE 3.3437 6.1486 8.3999 10.0487 11.3874
Modified Freundlich mmf 4.5722 3.8264 3.3890 3.0372 2.7955
kmf (l g1 min1) 0.0669 0.0535 0.0446 0.0367 0.0309
R2 0.9980 0.9851 0.9401 0.8791 0.8425
RMSE 2.0117 4.1203 6.6802 9.3838 12.3143
Sobkowsk–Czerwi kSC (min1) 0.1204 0.0883 0.0717 0.0589 0.0516
qe (mg g1) 10.0259 20.2402 30.5166 40.5816 49.9508
R2 0.9996 0.9979 0.9888 0.9711 0.9559
RMSE 0.9313 1.5343 2.8869 4.5901 6.5114

According to the Langmuir isotherm, the monolayer qmL bL Ce

qe ¼ ð18Þ
adsorption is taking place on a structurally homogeneous 1 þ bL Ce
adsorbent where all the adsorption sites are identical
and energetically equivalent (Langmuir, 1918). Langmuir where qmL = KL/bL (mg g1) is the maximum monolayer
Isotherm is: adsorption capacity predicted by Langmuir isotherm, KL
1330 N. Sivarajasekar, R. Baskar

Table 4 Kinetic parameters and statistical comparison values for three-parameter models at various initial concentrations.
Model Parameter 50 mg l1 100 mg l1 150 mg l1 200 mg l1 250 mg l1
Blanchard aBla 0.0121 0.0048 0.0026 0.0015 0.0012
kBla (min1) 0.0991 0.0462 0.0310 0.0235 0.0188
qe (mg g1) 10.0198 20.0332 30.2298 40.3710 49.3585
R2 0.9996 0.9971 0.9875 0.9701 0.9537
RMSE 0.9299 1.8074 3.0485 4.6629 6.6785
Elovich rE (mg g1 min1) 4.0432 4.5626 4.9665 4.7349 5.2836
bE (g mg1) 0.5842 0.2604 0.1633 0.1142 0.0931
R2 0.9986 0.9915 0.9678 0.9339 0.9223
RMSE 1.6584 3.1157 4.9022 6.9361 8.6491
Avrami nAv 0.2885 0.2680 0.2478 0.2340 0.2215
kAv (min1) 0.2885 0.2680 0.2478 0.2340 0.2215
qe (mg g1) 9.0534 17.8317 26.4046 34.6730 42.1618
R2 0.9997 0.9994 0.9971 0.9894 0.9789
RMSE 0.7388 0.8100 1.4782 2.7775 4.5028
Modified Ritchie bR 0.9931 0.9245 0.9367 0.9505 0.9260
kR (min1) 0.1212 0.0966 0.0775 0.0620 0.0570
qe (mg g1) 10.0198 20.0332 30.2298 40.3710 49.3586
R2 0.9996 0.9971 0.9875 0.9701 0.9537
RMSE 0.9299 1.8074 3.0485 4.6629 6.6785

(l g1) and bL (l mg1) are the Langmuir model constants. KS qmS C1=n
e
S

Weber and Chakravorti (1974) proposed a separation factor qe ¼ 1=nS

ð22Þ
1 þ KS Ce
(RL) to understand the favorability of isotherm that should
be less than one for favourable adsorption, defined as where KS (l g1) is the Sips isotherm constant, qmS (mg g1) is
the maximum monolayer adsorption capacity by Sips iso-
1
RL ¼ ð19Þ therm, and nS is the Sips model exponent.
1 þ C0 bL Hill (1910) postulated an isotherm to describe the binding
The empirical Freundlich isotherm model describes the of different solutes onto a homogeneous adsorbent. The model
non-ideal and reversible nature of adsorption. The multilayer assumes that adsorption is a cooperative occurrence, owing to
adsorption with non-uniform distribution of adsorption heat the ligand binding ability at one site on the macromolecule,
and affinities over the heterogeneous surface explained by its tends to influence different binding sites on the same macro-
relationship (Adamson and Gast, 1997): molecule. The Hill equation is:

qe ¼ KF C1=n F
ð20Þ qmH Cne H
e qe ¼ ð23Þ
1
KH þ Cne H
where KF (l g ) is the Freundlich isotherm constant, and nF is
Freundlich exponent. The value 1/nF < 1 indicates chemisorp- where qmH (mg g1) is the maximum monolayer adsorption
tion process, whereas 1/nF > 1implies cooperative adsorption capacity given by Hill isotherm, KH is the Hill isotherm Con-
(Haghseresht and Lu, 1998). stant and nH is Hill cooperativity coefficient. If nH > 1, posi-
The isotherm postulated by Temkin and Pyzhev (1940) tive cooperativity in binding, nH = 1, non-cooperative or
relates the effects of heat of adsorption that decreases linearly hyperbolic binding, and nH < 1, negative cooperativity in
with the coverage of the solute and the adsorbent interactions binding.
on the surface at moderate values of solute concentrations. It is Nonlinear SNE procedure was adopted to evaluate the
represented by: optimum parameters for the five types of isotherms. The error
functions, SNE values and optimum parameters are presented
RT
qe ¼ flnðaT Ce Þg ð21Þ in Tables 5 and 6. The HYBRID error function produced opti-
bT mum parameter set for all the selected isotherms due to their
where bT (J mol1) is the Temkin isotherm constant related to small SNE values. By analysing the R2 and RMSE values of
heat of sorption, aT (l g1) is the Temkin isotherm constant, R the isotherm models, the best fitting was observed using Sips
is the gas constant (8.314 J mol1 K1) and T (K) is the abso- (R2: 0.9945, RMSE: 0.5492) and Hill (R2: 0.9945, RMSE:
lute temperature. 0.5494) isotherms. The Langmuir isotherm (R2: 0.9918,
Sips (1948) proposed a combined form of Langmuir and RMSE: 0.6731) reasonably fitted the data followed by Freund-
Freundlich isotherms deduced for predicting the heteroge- lich isotherm (R2: 0.9183, RMSE: 2.1254) but Temkin iso-
neous adsorption systems. At low solute concentrations it therm failed to define the equilibrium data well. The
effectively reduces to Freundlich isotherm and at high solute adequacy of Sips and Hill isotherms confirmed that the homo-
concentrations, it predicts characteristics of monolayer sorp- geneous adsorption on the heterogeneous surface of IMSAC
tion capacity of the Langmuir isotherm. Sips isotherm is given and the co-operative manifestations of the adsorptive BM2
by molecules. The maximum adsorption capacity predicted by
Adsorption of Basic Magenta II onto H2SO4 activated immature Gossypium hirsutum seeds 1331

Table 5 Error functions and sum of normalized errors for isotherms.

S. No. Isotherm ERRSQ HYBRID MPSD ARE EABS SNE
1. Langmuir ERRSQ 0.8493 0.0385 0.0019 0.0834 1.8543 4.6053
HYBRID 0.9061 0.0355 0.0015 0.0730 1.8684 4.2504
MPSD 0.9931 0.0364 0.0015 0.0729 1.9353 4.3530
ARE 1.1345 0.0428 0.0017 0.0702 1.7832 4.6403
EABS 0.9855 0.0411 0.0019 0.0803 1.7951 4.6840
2. Freundlich ERRSQ 7.5182 0.4197 0.0333 0.2928 5.8773 4.3728
HYBRID 9.0342 0.3307 0.0166 0.2408 5.7892 3.6112
MPSD 12.8966 0.3846 0.0131 0.2346 6.4597 4.0026
ARE 10.0446 0.4769 0.0317 0.2850 5.5803 4.5686
EABS 10.1167 0.4744 0.0311 0.2831 5.5669 4.5410
3. Temkin ERRSQ 13.2476 0.8414 0.0663 0.4699 7.1560 4.3267
HYBRID 15.8049 0.6896 0.0376 0.3614 7.8047 3.6700
MPSD 24.0371 0.7986 0.0320 0.3308 8.7519 4.0959
ARE 18.4299 0.8783 0.0448 0.2697 7.0094 3.8178
EABS 13.3339 0.8427 0.0650 0.4581 7.0039 4.2693
4. Sips ERRSQ 0.5415 0.0329 0.0023 0.0828 1.3775 3.9045
HYBRID 0.6032 0.0290 0.0016 0.0740 1.5357 3.6103
MPSD 0.7937 0.0318 0.0014 0.0725 1.7705 3.9426
ARE 0.8725 0.0490 0.0028 0.0591 1.0789 4.3235
EABS 0.5641 0.0356 0.0025 0.0809 1.2727 3.9801
5. Hill ERRSQ 0.5415 0.0328 0.0023 0.0827 1.3784 3.9305
HYBRID 0.6038 0.0290 0.0016 0.0740 1.5362 3.6365
MPSD 0.7936 0.0318 0.0014 0.0725 1.7702 3.9705
ARE 0.8640 0.0484 0.0027 0.0521 1.0060 4.1986
EABS 0.5643 0.0354 0.0025 0.0806 1.2732 4.0040

Table 6 Parameters and statistical comparison values for isotherms.

S. No. Isotherm Parameters R2 RMSE
1
1. Langmuir qmL (mg g ) 86.24 0.9918 0.6731
bL (l g1) 0.02
RL 0.22
2. Freundlich KF (mg g1) (l g1)nF 3.30 0.9183 2.1254
nF 1.42
3. Temkin aT (l g1) 0.37 0.8571 2.8111
bT (J mol1) 174.80
4. Sips qmS (mg g1) 77.76 0.9945 0.5492
bS 0.03
nS 0.95
5. Hill qmH (mg g1) 77.78 0.9945 0.5494
nH 1.05
KH 39.71

the Sips (77.76 mg g1) and Hill (77.78 mg g1) isotherms were tion onto IMSAC was in favourable region (RL < 1). Fig. 2
lower than Langmuir (86.24 mg g1) isotherm. The value of collectively represents all the isotherm models.
Sips exponent (0.95  1) conveyed the idea that the sorption
data was more of a Langmuir form rather than that of Freund- 3.4. Sorption mechanisms
lich isotherm. In turn, Freundlich isotherm almost fitted to the
equilibrium data supporting the assumptions of heterogeneous The knowledge of the rate-limiting step is an important one to
mode of adsorption to certain extend. The Hill exponent nH be considered in the adsorption process. It is governed by the
was greater than unity (1.05) depicted that the binding interac- adsorption mechanism which depends on the physical and
tion between BM2 molecule and IGHSAC was in the form of chemical characteristics of the adsorbent as well as on the mass
positive cooperativity. The separation factor (RL) value deter- transfer process (Metcalf and Eddy, 2003). For a solid–liquid
mined from the Langmuir isotherm indicated that dye adsorp- sorption process, the solute transfer is usually characterized
1332 N. Sivarajasekar, R. Baskar

The common technique used for identifying the mechanism

involved in the adsorption process is described by Weber and
Morris (1963) via fitting a plot for the following equation:
qt ¼ Kid t0:5 ð26Þ
where Kid is intraparticle diffusion rate constant (mg g1
min0.5). Therefore to realize the exact diffusion mechanism,
qt values were plotted against t0.5 and presented in Fig. 3(b).
As seen, the two stages in the intraparticle diffusion plot sug-
gested that the sorption process proceeded by surface sorption
and intraparticle diffusion. The initial curved portion of the
plot indicated that at first, BM2 molecules diffused through
the surrounding boundary layer to the external surface of the
IGHSAC particles. The later linear portion is attributed to
intraparticle or pore diffusion of BM2 molecules to the
Figure 2 Comparison of isotherms. adsorptive active sites located on the IGHSAC particles.
by external mass transfer or intraparticle diffusion, or both. Therefore intraparticle diffusion rate constant Kid was calcu-
The three steps involved in the mechanism of adsorption as lated from the slope of the second linear portion of the plot
follows: and is listed in Table 7. The intraparticle diffusion rate con-
stants seemed to increase with increasing initial BM2 concen-
(1) Transport of the solute from bulk solution through trations, perhaps as a result of a raise in the concentration
boundary layer to the adsorbent exterior surface (film gradient leading to a rapid upturn in the driving force for
diffusion); the mass transfer. On the other hand, the intercept of the plot
(2) Transport of the solute within the pores of the adsorbent reflected the idea that intraparticle diffusion was not only rate
(particle diffusion); controlling one but boundary layer diffusion also controlled
(3) Adsorption of the solute on the exterior surface of the the adsorption of BM2 to some extent. The larger the value
adsorbent (equilibrium reaction). of intercept, the greater is the contribution of the surface sorp-
tion in the rate-controlling step. The boundary layer diffusion
Usually, the last step is very rapid; the resistance is there- rate constants (kf) were obtained as the intercept of the second
fore assumed to be negligible. The slowest step determines portion of the plot and presented in Table 7.
the rate-controlling parameter in the adsorption process. To understand the diffusion mechanism quantitatively and
Yet, the rate-controlling parameter may be distributed to estimate the rate determining step (pore diffusion or film
between intraparticle and film diffusion mechanisms. Irrespec- diffusion), it is prerequisite to calculate their coefficients. By
tive of the case external diffusion will be involved in the sorp- assuming the adsorbent particle to be a sphere of radius ‘r’
tion process. In general, external diffusion or external mass and the diffusion follows Fick’s law, the adsorption kinetic
transfer is characterized by the initial solute uptake (McKay data was further analysed using the relationship between frac-
et al., 1981) which can be calculated from the slope of Furus- tional attainment of equilibrium and time according to Rei-
awa and Smith plot assuming a linear relation between Ct/Ci chenberg and Helfferich (Reichenberg, 1953; Vadivelan and
and time for the first initial rapid phase (Vadivelan and Kumar, 2005):
Kumar, 2005). That is,  "   #
qt Dt
0:5 X1
pr D
0:5
  ¼6 2 p þ 2 ierfc 0:5
3 2 ð27Þ
dðCt =C0 Þ qe r n¼1 D r
¼ km S ð24Þ
dt t!0
At smaller times (t tends to 0) D is substituted by Df and
where km (cm s1) is external mass transfer coefficient and S Eq. (18) reduces to:
(cm2/cm3) is surface area of the adsorbent per unit volume  0:5
qt Dt
of particle which is defined as: ¼6 2 t0:5 ð28Þ
qe r
6M
S¼ ð25Þ where Df (cm2 s1) is film diffusion coefficient. The fractional
Vdp qð1  ep Þ
uptake (qt/qe) values were plotted against square root of time
(t0.5) (Fig. 3(c)) and the calculated film diffusion coefficients
where dp is particle diameter (cm), q is bulk density (g cm3)
Df are listed in Table 7. At larger times (t tends to 1) Eq.
and ep is porosity. The external mass transfer rate values were
(27) can be written as:
determined at different initial concentrations of BM2 using " #
 2 2
Fig. 3(a) and presented in Table 7. The slopes of the curves qt 6X 1
1 n p Dp t
were calculated based on the assumption that the relationship ¼1 2 exp  ð29Þ
qe p n¼1 n2 r2
is linear for the first initial rapid period of time (<30 min). As
seen, the external mass transfer rates decreased with increasing where Dp (cm2 s1) is pore diffusion coefficient. If the Biot
initial concentration of dye may be due to the nature of molec- number B = (Dpp2/r2), Eq. (29) can be simplified to:
ular associations or interionic groups present in the dye; which 
q
may reduce the activity coefficient of the dye and effective dif- Bt ¼ 0:4977  ln 1  t ð30Þ
fusivity (McKay et al., 1981). qe
Adsorption of Basic Magenta II onto H2SO4 activated immature Gossypium hirsutum seeds 1333

Figure 3 (a) Furusawa and Smith Plot; (b) Weber and Morris Plot; (c) Reichenberg and Helfferich plot and (d) Boyd plot.

The calculated Bt values were plotted against time and pre- the film diffusion was the rate controlling one (Reichenberg,
sented in Fig. 3(d). As seen these plots were linear at all con- 1953). The pore diffusion coefficients Dp (cm2 s1) were
centrations but does not pass through the origin, conforming obtained from the calculated Biot number values using Eq.
1334 N. Sivarajasekar, R. Baskar

Table 7 Mass transfer parameters for adsorption of BM2 onto IGHSAC.

1
C0 (mg l ) Kid (mg g1 min0.5) kf Df · 108 (cm2 s1) Dp · 106 (cm2 s1) Ks (cm s1)
50 0.0842 8.1695 4.9088 9.4448 0.0294
100 0.2741 14.755 4.5861 9.5233 0.0283
150 0.4122 21.606 4.2690 8.1881 0.0274
200 0.6427 26.776 4.0152 7.2848 0.0265
250 0.8874 30.926 4.0047 6.2049 0.0261

The change in entropy DS0 (J mol1 K1) and Gibbs free

energy DG0 (kJ mol1) can be related at constant temperature
as follows:
DG0 ¼ DH0  TDS0 ð32Þ
1 1
where R is gas constant (8.314 J mol K ) and T is the abso-
lute temperature (K). The values of enthalpy and entropy
changes were obtained from the slope and intercept of
Fig. 4(a) and are given in Table 8. As observed that the adsorp-
tion of BM2 by IGHSAC was spontaneous and feasible with
the negative values of DG0. The positive standard enthalpy
change DH0 values confirmed the endothermic nature of the
overall adsorption process. In general, the enthalpy change
due to chemisorption (>40 J mol1) is considerably larger
than that of physi-sorption (<40 J mol1). The higher order
of magnitude of DH0 (613.26 J mol1) conformed the chemi-
sorption mechanism of BM2 molecules onto IGHSAC
(Vinod and Aniruthan, 2001). The positive DS0 values indi-
cated that an increased disorder at the IGHSAC surface and
dye solution interface with some structural changes in the
IGHSAC particles as well as BM2 dye molecules during the
adsorption process. This positive value also suggested the
affinity BM2 molecules towards the IGHSAC particles and
an increased degree of freedom of the adsorbed BM2 mole-
cules (Senthilkumaar et al., 2006).
The apparent isosteric heat of adsorption DHis (kJ kg1)
can be calculated from the Clausius–Clapeyron equation:
Figure 4 (a) Vant’s Hoff plot and (b). Isoster plot.
dðln Ce Þ DHis
¼ ð33Þ
dT RT2
(21) and presented in Table 7. Pore diffusion coefficient values At constant qe values the above equation becomes
are to be in the range of 1011–1013 cm2 s1 for pore diffusion
controlled adsorption mechanism (McKay and Poots, 1980) dðln Ce Þ
DHis ¼ ð34Þ
and the film diffusion coefficient values are to be in the range dð1=TÞ
of 106–108 cm2 s1 for film diffusion controlled adsorption DHis was calculated from slope of the plot ln(Ce) versus 1/T
mechanism (Michelson et al., 1975). Diffusion coefficients data (Fig. 4(b)). The positive values of DHis confirmed the endo-
(Table 7) revealed that the values of film coefficients are in the thermic nature of the adsorption process (Lataye et al., 2009).
order of 108 and 106 cm2 s1, respectively which indicated
that the adsorption of BM2 onto IGHSAC was controlled 3.6. Process design
purely by film diffusion at the studied concentration range
which was supported by the results derived from Boyd plot.
Single stage batch adsorber can be designed using empirical
design procedures based on adsorption isotherms for predict-
3.5. Sorption thermodynamics

Thermodynamic parameters including the changes in Gibbs

free energy DG0 (J mol1) enthalpy DH0 (J mol1) and entropy Table 8 Thermodynamic parameters for adsorption of BM2
DS0 (J mol1 K1) can be calculated in order to illustrate the onto IGHSAC.
thermodynamic behaviour of adsorption process. The adsorp- T (K) DG (J mol1) DH (J mol1) DS (J mol1 K1) DHis (J kg1)
tion equilibrium constant (Kad) can be correlated to the Gibbs 293 40560.05 613.26 140.52 4478.40
free energy change DG0 as (Smith and Van Ness, 1987): 303 41965.28
 313 43370.52
qe DS0 DH0
lnðKad Þ ¼ ln ¼  ð31Þ 323 44775.75
Ce 2:303R 2:303R
Adsorption of Basic Magenta II onto H2SO4 activated immature Gossypium hirsutum seeds 1335

Figure 5 (a) Single stage batch adsorber and (b) adsorbent mass (g) against the volume of dye solution treated (l).

ing the adsorber size and performance (McKay et al., 1981; and 5 l respectively. Therefore Fig. 5(b) can be utilized to pre-
Vadivelan and Kumar, 2005). The schematic single stage batch dict the amount of IGHSAC required for desired purification
adsorber is shown in Fig. 5(a). With the design objective as to the fixed concentration of 150 mg l1.
BM2 solution with initial concentration of C0 (mg l1) and
effective volume of V (l) to be reduced to Ct (mg l1) with 4. Conclusion
the IGHSAC loading of M (g), mass balance equation can
be written as follows The adsorption of BM2 onto IGHSAC experimental data was
VðC0  Ct Þ ¼ Mðq0  qt Þ ð35Þ analysed using different kinetic models by nonlinear regres-
sion. Error functions such as ERRSQ, HYBRID, MPSD,
Since the equilibrium data for BM2 onto IGHSAC was
ARE and EABS were used to evaluate the SNE values and
explained well by Sips isotherm, qt values at equilibrium (qe)
based on the minimum SNE values optimum parameter sets
can be evaluated from Sips isotherm, therefore at equilibrium
for kinetics were evaluated. The obtained parameter set was
the Eq. (35) turned to
further analysed using R2 and RMSE to gauge the goodness
M C0  Ce C0  Ce of fit. Avrami second-order model well described the kinetic
¼ ¼ ð36Þ
V qe 1=n
KS qmS Ce S data for different initial BM2 concentrations. Equilibrium con-
1=n
1þKS Ce S centrations were calculated with the equilibrium adsorption
capacity obtained from the Avrami kinetic model. Different
Fig. 5(b) shows the plots obtained from Eq. (25) indicating
isotherms were investigated to understand the nature of
the predicted amount of IGHSAC required for removing dye
adsorption with the help of nonlinear-SNE procedure.
solution of initial concentration 150 mg l1 to the extent of
Adsorption equilibrium data was in good agreement with Sips
75–90% colour removal at different solution volumes (1–5 l).
and Hill isotherm models. The adsorption process was found
For instance, the amount of IGHSAC required to reduce the
to be controlled by film diffusion at the studied concentrations
colour of 150 mg l1 to the degree of 90% was 6.3, 12.7,
range. The thermodynamic study revealed that adsorption of
19.1, and 25.4, 31.7 g for dye solution volumes of 1, 2, 3, 4
1336 N. Sivarajasekar, R. Baskar

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