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P.Muthamilselvi, P.Balamurugan, Dr.R.Karthikeyan / International Journal of Engineering
          Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com
                     Vol. 2, Issue 5, September- October 2012, pp.727-731
       Adsorption Of Phenol From Aqueous Solution By Allium
                         Sativum Linn Peel
            P.Muthamilselvi*, P.Balamurugan**, Dr.R.Karthikeyan***
                   *Department of Chemical Engineering,SRM University,TamilNadu,India
                     **Department of Technology,Annamalai University,TamilNadu, India
               ***Principal,Anjalai Ammal Mahalingam Engineeering College,Tamil Nadu, India

ABSTRACT
         The adsorption studies of phenol from              of rigid limits on the acceptable level of phenol in the
aqueous solution on allium sativum peel have been           environment. Phenol is also toxic to plants and
studied in the range of 50-250 mg/L initial phenol          aquatic life, which is reflected by low acceptance
concentration .The study was carried out as                 criteria where these receptors are to be protected.
function of contact time, pH, initial phenol                Different water treatment technologies are used to
concentration,allium sativum Linn peel dosage               remove phenolic pollutants. Destructive process such
and temperature. The experiment demonstrated                as destructive oxidation with ozone, hydrogen
the maximum phenol was obtained at in pH of 2               peroxide, or manganese oxides and recuperative
and it takes 6h to attain equilibrium .The                  process such as adsorption into porous solids (Tor
adsorption data was analyzed using the Langmuir             et.al.,,2006),membrane separation and solvent
and Freundlich isotherm models and it was found             extraction. Adsorption is a well-known removal
that Langmuir isotherm model represented the                technique for organic compounds from water, but the
measured sorption data well. Batch adsorption               cost of adsorptive removal process is high when pure
models based on the assumption of the pseudo-               sorbents (i.e. activated carbon, etc.) are used due to
first order and pseudo-second order mechanism               their high price. Consequently, the cost of pure
were applied to examine the kinetics of the                 adsorbents may be a limitation for many treatment
adsorption. The results showed that kinetic data            applications and there is a strong motivation to find
were followed more closely the pseudo-second                cost-efficient alternative sorbents obtained from
order model than the pseudo-first order                     industrial and agricultural waste such as bagasse fly
                                                            ash (Rong et al.,2005) petroleum coke[3], paper mill
Keywords:Adsorption,diffusion,equilibrium                   sludge, red mud , fertilizer and steel industries
isotherm, kinetics phenol.                                  waste[4], lignin ,wood charcoal[5], etc.
                                                                      This study was to investigate the adsorption
1. Introduction                                             potential of Allium sativum linn peel for the removal
          Phenols are pollutants of high priority           of phenol from aqueous solutions. The structure of
concerns because of their toxicity and possible             Allium sativum linn peel is characterized by Fourier
accumulation in the environment. It is a derivative of      Transform Infrared (FTIR) spectroscopy. The effects
benzene, is an important raw material and/or product        of experimental parameters such as initial pH of the
of chemical and allied industries (e.g. petrochemicals,     solution, contact time, initial phenol, concentration,
oil refineries, plastics, leather, paint, pharmaceutical,   adsorbent dosage, temperature were studied. The
steel industries and pesticides). It is highly soluble in   adsorption mechanism of phenol onto Allium
water and is very toxic in nature. It is a colorless,       sativum were evaluated in terms of kinetics. The
hygroscopic and crystalline substance, which turns          adsorption isotherms were described by using
pink in air owing to its oxidation. It is a weak acid       Langmuir and Freundlich isotherm models.
dissociating slightly in aqueous solution. For this
reason it is also known as carbolic acid. The Ministry      2 .Materials and Methods
of Environment and Forests (MOEF), Government of            2.1Adsorbent and their Characterization
India and EPA, USA, have listed phenol and phenolic                  Allium sativum linn peel collected from
compounds on the priority-pollutants list. Chronic          local market was washed with distilled water to
toxic effects due to phenols reported in humans             remove the water soluble adherent impurities. This
include vomiting, difficulty in swallowing, anorexia,       was followed by drying in to get rid of the moisture
liver and kidney damage, headache, fainting and             and other volatile impurities. The dried peel were
other mental disturbances. The MOEF has set a               grounded and sieved to a uniform particle size.The
maximum concentration level of 1.0 mg/l of phenol           FTIR Spectra in the wave numbers ranging from
in the industrial effluents for safe discharge into         3500 to 500 cm-1 of the Allium sativum linn peel are
surface waters, the WHO recommends the                      presented in Fig 2.1 The characteristic bands at 3543
permissible phenolic concentration of 0.001 mg/l in         - 3528 cm-1 as a broad bands is assigned to OH
potable waters. That phenol is highly toxic and             stretching vibrations(VoH) which may arise from the
difficult to degrade biologically have led to setting up    isomorphic substitution in the tetra and octahedral



                                                                                                    727 | P a g e
P.Muthamilselvi, P.Balamurugan, Dr.R.Karthikeyan / International Journal of Engineering
          Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com
                     Vol. 2, Issue 5, September- October 2012, pp.727-731
layers. The characteristic bands at 505 -544 cm-1 as a   shown in Fig 3.1. At any time the amount of phenol
broad bands is assigned to amino groups.                 adsorbed per unit weight of adsorbent increased with
                                                         increasing Co. The Co provides the necessary driving
                                                         force to overcome the resistances to the mass transfer
                                                         of phenol between the aqueous and the solid phases.
                                                         The increase in Co also enhances the interaction
                                                         between phenol and the allium sativum linn peel .
                                                         Therefore, an increase in Co of phenol enhances the
                                                         adsorption uptake of phenol.[6]




Fig 2.1 FTIR spectra of Allium sativum linn peel
2.2 Adsorbate
          Phenol of analytical reagent grade (AR)               Fig 3.1 Effect of initial phenol concentrations
                                                               (pH: 7.5, T: 30◦C, t : 6 h, dosage: 2g, speed : 120rpm)
supplied by southern scientific corporation India
chemicals Ltd., India. It was used for the preparation   3.2 Effect of pH
of the synthetic adsorbate solution of various Co in               The initial pH of adsorption medium is one
the range of 50-250 mg/l. stock solution as required     of the most important parameters affecting the
was prepared every day and was stored in a brown         adsorption process. Fig.3.2 shows that, the uptake of
color glass reservoir of 2 litre capacity to prevent     phenol increased with decreasing initial pH and was
photo oxidation. The Co was as certained before the      the greatest at pH 2.0. The pH primarily affects the
start of each experimental reaction.                     degree of ionization of the phenol and the surface
                                                         properties of allium sativum linn peel. At low pH
2.3 Analysis of phenol                                   values, the functional groups of allium sativum linn
         The concentration of phenol in the aqueous      peel would be protonated and result in a stronger
solution    was      determined      using    a   UV     attraction for negatively charged ions in the
spectrophotometer at wavelength 510nm.Prior of           adsorption medium. Phenol being weakly acidic
analysis, a technical calibration curve has been         would be partially ionized in solution. These ions will
obtained and it was very reproducible and linear over    be negatively charged and will be directly attracted
the concentration range used in this work, no            due to electrostatic forces by the protonated amino
disturbance of supernatant of the Allium sativum linn    groups of the allium sativum linn peel. As the pH
peel exhibited at this particular wavelength.            increased, the overall surface charge of the allium
                                                         sativum linn peel became negative and adsorption
2.4 Adsorption studies                                   decreased.[7]
         For each experiment, 100 ml of the phenol
stock solution of known Co,pHo and a known amount
of adsorbents were taken in a 250 ml of stoppers
conical flask. This mixture was agitated in a
temperature controlled shaking water bath at a
constant speed of 120 rpm. Small amount of the
sample was withdrawn after 30 min and was filtered
through whatman filter paper no.42 and analyzed for
phenol concentration.The percentage removal of
phenol and equilibrium adsorption uptake were
calculated.
                                                               Fig 3.2 Effect of pH on the phenol adsorption
3. Results And Discussion                                (C0 = 50mg/l, pH: 7.5, T: 30◦C, t : 6 h dosage: 2g, speed : 120rpm)
3.1 Effect of initial concentration                      3.3Effect of Adsorbent Dosage
         The effect of Co on the extent of adsorption    The adsorbent dosage is an important parameter
on allium sativum linn peel as a function of time is     because this parameter determines the capacity of
                                                         adsorbent for a given phenol concentration and also


                                                                                                          728 | P a g e
P.Muthamilselvi, P.Balamurugan, Dr.R.Karthikeyan / International Journal of Engineering
          Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com
                     Vol. 2, Issue 5, September- October 2012, pp.727-731
determines sorbent–sorbate equilibrium of the                Adsorption kinetic is important from the point of
system. The effect of adsorbent dosage on the                view to control the process efficiency. Various
adsorption of phenol was determined within the               kinetic models have been used by various
adsorbent dosage range of 0.5–2.5 g and the results          researchers, where the pseudo-first-order           and
are represented in Fig. 3.3 It is known that the             pseudo-second-order models were studied. The
increase in adsorbent concentration resulted in              mechanism of adsorption depends on the physical
decreased the adsorption amount due to the partial           and/or chemical characterstics of the adsorbent as
aggregation or overlapping of adsorbent, which               well as on the mass transfer process. The kinetics of
results in a decrease in effective surface area for the      adsorption is important from the point of view that it
adsorption. Therefore, the optimum amounts of                controls the process efficiency. Various researchers
allium sativum linn peel adsorption experiments were         has been several kinetics models,where the
selected as 1.5g[8]                                          adsorption is treated as a pseudo first order and
                                                             pseudo second order process.In the present study the
                                                             adsorption of phenol by allium sativum linn peel has
                                                             been described by the pseudo second order
                                                             model.The pseudo-first-order rate equation of
                                                             Lagergren is generally described by the following
                                                             equation:
                                                                                  dqt
                                                                                        K t q e  qt 
                                                                                   dt
                                                             Where kt is the pseudo-first-order rate constant. After
                                                             integration,by applying the conditions, qt=0 at t=0
                                                             and at t=t, qt=qt, the above Equation becomes
                                                                                                         kt
                                                                      log q e  q t   log q e 
                                                                                                      2303 t 
                                                             Where qe is the amount of phenol adsorbed at
       Fig 3.3: Effect of adsorbent dosage                   equilibrium in mg/g. Value of kt was calculated from
(C0 = 50mg/l, pH: 2, T: 30◦C, t : 6 h, speed : 120rpm)       the plots of log (qe−qt) versus t for different
                                                             concentrations of phenol.
3.4 Effect of temperature                                    The pseudo-second -order kinetic model is expressed
The effect of temperature on the removal efficiency          as follows:
was investigated in the temperature range of 25–45                                  t       1       t
◦C. The experiments were carried out with allium                                             2
                                                                                                 
sativum linn peel of 1.5 g and initial phenol                                       q    k 2 qe    qe
concentration of 50mg/l pH 2. when increasing the            Where k2 is the second-order rate constant (g/mg
temperature from 25 to 45 ◦C, indicating that phenol         min), by plotting of t/q versus t is a linear
uptake was favored at lower temperatures Fig.3.4.            relationship. Values of k 2and q e . were calculated
The decrease in adsorption with the rise of                  from the intercept and slope of the plots of t/q versus
temperature may be due to the weakening of                   t. The results of k2 and correlation coefficients (r 2)
adsorptive forces between the active sites of the            were shown in Table.1.The correlation coefficients of
adsorbent and adsorbate species Similar results were         the second-order kinetic model were greater than the
obtained by literature. with adsorption of 2,4,6-            first-order kinetic model.[11]
trichlorophenol by activated clay.[13]




                                                             Fig 4.1:pseudo First order plot for adsorption of
       Fig 3.4 Effect of temperature                         phenol
(C0 = 50mg/l, pH: 2, t : 6 h, dosage:1.5g, speed : 120rpm)   (C0 = 50mg/l, pH: 7.5, t : 6 h, dosage:2g , speed : 120rpm)
4. Kinetic model




                                                                                                        729 | P a g e
P.Muthamilselvi, P.Balamurugan, Dr.R.Karthikeyan / International Journal of Engineering
                         Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com
                                    Vol. 2, Issue 5, September- October 2012, pp.727-731
                                                                             Ce      1  aL 
                                                                                             C       - - - -(3)e
                                                                              qe K L  K L 
                                                                                               
                                                                                                  1
                                                                             log q e  log K F  log C e      (4)
                                                                                                  n




           Fig 4.2: pseudo second order plot for adsorption of
           phenol
               (C0 = 50mg/l, pH: 7.5, t : 6 h, dosage:2g , speed : 120rpm)

           Table :1 kinetic constants for phenol-Allium sativum
           Linn peel adsorption
                                                                                      Fig 5..1 Langmuir isotherm plot
Con               Pseudo first order            Pseudo second order                (T:30oC,t:6h,dosage:2gm/l, Co:50mg/l,pH:7.5)
.     qe,exp              qe,cal                        qe,cal
(mg   (mg/        K1(h- (mg/g                   K2(h- (mg/
                  1
/l)   g)            )     )          R2         1
                                                  )     g)      R2
50    2.20        0.142 1.725 0.284             0.192 3.2       0.969
100   3.7         0.191 4.315 0.446             0.679 3.0       0.954
150   5.3         0.247 8.260 0.440             0.733 5.7       0.956
200   6.2         0.225 10.02 0.559             0.180 5.8       0.895
250   6.9         0.234 9.66         0.503      0.182 6.2       0.821

           5. Adsorption Isotherms
                    Adsorption isotherm reflects the relationship
           between the amount of a solute adsorbed at constant
           temperature and its concentration in the equilibrium
           solution. It provides essential physiochemical data for
           assessing the applicability of the adsorption process                              Fig.5.2:Freundlich isotherm
           as a complete unit operation. Langmuir and                            (T:30oC,t:6h,dosage:2gm/l, Co=50mg/l pH:7.5)
           Freundlich isotherm models are widely used to
           investigate the adsorption process [9,10]. The model              Table2. Langmuir and freundlich coefficients
           parameters can be construed further, providing                           Langmuir parameters             Freundlich parameters
           understandings on sorption mechanism, surface                            Qo            aL                Kf
           properties, and an affinity of the adsorbent.The                  Adso (mg     KL      (l mg-            (mg g-
                                                                                     -1      -1   1         2       1
           Langmuir isotherm was developed on the assumption                 rb.    g )   (lg )     )     R           )(lm)  n       R2
           that the adsorption process will only take place at               Alliu
           specific homogenous sites within the adsorbent                    m
           surface with uniform distribution of energy level.                sativ
           Once the adsorbate is attached on the site, no further            um
           adsorption can take place at that site; which                     linn   8.62 0.315 0.036 0.992 0.88              2.21 0.983
           concluded that the adsorption process is monolayer in
           nature[12]. Contrarily to Langmuir, Freundlich                    6. Conclusion
           isotherm was based on the assumption that the                               In this study, the adsorption of phenol from
           adsorption occurs on heterogeneous sites with non-                aqueous solution was investigated using a Allium
           uniform distribution of energy level. The Freundlich              sativum Linn peel.The results indicated that
           describes reversible adsorption and is not restricted to          adsorption capacity of the adsorbent was
           the formation of monolayer.The linear form of                     considerably affected by initial pH, temperature and
           Langmuir and Freundlich equations are represented                 initial phenol concentration. The optimum pH value
           by equation(3) and (4) respectively.                              was found to be 2.0. The Langmuir and Freundlich
                                                                             adsorption equations were used to express the
                                                                             adsorption phenomenon of the phenol.The


                                                                                                                    730 | P a g e
P.Muthamilselvi, P.Balamurugan, Dr.R.Karthikeyan / International Journal of Engineering
          Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com
                     Vol. 2, Issue 5, September- October 2012, pp.727-731
equilibrium data were well described by the                     Environ.Sci. Technol., 39, (11),3990-3998,
Langmuir model.The pseudo-first order and pseudo-               (2005)
second order kinetic models were used to analyse          [7]. Indu C Nair, Jayachandran K. and Shankar
data obtained for phenol adsorption onto Allium                 Shashidhar, Biodegradation of phenol,
sativum linn peel. The results indicated that the               African Journal of Biotechnology 7 (25),
pseudo-second order equation provided the better                4951 – 4958(2008)
correlation for the adsorption data. It can be            [8] Thinakaran, N. Baskaralingam P.,. Pulikesi,
concluded that the Allium sativum Linn peel is an               M. Panneerselvam P, Sivanesan S.,Removal
efficient adsorbent for the removal of phenol from              of Acid Violet 17 from aqueous solutions by
aqueous solution.                                               adsorption onto activated carbon prepared
                                                                from sunflower seed hull, J. Hazard. Mater.
REFERENCES                                                      151 ,(2-3) 316–322 (2008)
  [1]   Tor A.,. Cengeloglu Y, Aydin M.E., Ersoz,        [9]. Satyawali, Y Balakrishnan M., Removal of
        M. Removal of phenol from aqueous phase                 color    from     biomethanated distillery
        by using neutralized red mud, J. Colloid                spentwash by treatment with activated
        Interface Sci. 300, (2),498–503(2006)                   carbons Biores. Technol. 98,(14), 2629-
  [2]   Rong R., Ding Y.,. Li, M. Yang C, Liu H.                2635,(2007)
        and Sun Y., Utilization of powdered peanut       [10] Hameed B.H., Ahmad A.A.,. Aziz N,
        hull as biosorbent for removal of anionic               Isotherms, kinetics and thermodynamics of
        dyes from aqueous solution Dyes Pigments,               acid dye adsorption on activated palm ash
        64 , (3),187-192 (2005)                                 Chem. Eng. J. 133 ,(1-3), 195-203, (2007)
  [3]   Figueiredo S.A.,. Loureiro J.M and.              [11]. Sulak M.T, Demirbas, E.           Kobya M.,
        Boaventura R.A, Natural waste materials                 Removal of Astrazon Yellow 7GL from
        containing chitin as adsorbents for textile             aqueous solutions by adsorption onto wheat
        dyestuffs: Batch and continuous studies                 bran Biores. Technol. 98,(13), 2590-2598,
        Water Res., 39,(17),4142-4152 (2005)                    (2007)
  [4]   Gupta V.K., Ali I., Suhas, Saini V.K.,            [12]. Osma J.F. Saravia, V Toca-Herrera J.L.,.
        Adsorption of 2,4-D and carbofuran                      CoutoSunflower seed shells: A novel and
        pesticides using fertilizer and steel industry          effective low-cost adsorbent for the removal
        wastes J. Coll.Interface Sci., 299,(2), 556-            of the diazo dye Reactive Black 5 from
        563 (2006)                                              aqueous solutions, J. Hazard. Mater.
  [5]   Gupta V.K., Mohan D., Suhas,. Singh K.P,                147,(3)900-905(2007)
        Removal of 2-aminophenol using novel             [13] Rajendran        Subha      and      Chinnaiya
        adsorbents Ind.Eng. Chem. Res., 45 ,(3)                 Namasivayam., modeling of adsorption
        1113-1122(2006)                                         isotherms     and    kinetics    of    2,4,6-
  [6]   Jiri L.        and Petr Z., Microchem.                  Trichlorophenol onto microporous zncl2
        J.,Dongqiang, K. Seokjoon and. Joseph                   activated coir pithCarbon J. Environ. Eng.
        J.P,Adsorption of single-Ring organic                   Manage., 18 (4), 275-280 (2008)
        compounds to wood charcoals prepared
        under different thermochemical conditions,




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  • 1. P.Muthamilselvi, P.Balamurugan, Dr.R.Karthikeyan / International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com Vol. 2, Issue 5, September- October 2012, pp.727-731 Adsorption Of Phenol From Aqueous Solution By Allium Sativum Linn Peel P.Muthamilselvi*, P.Balamurugan**, Dr.R.Karthikeyan*** *Department of Chemical Engineering,SRM University,TamilNadu,India **Department of Technology,Annamalai University,TamilNadu, India ***Principal,Anjalai Ammal Mahalingam Engineeering College,Tamil Nadu, India ABSTRACT The adsorption studies of phenol from of rigid limits on the acceptable level of phenol in the aqueous solution on allium sativum peel have been environment. Phenol is also toxic to plants and studied in the range of 50-250 mg/L initial phenol aquatic life, which is reflected by low acceptance concentration .The study was carried out as criteria where these receptors are to be protected. function of contact time, pH, initial phenol Different water treatment technologies are used to concentration,allium sativum Linn peel dosage remove phenolic pollutants. Destructive process such and temperature. The experiment demonstrated as destructive oxidation with ozone, hydrogen the maximum phenol was obtained at in pH of 2 peroxide, or manganese oxides and recuperative and it takes 6h to attain equilibrium .The process such as adsorption into porous solids (Tor adsorption data was analyzed using the Langmuir et.al.,,2006),membrane separation and solvent and Freundlich isotherm models and it was found extraction. Adsorption is a well-known removal that Langmuir isotherm model represented the technique for organic compounds from water, but the measured sorption data well. Batch adsorption cost of adsorptive removal process is high when pure models based on the assumption of the pseudo- sorbents (i.e. activated carbon, etc.) are used due to first order and pseudo-second order mechanism their high price. Consequently, the cost of pure were applied to examine the kinetics of the adsorbents may be a limitation for many treatment adsorption. The results showed that kinetic data applications and there is a strong motivation to find were followed more closely the pseudo-second cost-efficient alternative sorbents obtained from order model than the pseudo-first order industrial and agricultural waste such as bagasse fly ash (Rong et al.,2005) petroleum coke[3], paper mill Keywords:Adsorption,diffusion,equilibrium sludge, red mud , fertilizer and steel industries isotherm, kinetics phenol. waste[4], lignin ,wood charcoal[5], etc. This study was to investigate the adsorption 1. Introduction potential of Allium sativum linn peel for the removal Phenols are pollutants of high priority of phenol from aqueous solutions. The structure of concerns because of their toxicity and possible Allium sativum linn peel is characterized by Fourier accumulation in the environment. It is a derivative of Transform Infrared (FTIR) spectroscopy. The effects benzene, is an important raw material and/or product of experimental parameters such as initial pH of the of chemical and allied industries (e.g. petrochemicals, solution, contact time, initial phenol, concentration, oil refineries, plastics, leather, paint, pharmaceutical, adsorbent dosage, temperature were studied. The steel industries and pesticides). It is highly soluble in adsorption mechanism of phenol onto Allium water and is very toxic in nature. It is a colorless, sativum were evaluated in terms of kinetics. The hygroscopic and crystalline substance, which turns adsorption isotherms were described by using pink in air owing to its oxidation. It is a weak acid Langmuir and Freundlich isotherm models. dissociating slightly in aqueous solution. For this reason it is also known as carbolic acid. The Ministry 2 .Materials and Methods of Environment and Forests (MOEF), Government of 2.1Adsorbent and their Characterization India and EPA, USA, have listed phenol and phenolic Allium sativum linn peel collected from compounds on the priority-pollutants list. Chronic local market was washed with distilled water to toxic effects due to phenols reported in humans remove the water soluble adherent impurities. This include vomiting, difficulty in swallowing, anorexia, was followed by drying in to get rid of the moisture liver and kidney damage, headache, fainting and and other volatile impurities. The dried peel were other mental disturbances. The MOEF has set a grounded and sieved to a uniform particle size.The maximum concentration level of 1.0 mg/l of phenol FTIR Spectra in the wave numbers ranging from in the industrial effluents for safe discharge into 3500 to 500 cm-1 of the Allium sativum linn peel are surface waters, the WHO recommends the presented in Fig 2.1 The characteristic bands at 3543 permissible phenolic concentration of 0.001 mg/l in - 3528 cm-1 as a broad bands is assigned to OH potable waters. That phenol is highly toxic and stretching vibrations(VoH) which may arise from the difficult to degrade biologically have led to setting up isomorphic substitution in the tetra and octahedral 727 | P a g e
  • 2. P.Muthamilselvi, P.Balamurugan, Dr.R.Karthikeyan / International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com Vol. 2, Issue 5, September- October 2012, pp.727-731 layers. The characteristic bands at 505 -544 cm-1 as a shown in Fig 3.1. At any time the amount of phenol broad bands is assigned to amino groups. adsorbed per unit weight of adsorbent increased with increasing Co. The Co provides the necessary driving force to overcome the resistances to the mass transfer of phenol between the aqueous and the solid phases. The increase in Co also enhances the interaction between phenol and the allium sativum linn peel . Therefore, an increase in Co of phenol enhances the adsorption uptake of phenol.[6] Fig 2.1 FTIR spectra of Allium sativum linn peel 2.2 Adsorbate Phenol of analytical reagent grade (AR) Fig 3.1 Effect of initial phenol concentrations (pH: 7.5, T: 30◦C, t : 6 h, dosage: 2g, speed : 120rpm) supplied by southern scientific corporation India chemicals Ltd., India. It was used for the preparation 3.2 Effect of pH of the synthetic adsorbate solution of various Co in The initial pH of adsorption medium is one the range of 50-250 mg/l. stock solution as required of the most important parameters affecting the was prepared every day and was stored in a brown adsorption process. Fig.3.2 shows that, the uptake of color glass reservoir of 2 litre capacity to prevent phenol increased with decreasing initial pH and was photo oxidation. The Co was as certained before the the greatest at pH 2.0. The pH primarily affects the start of each experimental reaction. degree of ionization of the phenol and the surface properties of allium sativum linn peel. At low pH 2.3 Analysis of phenol values, the functional groups of allium sativum linn The concentration of phenol in the aqueous peel would be protonated and result in a stronger solution was determined using a UV attraction for negatively charged ions in the spectrophotometer at wavelength 510nm.Prior of adsorption medium. Phenol being weakly acidic analysis, a technical calibration curve has been would be partially ionized in solution. These ions will obtained and it was very reproducible and linear over be negatively charged and will be directly attracted the concentration range used in this work, no due to electrostatic forces by the protonated amino disturbance of supernatant of the Allium sativum linn groups of the allium sativum linn peel. As the pH peel exhibited at this particular wavelength. increased, the overall surface charge of the allium sativum linn peel became negative and adsorption 2.4 Adsorption studies decreased.[7] For each experiment, 100 ml of the phenol stock solution of known Co,pHo and a known amount of adsorbents were taken in a 250 ml of stoppers conical flask. This mixture was agitated in a temperature controlled shaking water bath at a constant speed of 120 rpm. Small amount of the sample was withdrawn after 30 min and was filtered through whatman filter paper no.42 and analyzed for phenol concentration.The percentage removal of phenol and equilibrium adsorption uptake were calculated. Fig 3.2 Effect of pH on the phenol adsorption 3. Results And Discussion (C0 = 50mg/l, pH: 7.5, T: 30◦C, t : 6 h dosage: 2g, speed : 120rpm) 3.1 Effect of initial concentration 3.3Effect of Adsorbent Dosage The effect of Co on the extent of adsorption The adsorbent dosage is an important parameter on allium sativum linn peel as a function of time is because this parameter determines the capacity of adsorbent for a given phenol concentration and also 728 | P a g e
  • 3. P.Muthamilselvi, P.Balamurugan, Dr.R.Karthikeyan / International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com Vol. 2, Issue 5, September- October 2012, pp.727-731 determines sorbent–sorbate equilibrium of the Adsorption kinetic is important from the point of system. The effect of adsorbent dosage on the view to control the process efficiency. Various adsorption of phenol was determined within the kinetic models have been used by various adsorbent dosage range of 0.5–2.5 g and the results researchers, where the pseudo-first-order and are represented in Fig. 3.3 It is known that the pseudo-second-order models were studied. The increase in adsorbent concentration resulted in mechanism of adsorption depends on the physical decreased the adsorption amount due to the partial and/or chemical characterstics of the adsorbent as aggregation or overlapping of adsorbent, which well as on the mass transfer process. The kinetics of results in a decrease in effective surface area for the adsorption is important from the point of view that it adsorption. Therefore, the optimum amounts of controls the process efficiency. Various researchers allium sativum linn peel adsorption experiments were has been several kinetics models,where the selected as 1.5g[8] adsorption is treated as a pseudo first order and pseudo second order process.In the present study the adsorption of phenol by allium sativum linn peel has been described by the pseudo second order model.The pseudo-first-order rate equation of Lagergren is generally described by the following equation: dqt  K t q e  qt  dt Where kt is the pseudo-first-order rate constant. After integration,by applying the conditions, qt=0 at t=0 and at t=t, qt=qt, the above Equation becomes kt log q e  q t   log q e  2303 t  Where qe is the amount of phenol adsorbed at Fig 3.3: Effect of adsorbent dosage equilibrium in mg/g. Value of kt was calculated from (C0 = 50mg/l, pH: 2, T: 30◦C, t : 6 h, speed : 120rpm) the plots of log (qe−qt) versus t for different concentrations of phenol. 3.4 Effect of temperature The pseudo-second -order kinetic model is expressed The effect of temperature on the removal efficiency as follows: was investigated in the temperature range of 25–45 t 1 t ◦C. The experiments were carried out with allium  2  sativum linn peel of 1.5 g and initial phenol q k 2 qe qe concentration of 50mg/l pH 2. when increasing the Where k2 is the second-order rate constant (g/mg temperature from 25 to 45 ◦C, indicating that phenol min), by plotting of t/q versus t is a linear uptake was favored at lower temperatures Fig.3.4. relationship. Values of k 2and q e . were calculated The decrease in adsorption with the rise of from the intercept and slope of the plots of t/q versus temperature may be due to the weakening of t. The results of k2 and correlation coefficients (r 2) adsorptive forces between the active sites of the were shown in Table.1.The correlation coefficients of adsorbent and adsorbate species Similar results were the second-order kinetic model were greater than the obtained by literature. with adsorption of 2,4,6- first-order kinetic model.[11] trichlorophenol by activated clay.[13] Fig 4.1:pseudo First order plot for adsorption of Fig 3.4 Effect of temperature phenol (C0 = 50mg/l, pH: 2, t : 6 h, dosage:1.5g, speed : 120rpm) (C0 = 50mg/l, pH: 7.5, t : 6 h, dosage:2g , speed : 120rpm) 4. Kinetic model 729 | P a g e
  • 4. P.Muthamilselvi, P.Balamurugan, Dr.R.Karthikeyan / International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com Vol. 2, Issue 5, September- October 2012, pp.727-731 Ce 1  aL    C       - - - -(3)e qe K L  K L    1 log q e  log K F  log C e      (4) n Fig 4.2: pseudo second order plot for adsorption of phenol (C0 = 50mg/l, pH: 7.5, t : 6 h, dosage:2g , speed : 120rpm) Table :1 kinetic constants for phenol-Allium sativum Linn peel adsorption Fig 5..1 Langmuir isotherm plot Con Pseudo first order Pseudo second order (T:30oC,t:6h,dosage:2gm/l, Co:50mg/l,pH:7.5) . qe,exp qe,cal qe,cal (mg (mg/ K1(h- (mg/g K2(h- (mg/ 1 /l) g) ) ) R2 1 ) g) R2 50 2.20 0.142 1.725 0.284 0.192 3.2 0.969 100 3.7 0.191 4.315 0.446 0.679 3.0 0.954 150 5.3 0.247 8.260 0.440 0.733 5.7 0.956 200 6.2 0.225 10.02 0.559 0.180 5.8 0.895 250 6.9 0.234 9.66 0.503 0.182 6.2 0.821 5. Adsorption Isotherms Adsorption isotherm reflects the relationship between the amount of a solute adsorbed at constant temperature and its concentration in the equilibrium solution. It provides essential physiochemical data for assessing the applicability of the adsorption process Fig.5.2:Freundlich isotherm as a complete unit operation. Langmuir and (T:30oC,t:6h,dosage:2gm/l, Co=50mg/l pH:7.5) Freundlich isotherm models are widely used to investigate the adsorption process [9,10]. The model Table2. Langmuir and freundlich coefficients parameters can be construed further, providing Langmuir parameters Freundlich parameters understandings on sorption mechanism, surface Qo aL Kf properties, and an affinity of the adsorbent.The Adso (mg KL (l mg- (mg g- -1 -1 1 2 1 Langmuir isotherm was developed on the assumption rb. g ) (lg ) ) R )(lm) n R2 that the adsorption process will only take place at Alliu specific homogenous sites within the adsorbent m surface with uniform distribution of energy level. sativ Once the adsorbate is attached on the site, no further um adsorption can take place at that site; which linn 8.62 0.315 0.036 0.992 0.88 2.21 0.983 concluded that the adsorption process is monolayer in nature[12]. Contrarily to Langmuir, Freundlich 6. Conclusion isotherm was based on the assumption that the In this study, the adsorption of phenol from adsorption occurs on heterogeneous sites with non- aqueous solution was investigated using a Allium uniform distribution of energy level. The Freundlich sativum Linn peel.The results indicated that describes reversible adsorption and is not restricted to adsorption capacity of the adsorbent was the formation of monolayer.The linear form of considerably affected by initial pH, temperature and Langmuir and Freundlich equations are represented initial phenol concentration. The optimum pH value by equation(3) and (4) respectively. was found to be 2.0. The Langmuir and Freundlich adsorption equations were used to express the adsorption phenomenon of the phenol.The 730 | P a g e
  • 5. P.Muthamilselvi, P.Balamurugan, Dr.R.Karthikeyan / International Journal of Engineering Research and Applications (IJERA) ISSN: 2248-9622 www.ijera.com Vol. 2, Issue 5, September- October 2012, pp.727-731 equilibrium data were well described by the Environ.Sci. Technol., 39, (11),3990-3998, Langmuir model.The pseudo-first order and pseudo- (2005) second order kinetic models were used to analyse [7]. Indu C Nair, Jayachandran K. and Shankar data obtained for phenol adsorption onto Allium Shashidhar, Biodegradation of phenol, sativum linn peel. The results indicated that the African Journal of Biotechnology 7 (25), pseudo-second order equation provided the better 4951 – 4958(2008) correlation for the adsorption data. It can be [8] Thinakaran, N. Baskaralingam P.,. Pulikesi, concluded that the Allium sativum Linn peel is an M. Panneerselvam P, Sivanesan S.,Removal efficient adsorbent for the removal of phenol from of Acid Violet 17 from aqueous solutions by aqueous solution. adsorption onto activated carbon prepared from sunflower seed hull, J. Hazard. Mater. REFERENCES 151 ,(2-3) 316–322 (2008) [1] Tor A.,. Cengeloglu Y, Aydin M.E., Ersoz, [9]. Satyawali, Y Balakrishnan M., Removal of M. Removal of phenol from aqueous phase color from biomethanated distillery by using neutralized red mud, J. Colloid spentwash by treatment with activated Interface Sci. 300, (2),498–503(2006) carbons Biores. Technol. 98,(14), 2629- [2] Rong R., Ding Y.,. Li, M. Yang C, Liu H. 2635,(2007) and Sun Y., Utilization of powdered peanut [10] Hameed B.H., Ahmad A.A.,. Aziz N, hull as biosorbent for removal of anionic Isotherms, kinetics and thermodynamics of dyes from aqueous solution Dyes Pigments, acid dye adsorption on activated palm ash 64 , (3),187-192 (2005) Chem. Eng. J. 133 ,(1-3), 195-203, (2007) [3] Figueiredo S.A.,. Loureiro J.M and. [11]. Sulak M.T, Demirbas, E. Kobya M., Boaventura R.A, Natural waste materials Removal of Astrazon Yellow 7GL from containing chitin as adsorbents for textile aqueous solutions by adsorption onto wheat dyestuffs: Batch and continuous studies bran Biores. Technol. 98,(13), 2590-2598, Water Res., 39,(17),4142-4152 (2005) (2007) [4] Gupta V.K., Ali I., Suhas, Saini V.K., [12]. Osma J.F. Saravia, V Toca-Herrera J.L.,. Adsorption of 2,4-D and carbofuran CoutoSunflower seed shells: A novel and pesticides using fertilizer and steel industry effective low-cost adsorbent for the removal wastes J. Coll.Interface Sci., 299,(2), 556- of the diazo dye Reactive Black 5 from 563 (2006) aqueous solutions, J. Hazard. Mater. [5] Gupta V.K., Mohan D., Suhas,. Singh K.P, 147,(3)900-905(2007) Removal of 2-aminophenol using novel [13] Rajendran Subha and Chinnaiya adsorbents Ind.Eng. Chem. Res., 45 ,(3) Namasivayam., modeling of adsorption 1113-1122(2006) isotherms and kinetics of 2,4,6- [6] Jiri L. and Petr Z., Microchem. Trichlorophenol onto microporous zncl2 J.,Dongqiang, K. Seokjoon and. Joseph activated coir pithCarbon J. Environ. Eng. J.P,Adsorption of single-Ring organic Manage., 18 (4), 275-280 (2008) compounds to wood charcoals prepared under different thermochemical conditions, 731 | P a g e