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Use of super absorbent hydrogels derivative from acrylamide with itaconic acid and itaconates to remove
Use of super absorbent hydrogels derivative from acrylamide with itaconic acid and itaconates to remove

Use of super absorbent hydrogels derivative from acrylamide with itaconic acid and itaconates to remove metal ions from aqueous solutions

Amal El-Halah, 1 Daniel Machado, 2 Nain González, 1 Jesús Contreras, 1 Francisco López-Carrasquero

1 Grupo de Polímeros, Departamento de Química, Facultad de Ciencias, Universidad de Los Andes, Mérida, 5101-A, Venezuela

2 Laboratorio de Investigación en Análisis Químico, Industrial y Agropecuario (LIAQIA), Departamento de Química, Facultad de

Ciencias, Universidad de Los Andes, Mérida, 5101-A, Venezuela

Correspondence to: F. López-Carrasquero (E-mail: opezc@ula.ve)

to: F. López-Carrasquero (E-mail: fl opezc@ula.ve ) 1 ABSTRACT: Poly(acrylamide- co -itaconic acid) (AAm/IA)

1

ABSTRACT: Poly(acrylamide-co -itaconic acid) (AAm/IA) and poly(acrylamide-co-monomethoxyethyl itaconate) (AAm/MEI) hydrogels (HGs) synthesized at different molar ratios were used to study the adsorption of some metal ions as Cu 2+ , Ni 2+ , Pb 2+ , Cd 2+ , and Fe 3+ in aqueous solutions at different concentration: 10, 50, 100, 500, and 1000 mg L 1 . Statistical analysis was performed and the effect of the metal ion, ion concentration, and hydrogel (HG) composition, on adsorption and adsorption efciency, was evaluated for both HGs studied (AAm/IA and AAm/MEI) and each factor gave rise to signi cant differences ( P 0.05). The adsorption depends on the type of ion, its concentration, and also inuenced by the type and composition of the HGs. For each system the adsorption ef ciencies for all ions were similar with exception of Fe 3+ , which showed the highest adsorption efciency in AAm/MEI HG, but the less for the AAm/IA. For both systems, the maximum adsorption efciency was observed when the molar ratio AAm/IA or AAm/MEI is 80/20. When the adsorption was carried out with individual ions, AAm/MEI HG was more ef cient than AAm/IA. For a multielement sample of Cu 2+ , Ni 2+ , Pb 2+ , and Cd 2+ , both HGs could adsorb all the ions and their behavioral trend was the same in both cases, in which the adsorption efciency was Pb 2+ > Cu 2+ > Cd 2+ > Ni 2+ . The results of the statistical analysis evidence the advantage of its use in this type

of studies. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018, 135, 46999.

KEYWORDS: hydrogels; ion adsorption; itaconic acid; poly(acrylamide-co-itaconic acid); poly(acrylamide-co-monomethoxyethyl itaco- nate); statistical analysis

Received 23 March 2018; accepted 4 July 2018

DOI: 10.1002/app.46999

INTRODUCTION

Industrial development has rapidly increased the water pollution of the planet. Among the pollutants discharged into the water sources, there is a large amount of metal ions as Cu 2+ , Pb 2+ , Fe 2+ , Fe 3+ , Al 3+ , As 5+ , Zn 2+ , Cd 2+ , Cr 3+ , and Cr 6+ coming from fabric, automotive, chemical, p harmaceutical, metallurgical, agro-food, mining industries or from the glass, and ceramics manufacture. 1 3

Currently there are different methods for the decontamination of wastewater containing metal ions. The literature make men- tion of some techniques that are useful for the direct recovery of metal ions, among them, ion exchange, chemical precipita- tion, separation using membranes, and others which involve adsorption phenomena using substances, such as activated charcoal, zeolites, chelating products, bio-absorbents, and HGs. 4 7

HGs have been widely used in water purication studies, as they have not only been shown to be effective in the adsorption of metal ions, but also because the synthesis of most of them is relatively easy, inexpensive, and also these materials can be reused. 8 13 Acryl- amide HGs that contain low amounts of itaconic acid (IA) and ita- conate units in the structure had received some attention. These HGs were used for swelling studies, cationic dyes, and uranyl removal and adsorption of bovine serum albumin. 14 18 The interest in the preparation of IA or itaconate containing polymers and HGs is due not only to their structure being similar to that of acrylates and methacrylates, but also to the fact that IA is a water-soluble nat- ural monomer having two carboxylic acid groups which are able to be esteried selectively. 19 Conversely, the IA and its esters have been easily copolymerized with AAm, which produce copolymers with pendant carboxyl groups that are highly hydrophilic. Therefore, if these copolymers are properly cross-linked, they give rise to highly

Additional Supporting Information may be found in the online version of this article.

© 2018 Wiley Periodicals, Inc.

version of this article. © 2018 Wiley Periodicals, Inc. 46999 (1 of 11) J. APPL. POLYM.

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ARTICLE WILEYONLINELIBRARY.COM/APP ef fi cient networks in the absorption of water. 2 0 – 2 4

efcient networks in the absorption of water. 20 24 Small amounts of IA in an acrylamide HG increase the degree of swelling of the gel network. 14,20 Even more, when the proportion of IA or mono- methoxyethyl itaconate (MEI) in the poly(acrylamide-co-itaconic acid) (AAm/IA) or poly(acrylamide-co-monomethoxyethyl itaco- nate) (AAm/MEI) HGs is higher than 10 mol %, the swelling increases considerably, reaching values near 40 000% when the con- tent of itaconate is 30 mol %. 25

IA HGs and their esters have also been proved to be effective for metal ions adsorption. HGs that contain itaconic acid effectively adsorb Pb 2+ , Cd 2+ , Cu 2+ , and Zn 2+ ions. 26 29 In addition, poly(octadecyl diitaconate) has been used as ller material for pre- concentration of cadmium, showing to be a good sorbent material for Cd 2+ . 30 These studies strongly suggest that these materials, espe- cially when they have high contents of IA or itaconate units in the polymeric chain, could be effective HGs to be used for recover metal ions from contaminated waters. However, in the literature there are few reports in ions adsorption studies with AAm/IA, 31,32 while AAm/MEI or poly (acrylamide-co-dimethoxyethyl itaconate) (AAm/DEI) HG have not been used for ion adsorption.

This article describes the study of the adsorption of some metal ions as Cu 2+ , Ni 2+ , Pb 2+ , Cd 2+ , Fe 2+ , and Fe 3+ in aqueous solutions using poly(acrylamide-co-itaconic acid) (AAm/IA), poly(acrylamide-co- monomethoxyethyl itaconate) (AAm/MEI), and poly(acrylamide- co-dimethoxyethyl itaconate) (AAm/DEI) HGs synthetized at differ- ent molar ratios with the main objective to determinate how the chemical HG structure and composition inuence the adsorption of metal ions. It is noteworthy that amounts of IA and itaconates in these HGs are higher than those used by others authors. 14 18,20

The effects of the ion concentration in the solution and the HG composition on the adsorption for different ions were studied using a multifactorial experimental design and statistical analysis, ANOVA, which are useful tools that allows evaluate in the same experiment the effects of several factors, as the factorial design need less measurements than the classical approximation to obtain the same precision. The competition on the adsorption of some ions in a multielemental solution was also evaluated.

EXPERIMENTAL

Experimental Design To evaluate the effects on adsorption, the experimental design was a complete factorial arrangement that takes into account the following factors:

1. Metal ion: Cu 2+ , Ni 2+ , Fe 3+ , Cd 2+ and Pb 2+ .

2. Initial concentration of the metal ion (mg L 1 ): 10, 50, 100, 500, and 1000 (nominal).

3. Composition of the copolymers: HGs of AAm/IA and AAm/MEI with a molar ratio of 90/10, 80/20, and 70/30.

This implies 75 combinations (cases) for each HG (AAm/IA and AAm/MEI). Adsorption and adsorption ef ciency were calculated in three replicates for each case.

Materials The poly AAm, AAm/IA, AAm/MEI, and AAm/DEI HGs used in this work were synthesized and characterized in our previous

work. 25 All the details about the synthesis and characterization were reported in this reference. The idealized structure of these HGs is shown in the Scheme 1.

For the preparation of saline solutions, the following salts were used: Nickel(II) nitrate hexahydrate, (Ni[NO 3 ] 2 6H 2 O), copper (II) nitrate hemihydrate (Cu[NO 3 ] 2 2 1/2H 2 O), lead (II) nitrate (Pb[NO 3 ] 2 ), cadmium (II) nitrate (Cd[NO 3 ] 2 ), Iron(III) nitrate nonahydrate (Fe[NO 3 ] 3 9H 2 O), Iron (II) chloride tetrahydrate (FeCl 2 4H 2 O), and Iron (II) hexahydrate (FeCl 3 6H 2 O), supplied by Riedel-de Haën.

Swelling Measurements Maximum swelling (Hp max ) was measured using conventional gravimetric procedure. Dry gel samples (Xerogel) were immersed in double-distilled water and in a Cu(NO 3 ) 2 0.02 M solution at 25 C until the equilibrium was reached. Then, the HGs were removed from the solution, wiped with lter paper, and weighed on an electronic balance. The maximum swelling (Hp max ) was calculated using the following equation 25 :

Hp max =

W eq W 0

=W 0 × 100

ð 1Þ

Where W eq is the weight of swollen HG at equilibrium and W 0 is the weight of the dry gel. All swelling measurements were done by triplicate.

Metal Ions Adsorption The initial and nal concentrations of metal ions in solution were measured with inductively coupled plasma optical emission spec- troscopy (ICP-OES) equipment; brand ICP-ES LIBERTY SERIE II.

All saline solutions were prepared in water 18.2 MΩ cm 1 at con- centrations of about 10, 50, 100, 500, and 1000 mg L 1 and then, the initial real concentrations (Conc i ) were measured by ICP. The initial pH (pH i ) of all solutions was also determined.

The xerogel samples (pellets) were cut with a very thin steel cutting blade and weighed, trying to maintain a weight between 30 to 60 mg for all of them. Then, they were immersed in 50 mL of each of the separately prepared solutions, allowed to absorb for 24 h. Then, were removed and weighed. The nal concentration (Conc f ) and pH (pH f ) of the resulting solutions were measured. The pellets were left dried at room temperature until the samples reach constant weight. The procedure was performed by triplicate for all samples.

Data Treatment Adsorption Calculation. The adsorption of the ions by the HGs was evaluated by the following 10 :

A =

ð

Conc Conc

i

f

Þ V

m HG

ð

2Þ

Where A represents the amount of ion adsorbed in mg of ion per gram of HG, Conc i , and Conc f are the initial and nal concentra- tions (mg L 1 ) of the saline solution, respectively, V is the volume (mL) of the saline solution used and m HG is the weight (g) of the dry HG.

used and m H G is the weight (g) of the dry HG. 46999 (2 of

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ARTICLE WILEYONLINELIBRARY.COM/APP Scheme 1. Idealized structure of the different HGs used in this work. Adsorption Ef
ARTICLE WILEYONLINELIBRARY.COM/APP Scheme 1. Idealized structure of the different HGs used in this work. Adsorption Ef

Scheme 1. Idealized structure of the different HGs used in this work.

Adsorption Ef ciency. As the changes in the value of A depend on the initial concentration of the solution, in this work, we pro- pose the use of a parameter E. This value represents the efciency of the HG to adsorb a metal ion (adsorption efciency) and can be calculated by:

E =

ð

Conc Conc Conc i

i

f

Þ

×

1 HG

m

ð 3Þ

Where E is the adsorption ef ciency (g 1 ), Conc i and Conc f are the initial and nal ion concentration (mg L 1 ) of the saline solu- tion, respectively, and m HG is the initial weight (g) of the dry HG. The parameter E has the advantage that allows the compari- son of the adsorption at different initial concentrations and com- parison between ions with different atomic weight, because E has the same calculated value using the concentration in weight (mg L 1 ) or in number of particles (mmol L 1 ).

Adsorbed Metal Ion. Adsorbed ion (mmol) was calculated using the data obtained from the ICP-OES equipment using the following:

Ion mmol adsorbed =

ð

Conc Conc

i

f

ÞV

PA

ð 4Þ

Where V is the volume of the solution (mL) and PA is the atomic weight of the metal ion.

Generated Hydrogen Ions. The amount of hydrogen ions gener- ated in the adsorption process was calculated from the difference among initial and nal pH.

The pH was measured with a pH meter Thermo Electron Corpo- ration Orion 3 star pH Benchtop.

Statistical Analysis. The data analysis was performed using the classical variance analysis technique, ANOVA 33 and the differ- ences between the means of the analyzed variables ( A and E) were evaluated using the Tukey, HDStest. For both statistical analyses a level of signicance of 95% ( P 0.05) was used. This analysis was carried out with the STATGRAPHYCS Centurion XVI program.

In the graphs presented below, for the means of A or E variables, the standard error of the mean ( SEM) was calculated as:

SEM = p S ffiffiffi

n

ð

5Þ

Where S is standard deviation and n is the number of measures.

Complex Formation Enthalpies The complex formation enthalpies ( ΔH f ) between the different metal ions and the HG in the adsorption process, was estimated through an exploratory simulation study performed with a com- putational program for chemical analysis MOPAC 2012 with

putational program for chemical analysis MOPAC 2012 with 46999 (3 of 11) J. APPL. POLYM. SCI.

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ARTICLE WILEYONLINELIBRARY.COM/APP Table I. Maximum Swelling ( Hp m a x ) Reached by AAm, AAm/DEI,
ARTICLE WILEYONLINELIBRARY.COM/APP Table I. Maximum Swelling ( Hp m a x ) Reached by AAm, AAm/DEI,

Table I. Maximum Swelling ( Hp max ) Reached by AAm, AAm/DEI, AAm/MEI, and AAm/IA 80/20 HG in Water and in a 0.02 M Cu(NO 3 ) 2 Solution a

AAm

AAm/DEI

AAm/MEI

AAm/IA

Water

Cu(NO 3 ) 2

Water

Cu(NO 3 ) 2

Water

Cu(NO 3 ) 2

Water

Cu(NO 3 ) 2

Hp max

Hp max

Hp max

Hp max

2534

1919

10 043

10 497

30 329

380

20 330

265

a The weight of all de HG samples used was of about 50 mg. The volume of water and solution of Cu(NO 3 ) 2 used was 100 mL.

semi-empirical method PM7, using the metal ions and the differ- ent monomer involved in the HG structure.

Morphological Study The morphology of xerogels was obtained through SEM images from the surface of lyophilized swollen samples. For this purpose, the samples were swollen to equilibrium, cooled in liquid nitro- gen and then lyophilized in a LABCONCO apparatus during 24 h. The images were obtained using a scanning electron micro- scope (HITACHI S-2500) operating at 12 kV with a magnica- tion of 500 times. Before the analysis, the aerogel samples were coated with a thin layer of gold in an ion coater SPI model 11430E to provide proper surface conduction.

The average pore size was calculated from the data obtained with the SEM images, using the following equations:

S pn = 1 =Σ F i = T i Þ or ΣF i =Σ F i =T i Þ

ð

ð

S pw = Σ F i

ðÞ

:T i

ð

6Þ

ð 7Þ

Where S pn is the number-average pore size, S pw is the weight- average pore size, and F i is the fraction of pores with a size T i .

RESULTS AND DISCUSSION

Preliminary Experiments To determine the HGs that would be used for this work, a pre- liminary swelling experiment was carried out immersing samples of AAm, AAm/DEI, AAm/IA, and AAm/MEI 80/20 HGs, in water and in 100 mL of a 0.02 M solution of Cu(NO 3 ) 2 . In the solution of Cu(NO 3 ) 2 , AAm and AAm/DEI HGs acquire a very pale blue color after submerging, while AAm/MEI and AAm/IA HGs take a deep blue color.

As explained in Table I, AAm and AAm/DEI HGs, reached almost the same degree of swelling both in the Cu(NO 3 ) 2 solu- tion and in pure water. Whereas, AAm/MEI and AAm/IA swelled much less in the Cu(NO 3 ) 2 solution than in pure water, about 2 order of magnitude. Furthermore, when these HGs were dried and submerged in water again, the AAm and AAm/DEI completely loosed the color indicating the output of the ions, while the HGs of AAm/MEI and AAm/IA retained it. In addi- tion, AAm and AAm/DEI HG swelled during the process reach- ing the Hp max , whereas AAm/MEI and AAm/IA did not. These results strongly suggest that between AAm and AAm/DEI HGs and the solvated Cu 2+ ion, the interaction process is mainly phys- ical; this means that the solvated ions together with the water penetrate the HG through the pores without practically establish- ing any type of chemical interaction with the material. Once the

HG dries, the copper salt remains there. But when the HG is sub- merged in water again, the copper salt is release and leaves from the HG. While for AAm/IA and AAm/MEI a strong chemical interaction or a complex formation between Cu 2+ and the HG are taking place. Therefore, AAm and AAm/DEI HGs were dis- carded for use in the analysis of ion adsorption.

Once the HGs to be used were selected, a series of assays were carried out to determine the HG amount, solution volume, con- centrations, and adsorption times to be used in the adsorption experiments. Samples of about 30 60 mg of HG were chosen. For these amounts, 50 mL of the Cu(NO 3 ) 2 solution was ade- quate to carried out all the adsorption experiments. The use of less volume of solution was not enough for some samples, espe- cially those with high content of IA or MEI because they absorb all the liquid. It was determined that at 24 h, the HG reach the maximum adsorption and for longer time, 48 and 72 h, it

remains constant. Therefore, this was the time used in the experi- ments. The solutions concentrations of 1000, 500, 100, 50, and 10 mg L 1 were the same used by other authors. 10,26,34

Adsorption Studies Factor Analysis. Once the best experimental conditions were established, a complete analysis of the effect of the different fac- tors on the adsorption of the metal ions was carried out.

As an example of the obtained results, in Table II, are shown the adsorption values for AAm/MEI 80/20 at different concen- trations. There, it can be observed that the weight of the HGs increases as the concentration of the solution decreases and this trend is observed throughout all the concentration gradi- ent. It happens because in the more diluted solutions, the water penetration to the netwo rk is favored. It was also noted for all solutions, except for iron, that during the adsorption process take place a decreasing of the pH of the ionic solution. This fact suggests that an ionic exchange occurs between the metal ion of the outer solution and the hydrogen bounded to the acidic groups of the HG. A similar behavior was previously reported by Katime and Rodríguez in 2001, for acrylic acid/ita- conic acid HGs. 26

Conversely, for all samples analyzed, it was observed that the amount of H + ions generated is at least 1 order of magnitude less than the adsorbed metal ions (Table II). This suggests that the adsorption mechanism is not only related to an ion exchange with the H + groups associated with the acid groups of the HG structure, but there may also be a chemical interac- tion between the metal ion with the oxygens of the carbonyl groups of the itaconate and of the acrylamide, in both cases forming complex-type interactions, such as it was suggested by

complex-type interactions, such as it was suggested by 46999 (4 of 11) J. APPL. POLYM. SCI.

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ARTICLE WILEYONLINELIBRARY.COM/APP Table II. Comparative Adsorption Results for AAm/MEI 80/20 at Different Concentrations
ARTICLE WILEYONLINELIBRARY.COM/APP Table II. Comparative Adsorption Results for AAm/MEI 80/20 at Different Concentrations

Table II. Comparative Adsorption Results for AAm/MEI 80/20 at Different Concentrations

Concentration (mg L 1 )

 

HG Initial

HG nal

 

M n+ adsorbed g

H + generated h

M

n+

Initial

Final

weight (g)

a

b

weight (g)

pH

i c pH

f

d

A (mgg

1 e

)

E (g

1 f

)

(mmol)

(mmol)

Cu 2+

1100

1011

0.0394

0.2124

4.42

3.70 113

 

2.00

6.98E-02

8.00E-03

550

457

0.0382

0.2676

4.86

3.95 122

4.51

7.32E-02

4.96E-03

110

72

0.0422

1.5471

5.27

4.14

45

8.27

2.99E-02

3.33E-03

55

35

0.0334

2.6605

5.49

4.38

30

11.04 1.59E-02

1.92E-03

11

2

0.0389

20.3518

5.72

5.09

12

22.40 7.29E-03

3.08E-04

Ni 2+

1100

1009

0.0384

0.7438

5.70

4.28 118

 

2.18

7.73E-02

2.54E-03

550

481

0.0387

0.9945

5.69

4.38

89

3.25

5.88E-02

1.98E-03

110

80

0.0339

2.6634

5.95

4.56

44

8.14

2.56E-02

1.31E-03

55

36

0.0344

4.9160

5.89

4.78

28

10.49 1.65E-02

7.59E-04

11

1

0.0363

20.9974

6.25

5.62

14

24.90 8.46E-03

9.18E-05

Cd 2+

937

887

0.0380

0.5374

5.24

4.00

66

1.41

2.23E-02

4.67E-03

469

420

0.0357

1.0197

5.54

4.29

69

3.01

2.20E-02

2.42E-03

94

61

0.0329

4.0459

5.89

4.71

51

10.91 1.48E-02

9.18E-04

47

25

0.0334

7.4387

6.02

4.89

33

14.42 9.87E-03

5.96E-04

9

2

0.0307

18.4709

6.21

5.59

12

26.56 3.25E-03

9.77E-05

Pb 2+

1093

825

0.0348

0.1700

4.76

3.66 121

 

2.33

2.03E-02

1.01E-02

520

271

0.0370

0.2356

5.14

3.79 134

5.17

2.39E-02

7.75E-03

104

22

0.0411

5.6317

5.47

4.27

61

12.90 1.22E-02

2.50E-03

52

25

0.0358

10.0920

5.78

4.67

38

14.82 6.60E-03

9.94E-04

10

8

0.0376

28.1909

5.26

6.01

2

4.94

4.22E-04

ND

Fe 3+

1176

490

0.0438

0.1237

2.33

2.49 784

 

13.79 6.15E-01

i

572

232

0.0378

0.1309

2.45

2.59 450

15.92 3.04E-01

i

113

28

0.0341

0.3665

2.77

3.04 127

22.23 7.73E-02

i

57

16

0.0369

0.7284

2.93

3.26

55

19.96 3.66E-02

i

13

4

0.0374

4.9705

3.47

4.55

11

17.93 7.62E-03

i

a Weight of the dry HG (xerogel).

b Weight of the swell HG after 24 h.

c Initial pH of the saline solution.

d Final pH of the saline solution (after 24 h).

e Adsorption.

f Adsorption ef ciency.

g mmols of the adsorbed ion, determined from ICP data.

h mmols of H + generated during the adsorption process, calculated with the pH variation. ND Not determined.

i Generation H + was not observed. All results are the average of 3 assays.

El-Hag Ali. 10 The physical absorption of the solution of the solvated ion should also happen together with the other pro- cesses. The formation of complex between HG and metal ions

has been reported, 35 40 but at the moment the structure of complex between these HG and the metal ions is not complete clear. At this time in our laboratory, are conducting new

clear. At this time in our laboratory, are conducting new Figure 1. Average adsorption (mg g

Figure 1. Average adsorption (mg g 1 ) of all ions concentrations and compositions of the HGs (A) AAm/IA and (B) AAm/MEI, for each metal ion. The thin bar represents the SEM of the sample. The means indicated with the same letter in each graphic do not present signicant differences between them (Tukey, HSD,P 0.05, n = 45).

them ( “ Tukey, HSD, ” P ≤ 0.05, n = 45). 46999 (5 of 11)

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ARTICLE WILEYONLINELIBRARY.COM/APP experiments to obtain further experimental evidence that would allow to determine the

experiments to obtain further experimental evidence that would allow to determine the nature and structure of each one of these complexes.

As may be observed in Table II, the adsorption of the ion is highly dependent of the concentration and nature of the ion.

At this point, AAm/IA and AAm/MEI systems, depending on

the conditions, reach adsorption values as high as 126 and

192

mg g 1 for Cu 2+ , 35 and 120 mg g 1 for Ni 2+ , 60 and

455

mg g 1 for Fe 3+ , 102 and 60 mg g 1 for Cd 2+ , and 217 and

144

mg g 1 for Pb 2+ , respectively. Conversely, the highest

values found in the literature for the adsorption of these metal ions with others HGs, were 119 mg g 1 for Cu 2+ and 204 mg

g 1 for Pb 2+ obtained with poly( N -isopropylacrylamide- co - N,N´- dimethylacrylamide) by García and Alvarez. 4 Ozay 40 reported adsorption values of 105.4 for Ni 2+ , 102 for Fe 3+ ,

134 for Cd 2+ , and 126 for Pb 2+ with poly(2-acrylamido-

2-methyl-1-propanesufonic acid) HG and Chowdhury and co- workers 41 found adsorption values of l38 mg g 1 for Fe 3+ with

HG based in poly(vinyl alcohol)/polysaccharides. These results, compared with that obtained in this work suggest that the performance of AAm/IA and AAm/MEI HGs, under the conditions studied, in the most of the cases is as good as or better than the others.

The statistical analysis was developed with the purpose of analyz- ing the effect of each factor (metal ion, ion concentration, and HG composition) on the dependent variables (A and E). This was eval- uated for both HGs studied (AAm/IA and AAm/MEI) and each factor gave rise to signicant differences ( P 0.05), which means that all of them affect the studied variables in a signi cant way. The results of these effects are presented graphically below.

Metal Ion. Figure 1 shows, in a comparative way, the adsorption of the different metal ions by both HGs used. From the Figure 1 (A) is clear that the Pb 2+ ion is the most adsorbed with AAm/IA followed by Cu 2+ , Cd 2+ , Fe 3+ , and Ni 2+ ion. However, for the AAm/MEI system (Figure 1(B)), the Fe 3+ ion is the most adsorbed, while the other ions were adsorbed more or less in the same way as with the previous system.

As was explained before, the adsorption process may involve a chemical interaction between the carbonyl groups of the mono- mer units with the metal ions which may produce complex-type interactions. To corroborate this fact, an exploratory simulation study to allow determine complex formation enthalpies ( ΔH f ) was carried out and the obtained results are shown in Table III.

carried out and the obtained results are shown in Table III. Figure 2. Structure obtained by

Figure 2. Structure obtained by simulation, of the Pb 2+ complexes with both monomers. (A) IA-Pb 2+ and (B) MEI-Pb 2+ .

As it can be seen, in all cases the ΔH f follow the sequence MEI < IA < AAm. These values conrm that the complex formation take place mainly with the itaconate or IA units. For both MEI and IA, the lowers enthalpies were obtained for the Pb 2+ ion, sug- gesting that the complex formation between the itaconic unit and this ion is the most favored. Conversely, it can be observed that Fe 3+ is the ion with the highest ΔH f value indicating that this is the less favorable ion to form complex. These facts explain satis- factorily the adsorption observed for the system AAm/IA [- Figure 1(A)], where the Pb 2+ is the most adsorbed ion and the Fe 3+ followed by the Ni 2+ , which showed detection problems at high concentrations, are the less adsorbed. Although these values were calculated with the monomers and not with the polymer, they satisfactorily explain the obtained results.

Figure 2 shows, as an example, the more stable structure of the complexes of Pb 2+ with both monomers. As may be seen, the complexes are formed between the metal ions with the oxygens of the carbonyls groups.

For AAm/MEI HG the Fe 3+ ion showed the highest adsorption, this fact can not be explained from the point of view of the com- plex formation, because here its ΔH f is at least 2.5 times higher than the others ions. However, it can be explained because the ingress of the solvated ion into the HG should be in uenced by the pore size of the HG and the hydrated ionic radius. As may be observed in Table III, Fe 3+ ion has the smaller hydrated ionic radius and the results obtained for the SEM micrographs of AAm/IA and AAm/MEI 90/10 HGs (Figure 3), as it will be explained after, indicate that the AAm/MEI system has a smaller average pore size than the AAm/IA.

In reference to the average pore sizes, they were determined from the histograms shown in Figure 3 for plot (A) AAm/IA and plot (B) AAm/MEI 90/10 HG swelling in water after reaching equilibrium.

Table III. Hydrated Ionic Radius of the Metal Ions Used in this Work and Their Complex Formation Enthalpy With the Monomers Used in the HGs Synthesis a

M n +b

Fe 3+ (0.66 Å)

Fe 2+ (0.78 Å)

Ni 2+ (0.72 Å)

Cu 2+ (0.94 Å)

Cd 2+ (0.96 Å)

Pb 2+ (1.20 Å)

Monomer

ΔH (K J mol 1 )

AAm

4015

2184

1890

1800

1554

1599

MEI

2597

1844

939

977

722

709

IA

3255

1100

1312

1123

1446

1071

a The enthalpies were calculated using the program MOPAC2012.

b The values between parentheses correspond to the hydrated ionic radius of each ion. 42

correspond to the hydrated ionic radius of each ion. 4 2 46999 (6 of 11) J.

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ARTICLE WILEYONLINELIBRARY.COM/APP Figure 3. SEM micrographs and histograms of HG 90/10 (A) AAm/IA and (B) AAm/MEI.
ARTICLE WILEYONLINELIBRARY.COM/APP Figure 3. SEM micrographs and histograms of HG 90/10 (A) AAm/IA and (B) AAm/MEI.

Figure 3. SEM micrographs and histograms of HG 90/10 (A) AAm/IA and (B) AAm/MEI.

and histograms of HG 90/10 (A) AAm/IA and (B) AAm/MEI. Figure 4. Adsorption ef fi ciency

Figure 4. Adsorption ef ciency ( E) of AAm/IA and AAm/MEI 80/20 HGs with solutions of FeCl 2 and FeCl 3 of 50 mg L 1 . The thin bar represents the standard deviations.

For AAm/IA the weight and number-average pore size ( S pw and S pn ) are 17 μ m and 16 μ m, respectively, while for AAm/MEI are 15 μ m and 14 μ m. Moreover, the proportion of pores with a size higher than 17 μ m is 47.8% for AAm/IA and only 25.6% for AAm/MEI, which indicate that not only the average pore size is

smaller for the last, but it has a considerable less amount of larges pores than AAm/IA.

At this point, it is necessary to emphasize that in the xerogel the pores are totally collapsed and in this state their diameters are substantially smaller than the aerogel. Experimentally it has been observed that AAm/IA and AAm/MEI HGs have preference for the adsorption of the ions than for the water, and that during the ion adsorption, the swelling process practically does not occur (see Table I), therefore the pores do not expand. 28 As it is logical to suppose, the ratio of the pore diameters between AAm/MEI and AAm/IA must be maintained in the xerogel, therefore, the pore diameter of the AAm/MEI must be lower than the AAm/IA, this fact strongly suggests that the ions with the lowest hydrated ionic radius, as in the case of Fe 3+ , should enter in the MEI/AAm matrix easier than the other ions.

To verify that the size of the ion certainly in uences the adsorp- tion, a simple study was performed using the FeCl 2 and FeCl 3 salts with a concentration of 50 mg L 1 with both HGs. As may be seen in Figure 4, the Fe 3+ ion is the most easily adsorbed for the HG AAm/MEI. It may be due to the fact that its hydrated ionic size is smaller (0.66 Å) than Fe 2+ (0.78 Å ). Conversely, for the HG

Å ) than Fe 2 + (0.78 Å ). Conversely, for the HG Figure 5. Average

Figure 5. Average adsorption ef ciency (g 1 ) of all ions concentrations and compositions of the HGs (A) AAm/IA and (B) AAm/MEI, for each metal ion. The thin bar represents the SEM of the sample. The means indicated with the same letter in each graphic do not present signicant differences between them (Tukey, HSD,P 0.05, n = 45).

them ( “ Tukey, HSD, ” P ≤ 0.05, n = 45). 46999 (7 of 11)

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ARTICLE WILEYONLINELIBRARY.COM/APP Figure 6. Average Adsorption (mgg − 1 ) of all metal ions and compositions
ARTICLE WILEYONLINELIBRARY.COM/APP Figure 6. Average Adsorption (mgg − 1 ) of all metal ions and compositions

Figure 6. Average Adsorption (mgg 1 ) of all metal ions and compositions of the HGs (A) AAm/IA and (B) AAm/MEI, for the different concentrations of the ions. The thin bar represents the SEM of the sample. The means indicated with the same letter in each graphic do not present signicant differences between them (Tukey, HSD,P 0.05, n = 45).

them ( “ Tukey, HSD, ” P ≤ 0.05, n = 45). Figure 7. Average Adsorption

Figure 7. Average Adsorption Ef ciency (g 1 ) of all metal ions and compositions of the HGs (A) AAm/IA and (B) AAm/MEI, for the different concentra- tions of the ions. The thin bar represents the SEM of the sample. The means indicated with the same letter in each graphic do not present signicant differ- ences between them (Tukey, HSD,P 0.05, n = 45).

AAm/IA, that has a higher pore size, no signicant difference was found between the adsorption ef ciency for Fe 2+ and Fe 3+ .

The E results obtained are shown in Figure 5. It is clear that both systems show a more or less similar ef ciencies for all ions with exception of Fe 3+ . The Fe 3+ shows the highest adsorption ef - ciency in AAm/MEI HG, but the less in the AAm/IA.

These results indicate that the adsorption depends on the ease with which the metal ion interacts with the carboxyl groups pre- sent in the HG and also on the relationship between the hydrated ionic radius and the pore size of the HG.

The chemical interaction (complex formation) is the predomi- nant factor in the ion adsorption. However, the relation between the pore size and hydrated ion size also in uences the ion input.

Ion Concentration. For both systems, when the concentration of the metal ions increases, the adsorption raises as may be seen in Figure 6. This occurs because higher concentration of the solu- tion, the ions will be more available. However, as may be seen in Figure 6(A), for the AAm/IA system above 500 mg L 1 , the adsorption value does not increase, on the contrary, this seems to decrease slightly, and this fact strongly suggests that over this concentration value the system becomes saturated.

Conversely, adsorption ef ciency shows a contrary trend, in this case the efciency decrease as the concentration raises (Figure 7), because the relative adsorption in most diluted solution respect to the initial concentration is higher. However, both HGs tested; do not show the same behavior, while AAm/IA HGs ef ciency is practically equal between concentrations from 10 to 100 mg L 1 ,

between concentrations from 10 to 100 mg L − 1 , Figure 8. Average Adsorption (mg

Figure 8. Average Adsorption (mg g 1 ) of the metals ions and compositions of the different HGs (A) AAm/IA and (B) AAm/MEI, for the different concen- trations of the ions. The thin bar represents the SEM of the sample. The means indicated with the same letter in each graphic do not present signi cant dif- ferences between them (Tukey, HSD,P 0.05, n = 75).

them ( “ Tukey, HSD, ” P ≤ 0.05, n = 75). 46999 (8 of 11)

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ARTICLE WILEYONLINELIBRARY.COM/APP Figure 9. Average Adsorption Ef fi ciency (g − 1 ) of all the
ARTICLE WILEYONLINELIBRARY.COM/APP Figure 9. Average Adsorption Ef fi ciency (g − 1 ) of all the

Figure 9. Average Adsorption Efciency (g 1 ) of all the ions and concentrations for the different compositions of the HGs (A) AAm/IA and (B) AAm/MEI. The thin bar represents the SEM of the sample. The means indicated with the same letter in each graphic do not present signicant differences between them (Tukey, HSD,P 0.05, n = 75).

for AAm/MEI the efciency increase gradually with the diminu- tion of the concentration.

Both, adsorption and efciency are higher for AAm/MEI than AAm/IA for each concentration of the solutions.

Hydrogel Composition. The inuence of the HG composition both in the adsorption and efciency is shown in Figures 8 and 9. In Figure 8, it can be seen that the 80/20 and 70/30 M ratios reach the higher adsorptions for AAm/IA HGs while for AAm/MEI sys- tem, the order in the adsorption is 80/20 > 70/30 > 90/10.

Conversely, as may be seen in Figure 9, the average adsorption efciency is signicantly higher for the 80/20 ratio than the 90/10 and 70/30 ratios for both systems.

As mentioned above, the adsorption processes are mainly due to the interaction between the carboxylic acid groups with the metal ions, through an ionic exchange of the metal ion with the hydroxyl group and also by complex-type interactions with the oxygen atoms of the carbonyl group. The 90/10 M ratio in both systems has fewer itaconate units and therefore less carboxylic groups, for this reason it shows the less adsorption. The HGs with the 70/30 M ratio has the highest proportion of itaconate or itaconic acid, and then the ion adsorption should be the largest. Nevertheless, in this case a competition process between the ion and water occur. Then, the greater amount of water over the ions, favors the adsorption of the former. This is evident in the more dilute solutions, especially in the 10 mg L 1 , there, HGs with a co-monomers ratio of 70/30 absorb a large amount of water, 25 and in almost all cases, at very dilute concentrations, the amount of ions that retain these HG are lower than those having a 90/10 M ratio.

Finally, taking this fact into account, the maximum adsorption could be reach with HGs with a molar ratio of 80/20, which has more IA or MEI unit than 90/10 HG, and where the com- petition with water is less than the observed with a molar ratio of 70/30.

Nature of the Itaconic Co-Monomer. The obtained results indi- cate that HGs of AAm/MEI are more effective for ion adsorption than AAm/IA as it may be seen graphically in Figure 10.

This fact is not easy to explain and it is possible that the higher adsorption of the AAm/MEI may be because of the combination of a series of factors. For all the ions systematically studied in this work, the formation enthalpies ( ΔH f ) of the complex obtained with AAm/MEI HG are lower than those obtained with AAm/IA (Table III), this could be favoring the higher adsorption for the former. Although the pore size of AAm/MEI HG is lower, is pos- sible that at molecular level the presence of a longer side chain increase the exibility of the network allowing that the entry and the interaction with the ion occurs more easily. Moreover, in the case of the AAm/IA HG, the density of hydrogen bonds is higher making the network more rigid.

These results suggest that the side chains of the itaconic unit and its proportion in the HG could have some in uence on the adsorption.

Multielement Solution Analysis. Finally, a study was performed to evaluate the behavior of these HGs in a solution with a mixture of different ions and determinate if any of two showed some kind of selectivity by some of the ions. To do this, two HGs AAm/IA and AAm/MEI 80/20 were used to evaluate a multielement solution

AAm/MEI 80/20 were used to evaluate a multielement solution Figure 10. (A) Average adsorption (mgg −

Figure 10. (A) Average adsorption (mgg 1 ) and (B) average ef ciency (g 1 ) of all metal ions, concentrations ions and HG compositions for HG AAm/IA and AAm/MEI. The thin bar represents the SEM of the sample. The comparison was made with Tukey HDS,P 0.05, n = 225.

was made with “ Tukey HDS, ” P ≤ 0.05, n = 225. 46999 (9 of

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ARTICLE WILEYONLINELIBRARY.COM/APP Figure 11. Adsorption ef fi ciency ( E ) for each one of the
ARTICLE WILEYONLINELIBRARY.COM/APP Figure 11. Adsorption ef fi ciency ( E ) for each one of the

Figure 11. Adsorption efciency (E ) for each one of the ions in a multielement solution. (A) For AAm/IA and (B) for AAm/MEI. The thin bar represents the standard deviation of the sample.

thin bar represents the standard deviation of the sample. Figure 12. Comparison of the adsorption ef

Figure 12. Comparison of the adsorption efciency (E ) between the summation averages of E for 500 mg L 1 and 100 mg L 1 in separated ions solutions with the same ions in a multielement solution. (A) HG AAm/IA 80/20 and (B) to HG AAm/MEI 80/20. The thin bar represents the standard deviation of the sample.

composed of Cu 2+ , Cd 2+ , Ni 2+ , and Pb 2+ ions with a concentration of 50 mg L 1 of each one, giving a total concentration of 200 mg L 1 . The obtained result indicates that both HGs adsorb all the ions and their behavioral trend is the same in both cases.

As may be appreciated in Figure 11, the AAm/IA results more efcient than AAm/MEI system and in both cases the adsorption efciency is Pb 2+ > Cu 2+ > Cd 2+ > Ni 2+ . Figure 12 compares the adsorption efciency using the total concentration of the multie- lement solution (200 mg L 1 ) with those obtained as an average of the separated solutions for 100 and 500 mg L 1 . Although in the case of the multielement solution only one concentration and a molar ratio are being considered, in both cases it is observed that this solution follows the same tendency showed in Figure 7. For HG AAm/IA it is observed that the E value decreases from 100 to 500 mg L 1 . This behavior agrees with the general trend shown in Figure 7(A). For HG AAm/MEI, the observed E value of the 200 mg L 1 solution is comparable to that of 500, but less than 100 mg L 1 , which is in agreement with that shown in Figure 7(B).

The results obtained in this experiment indicate that these sys- tems are capable of absorbing different metal ions in a multiele- ment sample. However, additional experiments are needed to obtain more conclusive results and to determine the true poten- tial of these systems for use in remediation of water sources.

CONCLUSIONS

These results indicate AAm/IA and AAm/MEI HGs are effective systems for adsorption ions and their capacity depend on the ion involved, its concentration and composition of the HGs. For both

systems, the maximum adsorption efciency was observed when the molar ratio AAm/IA or AAm/MEI is 80/20.

Each HG shows comparable adsorption efciency for all ions with exception of Fe 3+ which shows the highest adsorption ef- ciency in AAm/MEI HG, but the less for the AAm/IA.

AAm/MEI HG is more ef cient than AAm/IA when the adsorp- tion was carried out with single ions. For a multielement sample of Cu 2+ , Ni 2+ , Pb 2+ , and Cd 2+ , both HGs can absorb all the ions and their behavioral trend is the same in both cases, in which the adsorption efciency is Pb 2+ > Cu 2+ > Cd 2+ > Ni 2+ .

The use of the adsorption efciency ( E ) of a HG allows to com- pare the adsorption of metal ions with different atomic weight and evaluate the adsorption in multielement solutions better than using adsorption ( A).

As methodologic point of view, the use of a multifactorial experi- mental design with its respective statistical analysis brought important conclusions about the effects of selected factors on the ions adsorption by HGs. This fact evidences the advantage of using a statistical approach for this type of studies.

ACKNOWLEDGMENTS

The authors gratefully acknowledge the nancial support of CDCHTA-ULA, Mérida Venezuela, through grant number C-2001-18-08-A. The authors also wish to thank to Andres E. Mora and Jorge Fernandez of LAQUEM-ULA, for their help with the SEM experiments, to Lic. William Velázquez of LARSA- ULA, for his help with the ICP measures and MSc. Eduardo Car- dozo of the Group of Organometallics of the Chemistry

Car- dozo of the Group of Organometallics of the Chemistry 46999 (10 of 11) J. APPL.

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ARTICLE WILEYONLINELIBRARY.COM/APP Department-ULA for his helpful with the computational program for complex formation

Department-ULA for his helpful with the computational program for complex formation enthalpies estimation.

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