Kinetics of chromate removal from water by novel CTAB-silica gelatin composite

Gennaro Bufalo2, Francesco Venditti1, Francesco Lopez1, Luigi Ambrosone1

1) CSGI c/o DISTAAM, 1

CSGI c/o DISTAAM, Universit del Molise, I-86100 Campobasso, Italy 2 ISPESL,Department of Naples, via Lomonaco 3, 80121 Naples Italy
KINETIC PROPERTIES
The samples were placed in shaking water bath. At regular time intervals, samples of solutions were withdrawn from the reaction medium and spectrophotometrically analyzed. The distribution of solute in the solution exterior to the adsorbent can be calculated using a three-step model: 1) Mass transfer of chromate from bulk solution to solid surface

INTRODUCTION
The removal of toxic ions from wastewater is an important and widely studied research area. One of heavy metals that have been major focus in wastewater is chromium. Recent studies have led to the development of a new CTAB-silica-gelatin composite adsorbent [1]. They demonstrated that the composite containing the adorbed hexavalent chromium left in water f0r 30 days undergoes a changes in color from yellow to green. This change is an indication of the reduction in situ of Cr(VI)[2]. In the current work we analyze the kinetic behaviour of the CTAB-silica gelatin composite obtained by hardening the organogel CTAB/water/hexane/pentanol/gelatin system [2] in the removal process of hexavalent chromium from water at neutral pH.

COMPOSITE PREPARATION

dC (t ) V = S s n Dc(r, t ) on outer solid surface dt

C = C0 t = t0 (initial condition)
Schematic representation of the composite preparation [1] 2) Intraparticle diffusion

C = Chromate concentration in the bulk V = bulk volume Ss = outer surface of composite particle n = unit vector

The temperature Tg and the overall amount of TEOS are two important parameters two modulate the adsorptive performance of the material

c(r,t) = Chromate concentration in liquid-filled pore at position r and time t with n Dc(r, t ) = K s (c(r, t ) C (t )) on outer solid surface = fractional void volume s = density of composite paerticle and c(r, 0) = 0 (initial condition)
2

c(r, t ) q ) + s D c(r, t= t t

3) Adsorption at an interior site It is assumed that step 3 is rapid with respect to the first two steps so that

q = f (c) is the adsorption isotherm.

When intraparticle-diffusion resistance is negligible ( the single-resistance case) this equations can be transformed dC 1 into

dt

= C c) (

EQUILIBRIUM PROPERTIES
Equilibrium water swelling. As issue characteristic of diffusion in gels is that the gel volume may not remain constant
throughout the experiment. This will occur if the gel has not reached its equilibrium of swelling before exposure to a solution from which solute diffusion take place. This effect can be eliminated by first equilibrating the gel in water for a prolungated period of time in order to avoid swelling during the experiment. The equilibrium water swelling (Sw) of the composite is defined as the ratio between the mass of composite in the swollen state Ws ( at equilibrium) and in the dried state Ws

dq 1 (C c) = dt s f '(c)

K s SS S = V

characteristic time for the mass transfer

Since the isotherm is experimentally known, these equations can be solved numerically. For deciding if intraparticle diffusion affects the adsorption we compare the experimental results with the solution of the single-resistence.
mass of the sample ( mg)
1

Initial Concentration (mM) 1

Sw =

C/C0
0,8

5.70 30.4 42.61

C/C

0.08

WD

0,8

0.16

0,6 47.52 0,4 49.0

0,6

0.32

0.96 0,4

This parameter is dependent on the Temperature Tg and overall amount of TEOS

0,2

10wt% TEOS; C0 = 0.16 mM; V = 25 cm3

0,1 1 10

82.2

1.92
140.2 166.7

0,2

30wt% TEOS; V = 50 cm3;

0,1 1 10

0 0,01

9.92

t/s 100

0,01

t/

100

solid lines were predicted from single-resistance model

CORRELATIONS
Adsorption Isotherm. The concentration of q of chromate adsorbed on composite was calculated from equation q = The Freundilich isotherm (at 25C )
C0 Ce

The parameter s, calculated by initial slope of experimental data, is correlated to the water volume absorbed in the swelling process and initial concentration, respectively:
100
20
s (h)

q = KCem

fits the experimental data. K and m values depend on

s (h)

Temperature Tg and of the TEOS content.

10

15

10

1
5

q (mmol/g)

0,2 TEOS 30% T = 72C

g

0,1 10 100 V 1000

w

0 0 0,5 1 1,5 2 2,5 3 (mM 0.5 ) 3,5

0,15

0,1

TEOS 10%Tg = 65C

0,05

0 0 0,2 0,4 0,6 0,8 C (mM) 1

Comparison between samples containing the same amount of TEOS prepared using two different temperatures Tg

(s0.5)

REFERENCES
[1] F. Venditti, F. Lopez, G. Palazzo, G. Colafemmina, R. Angelico, L. Ambrosone, A. Ceglie IT. Patent. 7490, 2006 [2] F. Lopez, F. Venditti, L. Ambrosone, G. Colafemmina, A. Ceglie G. Palazzo Langmuir 20 (2004) 9449 [3], F. Venditti, A. Ceglie, G. Palazzo, G. Colafemmina, F. Lopez Colloid Interf. Sci 310 (2007) 353

CONCLUSIONS
Adsorption measurements carried out on CTAB-silica gelatin composite were found to agree with those obtained by single-resistence model. An important conclusion of is that the temperature Tg and TEOS amount can be

used to modulate the adsorption capability of the material