International Journal of Biological Macromolecules 139 (2019) 153–160

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International Journal of Biological Macromolecules

journal homepage: http://www.elsevier.com/locate/ijbiomac

Synthesis and characterization of modified sulfonated chitosan for

beryllium recovery
Asmaa M. Abu El-Soad a,b,⁎, Mahmoud O. Abd El-Magied b, Mohamed S. Atrees b,
Elena G. Kovaleva a, Giuseppe Lazzara c,⁎
a
Ural Federal University, Mira St. 19, Yekaterinburg 620002, Russia
b
Nuclear Materials Authority, P.O. Box 530, El Maadi, Cairo, Egypt
c
Dipartimento di Fisica e Chimica, Università degli Studi di Palermo, Viale delle Scienze, Parco d'Orleans II, Ed. 17, 90128 Palermo, Italy

a r t i c l e i n f o a b s t r a c t

Article history: A new adsorbent, sulfated crosslinked chitosan (SGCH), has been synthesized for the effective extraction of be-
Received 27 June 2019 ryllium ions from their aqueous solutions. In recent times, beryllium extraction has been of great importance be-
Received in revised form 9 July 2019 cause beryllium can be used in many applications such as in nuclear reactor, heat shields, high-technology
Accepted 25 July 2019
ceramics, alloys and electronic heat sinks. SGCH has been synthesized by two successive phases. The first is the
Available online 26 July 2019
conversion of chitosan (CH) into non-soluble cross-linked chitosan (GCH) through the interaction between chi-
Keywords:
tosan and glutaraldehyde. The second step is the formation of functional sulfonate groups onto the adsorbent ma-
Beryllium terial through the interaction of GCH with chlorosulfonic acid (sulfating agent). The role played by the sulfonate
Remediation groups in the adsorption process was analyzed using FT-IR and SEM. Also, the role played by the solution pH,
Chitosan time, beryllium concentration and temperature on the batch adsorption process was investigated. Our results
Biosorption point to the successful preparation of SGCH adsorbent with high affinity for beryllium ions. The maximum sorp-
tion values of beryllium ions on the investigated biosorbent is 40.6 mg/g. The desorption of the loaded beryllium
ions from the SGCH was achieved by using 1.5 M urea acidified by 0.6 M H2SO4.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction response of the human immune system to Be exposure, skin contact

Beryllium is a brittle metal that is found in nature as a mineral. It is
the 44th most abundant metal in the earth's crust. The main ores used
for beryllium extraction are beryl (Al2Be3Si6O18) and bertrandite (Be4
(OH)2Si2O7). Beryllium prefers tetrahedral coordination to ‘hard’
donor ligands and its stability increased when coordinated in six-
membered chelate rings. It isn't soluble at neutral pH [1].
In recent decades, scientists have given serious attention to the ex-
traction of beryllium due to its high importance. It has been used in a
wide range in nuclear weapons and nuclear reactors, inertial guidance
components, x-ray tubes, space optics, and microelectronics due to its
light weight and high strength [2]. Beryllium is of great importance in
nuclear applications because it is one of the most suitable materials
that can be used for beam windows and target components in the
next generation of neutrino sources [3]. Although of the high impor-
tance of beryllium in many fields, Beryllium is reported to carcinogenic
when inhaled or eaten by beryllium contaminated food. Because of the
⁎ Corresponding authors.
E-mail addresses: aabuelsoad@urfu.ru (A.M. Abu El-Soad), giuseppe.lazzara@unipa.it
(G. Lazzara).
may cause beryllium sensitization [4,5].
Biopolyelectrolytes as well as nanoclays represent the most promising
green materials for selective adsorption of charged species. [6–10] More-
over, the peculiar physico-chemical properties of biopolyelectrolytes
makes them suitable for designing functional nanoarchitectures to be
exploited in a wide range of industrial applications [11–13].
Although there are many methods for the extraction and concentra-
tion of beryllium, adsorption stands as the most effective method [14].
Sorption of beryllium by inorganic and organic low- cost materials
have been reviewed by many researcher [15–18]. Chitosan occupies
the highest position among these materials. It has strong affinity for
metal ions either by an ion exchange mechanism or by chelation
mechanism [19,20]. It is obtained by the deacetylation of chitin (from
crustaceans' shells) using sodium hydroxide [21]. Chitosan can be
considered as a natural polyelectrolytes and dried films have been al-
ready investigated for sustainable packaging applications, [22–25]
drug delivery [26–28], environment remediation [29,30] and tissue
engineering [31–33]. Because of the rapid dissolution of chitosan in di-
lute mineral acids, crosslinking treatments have been developed to rein-
force chitosan stability in acidic solutions. The crosslinking treatments
can be done by using different reagents such as Ethylene Glycol
Diglycidyl ether, Epichlorohydrin, Hexamethylenediisocyanate or

https://doi.org/10.1016/j.ijbiomac.2019.07.162
0141-8130/© 2019 Elsevier B.V. All rights reserved.
154 A.M. Abu El-Soad et al. / International Journal of Biological Macromolecules 139 (2019) 153–160
glutaraldehyde [34,35]. Sulfated chitosan is a water-soluble anionic chi-
tosan derivative [36].
In the current work, chitosan is sulfated –after crosslinking with glu-
taraldehyde. The sorption properties of the crosslinked sulfated chito-
san (SGCH) have been tested by using the batch method to achieve
equilibrium parameters.
2. Experimental
2.1. Materials
Chitosan (80.5%) and beryllium sulfate were obtained from Fluka.
Glutaraldehyde (G) and chlorosulfonic acid were purchased from
Himedia (Mumbai, India). Chrome azurol S and N, N-
dimethylformamide (DMF) were Sigma-Aldrich product. All the solu-
tions used in this work were prepared by demineralized water.
2.2. Synthesis of cross-linked sulfated chitosan
Sulfated cross-linked chitosan (SGCH) has been synthesized through
two steps. The first step was performed, in order to prohibit the solubility
of chitosan, through crosslinking of chitosan by using glutaraldehyde. The
Fig. 1. Synthetic route (a) FT-IR spectra (b) EDX analysis (c) and SEM image (d) of SGCH.
second step was performed by using chlorosulfonic acid as a sulfating
agent.
In brief, Chitosan solution was prepared by dissolving 3 g chitosan in
100 mL acetic acid (3.5 M). After that, 2 ml G solution was added, the mix-
ture was agitated under gentle heating until the gelatinous product (chi-
tosan/glutaraldehyde) was obtained. The obtained product was washed
several times with 70% ethanol followed by demineralized water [37].
Sulfated cross-linked chitosan (SGCH) was obtained by dropwise ad-
dition of 4.5 mL chlorosulfonic acid with stirring to 30 mL DMF previ-
ously cooled at 4 °C. The reaction mixture was stirred without cooling
until the solution reached 25 °C. After that, the cross-linked chitosan
that has been obtained in the previous step (GCH) (2.0 g) was added
to 30 ml DMF and stirred for 12 h at room temperature. The excess of
solvent was eliminated by filtration to give a solvated (GCH). The sol-
vated (GCH) was added to the sulfating complex and the reaction was
run at 20 °C for 4.5 h with stirring. Finally, the obtained sorbent was pre-
cipitated with methanol in an ice bath. The final product was obtained
by centrifugation then washed several times with methyl alcohol and fi-
nally was air dried. The Scanning Electronic Microscope (SEM/EDX, XL
30 ESEM) was used to confirm the surface features of the (SGCH).
Fourier-transform infrared spectroscopy spectra were recorded in KBr
pellets using Perkin -Elmer FT-IR-1600.
 A.M. Abu El-Soad et al. / International Journal of Biological Macromolecules 139 (2019) 153–160
2.3. Sorption experiments
Sorption experiments were achieved by contact of a dry mass of
(SGCH) sorbent (20 mg) with a fixed volume (50 ml) of aqueous beryl-
lium sulfate solution that has a concentration (100 ppm) with a variation
of pH values (2–5) in a conical flask. The flasks were agitated for 120 min.
(rotation speed, v = 500 rpm) at 25 °C. After equilibration and phase sep-
aration, the residual beryllium concentration in the aqueous phase (Ceq,
ppm) was determined by using LABOMED, INC double beam spectropho-
tometer (USA) [38]. The capacity of the sorbent was determined by using
the mass balance equation (Qeq = ((Co − Ceq) V/m), while Co, Ceq are the
initial and equilibrium concentration of beryllium ions in the solution
(ppm), (V) is the volume of the solution (L) and (m) is the weight of
the sorbent (g). Uptake kinetics was achieved by mixing 20 mg of the sor-
bent with 50 ml of beryllium sulfate solution (120 ppm) at room temper-
ature and agitation period (i.e., 10–100 min.). Isotherm studies were
achieved by mixing 20 mg of the sorbent with 50 ml of beryllium sulfate
solution with varying temperature and initial concentrations
(i.e., 30–120 ppm) and agitation period was fixed at 100 min.
3. Results and discussion
3.1. Characterization of the sorbent
Cross-linked sulfated chitosan was prepared and characterized using
FT-IR, EDX and SEM (Fig. 1). The FT-IR spectrum of chitosan shows a
broad band of medium intensity at 3379 cm−1 attributed to the O\\H
stretching and N\\H stretching vibration of primary amine. The weak
to medium intensity bands, that appear at 2966 cm−1, 2810 cm−1, are
attributed to asymmetric and symmetric stretching of CH2 group of pri-
mary alcohol while the peak at 1484 cm−1 represents scissor vibration
of CH2 group. N\\H deformation vibration of primary amines appears
near 1600 cm−1, while the weak band at 1026 cm−1 refers to C\\N
stretching absorption of primary amines. The broad band of weak inten-
sity at 628 cm−1 may be due to absorption of primary amines [39].
The FT-IR spectrum of the chitosan/glutaraldehyde shows the signals
from chitosan with some additional bands that prove the crosslinking of
the polymer. In particular, the signal at 1647 cm−1 that indicates the pres-
ence of conjugated imine group and the signal at 1020 cm−1 that is attrib-
uted to glycosidic linkage (\\C\\O\\C\\) in the chitosan ring.
The successful synthesis of SGCH was proved by the presence of the
peaks at 2777, 2432 cm−1 related to O\\H stretching of sulphinic acids
\\SO\\OH. Moreover, the asymmetric and symmetric stretching vibra-
tions of SO2 group are noticed in the two bands that appear at 1176,
1463 cm−1. In the fingerprint region, the sharp peak that appears at
597 cm−1 is due to the scissor vibration of the\\SO2 group and the sig-
nals at 859 and 721 cm−1 are attributed to the asymmetric and sym-
metric S\\O\\C stretching vibration. Finally, the band at 1019 cm−1 is
attributed to S_O stretching in case of aryl sulphinic acids. In should
be noted that the reduced intensity and the shifts of the bands to a
lower or higher wavenumber, when compared cross-linked chitosan/
cross-linked sulfated chitosan also reflect the successful preparation of
SGCH. Fig. 1(c) shows EDX of SGCH, the presence of a large peak of Sul-
phur and oxygen indicates the high content of these elements and indi-
cates the successful synthesis of SGCH. Fig. 1(d) shows the morphology
of small particles in the range of (4.64–11.7) μm. The combination of
SEM and EDX analysis provided a comprehensive elemental and mor-
phological evaluation of the sample.
3.2. Sorption experiments
3.2.1. Effect of pH
pH affects strongly on the charge of beryllium ions in the aqueous
media and hence affects the adsorption process, so batch experi-
ments have been done. Many studies have been done to explain
the hydrolysis and aggregation of beryllium ions, it was found that
155
beryllium ions readily hydrolyze in solution and form condensed
species containing more than one beryllium atom. It appears that
as the concentration of beryllium increases and the acidity de-
creases, these condensation products increase in size to become col-
loidal and finally to precipitate. At pH below 3, beryllium is present
as [Be (H2O) 4]2+, while at pH above 3, there is appreciable hydroly-
sis, which decreases the average charge per beryllium atom. It is still
debated in the literature on the presence of Be3(OH)3+3 and Be2(OH)
3+
in acid solutions and Be (OH)3− and Be (OH)2− 4 in strongly basic
solutions. Fig. 2 shows the maximum sorption of beryllium at pH 4
where the suggested mechanism is cation exchange according to
Eqs. (1) and (2).
2ðR−SO3HÞðresinÞ þ Be2þ ðaqÞ →ðR−SO3Þ2 BeðresinÞ þ 2Hþ
ðaqÞ ð1Þ
 3þ  3þ
3R−SO3HðresinÞ þ Be3 ðOH Þ3 ðaqÞ →3ðR−SO3− Þ Be3 ðOH Þ3 ðresinÞ
þ 3Hþ
ðaqÞ ð2Þ
3.2.2. Effect of stirring time
Stirring time affects the distribution of sorbate between sorbent and
solution. The influence of stirring time on sorption process at various
temperatures was studied between 5- and 100-min. Fig. 3(a) shows
the obtained results. A rapid initial sorption within a contact time of
40 min was observed. According to these results, stirring time for
100 min was chosen to be sufficient for the equilibrium investigation
of Be (II) sorption onto modified chitosan.
3.2.3. Dynamic modeling
To investigate the adsorption mechanism, experimental data are
tested by using different kinetic models. Lagergren suggested the fol-
lowing equation to describe the pseudo-first-order model.
 
log qeq −qt ¼ logQ 1 −
k1
t ð3Þ
2:303
where qeq and qt (mg/g) are the amount of beryllium ions adsorbed on
the adsorbent at equilibrium (eq) and at the time (t) (min.) respec-
tively. k1, (min.−1) is the rate constants of the pseudo-first-order
model. Q1 symbolizes the maximum calculated uptake of pseudo-first
order model at equilibrium. Fig. 3(b) shows the linear plot of (log qe-
qt) vs. t where Q1 and k1 were determined and reported in Table 1
[40,41].
Ho and Mckay suggested the following equation to represent the
pseudo- second order model.
t 1 1
¼ þ t ð4Þ
qt k2 Q 22 Q 2
45
30
qe (mg/g)
15
0
0 2 4 6
pH
Fig. 2. pH effect on beryllium ion adsorption process.
156 A.M. Abu El-Soad et al. / International Journal of Biological Macromolecules 139 (2019) 153–160

Fig. 3. Kinetic models for Be sorption. Effect of time on sorption (a), pseudo first order model (b), pseudo second order model (c), Intra-particle diffusion model (d), liquid film diffusion
model (e) and Bangham kinetic model (f).

where k2 (pseudo-second-order rate constant, g/(mg·min)), qt (mg/g) compared with that calculated (Q1) were found not to fit the pseudo-
indicates the amount of beryllium ion adsorbed at the time (t). Q2 is first order mode as given in Table 1. The biosorption interaction may
the maximum calculated uptake of the pseudo-second-order model at occur through a multi-step mechanism encompassing (external film
equilibrium. Fig. 3(c) shows the linear plot of (t/qt) vs. t where Q2 and or intraparticle diffusion and chemical or physical interaction of Be by
k2 were determined and reported in Table 1. The legality of each the adsorbent). To limit the rate-determining step, (qt/t) data was
model was checked by the consistency between experimental and cal- checked according to the Fickian diffusion low
culated adsorption values (qe and Q2 respectively) as well as the fitness
of the straight line (R2). The data was found to fit the pseudo-second- qt ¼ x þ kin t 0:5 ð5Þ
order model as shown in Fig. 3(c) and Table 1. Meantime the values of
(qe) obtained from the experimental adsorption process when where Kin refers to the boundary layer diffusion effects and qt (mg/g) is
the amounts of beryllium ion adsorbed at the time (t). The initial rate of
Table 1 the intraparticle diffusion [kin] (mg/(g min0.5)) was obtained from the
Kinetic data for the biosorption of Be (II) ions by SGCH. slope value Fig. 3(d) [42]. The effect of boundary layer diffusion reduces,
Kinetic model Model parameters pH 4 as the value of x reduces. The plot of qt vs. t 0.5 gives a straight line with
small values of an intercept, this means that the adsorption reaction is
Pseudo first order Q1 62.18
k1 0.079
limited by mixed effects (intraparticle diffusion and boundary layer dif-
R2 0.874 fusion). The obtained data were also tested by Bangham model [43],
Pseudo-second order Q2 49.75 which suggested the following equation:
k2 0.000993
R2 0.974    
Ci mKB
Weber-Morris diffusion model Kin 0.543 loglog ¼ log þ Blogt ð6Þ
I 0.11468 Ci −mqt 2:303 V
R2 0.8875
Bangham kinetic model KB 2.067778 where m is the weight of the resin per liter of solution (g/l), B and kB are
α 0.5259 Bangham constants. The linear plot was obtained by plotting Log log [ci/
R2 0.9366
(ci-mqt)] vs. log t as shown in Fig. 3(f). The values of Bangham constants
 A.M. Abu El-Soad et al. / International Journal of Biological Macromolecules 139 (2019) 153–160 157

(B and kB) were obtained from the slopes and intercepts of Bangham Table 2
plots (Table 1). The plot gives a straight line, with R2 equal 0.9366. Comparison of the sorption capacities of different sorbents for Be (II) ions.

The data obtained for R2 and the straight line obtained, confirming Chelating resins Active sites qe, (mg/g) Reference
that the rate determining step is limited by the pore diffusion. Modified polystyrene OH 16.00 [44]
Aerobic granule PO2−
3 , COONa, NH and NH2 14.00 [45]
3.2.4. Sorption isotherms and thermodynamic studies Amb-IR-120 SO3H 4.60 [46]
The sorption isotherms are shown in Fig. 4. The uptake values de- Modified silica OH 0.20 [47]
Modified Chitosan/silica OH and NH2 5.00 [48]
crease with temperature from 298 to 333 K. The used adsorbent gives
Carboxymethyl chitosan COONa, NH and NH2 44.96 [5]
uptake equal 40.6 mg/g at pH 4; this value was compared with those ob- Sulfated chitosan SO3H, OH, NH 40.6 This work
tained by others as shown in Table 2.
The experimental sorption data obtained were checked using differ-
ent isotherm models (Langmuir, Freundlich, Dubinin-Radushkevich, pH 4:
and Temkin).
Langmuir idealized the following equation: kl ci
θ¼ ð9Þ
1 þ k l ci
Ceq Ceq 1
¼ þ ð7Þ
qeq Q L KL Q L Freundlich Adsorption Isotherm characterized the adsorption pro-
cesses for the heterogeneous surface [51]. Freundlich proposed the fol-
where QL is the monolayer capacity (mg/g) and KL is the binding con- lowing empirical equation to describe the model.
stant. Fig. 4(b) shows the plot of ceq/qeq vs. ceq. Langmuir variables (KL
1
and QL at various temperatures) were obtained from the values of the logqeq ¼ logK f þ log Ceq ð10Þ
n
slope and intercept showed in Table 3. It should be noted that increasing
the temperature generates a decrease of both QL and KL values. where Kf and n are Freundlich constant and adsorption intensity con-
On the other hand, the value of the dimensionless constant (RL) is stant respectively. Fig. 5(b) shows the relation between log qe vs. log
correlated to the values of initial metal ion concentration and the values ceq at pH 4. The value of 1/n is below one which indicates that the sorp-
of Langmuir constant [49]. RL values were calculated at different beryl- tion process under operating conditions is not limited by Freundlich Ad-
lium ion concentrations using (Eq. (8)) [50]. sorption Isotherm [52]. The values of the monolayer capacity of
Langmuir model were more appropriate than that of the Freundlich
1
RL ¼ ð8Þ model. This indicates that the sorption process is stripped by the Lang-
1 þ KL Ci muir equation.
Temkin Isotherm (Eq. (11)) postulates that the decrease in the heat
Fig. 4(c) shows the value of RL at pH 4 indicating the compatibility of of adsorption is linear with the coverage and the distribution of binding
the sorption processes (convenient (zero b RL b 1); not convenient (RL energies is the main characteristic of adsorption process [53].
N 1); linear (unity); irreversible (zero)). The sorption of beryllium
under the operating conditions was found to be convenient according qeq ¼ BT ln Ceq þ BT ln AT ð11Þ
to the computed values of RL in Table 3. The surface coverage (θ) can
be computed using the Eq. (9), Fig. 4(d) shows the plot of (θ) vs. Ci at where AT is the Temkin binding constant correlated and BT is a constant

Fig. 4. Effect of temperature (a), Langmuir model (b), dimensionless constant (c), and the surface coverage of beryllium adsorption on SGCH (d).
158 A.M. Abu El-Soad et al. / International Journal of Biological Macromolecules 139 (2019) 153–160

Table 3 gas constant (R = 8.314 J./mol.K) and Ɛ is the Polanyi potential (Ɛ =

The isotherm parameters for the sorption process of Be (II) ions on SGCH at pH 4. RT ln [1 + (1/Ceq)]). The values of KDR and ln QDR can be computed
Kinetic model Parameters 289 K 313 K 323 K 333 K from the slope and intercept by plotting of ln qeq vs. Ɛ2 (Fig. 5(d)). The
Langmuir QL 43.1 70.9 91.7 278
constant K gives an indication about the mean free energy (E) of adsorp-
KL 43.3 26.1 19.2 6.01 tion per mole of the adsorbate when it is transferred from infinity in the
R2 0.9422 0.8557 0.999 0.1791 solution to the surface of the solid and can be computed by using this re-
Freundlich KF 0.107 0.171 0.203 0.225 lationship (Eq. (13)):
n 0.800 0.918 0.979 1.042
R2 0.970 0.9734 0.972 0.9842
1
Dubinin-Radushkevich QD 37.3 38.0 41.7 28.0 E¼ ð13Þ
KDR 2.00 × 5.00 × 2.00 × 4.00 × ð2Kad Þ0:5
10−7 10−7 10−7 10−7
E 1.58 1.0 1.58 1.12
The value of E is used to clarify the type of sorption process. The ob-
R2 0.885 0.9924 0.9547 0.9582
Temkin BT 24.0 17.1 14.4 12.1
tained data of E was found to be b8 kJ/mol, so the process is limited by
AT 0.043 0.048 0.050 0.050 physical sorption.
bT 103.3 152.2 185.7 227.9 Van't Hoff equation (Eq. (14)) provides a first approximation for the
R2 0.9365 0.9647 0.9439 0.9374 estimation of enthalpy (ΔH°) and entropy (ΔS°) change assuming that
the heat capacity change for the process is nearly negligible. This pro-
vides Eq. (14).
defines the heterogeneity of the adsorbent surface. The value of BT is
correlated to Temkin isotherm constant (bT) (BT = RT/bT). Through −ΔH ° ΔS °
ln KL ¼ þ ð14Þ
the value of AT, this isotherm being used for verifying the affinity of RT R
the sulfated cross-linked chitosan for beryllium ions. The plot of qeq vs.
ln Ceq is presented in Fig. 5(c) and Temkin variables were listed in We observed a linear plot of ln Kl vs. (1/T), as reported in Fig. 5
Table 3. The computed value of AT suggests the physical binding be- (a) and the computed values of ΔH°, ΔS° were listed in Table 4. It should
tween the beryllium ions and sulfated cross-linked chitosan active be noted that the correlation of Kl to temperature through the classical
sites (physisorption mechanism). van't Hoff equation might be inappropriate because of the presence of
Dubinin-Radushkevich (DR) isotherm model assumes a non- supramolecular interactions, and therefore because of the large varia-
homogenous distribution of adsorption sites. It proposes that the first tions of the stoichiometric ratios with temperature [55,56].
step takes place by binding of the ionic species with the most energeti- The computed value of ΔH° (−43 kJ/mol) indicates the exothermic
cally favorable sites and followed by multilayer adsorption [54]. The lin- nature of the sorption process in agreement with electrostatic interac-
ear of DR model is reported by the following equation: tions. The positive value of ΔS° (0.111 kJ/mol K−1) indicates that the ad-
sorption process is driven by both entropic and enthalpic factors.
ln qeq ¼ ln Q DR −KDR ε2 ð12Þ
3.3. Desorption of beryllium ions from the loaded sorbent
where KDR expresses the mean free energy of sorption per mole of ad-
sorbate, QDR refers to the DR theoretical saturation capacity (mg/g). Beryllium ions were loaded on the synthesized SGCH by contacting
The DR constant (Ɛ) is proportional to temperature (Kelvin), universal 0.2 g of SGCH with 500 ml of beryllium sulfate solution that has pH

Fig. 5. Van't Hoff (a), Freundlich (b), Temkin (c) and Dubinin-Radushkevich (d) plots of the adsorption process.
 A.M. Abu El-Soad et al. / International Journal of Biological Macromolecules 139 (2019) 153–160
Table 4
Thermodynamic parameters for the biosorption of Be (II) ions at pH = 4 and different
temperatures.
Temp. (K) Thermodynamic parameters
ΔH° (kJ/mol) ΔS° (kJ/mol.K) TΔS° (kJ/mol) ΔG° (kJ/mol)
298 33.1 −76.1
313 34.8 −77.7
323 35.9 −78.8
333 −42.9 0.111 37.0 −80.0
(4) with initial concentration (120 ppm) for 100 min at 25 °C. After that,
the desorption process was conducted using 0.02 g of the loaded SGCH
with different molar concentrations of hydrochloric acid, nitric acid, sul-
furic acid, sodium chloride, urea solution and urea solution acidified
with sulfuric acid. It was found that the maximum desorption of beryl-
lium ions from the loaded SGCH was done using 1.5 M urea acidified by
0.6 M H2SO4, desorbed about 65% of beryllium ions within 30 min.
4. Conclusions
Sulfated cross-linked chitosan has been synthesized, characterized
and used for adsorption of Beryllium ions from their acidic aqueous so-
lutions. The amount of the loaded beryllium ions on the investigated
SGCH biosorbent was 40.6 mg/g at pH 4. The results showed the spon-
taneous nature of the sorption process. In particular both enthalpy
and entropy favor the adsorption process. The kinetic studies showed
a pseudo-second-order and the intraparticle diffusion-controlled ad-
sorption process. The desorption of Beryllium ions from the loaded
SGCH was achieved using 1.5 M urea acidified by 0.6 M H2SO4. The ob-
tained results evidenced the possibility to use the modified chitosan for
controlled adsorption of beryllium ions and their triggered release. In
future works the selectivity toward different metal ions can be consid-
ered for application in water remediation as well as for the development
of separation/analytical methods with a green biopolymer platform.
Declaration of Competing Interest
The authors declare that there is no conflict of interest.
Acknowledgements
A.A. M thanks the head of project for beryllium extraction in nuclear
materials authority and the authors thank the Department of Chemistry
in Cairo University in Egypt for their help in making analysis.
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