Journal of the University V. Vassileva, E. Valcheva,andZheleva of Chemical Technology Z.

Metallurgy, 43, 3, 2008, 323-326

THE KINETIC MODEL OF REACTIVE DYE FIXATION ON COTTON FIBERS

V. Vassileva, E. Valcheva, Z. Zheleva

University of Chemical Technology and Metallurgy 8 Kl. Ohridski, 1756 Sofia, Bulgaria E-mail: violet@uctm.edu

Received 05 May 2008 Accepted 12 August 2008

ABSTRACT The kinetics of fixation of Bezaktiv rot HE-7B (CI Reactive red 141) on cotton fibers is studied at three temperature values. As a kinetic variable is used the Kubelka-Munk function(K/S) which is in direct ration to fibers dye concentration. It is found that the process rate is described by the power kinetic equation valid for exponentially inhomogeneous surfaces and is determined by entropy factors accounting for the number of the active sites, their accessibility and the steric hindrance present. The activation energy remains constant during the process of fixation and does not depend on the quantity of the fixed dye.The decrease of the rate of dye fiber interaction in the course of the process is attributed to the occupation of the active cites by bonding dye molecules. Keywords:kinetic model, power kinetic equation, reactive dyes, rate of fixation, activation energy.

INTRODUCTION The dyeing is a heterogeneous process which takes place at the interphase between the dyeing solution and the fibers. Its proceeding includes (i) diffusion of the dye in the bulk liquid phase; (ii) adsorption of the dye on the fibers outer surface; (ii) diffusion in the bulk of the fibers; (iv) adsorption on the inner surface of the fibers [1-3]. The dyeing with reactive dyes is completed by a chemical interaction between the dye molecules and the active cites of the fibers, i.e. by the process of fixation. Depending on the dyeing conditions each one of these steps can become limiting and hence determining the overall rate and the kinetic relations of the process. The last step the fixation of the dye on the fibrous material presents definite interest. The degree of dyes fixation is mainly affected by the chemical structure of the fibrous polymer which determines the affinity of the dye towards the fibers, the

number and the type of the potential active cites where the dye molecules physical and chemical adsorption take place. The cellulose macromolecule includes anhydroglucoside residues interconnected by 1-4--glucoside bonds each of which containing three hydroxyl groups. These groups have different reactivity towards dye molecules and the studies carried so far show that the fixation proceeds predominantly through the hydroxyl group at C6 [4, 5]. The physical structure of the fibers is of importance as well as it determines the accessibility of the active cites. Only some of the dye molecules sorbed on the fibers surface are able to interact with them. A favorable disposition is required. The physical properties of the fibers can be divided to surface and bulk one. Properties of the outer surface of the fibers like morphology and electric charges which appear at the interphase with the liquid solution refer to the first group, while those determined by porosity, crystallinity, degree of orientation, etc. belong to second one. The in-

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ner surface of the fibers affects essentially the kinetics of dye sorption especially in the initial stage of the process. The cotton fibers have a natural porosity a system of pores and microcapillaries whose accessibility can increase depending on the dyeing conditions. Dyeing with reactive dyes takes place in an alkaline medium which results in a considerable swelling of the cotton fibers and increase of their inner surface. As the fixation is preceded by dye molecules diffusion and sorption, their chemical structure and size are important too [6]. Most of the literature data refer to kinetic investigations connected with the presentation of models describing dyes adsorption behavior or following dyes quantity variation till the end of the dyeing process [79]. The study of the fixation kinetics provides to comment the dye molecules reactivity, the fibers structure and the active cites character. The present investigation is aimed to determine the kinetic relations describing reactive dyes fixation on cellulose textile materials on the ground of the methods of the heterogeneous chemical kinetics. EXPERIMENTAL The experiments described are carried out with cotton (100%) material and the reactive dye Bezaktiv rot HE-7B (CI Reactive red 141), containing two identical monochlorotriazine reactivity groups. 4%-dyeing is carried out in correspondence with the scheme presented in Fig.1. There A stands for the dye used (4% in respect to the textile material), B for Meropan DPE (1 g l-1), C Na2SO4(80 g l-1 introduced as C1 corresponding to 40% and C2 to 60% of the total amount, respectively), D Na2CO3 (5 g l-1) and NaOH (380 Be) in amount of 2.5 ml l-1. The ratio of the dyeing solution and the textile material equals to 100:1. The effect of the temperature is followed carrying out experiments at three temperature values in the range from 60oC to 80oC. The alkali introduction at the 70-th min is accepted to mark the beginning of fixation which proceeds further for another 60 min. The kinetics of the process is followed taking seven samples of the textile material within the time interval from the 5-th to the 60-th min.The samples reflectance was measured and

Fig. 1. Dyeing method for Bezaktiv HE dyes.

the values obtained were used to determine KubelkaMunk, K/S, function. The latter is directly proportional to the dye concentration in the textile material and is used as a kinetic variable in this investigation. The residual and the hydrolyzed dye is removed through multiple rinsing with hot and cold water followed by washing at 90oC for 30 min in TA(5 g l-1)/M (1:50) mixture. RESULTS AND DISCUSSION The kinetic curves obtained in the study of Bezaktiv rot HE-7B fixation at the three temperature values mentioned above are presented in Fig.2. It is seen that the values of K/S increase significantly during the first 30 min implying that this is the effective time for the formation of the dye-fiber bond. The applicability of different kinetic equations (the first order kinetic equation, the exponential kinetic equation, the power kinetic equation, etc.) valid for

Fig. 2. Kinetic curves of fixation of Bezaktiv rot HE-7B on cotton fibers at different temperatures:u -60 0C; n -70 0C;F -800C.

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Fig. 3. Linearized dependence of ln(K/S) on lnt.

Fig. 4. Temperature dependence of the rate constant k ( l ). Temperature dependence of the rate of the process of fixation at various values of K/S :4 (-u-) ; 5 (-F-) ; 6 (-n-).

heterogeneous chemical processes of diffusional or adsorption-chemical control was checked. It is found that the experimental data is best described by the power function: K/S = g.t (1) where gand do not vary at a constant temperature value. The linearization of the function which is illustrated in Fig. 3 verifies its applicability. Hence it can be concluded that the fixation process rate is not determined by the diffusion step which in turn leads to the application of the model of adsorption-chemical inter-

action between the dye molecules and the cellulose fibers. The slopes and the intercepts of the linear dependences presented in Fig. 3 provide the determination of the values of gand . They are presented in Table 1. As it is seen dopes not depend on the temperature while ggrows with temperature increase. Eq. (1) is the integral form of the power kinetic equation which describes the proceeding of surface chemical interaction on exponentially inhomogeneous surfaces [10,11]: V = d(K/S)/dt = k (K/S)-(1-)/ (2) The coefficient of proportionality khas the meaning of a rate constant and is connected with gfrom Eq. (1) in accordance with: (3) k=.g1/ The values of kcalculated with the application of Eq. (3) are presented in Table 1 as a function of the temperature studied. When the rate of a heterogeneous process taking place on exponentially inhomogeneous surfaces is determined by the surface chemical interaction, the power (1-)/characterizes in general the energy and entropy inhomogeneity of the solid phase surface. It is important to note that in case of an exponentially inhomogeneous surface the distribution of the active cites in energy and adsorbability follows an exponential law [10, 11]. It is seen from Table 1 that the values of (1-)/ from Eq. (2) and from Eq. (1) do not depend on the temperature applied. This means that the surface behaves as energetically homogeneous and that the activation energy will not change in the course of the process. This in turn implies that the power term characterizes the surface entropy inhomogeneity only which is usually connected with the variable number and accessibility of the active reaction cites. In such a case the process rate is determined by the preexponential factor in Arrhenius equation. It accounts for the entropy factors and is a function of the surface concentration.

Table 1. Dependence of the coefficients g and and the rate constant k on the temperature in case of fixation of Bezaktiv rot HE-7B.

g, min-1 k, min-1

600 0,62 1,13 0,73

700 0,62 1,82 1,79

800 0,55 3,45 4,68

av. 0,60

(1-)/ 0,66
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Journal of the University of Chemical Technology and Metallurgy, 43, 3, 2008

Table 2. Dependence of the rate v at different temperature and the preexponential factor A on K/ S values in case of fixation of Bezaktiv rot HE-7B.

600 K/S 4 5 6 0,291 0,255 0,223

700 V, min 0,690 0,607 0,532

-1

800 1,857 1,627 1,426

A, min-1 3,12.1013 2,74.1013 2,4.10 13

Eq. (2) is used to calculate the fixation process rate at different K/S values in the temperature range studied. The data obtained is summarized in Table 2. The temperature dependence of the rate at a given K/S value is described by Arrhenius equation: v = A . e(- E / R. T)(4) The linear dependences obtained are presented in Fig. 4. The latter shows the temperature dependence of the rate constant as well. The value of the activation energy stays constant and is equal to 89.5 kJ mol-1 . Besides it does not depend on the quantity of the dye fixed, i.e. on K/S. The preexponential factor A decreases with K/S increase as it is seen from Table 2. The application of Arrhenius equation to the rate and the rate constant in the power kinetic equation (Eq.2) leads to: lnA-(E/RT)=lnAk-(Ek/RT)-(1-)/ln (K/S) (5)

tive red 141) on cotton fibers is described by the power kinetic equation applicable to exponentially inhomogeneous surfaces. It is connected with surface chemical interaction with the participation of active cites identical from energetic point of view. The rate of dyeing is mainly affected by entropy factors attributed to active sites number and accessibility as well as to presence of steric hindrance. The rate decrease in the course of the process is attributed to the occupation of the active cites by bonding dye molecules. REFERENCES 1. G. E. Krichevskij, M. V. Korchagin, A. V. Senahov, Khimicheskaya tehnologiya tekstilnih materialov, Moscow, 1985, (in Russian). 2. G. E. Krichevskij, Diffuziya i sorbtziya v protzesah krasheniya i pechataniya, Moscow, 1981, (in Russian). 3. G. E. Krichevskij, Physico-khimicheskie osnovi primeneniya aktivnih krasitelej, Moscow, Lehkaya industriya,1977, p.106, (in Russian). 4. J.Vegmann, Text. Prax., !, 1958, 1058 5. J.Vegmann, Text. Prax., !, 1958, 936 6. T. Bikerstaff, Fizicheskaya khimiya krasheniya, Gizlergprom, 1956, p.574, (in Russian). 7. H. Tavanai, A. Z. Hamadani, M. Valizadeh, Iranian Polymer J.,  , 2006, 459. 8. P. Reys, R. Sperb, Text. Res. J., May, 1989, 643. 9. E. Matyjas, K. Blus, E. Rybicki, Fibers&Textiles in Eastern Europe,  , 2003, 66. 10. E. T. Valtcheva, Compt. rend. Acad. Bulg. Sci. ! , 1979, 1089. 11. E. T. Valtcheva, React. Kinet. Catal. Lett., ', 1985, 137.

In case of constant activation energy the preexponential factor A depends on K/S following: A=A.(K/S)-(1-)/ (6) where Ak is the preexponential factor determined from the temperature dependence of the rate constant. Its value is 7,67.1013 min-1. CONCLUSIONS The kinetic investigations carried out show that the process of fixation of Bezaktiv rot HE-7B (CI Reac-

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