Adsorption of a hazardous dye, erythrosine, over hen feathers

Journal of Colloid and Interface Science304(2006)

52–57

https://www.doczj.com/doc/5918341222.html,/locate/jcis

Adsorption of a hazardous dye,erythrosine,over hen feathers

Vinod K.Gupta a,?,Alok Mittal b,Lisha Kurup b,Jyoti Mittal b

a Department of Chemistry,Indian Institute of Technology Roorkee,Roorkee,247667(UA),India

b Department of Applied Chemistry,Maulana Azad National Institute of Technology,Bhopal,462007(MP),India

Received20July2006;accepted17August2006

Available online20September2006

Abstract

Erythrosine is a popular dye that is widely used in cosmetics,foodstuffs,medicines,and textiles.It is highly toxic to mankind and can lead to many diseases including carcinogenicity.Removal of erythrosine has been carried out using waste material—hen feathers—as adsorbent.The effects of pH,concentration of the dye,temperature,and adsorbent dosage have been studied.Adsorption of erythrosine over hen feathers has been correlated with Freundlich and Langmuir isotherms and satis?es both models.The adsorption process has been found endothermic in nature and thermodynamic parameters,Gibb’s free energy( G0),change in enthalpy( H0),and change in entropy( S0)have been calculated.The paper also includes results on the kinetic measurements of adsorption of the dye on hen feathers at different temperatures.The adsorption follows a?rst-order kinetics at all the temperatures and values of the rate constant(k ad)have been calculated as0.0179,0.0177,and0.0172s?1at30, 40,and50?C,respectively.By rate expression and treatment of data it has been ascertained that the adsorption of erythrosine over hen feathers follows a particle diffusion mechanism.

?2006Elsevier Inc.All rights reserved.

Keywords:Erythrosine;Hazardous dye;Low-cost adsorbents;Adsorption

1.Introduction

The unaesthetic look of dyes and their toxicological effects have drawn considerable attention toward the contamination caused by textile ef?uents.Public opinion is extremely sensi-tive to this kind of environmental impact and often becomes more intolerant with the type of colored wastewaters than with much more dangerous ones that do not seem as harmful as they are colorless.Due to their color and complexity of structure, dyes are not always removed through those normal methods of treatment,which are generally used to remove other pol-lutants.The disposal of dye ef?uents has always been a ma-jor problem to solve and in the past many methods dealing with color removal in textile ef?uents have been tested.Apart from adsorption other methods of color removal include chem-ical oxidation—especially by the use of hydrogen peroxide and chlorine,coagulation,settling,and?ltration[1,2].Among all these,adsorption has shown to be one of the most ef?cient *Corresponding author.Fax:+911332285043.

E-mail address:vinodfcy@iitr.ernet.in(V.K.Gupta).physicochemical processes.However,it has been observed that the most of the adsorbents showing high performance and ef-?ciency for the removal of pollutants are too expensive[3]. Research has been carried out to?nd alternative economic ma-terials of high ef?cacy[4].

Much work has been performed to detect the adsorption ca-pacity of natural and treated vegetal materials like peat[5], sugar cane bagasse[6],biomass[7],eucalyptus bark[8,9]and other biological materials with animal origin such as chitin and chitosan[10].Investigations dealing with low-cost adsor-bents of biological and mineral matrix[11,12]to remove dyes and metals in simulated liquid ef?uents of industry led to the conclusion that among the studied materials feathers revealed promising potential[13–17].We have also exploited the use of waste materials as potential adsorbents for the removal of some hazardous dyes[18–21].Moreover,adsorbent feathers are much easier to handle and exhibit excellent adsorbing ability.

Taking the above-noted facts into consideration,feathers are selected for carrying out the adsorption of erythrosine, a cherry-pink red,water-soluble,synthetic coal dye.Erythro-sine is widely used in dyeing a variety of materials such as

0021-9797/$–see front matter?2006Elsevier Inc.All rights reserved. doi:10.1016/j.jcis.2006.08.032

V.K.Gupta et al./Journal of Colloid and Interface Science304(2006)52–5753

wool,silk,and nylon.It is also used as colorant in drugs, cosmetics,cocktails,tinned cherries and fruits,biscuits,choco-lates,garlic sausages,salmon spreads,scotch eggs,stuffed olives,sweets,bakery items,snack foods,chewing gums,jel-lies,wines,drugs,ice creams,etc.[22,23].It is also being used for coloring food,in printing inks and lipstick,as a biologi-cal stain,a dental plaque disclosing agent,and a radio plaque medium[24,25].

Erythrosine is highly water soluble and belongs to the xan-thene class of dyes.It consists essentially of disodium2-(2,4,5,7-tetraiodo-3-oxidooxoxanthen-9-y1)benzoate monohy-drate.It tends to dispose with the industrial wastewater and poses a severe health threat to mankind[26,27].It has been found that erythrosine may affect thyroid activity due to the presence of iodine in the molecule,which may be released upon degradation.Thus,with respect to the previous studies,ery-throsine may be one of the causes of atopic diseases[28].Its consumption can also prove fatal,as it is carcinogenic in nature and can lead to tumors[29,30].The comet assay on the glan-dular stomach,colon,liver,kidney,urinary bladder,lung,brain, and bone marrow was performed and it was found that erythro-sine induced DNA damage in the gastrointestinal organs even at a low dose[31].Moreover research has proved that long-term use of erythrosine-containing lipsticks by Indian women of lower economic background may lead to abnormal embry-onic development[32].In addition the food color erythrosine (FD&C Red No.3)was hypothesized to be a neurotoxicant because it disrupted neurotransmitter uptake in vitro[33,34]. Moreover it is a xenoestrogen,which enhances the effect of es-trogens[35].

Thus keeping the toxicity of the dye erythrosine in view,it was considered worthwhile to carry out a systematic and de-tailed study for its removal from the water using waste material, hen feathers,as adsorbent.In the present study the uptake of erythrosine on feathers was examined under the variables of temperature,pH,adsorbent dose,and adsorbent concentration. The applicability of hen feathers as adsorbent was also exam-ined through adsorption isotherms and measuring the kinetic parameters.

2.Experimental

The chemicals used in this ongoing research work were all of A.R.grade.The dye,erythrosine,also known as FD&C Red3, Acid Red51and having the IUPAC name,disodium2-(2,4,5,7-tetraiodo-3-oxido-6-oxoxanthen-9-y1)benzoate monohydrate with the molecular formula C20H6I4Na2O5H2O(molecular weight897.88),was obtained from M/s Merck.To prepare the dye solutions doubly distilled water was used.The stock solution of1mM concentration was?rst prepared and then further used to prepare the solutions of varying dilutions.To check the concentration of dye in aqueous media their ab-sorbances were studied on a UV/visible spectrophotometer, Model117(M/s Systronics,Ahmedabad,India)over a wave-length of526nm.2.1.Preparation of adsorbent

Hen feathers were collected from poultry.The Barb portion of the feather was about1cm length.Before using it as adsor-bent it was subjected to thorough washing under agitation in a distilled water pool.The washed feathers were then dried and their rachises were removed after cutting soft barbs into about 0.1mm length.The small pieces of barbs were now treated with hydrogen peroxide(30%w/v)for about24h to remove organic materials present in feathers.The material thus obtained was then?ltered using Whatmann Filter Paper No.42and washed with doubly distilled water.The barbs were then kept in an oven at100?C for2h.The dried material obtained was then stored in a vacuum desiccator for subsequent use.

2.2.Adsorption studies

The preliminary examinations were performed in batches to check the susceptibility of the adsorption process with varying conditions of pH,concentration,time,amount of adsorbent,etc. After a good deal of investigation,the concentration range from 1×10?5to6×10?5M was chosen.Twenty-?ve milliliters of dye solutions of known concentrations was poured into100-ml measuring?asks with a known amount of adsorbent.The mixture was shaken intermittently and then kept for24h for saturation.Thereafter supernatant liquid was?ltered through Whatmann Filter Paper No.42and the amount of dye adsorbed was determined spectrophotometrically at theλmax526nm.

2.3.Kinetic studies

The kinetic investigations were carried out to study the time required for the attainment of equilibrium during the adsorp-tion of erythrosine on feather.For this25ml of dye solution of known concentration with de?nite pH and known amount of adsorbent was taken in different measuring?asks.The mixture was subjected to different temperatures of30,40,and50?C with intermittent shaking.The solutions were then?ltered at different time intervals using Whatmann Filter Paper No.42 and analyzed spectrophotometrically for the uptake of the dye.

3.Results and discussion

3.1.Characterization of adsorbent

Conventional chemical methods and analytical techniques were used for the analysis of adsorbent.The barbs of the pre-pared feather were found to have protein contents of around 84%along with the inorganic constituents like calcium,magne-sium,selenium,zinc,etc.However,raw feathers are relatively insoluble and have a very low digestibility due to the high ker-atin contents and strong disul?de bonding of amino acids.The feathers are found to be a“H”type of adsorbent as the pH of 100ml distilled water increases when1g of feather was dipped overnight into it.

54V .K.Gupta et al./Journal of Colloid and Interface Science 304(2006)

52–57

Fig.1.Effect of pH on uptake of erythrosine by hen feathers at 50?

C.

Fig.2.Effect of concentration for the uptake of erythrosine on hen feathers at different temperatures.

3.2.Adsorption studies

Adsorption studies were carried out by ?rst studying the effect of pH on the uptake of erythrosine by feathers.The pro-?le concerning pH shows that in the pH range of 3.16–8.39there was a very pronounced adsorption capacity increase with decrease in pH.For pH 8.39adsorption capacity was found extremely low and when pH decreased from 4.00to 2.00,ad-sorption capacity increased by twofold (Fig.1).All subsequent studies were performed at pH 3.0,which is the optimum value for adsorption.

The adsorption of erythrosine was also recorded in the con-centration range from 1×10?5to 6×10?5M,at a ?xed pH of 3.0.Temperature levels were chosen so as to be helpful to clarify the adsorption mechanism.The temperature levels were selected as 30,40,and 50?C,respectively.Fig.2indicates that the adsorption of erythrosine by feathers increases with the increase in temperature,thereby indicating the process to be endothermic in nature.It is observed that the initial removal of dye is fast and at higher concentrations the percentage uptake gradually

decreases.

Fig.3.Freundlich adsorption isotherm for erythrosine–hen feather

system.

https://www.doczj.com/doc/5918341222.html,ngmuir adsorption isotherm for erythrosine–hen feathers.Table 1

Freundlich and Langmuir constants of erythrosine adsorption by hen feathers at different temperatures Temperature (?C)Langmuir constants Freundlich constants Q 0×10(mol /g )b ×105(l /mol )n K F 30 1.754 2.9632.2800.00240 1.789 4.6472.0090.00650

2.314

3.868

1.909

0.010

Sorption data were also correlated with Freundlich and Langmuir models and it was observed that the uptake of the dye follows both adsorption isotherms.The values of Freundlich and Langmuir constants obtained from the plots (Figs.3and 4)are listed in Table 1.The adsorption isotherm data predict that the Q 0increases with an increase in temperature and the anal-ogous behavior is ascribed by the adsorption capacity (K F )as well.The logarithmic equations for the adsorption of stud-ied dye on feathers gave high linearity.The information thus obtained once again approves an endothermic nature of the ex-isting process.

V .K.Gupta et al./Journal of Colloid and Interface Science 304(2006)52–5755

To examine the favorability of the adsorption process,the method suggested by Weber and Chakraborti [36]was em-ployed.The dimensionless constant,separation factor r [37]was calculated by (1)

r =1

1+bC 0

,

where values b and C 0were obtained from Langmuir isotherm.The values of r are found to be 0.077803,0.06151,and 0.060707and temperatures at 30,40,and 50?C.These val-ues clearly specify that the ongoing adsorption process is much more favorable at higher temperatures as the r values show a decline with rise in temperature.The parameters indicate the shape of isotherm accordingly:

r value r >1r =10

Unfavorable

Linear

Favorable

Irreversible

The thermodynamic data were calculated from Langmuir isotherms (Table 2)using

(2)

G 0=?RT ln K,(3)

H 0=R T 2T 1T 2?T 1ln K 2

K 1,(4)

S 0= H 0? G 0

T

,where K ,K 1,and K 2are the equilibrium constants at temper-atures of 30,40,and 50?C,respectively,and obtained from the slopes of adsorption isotherms at different concentrations.

As far as the in?uence of temperature on adsorption is con-cerned it is known that if a physical adsorption process is in-volved it will be expected that its extension will be decreased with a temperature increase and when chemisorption is dealt with,usually,a temperature rise favors it.Youssef [11]stud-ied the adsorption of acid dyes by both cellulose and cellu-lose derivatives and observed that adsorption capacity increased with a temperature rise.Though an alteration in temperature usually implies costs,in the case under study these would not exist if a temperature increase favored the adsorption process because the ef?uents of wool dyeing baths are at an elevated temperature.

In the present case the viability and impulsive nature of the adsorption process is well con?rmed from the negative values of G 0.It was also observed that the values of G 0decrease with the increasing temperature,thereby indicating a greater feasibility of the process at higher temperatures (Table 2).The endothermic nature was also con?rmed from the positive values of enthalpy change ( H 0),while positive S 0values re?ect the af?nity of the adsorbent materials toward erythrosine (Ta-ble 2).

3.3.Kinetic studies

Attempts were also made to innovate cheap and easily avail-able adsorbents for effective designing and modeling of the process.For this purpose study of the kinetics of the adsorp-tion was carried out,which involves the effects of some major

Table 2

Values of thermodynamics parameters for the adsorption of erythrosine on hen feathers ? G 0(kJ /mol ) H 0(kJ /mol ) S 0

(J /(K mol ))30?C 40?C 50?C 31.739

33.444

34.550

10.642

140.211

Fig.5.Effect of contact time for the adsorption of erythrosine by hen feathers at different temperatures and at a concentration of 4×10?5M.

parameters such as contact time,amount of adsorbent,and con-centration of adsorbate solution on the uptake of erythrosine on feathers.

Preliminary investigations suggest that the uptake of ery-throsine within the ?rst hour was almost 50%(Fig.5).Time intervals between 90and 120min were found to be suf?cient for the attainment of equilibrium.Moreover,the measurement of kinetics at different temperatures (30,40,and 50?C)exhibits an increase in adsorption with the increase in temperature.The half-life of each process was also calculated and was found to decrease with increase in temperature.These results once again con?rm the endothermic nature of the ongoing process.

Adsorption of the dye was also carried out with different ad-sorbent dose.It was found that with the increasing dosage of adsorbent the rate of removal of adsorbate increases.The data obtained reveal that there is a substantial increase in adsorption when the amount of adsorbents is increased from 0.01to 0.10g (Fig.6);however,further introduction of the adsorbent amount did not increase the rate signi?cantly.Keeping this in view,in all subsequent kinetic studies the amount of feather was taken as 0.1g.The half-life (t 1/2)of the process was also calculated at different doses of each adsorbent and it was found that the half-life decreases with increasing amount,con?rming the de-pendence of rate of adsorption on the amount of adsorbent.3.4.Adsorption rate constant study

The speci?c rate constant of adsorption was determined by applying Lagergren’s ?rst-order rate expression [38].The value of log (q e ?q t )was calculated for each time interval at different

56V .K.Gupta et al./Journal of Colloid and Interface Science 304(2006)

52–57

Fig.6.Effect of amount of adsorbent for the removal of erythrosine using hen feathers at 50?

C.

https://www.doczj.com/doc/5918341222.html,gergren’s plot of time versus log (q e ?q t )for erythrosine adsorption on hen feathers at different temperatures.

temperatures,

(5)log (q e ?q t )=log q e =

k ad

2.303

×t,

where q e and q t are the amount adsorbed at equilibrium and time t ,respectively.The plots between log (q e ?q t )and t main-tained their linearity at 30,40,and 50?C (Fig.7),which con-?rms the ?rst-order nature of the processes involved.The values of the rate constant,k ad ,for each system were calculated from the respective Lagergren’s plots and found to be 0.0179,0.0177,and 0.0172s ?1at 30,40,and 50?C,respectively.3.5.Rate expression and treatment of data

The type of adsorption process involved governs the overall rate of removal of adsorbate.For an appropriate elucidation of experimental data,it is essential to identify the steps in the ad-sorption process.The process can either proceed by a particle diffusion or ?lm diffusion mechanism.In the particle diffu-sion mechanism,transport of adsorbate takes place within the pores of the adsorbent except for a small amount of adsorption occurring on the external surface.While in the ?lm diffusion method,transport of the ingoing ions takes place to the exter-nal surface of the adsorbent;i.e.,external transport is less than internal transport.Thus to interpret the ongoing process the ki-netic data obtained by the ?nite batch method,in each case,has been treated by ingenious mathematical treatment suggested by Boyd et al.[39]and Reichenberg [40].

The experimental data obtained from kinetic studies were used to derive the fractional attainment of equilibrium for dif-ferent temperatures at each time interval.A quantitative treat-ment of the sorption dynamics can be employed with the help of the following expression

(6)

F =1?6π

2

∞

1

1/n 2 exp ?n 2Bt ,where F is the fractional attainment of equilibrium at time t and is obtained by using Eq.(7)and n is the Freundlich constant of the adsorbate.

(7)F =Q t

Q ∞,where Q t and Q ∞are amounts adsorbed after time t and after in?nite time,respectively.

Reichenberg’s table [40]was used to evaluate B t values,which is analogous to the F values obtained in above case.Graphs between time and B t at different concentrations were found linear and passed through the origin,thereby

indicating

Fig.8.Plot of time versus B t for erythrosine uptake by hen feathers at different temperatures.

V.K.Gupta et al./Journal of Colloid and Interface Science304(2006)52–5757

the adsorption to be particle diffusion in nature.A typical B t versus time plot at a concentration of4×10?5M is presented in Fig.8.

4.Conclusions

Based on the above-presented results it can be safely con-cluded that the hen feather can be used as potential H-type adsorbent for the removal of the hazardous dye erythrosine in the pH range3to8.The strong linearity of the Freundlich and Langmuir isotherm represented the sorption of erythrosine onto hen feathers at different temperatures.The adsorption of the dye was found feasible and endothermic in nature.While val-ues of separation factor r indicated that the ongoing adsorption process is much favorable at higher temperatures.The kinetic studies apparently revealed that the removal is through a parti-cle diffusion process at all concentrations and temperatures.As feathers are quite abundant animal residue and can be procured at negligible cost;hence,the proposed method can be treated as a cheaper means to remove erythrosine from wastewater. References

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从实践的角度探讨在日语教学中多媒体课件的应用

从实践的角度探讨在日语教学中多媒体课件的应用 在今天中国的许多大学，为适应现代化，信息化的要求，建立了设备完善的适应多媒体教学的教室。许多学科的研究者及现场教员也积极致力于多媒体软件的开发和利用。在大学日语专业的教学工作中，教科书、磁带、粉笔为主流的传统教学方式差不多悄然向先进的教学手段而进展。 一、多媒体课件和精品课程的进展现状 然而，目前在专业日语教学中能够利用的教学软件并不多见。比如在中国大学日语的专业、第二外語用教科书常见的有《新编日语》（上海外语教育出版社）、《中日交流标准日本語》（初级、中级）（人民教育出版社）、《新编基础日语（初級、高級）》（上海译文出版社）、《大学日本语》（四川大学出版社）、《初级日语》《中级日语》（北京大学出版社）、《新世纪大学日语》（外语教学与研究出版社）、《综合日语》（北京大学出版社）、《新编日语教程》（华东理工大学出版社）《新编初级（中级）日本语》（吉林教育出版社）、《新大学日本语》（大连理工大学出版社）、《新大学日语》（高等教育出版社）、《现代日本语》（上海外语教育出版社）、《基础日语》（复旦大学出版社）等等。配套教材以录音磁带、教学参考、习题集为主。只有《中日交流標準日本語（初級上）》、《初級日语》、《新编日语教程》等少数教科书配备了多媒体DVD视听教材。 然而这些试听教材，有的内容为日语普及读物，并不适合专业外语课堂教学。比如《新版中日交流标准日本语（初级上）》，有的尽管DVD视听教材中有丰富的动画画面和语音练习。然而，课堂操作则花费时刻长，不利于教师重点指导，更加适合学生的课余练习。比如北京大学的《初级日语》等。在这种情形下，许多大学的日语专业致力于教材的自主开发。 其中，有些大学的还推出精品课程，取得了专门大成绩。比如天津外国语学院的《新编日语》多媒体精品课程为2007年被评为“国家级精品课”。目前已被南开大学外国语学院、成都理工大学日语系等全国40余所大学推广使用。

新视野大学英语全部课文原文

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