1. INTRODUCTION:

The drainage of the industrial wastewater that containing organic dyes are one of the most harmful environmental Challenges. In which the organic dyes extensively uses in textile dying, laser printing and textile paper. And there are about 100000 dyes available in the commercial field⁽¹⁾. The presence of these dyes in the water causes cancer, toxicity, birth defect, teratogenicity and reduce the light penetration through the water surface and consequently that will lead to prevents the photosynthesis of the aqueous plant ⁽²⁾. Can be classify the dyes as acid basic, azo, diazo, metal complex disperse, and anthraquinone based. The due for that bright, soluble and high tinctorial value rise the use of basic dyes in textile industry⁽³⁾. So in the currently days many treatment technologies are uses in order to removal of these contamination dyes and organic effluents that being drainage it to the water such as adsorption, precipitation, oxidation-ozonation, coagulation, coagulation-flocculation, ion exchange, and biological methods^(4,5).

All these methods except adsorption have some economic and environmental drawbacks, such as high capital and operating cost, sludge production and complexity of the treatment processes⁽⁶⁾. Adsorption method consider one of the most promising methodes due to its flexibility economic and high efficiency. In which the adsorption efficiency for the dyes removal depends on the nature of the materials that use as adsorbent^(7,8). Adsorption properties and equilibrium data, commonly known as adsorption isotherms, describe how pollutants interact with adsorbent materials and so are critical for optimizing the use of adsorbents⁽⁹⁾. The adsorption study for this dyes is important for different physic-chemical operations and for understanding of phenomena such as explanation and de pollution of industrial liquid wastes⁽¹⁰⁾. Coomassie Brilliant Blue (CBB) it is the triphenyl methane dye that use in a wid range for the stain proteins in electrophoretic profiles and in solution quantification. However there are two kinds of the CBB dyes, CBB R-250 and CBB G-250 in which R refers to the reddish tint of the product wherease G refers to the greenish tint of the dye. And the difference between them is the additional methyl group. Coomassie is a trademark name still detained by Imperial Chemical Industries (ICI, later acquired by Akzo Nobel Inc.), and the 250 code represents the dye content⁽¹¹⁾.

2. METHODS AND MATERIALS:

2.1. Characteristics of the dye:

Organic Coomassie brilliant blue G-250 dye were used. All chemicals used have high purity and commercially available. CBB solution preparation with concentration 100 mg/L was carried out by dissolving 0.02g of CBB in 200 ml of distilled water . And the dye properties are shown in Figure (1).

Table 1: Characteristics ofCoomassie brilliant blue G-250

Empirical Formula	C₄₇H₄₈NaO₇S₂
Solubility in water	Soluble
Molecular Weight	854.02g/mol
λ max	586 nm
C. I. No	42655

Fig. 1: Structural formula of Coomassie brilliant blue G-250⁽¹²⁾

2.2. Characteristics of theadsorbent (snail shell powder):

Snail shell was collected from dumo site and then carefully washed with tap water and deionized water to remove other particles from its surface. Then crushed, sieved and dried at 100 C0 for 24 hrs.

Figure 2. FT-IR Analysis for Snail Shellpowder

FT-IR (KBr, cm^-1): ν3427.45 (OH), 2918.98 (C-H),712.65 (Al-O).⁽¹³⁾

Batch Adsorption Experiments:

By using 0.02g adsorbent material added to 25ml of dye solutions 20mg/L. The complete solution was agitating by using thermostate shaker water bath 150rpm . The unadsorbed supernatant liquid of the residual dye in each treatment solution was analyzed by Shimadzu UV-Vis 1800 digital double beam instrument at a wavelength corresponding to the λ max. The PH and temperature effects were studied. The amount of adsorption is expressed by the ratio x/m which is defined as the quantity of adsorbate in mg held by weight of adsorbent g.

Removal % = [(C₀-Ce)/C₀]×100…………………….. (1)

Where :

C₀ and C_edenote the initial concentration and final residual concentration of dye in mg/L respectively⁽¹⁴⁾^.

3. RESULTS AND DISCUSSION:

3.1. Effect of Contact Time:

The adsorption of CBBG 250 on snail shell was investigated as a function of shaking time at 298K. The results indicate that the adsorption was depend on the time until reached a constant values after 30 min of shaking. So we kept this time for all other experiments. Figure 3. Illustrate the removal percent with time effect.

Fig.3: Effect of contact time on adsorption of CBB G-250 by Snail shell at temperature 298 K, Conc. of dye 20 mg/L and adsorbent Dosage 0.02 g.

3.2. Effect of Adsorbent Dos:

The adsorption experiments were carried out by varying the adsorbent weigh from0.01 to 0.08 g , whereas the dye concentration was constant 20 ppm. The equilibrium state at optimum conditions was achieved at following conditions 298k, 30 min, 0.02 g of adsorbent materials and 20 ppm of dye.

Fig.4:- Effect Adsorbent Dos on adsorption of CBB G-250 by Snail shell at temperature 298 K.

3.3. Effect of Ph:

The pH is the important factor that controls the adsorption process especially for dyes⁽¹⁷⁾. Fig. 5 shows the effect of pH for the adsorption of CBB G-250 on the Snail shell

Fig. 5: Effect pH on adsorption of CBB G-250 by Snail shell at temperature 298 K .

3.4. Effect of Temperature:

All experiments were carried out at dye concentration equal to 20.00 ppm over the temperature range (298, 308,318,328and 338)K in order to study the temperature effect. The Experimental results indicate that the sorption was exothermic process. From equations (2-5)⁽¹⁸⁾the Thermodynamic parameters (ΔG, ΔS, ΔH) were calculated.

ΔG=-RT lnKeq………..…………… (2)

Keq= (Qe m)/Ce v………………..… (3)

lnKeq=(-ΔH/RT) +con. .................... (4)

ΔS= (ΔH - ΔG)/T …………………... (5)

Fig. 6: Temperature dependence of the adsorption CBB G-250 dye on the Snail shell.

Table 2: Thermodynamic function ΔG, ΔH and ΔS of CBB G-250 dye on the adsorbent surface Snail shell at (298-338) K

Adsorbate	Temp. K	∆G (KJ/mol)	∆H (KJ/mol)	∆S (J/mol)
CBB G-250	298	4.5599-	-17.8717	0.0446-
	308	-4.0177		-0.04498
	318	-3.5803		0.04494-
	328	-3.1922		0.0447-
	338	-2.7114		0.0448-

The negative values of the free energy refers to spontaneous nature of the adsorption process and its values was decrease as the temperature increase, from that proportional we conclude that adsorption was physical adsorption^(19)(20). The negative value of ΔH implies the exothermic nature of the process⁽²¹⁾. The negative values of Δ𝑆 refers to the decreasing in the freedom randomness through the adsorption on the interface between the solid (snail shell) and liquid (CBB G-250 soltion)⁽²²⁾.

3.5. Adsorption Isotherm:

The filtered solution was analyzed by using UV-visible spectrophotometer and from equation (6) the amount of the pesticides adsorbed was calculated.

Qe= V (C_o – Ce) /m = x /m ………….…………….. (6)

Where :

Qe = x/m the quantity of adrobed material mg/g adsorbent, V volume of pesticide solution L that was used, C₀ Initial concentration mg/L, Ce Equilibrium concentration mg/L, m weight of adsorbent g⁽²³⁾.

The amount of adsorption is expressed by the ratio x/m which is defined as the quantity of adsorbate material in mg that held a specific weight of the adsorbent materials g. Fig.7. shows Adsorption isotherms: Langmuir, Freundlich and Temkin isotherms.

Fig.7: Adsorption Isothermof CBB G-250 adsorption from aqueous solution on the surface of the the Snail shell at different temperatures

The shapes of adsorption isotherms that obtained from the experimental results was identical with Giles classification⁽²⁴⁾.

Langmuir isotherm:

The Langmuir isotherms mathematical expressions were determined by following equations⁽²⁵⁾ .

Ce/Qe = 1/ab+ Ce/a ...................(7)

Where:

Ce: is the equilibrium concentration of the adsorbate mg/L .

Qe: the amount of adsorbate which get adsorbed per unit mass of adsorbate mg/g .

a: (mg/g) the maximum adsorption capacity according to Langmuir monolayer adsorption.

b (L/mg) is the Langmuir constant relates to affinity and free energy of adsorption⁽²⁶⁾.

A linear plot was obtained when Ce/Qe was plotted versus Ce.⁽²⁷⁾ as shown in Fig.8

Fig. 8:- The Langmuir isotherms for CBB G-250 dye atdifferent temperatures

The feasibility of the adsorption process is calculated through using the separation factor R_L, which is defined by equation (8).

R_L = 1 / (1 + b Co) ......................................................(8)

The value of R_L indicates the category of the isotherm to be either unfavorable (R_L> 1), linear RL = 1, irreversible R_L = 0 or favorable 0 < R_L< 1. ⁽²⁸⁾

Freundlich Isotherm

The second model is the Freundlich model is given by:

Log(Q𝑒) = Log(K_f) +1/ n Log(𝐶𝑒) ………………….(8)

where:

Qe and Ce are the same as defined above. KfL/mg and n are Freundlich constants related to adsorption capacity and adsorption intensity, respectively.⁽²⁹⁾

Fig.9: The Freundlich isotherms for CBB G-250 dye atdifferent temperatures.

The Temkin Isotherm:

Temkin isotherm have a factor that give illustration about the adsorbent interactions and adsorbing species. In which Tempkin isotherm assumes that the heat of adsorption for all molecules in the adsorption layer decreases linearly with increase the surface coverage due to the nature of the adsorbent−adsorbate interactions.

The Temkin isotherm is given as

qe= B lnA_t + B lnCe ………………………………...(9)

where:

A_t is the equilibrium binding constant that corresponds to the maximum binding energy

B is constant which related with the heat of adsorption. A linear plot was obtained when qe was plotted vstlnCe.⁽³⁰⁾

Fig.10: The Temkin isotherms for CBB G-250 dye atdifferent temperatures

Table 3: Langmuir,Freundlich and Temkin parameters of adsorption isotherms at(298 – 338) K

AdsorbateCBB G-250
Temp. K	Langmuir isotherm				Freundlich isotherm			IsothermTemkin
Temp. K	a (mg/g)	b (mg/L)	(r²)	R_L	(K_f)	(n)	(r²)	B	A_T	(r²)
298	-625	-0.0107	0.0607	1.2722	6.6788	0.9542	0.9826	23.622	1.0543	0.8909
308	-109.89	-0.0442	0.4226	8.6206	4.5835	0.8196	0.9789	27.117	0.7840	0.9148
318	-39.525	-0.0743	0.6283	2.0576	2.2599	0.6575	0.9785	32.215	0.5433	0.9071
328	-29.069	-0.0713	0.6124	-2.3474	1.3740	0.6175	0.9693	32.15	0.4378	0.8778
338	-24.691	-0.0682	0.6798	-2.7472	0.9767	0.5930	0.9779	31.969	0.3835	0.8684

*The Freundlich model gives r²=(0.98,0.97,0.97,0.96 and 0.97)so we conclude that adsorption was obeys Freundlich isotherms , this indicating that the adsorption of the CBB G-250 on the surface of snail shell was heterogeneous surface with multilayer sorption⁽³¹⁾ .

CONCLUSION:

1 The present study demonstrated that snail shell can be used as an effective adsorbent for the removal of CBB G250 dye from aqueous solutions.

2 Besides minimizing the wastes, the results also provide additional benefits to industrial wastewater treatment.

3 It was found that the equilibrium data fitted very well with Freundlich isotherm model. 4-Thermodynamic studies indicated that the adsorption process was exothermic, the degrees of freedom decrease at the solid- liquid values and spontaneous in nature .

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Received on 10.03.2019 Modified on 14.04.2019

Research J. Pharm. and Tech 2019; 12(10):4921-4925.

DOI: 10.5958/0974-360X.2019.00853.9