HUNGARIAN JOURNAL 
OF lNDUSTRIAL CHEMISTRY 

VESZPREM 
Vol. 30. pp. 7- 11 (2002) 

KINETIC STUDY OF BLUE M -EB DYE SORPTION ON ION EXCHANGE 
RESINS 

D. ~UTEU, D. BiLBA and C. ZAHARIA 1 

(Department of Analytical Chemistry 
1Department of Environmental Engineering, Faculty of Industrial Chemistry, Technical University of Iasi, Blvd. D. 

Mangeron nr. 71A, P.O. Box.lO- 2002, 6600 Iassy, ROMANIA) 

Received: February 9, 2001 

A kinetic study concerning the Blue M-EB reactive dye sorption from aqueous solutions on Purolite ion exchange resins 
of macroporous (A - 500) and gel (A - 400) type has been made. To establish the rate - controlling step, the time 

required for 50% sorption equilibrium( tv2 ), rate constant of the process ( K ), diffusion coefficient and activation energy 
(Ea) for both resins have been calculated. On the basis of the calculated values it is obvious that sorption process is in the 
diffusion domain, rate-controlling step is the particle diffusion. This result is confirmed by the fact that reactive dye Blue 
M-EB sorption is in good agreement with shell-progressive model. 

Keywords: exchange resins, dye removal, sorption, kinetic study, wastewaters, decontamination 

Introduction 

The decontamination of natural or wastewaters 
impurified with organic pollutants has become one of 
the needs of the day. The great diversity in chemical 
structure of the dyes as well as the variable 
concentrations of dyes and co-solutes, such as inorganic 
salts, sizing agents and surfactants in the effluents of 
dyehouse operations make impossible a general 
available method for removing textile dyes from waste 
water [1-3]. The several traditional wastewater 
treatment methods (biological processes, ozonation, 
coagulation, membrane filtration, etc.) are acceptable in 
decolorizing textile wastewaters with a satisfactorily 
cost-effectiveness [ 4]. 

Due to the polar nature of the their functional 
groups, most commonly-used dyes are relatively easy to 
remove by sorption on various materials: activated 
carbon [5], non ionic or ionic synthetic polymers [6,7], 
biomass-based exchangers [8], anionic clay minerals [9] 
and also adsorbents [lOJ. The dye binding potential of 
these materials is affected by physic-chemical 
characteristics of both sorbent and dye~ there 
compatibility, as well as the operating conditions 
(particle size of granulated sorbent, pH, ionic strength, 
temperature, solution flow rate, etc.) [11]. 

The economic use of various sorbents in removing 
color from textile effluents, but also a better 
understanding of these processes in natural systems 
require informations on the kinetics of dye uptake. 

The thermodynamic, kinetic characterization, the 
mechanism and determinant factors study of the 
sorption process of reactive dyes on Purolite ion 
exchangers are of major important stages in evaluation 
of these resins application . in the recovery of 
wastewaters of textile industry. 

This paper describes a study of Blue M-EB reactive 
dye sorption kinetics onto Purolite anion exchange 
resins. For this purpose, resin loading as a function of 
the contact time was monitored. 

Experimental 

The experiments were carried out using ion exchange 
resins purchased from Purolite International LTD (UK), 
their typical properties are listed in Table 1. 

The reactive bifunctional monochlortriazinic dye 
Blue M-EB (Fig.l) was used as a stock aqueous 
solution containing 0.4 g L"1• The working solutions 
were prepared by appropriate dilution of the stock 
solution with doubly distilled water. 

Contact information: E-mail: dsuteu@ch.tuiasi.ro.; D. Suteu, Stejar Str., 37 A, bl.Ah sc.B. et.l. ap.2, 6600, IASI, 
ROMANIA 



8 

Table 1 Properties of Purolite resins used in kinetic 
measurements 

Parameter Type of Purolite resins 
A-400 A-500 

Matrix polystyrene-
divinylbenzene 

gel 
R-(CH3)3N+ 

cr 

polystyrene-
divinylbenzene 
macroporous 
R-(CH3)3W 

cr 

Structure 
Functional group 
Ionic form 
Mean particle diameter/ 0.64 (± 0.03) 0.64 (± 0.03) 
mm 
Capacity*/ meqg1 3.72 3.93 

* determined by pH-metric titration of resins dried at room 
temperature for 72 hours 

Table 2 Sorption half times, tu2 at different concentrations and 
temperatures of Blue M - EB dye solution for the Purolite 

resins 

tu2f min 
Col gL-1 T/K 

A-400 A-500 
0.10 284.15 20 16 
0.10 296.15 17 10 
0.14 284.15 14 13 
0.20 284.15 11 9 

--(HH2 

Hl~r-NH Oll' OH Nf!--<N N 
N.._J~ ~ SJ- ~ N-{ 

j ~-N-N~-NH N-=N.~ Cl 
N~JS SOJNa Na03 NaOJS SO]Na 

Fig.] Structure of reactive dye blue M-EB 

The continuous kinetic experiments were performed 
by the ''limited bath" technique. Weighed amounts of 
anionic resin (1g) were contacted with 250 mL solution 
containing known amounts of reactive dye, under 
constant vigorous stirring. The temperature of solutions 
was held constant (284.15 and 296.15 K) during the 
experiment with a thermostatic bath. After the 
predetermined time intervals, varying from 5 to 60 
minutes, samples of 2mL supernatant were taken for 
measurements of dye content. Analysis of Blue M-EB 
dye was carried out by spectrophotometric method (Amax 
= 650 nm) with a HACH DR 200 UV-VIS 
spectrophotometer. 

The extent of sorption was expressed by the 

fractional attainment of equilibrium~ F = !!!._ where, qt is 
qfJ 

the amount of sorbed dye per gram of resin at time t and 
qo is the amount of dye sorbed per gram of resin after 24 
hours 

Results and Discussion 

In our previous work [ 12], the equilibrium sorption of 
reactive dye Blue M~EB onto Purolite anion exchange 
resins was studied. The low capacity of resins to remove 
Biue M-EB dye from industrial aqueous effluents has 

0.9 
0.8 

0.7 
0.6 -tr-O.lOg/L 

iJ:.. 0.5 --e-0.14g/L 

0.4 -e-0.20g/L 

0.3 

0.2 
0.1 

0 

0 20 40 60 80 

tin:e (min) 

Fig.2a Rate of sorption of Blue M-EB dye on Purolite A- 400 
resin at different initial concentration. Temperature= 296.15K 

1.2 

0.8 
-e-O.lO!ifL 

iJ:.. 0.6 -e-0.14!ifL 

0.4 
-e- 0.20!ifL 

0.2 

0 

0 20 40 60 80 

tirre (nin) 

Fig.2b Rate of sorption of Blue M-EB dye on Purolite A- 500 
resin at different initial concentration. Temperature= 296.15K 

been explained by the inability of large dye molecules 
to saturate exchange sites of the sorbent (the steric 
hindrance effect). By potentiometric titration of released 
chloride it was found that immobilization of the dye on 
the studied resins takes place by an ion-exchange 
mechanism, but also 1t-1t interactions between the 
organic matrix of sorbent and condensed rings of the 
dye have a considerable importance. The stoichiometry 
of dye association with the anion exchange sites is a I: 1, 
such relationship is in good agreement with other 
workers [ 13]. 

In this paper the kinetics of Blue M-EB reactive dye 
sorption on Purolite anion exchange resins (A-400 and 
A-500) were studied with respect to the following 
variables: initial dye concentration, dye solution 
temperature and structure type of resin. Sorption rates 
were measured for same particle size fractions and for a 
constant high degree of agitation to minimize the film 
diffusional resistance. 

The data, plotted as fractional attainment of 
equilibrium sorption (F) versus time (t), are reported in 
Figs.2 and 3~ 



0.9 

0.8 

0.7 

0.6 

0.5 -e-T(l) 
Jl.t 

0.4 -e-T (2) 

0.3 

0.2 

0.1 

0 

0 20 40 60 80 

time (min) 

Fig.3a Rate of sorption of Blue M-EB dye on Purolite A - 400 
resin at different temperatures, T/K, at initial concentration 

Co=O.l gL-1 

0.9 

0.8 

0.7 

0.6 

Jl.t 0.5 
-e-T(l) 

0.4 
-e-T (2) 

0.3 

0.2 

0.1 

0 

0 20 40 60 80 

time (min) 

Fig.3b Rate of sorption of Blue M-EB dye on Purolite A- 500 
resin at different temperatures, T/K, at initial concentration 

Co=O.l gL-1 

The influence of equilibrium parameters on the rate 
of sorption was quantitatively evaluated by means of 
sorption half-time (t112) (Table 2). 

It is seen that the initial dye concentration has a 
significant effect on sorption kinetics: increasing the 
dye concentration gradient between the solution and 
resins enhances sorption. Also~ the increasing of dye 
solution temperature with -283K has a beneficent effect 
on the rate of sorption (and increase of 1.2 - 1.8 times), 
the results indicate that the process under investigation 
occurs in diffusion region. 

In addition, due to the much greater accessibility of 
the sorption sites (the more open structure), the 
macroporous resin A-500 provides a better kinetic 

9 

2 1.2 

1.8 
1 

1.6 

10.8 1.4 

:! 
1.2 N --*-" T(l) 

1 6 '-" 0.6 -a-T(2) 
;a 

0.8 .s 
I 

0.4 
I 

0.6 

0.4 
0.2 

0.2 

0 0 

0 20 40 60 80 

time (min) 

Fig.4 Test of equations land 2 for sorption of the Blue M-
EB dye on Purolite A- 500 at C0 = O.lg L-1 and T 1 = 284.15K; 

T2 =296.15K 

properties toward dye ions than to the gel type resin A-
400. 

The ion sorption onto solid ion exchange resins must 
be considered as a liquid - solid phase reaction 
including the diffusion of ions from the solution to the 
resin surface, the diffusion of ions within the resin 
particle itself and chemical reaction between ions and 
functional groups [14]. The sorption kinetic is governed 
by the slowest of these processes. In most cases, the 
rate-determining step in the kinetics has been 
established to be diffusion through either the externally 
adherent liquid film or resin particle. Rate laws have 
been derived based on the Nernst - Planck equation for 
film and particle- diffusion controlled process [15]. 

If the liquid film diffusion controls the rate of 
process, the following expression can be used: 

- In ( 1 -F) = K t (1) 
where K = 30~ is the kinetic coefficient or rate 

r08C 

constant /sec-1, Dis the diffusion coefficient in the film 

/cm2s·1• C and C are concentration of the incoming ions 
in solution and in resin, respectively /mmol L·1; r0 is the 
radius of sorbent particle/em and 3 is the diffusion film 
thickness /em. 

The rate equation for intraparticle diffusion control 
is given as: 

-ln(J-1!)= Kt (2) 

where K = ~
2 

is the kinetic coefficient /s·1 ~ Dis the 
ro 

diffusion coefficient in the resin phaselcm2s" 1• 
The sorption data of Blue M-EB dye onto both 

studied resins were analyzed by the rate equations for 
the liquid film and the particle diffusion models (Figs.4 
and 5). 

Although the extremely low concentration of the dye 
in the initial solution suggests a liquid. film diffusion 



10 

Table 3 Kinetic parameters and the energy of activation for 
sorption of Blue M-EB dye ( C0 = 0.1 gL"

1
) onto Purolite 

resins 

Resin T/K K ls-1 D I cm2s-1 Ea/ Jmor
1 

A-400 284.15 5.33 X 10-S 1.53 X 10-S 36.25x10
3 

A-400 296.15 9.87 x w-s 2.83 x w-8 
A- 500 284.15 2.99 x w-4 8.36 x w-8 35.94x103 
A-500 296.15 5.37 x w-4 3.07 x to·7 

2 1 

1.8 0.9 

1.6 0.8 

1.4 0.7 

~ 
1.2 0.6 ,..,---

1 0.5 ~ 
.a 0.8 0.4 ..E! 

1 

-*-T (1) 

-e-T(2) 

0.6 0.3 

0.4 0.2 

0.2 0.1 

0 

20 40 60 

time (mfu.) 

Fig.S Test of equations land 2 for sorption of the Blue M-
EB dye on Purolite A- 500 at C0 = O.lg L-

1 and T 1 = 284.15K; 
T2 =296.15K 

controlled model, a linear correlation between -In (1-F) 
and time is observed orily during the initial minutes. The 
linear regression analysis shows that the kinetics of dye 
sorption onto both studied resins fit the rate equation for 
the particle diffusion model (the correlation coefficients, 
r = 0.9994 - 0.9997). 

The values of the sorption rate constants and of the 
diffusion coefficients in the resin phase calculated from 
the slope of the straight lines (Fig.4 and 5), summarized 
in Table 3, show that the macroporous type resin A-500 
is faster in reaching equilibrium. Also, an increase in 
temperature is favourable to increase the values of 
diffusion coefficients of Blue M-EB dye sorption with 
respect to ionites of both structures. 

Taking into account the rate constants, K , at two 
different temperatures, the activation energy~ Ea. 
required for sorption process was calculated using 
Arrhenius equation: 

K = Koexp( -EaiRT) (3) 
where Ea is the activation energy/ J mor1 and R- gas 
constant= 8.3144 Jmor1 K-1• 

The values of activation energy (Table 3) have 
confirmed the diffusion nature of dye sorption. 

To explain the dye concentration effect on the rate of 
sorption the .. moving boundary'y model of sorption 
kinetics bas been considered [16]. This model assumes a 

0.8 

0.7 

0.6 
EL:;' 0.5 ('.1 

~ 0.4 
~~ 

0.3 
C';l 0.2 
~ 

0.1 

0 

-0.1 

t:itre (min) 

Fig.6a Test of equation 5 for sorption of Blue M- EB dye on 
Purolite A- 400 (D) and A- 500 (.6.) resins at T1 = 284.15K 

~ 
~ 

~ 
C';l 
~ 

0.7 

0.6 

0.5 

0.4 

0.3 

0.2 

0.1 

0 

-0.1 

y 1 = 0.0076x- 0.0032 

R2 =0.9991 

20 40 

t:itre /rrim. 

Fig.6b Test of equation 5 for sorption of. Blue M- EB dye on 
PuroliteA-400 (D) andA-500 (0) resins at T2 =296.15K 

sharp boundary that separates a completely reacted shell 
from an unreacted core and that advances from the 
surface toward the center of the solid with the 
progression of sorption. The rate equation for the 
moving boundary model is given as: 

(4) 

K = 
6;_,~ is the kinetic coefficient /s-1, A - the 
qro 

molar distribution coefficient, q - the sorption capacity 
of the unreacted resin bead at equilibrium I mmol L"1• 

In order to test the moving boundary model for dye 
so~tion onto both Purolite resins, the plots of [ 3- 3(1-
F) - 2F 1 versus time have been presented in Fig.6. 

Linearity of the plots obtained show the validity of 
the moving boundary model, yielding correlation 
coefficients in the 0.9997. 



Conclusions 

Research on the kinetics of Blue M-EB reactive dye 
sorption by using Purolite anion exchangers of both gel 
and macroporous structures has resulted in the 
conclusion that dye sorption is limited by intraparticle 
diffusion and follows moving - boundary behavior. The 
dependencies found : ln( 1-F2) vs, t and [ 3- 3(1-F)213 -
2F ] vs, t proves this model. 

Dye sorption using macroporous resin proceeds 
faster than with gel type resin. 

The values of diffusion coefficients and activation 
energy of dye sorption on Purolite resins of both 
structures confrrms that the process in investigation 
occurs in diffusion region. 

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