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Adsorption Study of Acid Red 18 From Aqueous Solution on to Activated Carbon Prepared From Murraya Koenigii (Curry Tree) Seeds

Adsorption Study of Acid Red 18 From Aqueous Solution on to Activated Carbon Prepared From Murraya Koenigii (Curry Tree) Seeds

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Adsorption study of Acid Red 18 from aqueous solution on to activated carbon prepared from Murraya koenigii (curry tree) seeds
Adsorption study of Acid Red 18 from aqueous solution on to activated carbon prepared from Murraya koenigii (curry tree) seeds

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INTRODUCTION
Dyes are widely used in textile, paper, leather, coir pith,carpet and cosmetic industries. The textile industry is one of the largest producers of industrial waste water. The effluentreleased from these industries, if not treated properly, is a majorenvironmental concern. Effluents from the textile industry arehighly coloured and disposal of this coloured water into thereceiving water body causes damage to aquatic life andhumanbeings
1,2
. A lot of synthetic dyestuffs used in textile industrywere found to be toxic, carcinogenic and even mutagenic
3
.Thus the effluents need to be treated properly before beingreleased in to the environment.There are several treatment methods like photo degradation
4
,coagulation, flocculation
5
and electrochemical oxidation
6,7
available for the treatment of water containing dye effluents.Among these methods, adsorption
8
is one of the mosteffectiveprocesses used for the removal of dye from waste water.Considerable work has been done to remove toxic dyesfrom the effluents using low cost adsorbents. Some of thematerials used are apricot stone
9
, sugarcane bagasse
10
, rubber(
 Hevea brasiliensis
) seed coat
11
, neem (
 Azadirachta indica
)leaf powder
12
, coir pith
13
, bamboo dust, coconut shell, ground-nut shell, rice husk, straw
14
, orange peel
15
, sunflower seed
Adsorption of Acid Red 18 from Aqueous Solution onto ActivatedCarbon Prepared from
 Murraya koenigii
(Curry Tree) Seeds
S. S
URESH
1,*
, R. W
ILFRED
S
UGUMAR
2
and T. M
AIYALAGAN
3
1
Department of Chemistry, Panimalar Institute of Technology, Chennai-602 103, India
2
Department of Chemistry, Madras Christian College, Chennai-600 059, India
3
South African Institute for Advanced Materials Chemistry, University of the Western Cape, Bellville 7535, Cape Town, South Africa*Corresponding author: E-mail: avitsureshindia@gmail.com
 Asian Journal of Chemistry; Vol. 23, No. 1 (2011), 219-224
(
 Received 
: 3 February 2010;
 Accepted 
: 25 August 2010)AJC-9024This paper focuses on the adsorption of acid red 18 onto low cost adsorbent prepared from
 Murraya koenigii
seeds (MKS) from aqueoussolutions at room temperature (25 ºC). Batch experiments were conducted and the effect of different process parameters such as adsorbentdosage and initial dye concentration were studied. The adsorption isotherm data was analyzed using Langmuir, Freundlich and Temkinisotherm models. The equilibrium data fits well with Langmuir adsorption isotherm and the monolayer adsorption capacity was found tobe 53.19 mg/g. The adsorption kinetics was studied using pseudo-first order and pseudo-second order models. The rate of adsorption wasfound to conform to pseudo-second order kinetics with a good correlation (R
2
> 0.99). The activated carbon prepared was characterizedby SEM and FT-IR spectra. The results prove that
 Murraya koenigii
seeds is a good low cost adsorbent for the removal of acid red 18 fromaqueous solution.
Key Words: Activated carbon, Adsorption, Dye removal, Equilibrium, Kinetics.
hulls
16
, agricultural wastes
17
 
etc
. The present work is to investi-gate the adsorption phenomenon using
 Murraya koenigii
seedas an adsorbent. The seed of 
 Murraya koenigii
or as it iscommonly known as curry tree seed is abundantly availablein south India and hence it is used as an adsorbent material forthe removal of acid red 18 from aqueous solution.
EXPERIMENTAL
In this study a commercially available textile dyestuff namely acid red 18 is used as adsorbate. The molecular structureand properties of acid red 18 is shown in Fig. 1 and Table-1,respectively. The dye is widely used in textile industries. Theselected dyestuff is a dye contaminant in the discharged effluentscommonly used in dye houses.
NaO
3
SNNNaO
3
SHOSO
3
Na
Fig. 1. Molecular structure of acid red 18
 
TABLE-1PROPERTIES OF ACID RED 18Parameters ValueChemical nameCAS numberFormula weightIonizationMolecular formulaChromophoreMaximum wavelength
 
Acid Red 182611-82-7 604.47 Basic C
20
H
11
N
2
O
10
S
3
Na
3
 Monoazo507 nm
Preparation of activated carbon:
Activated carbon usedin this study was prepared by chemical activation method. The
 Murraya koenigii
seeds (MKS) was washed several times toremove all dirt, dust and other surface impurities. The washedseeds were dried for 24 h. The dried seed was then soaked in18 N H
2
SO
4
(sulphuric acid) in the ratio 1:2 (w/v) and kept ina muffle furnace for 12 h at 120 ºC. The carbonized materialwas finally crushed, sieved, dried and stored in plastic con-tainers.
Characterization:
The surface morphology of the activatedcarbon prepared from
 Murraya koenigii
seeds was studiedbefore and after dye adsorption by using scanning electronmicroscopy (Hitachi S3000N). The electronic structure of carbonsamples were analyzed using FT-IR (Perkin-Elmer) spectro-meter. The measurements were carried out in the range of 4000-450 cm
-1
. Carbon samples (0.33 wt %) were stirred with dryKBr (Merck, spectroscopy grade) and then pressed to formappropriate tablets.
Batch adsorption experiments:
The effect of variousprocess parameters like adsorbent dosage, pH and initial dyeconcentration for the removal of acid red 18, were carried outin batch experiments in an orbital shaker at a constant speedof 160 rpm. The adsorption isotherm studies were carried outby agitating 50 mL of dye solution of various concentrationsand fixed amount of adsorbent. After agitation, the dye solutionswere separated from the adsorbent by centrifuging (ResearchCentrifuge, Remi Scientific works, Mumbai) for 5 min. Thedye removal was determined spectrophotometerically (ELICO:SL 207) by monitoring the absorbance changes at the wave-length of maximum absorbance (507 nm). The effect of adsorbent dosage was studied with different adsorbent doses(25-150 mg). Kinetic experiments were carried out using amechanical stirrer in the concentration range of 60-100 mg/L.The percentage dye removal was accessed using the equation100C)CC( removaldyeof Percentage
ii
×=
(1)The amount adsorbed at equilibrium q
e
(mg/g) was cal-culated byMV)CC( )q(adsorbedAmount
ie
=
(2)where C
i
and C
are the liquid phase concentrations of the dyeat initial and equilibrium concentrations (mg/L), respectively,M = mass (g) of adsorbent and V = volume of dye solution (L)Langmuir and Freundlich isotherms were employed to studythe adsorption capacity of the adsorbent.
RESULTS AND DISCUSSION
Characterization of the adsorbent:
Morphological studyby SEM of the adsorbent shown in Fig. 2(a-b) revealed that
Fig. 2.SEM micrograph of prepared activated carbon (a) before dyeadsorption (b) After dye adsorption
there are marked changes on the surface morphology of theadsorbent before and after dye adsorption. From the SEMpictures, it is obvious that the porous nature
18
of the adsorbentwould have increased the possibility for the dye to be trappedon the adsorbent.The functional groups present on the adsorbent wereconfirmed by FT-IR spectra (Fig. 3). The adsorbent gives anumber of absorption peaks. The peak at 3387.5 cm
-1
represen-ted bonded hydroxyl groups. A weak alkyl C-H stretching bandis observed at 2931 cm
-1
. The peak at 1724.5 cm
-1
correspondsto C=O stretching. The peak at 1621.5 and 1231 cm
-1
corres-ponds to C=C stretching and -SO
3
stretching, respectively. Thepeak observed at 1054.5 and 885.5 cm
-1
could be assigned toC-O stretching vibration and C-H out of plane bendingvibration. The adsorbent exhibits reasonable anionic exchangecapacity due to the presence of polar functional groups on theadsorbent.
40003500300025002000150010005000510152025303540
3387.529311724.51621.512311054.5885.5581.
   T  r  a  n  s  m   i   t   t  a  n  c  e   (   %   )
wave number (cm
1
)
Fig. 3.FT-IR Spectra of the activated carbon prepared from
 Murrayakoenigii
seeds
220
 
Suresh
et al.Asian J. Chem.
 
Effect of adsorbent dosage:
A fixed concentration of dye (40 mg/L) was taken and the adsorbent dosage was variedin the range of 25-150 mg at a constant volume (50 mL) keepingall other experimental conditions constant.Fig. 4 shows that, an increase in adsorbent dosage increasesthe adsorption amount until a particular dosage at whichadsorption becomes constant. The increase in adsorptionfollowing an increase in adsorbent dosage can be attributed tothe availability of more adsorption sites
8
. However, the amountadsorbed per unit mass of the adsorbent decreases considerably.As the adsorption sites remain unsaturated during the adsorptionprocess there is a decrease in unit adsorption with increasingdose of adsorbent
16
. When the adsorbent and the solute concen-tration are low then the sorption rate is low. On the other hand,a high adsorbent to solute concentration ratio increases therate of adsorption on the adsorbent surface and hence there isa decrease in the solute concentration in solution.
20 40 60 80 100 120 140 16030405060708090
% Dye Removal vs Adsorbent Dosageq
e
vs Adsorbent dosage
Adsorbent Dosage (mg/50mL)
   %    D  y  e  r  e  m  o  v  a   l
1015202530
 q
 e 
 (  m g /   g )  
Fig. 4.Percentage of dye removal
versus
adsorbent dosage (C
0
= 40 ppm;V = 0.05 L; t = 8 h)
Effect of initial dye concentration (C
i
):
The effect of initial dye concentration was studied by using a fixedadsorbentdosage (50 mg) for different initial dye concentrations (40,50, 60, 70, 80,100 and 120 mg/L).From Fig. 5, it can be observed that the percentageremoval of dye decreases with the increase in initial concen-tration of dye. This is due to the saturation of the adsorptionsites at higher concentrations. It is also observed that theactualamount of dye adsorbed increases with the increase in initialdye concentration (C
i
). An increase in C
i
increases the inter-actions between the adsorbent and adsorbate. Therefore thereis an increase in the rate of adsorption of dye.
Adsorption isotherms:
In accessing the equilibriumnature of adsorption of the adsorbent, three well known isothermsnamely Langmuir, Freundlich and Temkin were selected forthe present study. An adsorption isotherm describes therelationship between the mass of the adsorbate that is adsorbedper unit weight on the adsorbent and the concentration of dissolved adsorbate in the liquid phase at equilibrium.
Langmuir adsorption isotherm:
The Langmuir adsorp-tion isotherm is based on the assumption
19
that an adsorbentadsorbs the dye at specific homogeneous sites and once thatsite is occupied, no further adsorption takes place at that site.
 
40 60 80 100 12035404550556065
% Dye Removal vs Initial dye concentrationAmount Adsorbed vs Initial dye concentration
Initial Dye Concentration (mg/L)
   %    D  y  e  r  e  m  o  v  a   l
2530354045
Am o un t  A d  s  o b  e  d  (  m g /   g )  
Fig. 5.Percentage dye removal
versus
initial dye concentration (m = 0.05g;V = 0.05 L; t = 8 h)
Theoretically, the adsorbent has a finite capacity to absorb theadsorbate and hence there is a limit beyond which no furtheradsorption can occur
20
. The monolayer capacity can be repre-sented by the expression:
eLeLme
CK1CKQq
+=
(3)The linear form of the above equation is represented as:
meLmee
QCKQ1qC
+=
(4)where K
L
= related to the free energy of adsorption (L/mg)and Q
m
= maximum adsorption capacity. The values of Q
m
and K
L
were calculated from the slope and intercept of thelinear plot (Fig. 6). The equilibrium concentration and hencethe amount of dye adsorbed were calculated by varying thedye concentration between 40 and 120 mg/L with a fixedadsorbent dose and all other experimental conditions keptconstant.
 
10 20 30 40 50 60 70 800.00.20.40.60.81.01.21.41.61.8
   C
  e
   /  q
  e   (  g   /   L   )
C
e
(mg/L)
Fig. 6.Langmuir isotherm for acid red 18 adsorption onto
 Murraya koenigii
seeds
The isotherm constants for the Langmuir isotherm understudy were calculated from the linear form of the model andthe correlation coefficients are given in Table-2.
Vol. 23, No. 1 (2011)Adsorption of Acid Red 18 onto Activated Carbon Prepared from Murraya koenigii (Curry Tree) Seeds 221

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