See

discussions, stats, and author profiles for this publication at: https://www.researchgate.net/publication/244294934

Immobilization of ethylenesulfide on silica

surface through solgel process and some
thermodynamic data of...

Article in Polyhedron April 2001

DOI: 10.1016/S0277-5387(01)00743-4

CITATIONS READS

37 38

2 authors:

Claudio Airoldi Luiza N H Arakaki

University of Campinas Universidade Federal da Paraba
490 PUBLICATIONS 9,315 CITATIONS 60 PUBLICATIONS 1,241 CITATIONS

SEE PROFILE SEE PROFILE

All content following this page was uploaded by Claudio Airoldi on 05 January 2015.

The user has requested enhancement of the downloaded file. All in-text references underlined in blue are added to the original document
and are linked to publications on ResearchGate, letting you access and read them immediately.
 Polyhedron 20 (2001) 929 936
www.elsevier.nl/locate/poly

Immobilization of ethylenesulfide on silica surface through sol gel

process and some thermodynamic data of divalent cation
interactions
Claudio Airoldi *, Luiza N.H. Arakaki
Instituto de Qumica, Uni6ersidade Estadual de Campinas, Caixa Postal 6154, 13083 -970 Campinas, Sao Paulo, Brazil

Received 27 May 2000; accepted 15 January 2001

Abstract

The silylant precursor agent 3-aminopropyltrimethoxysilane (APTS) reacted with ethylenesulfide to yield 2-{2-{3-(trimethoxysi-
lyl)propylamino}ethylthio}-ethanethiol, which was anchored on silica gel by using the sol gel process. The new synthetic silylant
agent displayed a chelating moiety containing one nitrogen and two sulfur basic centers, which are potentially favored for
adsorbing divalent cations from aqueous solution. Thus, the similar chemisorption isotherms for all cations were obtained by
batchwise method and the data were adjusted to a modified Langmuir equation to give the sequence of the maximum retention
capacity as Cu \Co\Ni. The same adsorption was followed by calorimetric titration and the enthalpic values of 7.4090.01,
1.5090.10 and 0.9890.02 kJ mol 1 for copper, nickel and cobalt respectively, were obtained. From the calculated Gibbs
free energy 25.8 90.1, 35.190.1 and 30.890.1 kJ mol 1, the variation in entropy were also obtained as 62 9 1, 4291
and 100 9 1 J K 1 mol 1 for the same above sequence. All thermodynamic values are in agreement with the spontaneity of the
proposed cation-basic center interactions for these chelating processes. 2001 Elsevier Science Ltd. All rights reserved.

Keywords: Immobilization; Ethylenesulfide; Solgel process; Calorimetric titration; Thermodynamic data

1. Introduction However, the conventional immobilization methods

A variety of chelating organic molecules covalently
attached on silica gel surface have been recently ex-
plored not only due to the fact that the support formed
is inexpensive, but also the inertness against most chem-
ical solvents, even at high temperature [1], and also the
surface properties are already well investigated [2,3].
The most commonly attached chelate ability for this
purpose is devoted for donor atoms, such as oxygen,
nitrogen and sulfur, which have large capability in
forming complexes with a series of metal ions, forcing,
in some cases, a distinguishable selective extraction
property [48].
The immobilization procedure using pure activated
silica gel can be useful at relatively high temperature,
being applied for several hours at more than 373 K.
* Corresponding author. Tel.: + 55-19-37883023; fax: +55-19-
37883055.
E-mail address: airoldi@iqm.unicamp.br (C. Airoldi).
that reach some desired applications normally explore
convenient chemical modification of the immobilized
molecule, which can derive a more complex backbone,
such as protein [9].
Apart from the design of a given molecule on the
surface through the anchoring procedure, the sol gel
method of immobilization characterizes by physical en-
trapment, without chemical modification. Following
such experimental approach a protein can be encapsu-
lated in a silica matrix, in which the final molecule
preserves the structure and its functionality, to give to
the protein a degree of protection against microorgan-
ism attack [9].
The great advantage of the sol gel technique for the
immobilizing molecule is the fact that the reactions can
be carried out at room temperature enabling the intro-
duction of organic molecules into an organic matrix
without deteriorating their functionalities [10].
Modified silica gel with chelating reagents were re-
ported to be good adsorbents for metal ions from

0277-5387/01/$ - see front matter 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 2 7 7 - 5 3 8 7 ( 0 1 ) 0 0 7 4 3 - 4
930 C. Airoldi, L.N.H. Arakaki / Polyhedron 20 (2001) 929936
solvent [11,12] and seawater [13], beside this, these
materials exhibit wide applicability in many areas such
as high-performance liquid chromatography [8,14],
catalysis of enzymatic reactions [15,16], and also for
rubber reinforcement [17]. Novel properties have been
obtained by the combination of organic and inorganic
elements, especially when are mixed at a molecular
level. For example, the mechanical strength of organic
polymers can be improved by incorporation of inor-
ganic segments [10]. High transparency is another im-
portant property of the polymer hybrids and is an
indispensable factor for development of optical waveg-
uides [10], optical biosensors [18,19], potentiometric
sensor [20], non-linear optical materials [10] and other
applications such as contact lenses [10].
The present investigation reports the immobilization
of ethylenesulfide on silica gel surface using solgel
process. In this coating a low-temperature process is
required and the organosilicate matrix is usually
formed, which comprises the hydrolysis of tetra-
ethoxysilane (TEOS) and immediately condensation of
the free silanol groups is formed. The silylant agent
produces a colloidal suspension of the sol, which causes
a gelation due to the polycondensation of the sol. As
the interconnection between these particles increases,
the viscosity of the sol starts to increase and leads to
the formation of a solid gel [12,18,21,22].
Immobilization of sylilant agent by sol gel process
seems very promissing specially due to the mild condi-
tions that are used, as well as the simplicity of the
procedure involved and the most important is that
provides a high concentration of funcional groups,
which moreover, are linked to the matrix via carbon
silicon bonds that are stable towards hydrolysis [12,21].
On the other hand, the sol gel method provides an
elegant way to obtain solid-state materials with variety
of organofunctional molecules [21]
One nitrogen and two sulphur basic centers of each
pendant chain of the new silylant agent were explored
in extracting divalent cobalt, nickel and copper from
aqueous solution, and this property is applied to obtain
the thermodynamic of cation basic centre interactions
by using calorimetric titrations.
2. Experimental
2.1. Chemicals
Ethyleneamine, ets, (Aldrich) was distilled before use.
Tetraethoxysilane, TEOS, (Aldrich) and 3-
(trimethoxysilyl)propylamine, APTS, (Aldrich) were
used without previous purification. Hydrated divalent
copper (Carlo Erba), nickel (Carlo Erba) and cobalt
(Vetec) nitrates were also used without purification and
the concentration was determined through complexo-
metric titration with standard EDTA solution. All
other chemicals have a reagent grade.
2.2. Synthese of 2 -{2 -{3 -(trimethoxysilyl)propylamino} -
ethylthio}ethanethiol (NSSH)
This new silylant agent was synthesized in anhydrous
condition by mixing 20.0 cm3 (57.28 mmol) of the
precursor 3-(trimethoxysilyl)propylamine (APTS) with
7.0 cm3 (114.56 mmol) of ethylenesulfide, maintained in
a slightly refluxed in sand bath at 373 K in a sealed
tube for 24 h to give the final product of reaction
NSSH.
2.3. Immobilization of silylant agent NSSH onto silica
gel
The synthesized silylant agent NSSH was anchored
on silica surface by hydrolysis of alkoxydes by using
ammonium hydroxide 8.0 10 2 mol dm 3 solution,
as catalyst [21]. In a typical immobilization, 24.0 cm3 of
TEOS and 17.0 cm3 of NSSH were mixed at room
temperature (r.t.). To this solution ethanol and water in
a 2:1 molar ratio were added. Finally, an amount of 3.0
cm3 of basic catalyst was added dropwise to the re-
sulted solution under stirring at 333 K. After 0.5 h the
gel was formed, which was aged for 48 h at 323 K, and
was maintained for another 48 h at r.t. The white solid
was filtered, washed with water, ethanol and dried in
vacuo at r.t. for another 8 h.
2.4. Physical measurements
The functionalized silica were characterized by the
determination of surface area through BET method [23]
by using Flowsorb II 2300 Micrometrics apparatus.
Mass loss determination were performed on DuPont
thermogravimetric instrument, model 951, using 515
mg of sample under argon atmosphere, with a pro-
grammed heating rate of 0.17 K s 1. Infrared spectra
of all compouds were obtained in a FTIR spectropho-
tometer MB-Bomem, using KBr pellets in 4000400
cm 1 region, with a resolution of 4 cm 1. The com-
pounds have the elements analyzed through a Perkin
Elmer 2400 Series II microelemental analyser
instrument. 13C and 29Si nuclear magnetic resonance
spectra for solid samples were obtained on an AC/300P
Bruker spctrometer with cross polarization and magic
angle spinning at a frequency of 75.47 MHz with
acquisition time of 0.311 s, pulse repetition time of 4 s,
contact times 1 ms and the number of scans were 20480
for 13C, and 59.62 MHz with acquisition time 0.110 s
pulse repetition time at 4 s contact time 1 ms and the
number of scans were 1303 for 29Si.
 C. Airoldi, L.N.H. Arakaki / Polyhedron 20 (2001) 929936 931

2.5. Calorimetry 3. Results and discussion

The thermal effect evolved from the interaction of The current method to anchor a silylant agent on
the cations with pendant groups attached to the suport silica gel surface consists of exploring the ability of the
in the solidliquid interface was followed by an LKB-
2277, heat-flow microcalorimeter [24,25]. Samples of
functionalized silica, varying from 15.0 to 50.0 mg were
suspended in 2.0 cm3 of water and vigorously stirred at
298.159 0.02 K. After equilibrium, the thermostated
solutions of the cation varying in the range of 3.0
10 3 to 0.10 mol dm 3 were added into the calorimet-
ric vessel through a microserynge. For each increment
of solution a correspondent thermal effect of the titra-
tion (DtitH) was recorded until saturation was reached,
indicating a constant thermal effect. Thus, in the same
experimental conditions, dilution of the cation solution
were done in the absence of the support (DdilH). A null
thermal effect was observed when water was added to
the calorimetric vessel containing the suspension of the
modified support. By combining those effects, the re-
sulting integral thermal effect of adsorption (DrH) can
be determined through the expression: DrH =DtitH
DdilH. The change in enthalpy associated to cationma-
trix interaction can be determined by adjusting the
adsorption data to a modified Langmuir equation
[24,25].
2.6. Isotherms of adsorption
The isotherms of adsorption were obtained by using
the batchwise method, which consisted in suspending
50.0 mg of modified silica in 20.0 cm3 of an aqueous
solution of cations at several concentrations, varying
from 1.010 3 to 3.5 10 2 mol dm 3 and was
mechanically stirred at 2989 1 K. Based on the time
required to reach equilibrium, which was previously
established as 12 h for all experiments, 15 h was chosen
to ensure maximum adsorption. After this time, the
solid was separated by centrifugation and dried at 313
K. Samples of the supernatant containing the remain-
ing amount of the metal were determined by the con-
ventional EDTA complexometric titration, using the
appropriate indicator [26] for each metal. The adsorp-
tion capacity (mmol g 1) was calculated by following
the expression nf = (ni ns)m, where nf is the number of
moles adsorbed on the silica surface, ni and ns are the
number of moles of the initial solution and of the
supernatant after the equilibrium, and m the mass of
modified silica. The adsorption procedure was repeated
with untreated silica gel for each cation solution with-
out any adsorption being detected [27 29].
available alkoxide group attached to the agent interact-
ing with the free silanol group on a silica surface,
establishing a covalent bond between the inorganic
backbone and the pendant organic chain. These synthe-
sized materials have advantages over organic resins due
to the fact that they have good thermal and hydrolytic
stability and do not swell in organic solvents [28].
A direct reaction of the synthesized silylant agent
with activated silica gel in non-aqueous solvent yields
the immobilized compound. When the objective is to
expand the organic chain, in order to include a series of
desirable functions, two main routes are followed: (i)
heterogeneous the previous anchored silica gel re-
acts to another molecule or (ii) homogeneous the
silylant agent is firstly prepared before immobilizing
[27,28]. However, in situ immobilization through a
hydrolysis process an inorganic backbone can be
formed, by using an alkoxysilane compound, which
causes a considerable increase in the anchored pendant
groups, due to the solgel process.
In attempting to increase in size the precursor silylant
molecule in homogeneous condition, the reaction of the
agent APTS with cyclic three member molecule con-
taining sulfur, ethylenesulfide (etn) was performed. The
final obtained product conducted to the new agent
2 - {2 - [trimethoxysilyl)propylamino]ethylthio} - ethane-
thiol (NSSH), as is illustrated by the reaction:
The elemental analysis for NSSH compound gave
39.10; 8.06; 5.08 and 21.10% for carbon, hydrogen,
nitrogen and sulfur, respectively. For this synthesized
compound the values 40.10; 8.36; 4.68 and 21.30% were
calculated for the same sequence of elements. As ob-
served, these series of values are in good agreement
with the synthesized compound. The success of this
synthetic procedure can be proven by considering the
proximity of the calculated and expected values for C/S
ratio, which gave 3.5 and 3.4, respectively.
The infrared spectrum showed the appearance of a
new weak band at 2553 cm 1 that is assigned to SH
stretching frequency. Two medium bands at 3376 and
3299 cm 1 belong to the precursor silylant agent
APTS, that were attributed to NH2 stretching vibra-
tional modes of the primary amine. However, these
bands disappeared after reacting to give a large one
located at 3303 cm 1, which was attributed to NH
streching vibrational mode of the secondary amine.
Furthermore, this compound presented two well
932 C. Airoldi, L.N.H. Arakaki / Polyhedron 20 (2001) 929936
defined bands at 2937 and 2839 cm 1 assigned to CH
stretching vibrations [27,28].
This new silylant agent NSSH reacted with TEOS
and the copolymerization occurred due to the silica
backbone formation, caused by the basic catalyst. The
new material combines the stability of the inorganic
matrix, which is associated with the chemical proprierty
of the organic molecule [12,21,30], as represented by the
reaction:
The elemental analysis of this new organofunctional-
ized material SilNSSH, showed for carbon, nitrogen
and sulfur: 24.32% (20.47 mmol), 3.50% (2.50 mmol)
and 19.11% (5.97 mmol), respectively. The relative
number of moles of these elements immobilized per
each gram of silica is 2.50 mmol, this value was calcu-
lated from elemental analysis results and is in agree-
ment with the expected above composition indicated in
the reaction. These values clearly show that the solgel
process is a very good synthetic route when a high
degree of functionalization is desired [21]. This degree
of immobilization contrasts to the previous value of
0.90 mmol obtained by using a classical procedure [31].
The infrared spectrum of Sil NSSH showed the
same sequence of frequencies observed for the free
silylant agent, NSSH, evidencing that the sol gel syn-
thetic process does not cause any damage to the organic
chain, as expected for this stable organic moiety
[9,10,21].
Fig. 1. 13C CP/MAS NMR spectra of silica Sil NSSH synthesized
through basic catalysis.
Carbon NMR spectrum of the anchored surface gave
a series of peaks as shown in Fig. 1. A large expected
peak around 55 and 52 ppm, could be attributed, in
principle, to the presence of ethoxy groups. This possi-
bility was negleted due to the fact that the reaction was
done in aqueous medium so all ethoxy groups should
be hydrolyzed. The main reason to confirm such an
assumption is owing to 29Si NMR spectroscopy. This
spectrum presented an intense peak at 67.3 ppm,
that is attributed to silicon atoms bonded to three
siloxane groups and one pendant organic chain [21,28].
Therefore, the large peak in 13C NMR spectrum could
be attributed to carbons 3 and 4, whose proposed
structure and the number of each carbons are indicated
on top of left hand side of Fig. 1. Then, the series of
peaks were attributed as: at 33.1 ppm to carbons 6 and
5, at 23.8 ppm to carbons 2 and 7 and at 11.3 ppm to
carbon 1 [2831].
As mentioned, 29Si CP/MAS NMR spectrum pre-
sented a peak at 67.3 ppm followed by another two
peaks as shown in Fig. 2. The peak at 109.9 ppm can
be attributed to the presence of silicon atoms bonded to
four siloxane groups, as represented by Si(OSi)4. The
other one at 101.5 ppm indicated the existance of an
isolated silanol group, where the silicon atom is bonded
to a silanol group and three other siloxane groups, such
as represented by (OH)Si(OSi)3 [12,21,3234].
The determination of the specific surface area [23],
SBET, based on the adsorption of gaseous nitrogen at
several pressures at 77 K, gave to SilNSSH the value
of 8296 m2 g 1. This lower surface area is due to the
presence of pendant groups which block the access of
molecules of gaseous nitrogen into the structure of the
anchored silica [23,2729].
The thermogravimetric curve of the immobilized Sil
NSSH compound, showed a total mass loss of 51%,
without any definition of steps, which could be corre-
spondent to the decomposition of the organic groups
[35]. However, the continous decomposition occurred
together with the condensation of remaining silanol
groups to yield the final residue of siloxane.
This organofunctionalized surface can be used for the
adsorption of cations as observed for various anchored
silicas [6,7,2729,36,37]. The adsorption phenomena at
the solid/liquid interface demand a competition be-
tween the solvent (solv) bonded to the anchored surface
(AS), which is gradually displaced by the solute dis-
persed in solution to reach the equilibrium, as outlined
schematically in the reaction:
 C. Airoldi, L.N.H. Arakaki / Polyhedron 20 (2001) 929936 933

29
Fig. 2. Si CP/MAS NMR spectra of Sil NSSH synthesized through basic catalysis.

AS(solv) + M(NO3)2(solv) ? AS.M(NO3)2(solv) +solv The maximum adsorption capacity of modified sur-
face n s, listed in Table 1, showed that the sequence is in
When the adsorption remains constant, a monolayer good agreement with experimental nf values. Copper
is supposed to form and the chemical interaction in- cation showed a large adsorption capacity of 1.46 mmol
volving metallic ion-surface may be followed by apply- g 1, followed by cobalt and nickel with 1.17 and 1.11
ing the modified Langmuir equation that defines the mmol g 1, respectively. Based on these values, the
isotherm as represented by Eq. (1): sequence of adsorption gives the order Cu\ Co \Ni.
Cs Cs 1 The extension of adsorption depends not only on the
= s+ s (1) solubility of the adsorbent, but also on the degree of
nf n nb
the pendant groups anchored on surface. The ratio
were Cs is the concentration of supernatant cations between the amount of ions adsorbed with that of
(mol dm 1) in the equilibrium, nf is defined previously available sites to bond on immobilized silyant agent,
and n s is the maximum amount of solute adsorbed per which were 2.50 mmol of nitrogen or 5.97 mmol of
gram of the silica surface, which depends on the sulfur per gram of silica, gave values for cations in
amount of adsorption sites and b is a constant. From agreement that two pendant groups are used as ligands
angular and linear coeficients of the linearized form of
the adsorption isotherms, n s and b values are obtained Table 1
by plotting Cs/nf versus Cs. Number of moles adsorbed (nf), maximum adsorption coefficient (n s),
volume of hydration (Vhyd) and correlation coefficient (r) for the
In present case, the anchored molecule contains three
interactions of divalent cations (M) with modified surface, SilNSSH,
centers composed by one nitrogen and two sulfur atoms at 298 9 1 K
that are potentially available as chelating basic atoms
to complex cations. The ability of this surface to extract Metal(II) nf (mmol n s (mmol Vhyd (cm3 r
divalent cations such as copper, nickel and cobalt from g1) g1) mol1)
aqueous solutions was evaluated by measuring the
Cu(NO3)2 1.46 90.01 1.66 9 0.01 147.8 0.9983
sorption isotherms [6,7,27,28,36,37]. A summary of the Ni(NO3)2 1.11 9 0.10 1.42 9 0.10 147.8 0.9911
results involving adsorption of these cations on Co(NO3)2 1.17 90.02 1.26 9 0.02 169.6 0.9995
modified surface are presented in Table 1.
934 C. Airoldi, L.N.H. Arakaki / Polyhedron 20 (2001) 929936
Fig. 3. Isotherms of adsorption of divalent metal on anchored silica
gel surface containing ethylenesulfide attached to the nitrogen and
thiol groups for Cu (
), Ni () and Co ( ) in aqueous solution at
2989 1 K.
Fig. 4. The linearized forms of the isotherms of adsorption for Cu
(
), Ni () and Co ( ) in aqueous solution at 298 9 1 K.
Fig. 5. Calorimetric titration of nickel nitrate on modified surface
SilNSSH. The points in the experimental curve are the sum of the
thermal effects S tit h (
), S dil h ( ) and Sres h (). values other thermodynamic data, such as DintG
to establish the stoichiometry for basic center:cations
near to 2:1 proportion for the cations involved.
An important feature related to acidbase interac-
tion in ion-exchange, involving lamellar structure, is
that the process is governed by the degree of hydration
of the hard cations [38]. The present cations have values
of hydration of 169.6 cm3 mol 1 for cobalt and identi-
cal values of 147.8 cm3 mol 1 for nickel and copper
[39]. The sequence did not show any correlation with
this property of these cations. This behavior can be
explained by considering the homogeneity of pendant
groups on surface of silica, where flexible distribution
became easier because of the diffusion of bulky cation
in interacting to available basic centres. The adsorption
isotherm of these divalent cations and the linearized
form of the isotherms are illustrated in Figs. 3 and 4,
respectively.
Thermal effect values for cationbasic center intera-
tions disposed on modified surface, obtained from
calorimetric titrations, were adjusted to the Langmuir
modified equation as represented by Eq. (2):
X X 1
= + (2)
DrH DmonH DmonH(K 1)
where X is sum of mole fraction of the each cation in
solution after adsorption obtained for each experimen-
tal point of the titrand addition by using the modified
Langmuir equation, which was previously shown to be
a good asjustable model for such heterogeneous sys-
tems [24,25,37,38,40], DrH is the integral enthalpy of
adsorption for each point of the calorimetric titration (J
g 1) obtained by dividing the thermal effect resulting
from adsorption by the number of moles of the adsor-
bate. K is a proportionality that also includes the
equilibrium constant and DmonH is the thermal effect of
formation of the metal monolayer on the surface. A
plot of the X/DrH versus X gives the values of DmonH
and K, obtained from angular and linear coefficients of
the linearization of calorimetric isotherms, respectively.
An illustration of the complete calorimetric titration
of the system composed by nickel nitrate and Sil
NSSH showed the effects of dilution, the interactive
process to yield the resultant curve is represented in
Fig. 5. The resulting calorimetric curve obtained for
copper nitrate was adjusted to the above Langmuir
modified equation as shown in Fig. 6. The molar
fraction X of metal each cation in equilibrium was
calculated with the aid of the batch adsorption process
on the supernatant for each experimental point of the
titration [24,36,37]. These values associated with the
calorimetric titration data permit to obtain the enthalpy
of a monolayer formed on surface (DmonH) and simul-
taneously K values as explained above. From these
and DintS were calculated [24,36,37,41] based on the
expressions DintG= RT ln K and DintS= (DintH
DintG)T 1 and the results are listed in Table 2.
 C. Airoldi, L.N.H. Arakaki / Polyhedron 20 (2001) 929936
These thermodynamic data showed that the anchored
silica SilNSSH forms stable complexes with these
divalent cations. The cation basic center interations
with the chelating atoms on pendant groups gave
enthalpic values of 7.40 90.01; 1.50 9 0.10 and
0.989 0.02 kJ mol 1 for copper, nickel and cobalt,
respectively. The obtained enthalpic sequence is Cu\
Ni \ Co and this behavior follows the same order of
the enthallpy of hydration [34,39] of these cations,
which are 2976, 2965 and 2889 kJ mol 1. For all
determinations the cation basic center interations on
the surface demonstrate the spontanaeity of the pro-
posed reactions, as shown by the negative DintG values.
The entropy values is more pronounced for cobalt
that gave 10091 J K 1 mol 1. In each case, the
entropy can be directly related to cation solvation.
After complexing the water molecules associated to the
modified silica gel surface and those coordinated
cations are released to the medium. The cation desolva-
tion disturbs with more intensity the structure of the
solvent, causing an entropic enhancement. The transfer-
ence of water molecules from the hydration sphere to
the medium of the reaction promotes the disorganiza-
tion of the system and consequently leads to an increase
in the entropy in all exchanged reactions [24,36,37,42],
with predominance of cobalt due to the largest volume
of hydration.
Fig. 6. Isotherm of calorimetric titration of Sil NSSH surface with
copper nitrate at 298.15 9 0.02 K. The straight line is a linearized
form of the isotherm.
Table 2
Thermodynamic data for the interactions of divalent cations (M) on
modified surface of SilNSSH at 298.15 90.02 K
M DintH (kJ DintG (kJ DintS (J r [15]
mol1) mol1) K1mol1)
Cu 7.40 9 0.01 25.8 90.1 629 1 0.9989
Ni 1.50 9 0.10 35.1 90.1 42 9 1 0.9999
Co 0.98 9 0.02 30.8 90.1 100 9 1 0.9998
935
4. Conclusion
The immobilization of cyclic molecule ethylenesulfide
was done by solgel procedure and the degree of
functionalization was higher than that used by conven-
tional method of preparation. The new synthesized
silylant agent is contained by three basic centers, that
was anchored on surface of silica. The immobilized
surface has great ability to adsorb divalent cations such
as copper, nickel and cobalt from aqueous solution.
The intensity of the color acquired by treating silica
samples just after the contact with metal salt solution
reveals that cations are extracted from aqueous solu-
tions, due to metal complex formation with the grafted
ligands.
Calorimetric titration of modified silica with cations
resulted in the detemination of the variation of en-
thalpy, Gibbs free energy and entropy. For all systems
excellent coefficient correlation values of each lineariza-
tion were obtained. The thermodynamic of adsorption
on this modified surface showed favorable interactions,
as regards to the variation of enthalpy, Gibbs free
energy and entropy values.
Acknowledgements
The authors thank CNPq for fellowships and
FAPESP for financial support.
References
[1] K.D. Behringer, J. Blumel, Inorg. Chem. 35 (1996) 1814.
[2] D.W. Sindorf, G.E. Maciel, J. Phys. Chem. 86 (1982) 5208.
[3] R.K. Iler, The Chemistry of Silica, Wiley, New York, 1979.
[4] M.E. Mahmoud, E.M. Soliman, Talanta 44 (1997) 1063.
[5] A. Tong, Y. Akama, S. Tanaka, Anal. Chim. Acta 230 (1990)
179.
[6] E.F.S. Vieira, J.A. Simoni, C. Airoldi, J. Mater. Chem. 7 (1997)
2249.
[7] E.F.S. Vieira, A.R. Cestari, J.A. Simoni, C. Airoldi, Ther-
mochim. Acta 328 (1999) 247.
[8] W. Wasiak, Chromatographia 41 (1995) 107.
[9] E.H. Lan, B.C. Dave, J.M. Fukuto, B. Dunn, J.I. Zink, J.S.
Valentine, J. Mater. Chem. 9 (1999) 45.
[10] K. Tamaki, Y. Chujo, K. Kuraoka, T. Yazawa, J. Mater. Chem.
9 (1999) 1741.
[11] W. Wasiak, Chromatographia 690 (1995) 93.
[12] U. Deschler, P. Kleinschmit, P. Panster, Angew. Chem., Int. Ed.
Engl. 25 (1986) 236.
[13] T.P. Hsieh, L.K. Liu, Anal. Chim. Acta 282 (1993) 221.
[14] C.R. Silva, I.C.S.F. Jardim, C. Airoldi, HRC J. High Resolut.
Chromatogr. 22 (1999) 103.
F.A. El-Essi, A.Z.A. Zuhri, S.I. Al-Khalil, M.S.A. Latif, Talanta
44 (1997) 2051.
[16] O.A.C. Monteiro Jr., C. Airoldi, J. Appl. Polym. Sci. 77 (2000)
797.
[17] V. Thammathadanukul, J.H. OHaver, J.H. Harwell, S. Osuwan,
N.N. Ronong, W.H. Waddell, J. Appl. Polym. Sci. 59 (1996)
1741.
936 C. Airoldi, L.N.H. Arakaki / Polyhedron 20 (2001) 929936
[18] B.C. Dave, B. Dunn, J.S. Valentine, J.I. Zink, Anal. Chem. 22
(1994) 1120A.
[19] C.M. Ingersoll, F.V. Bright, Chemtech 1 (1997) 26.
[20] A.A.S. Alfaya, Y. Gushiken, J. Colloid Interface Sci. 209 (1999)
428.
[21] C.R. Silva, C. Airoldi, J. Colloid Interface Sci. 195 (1997) 381.
[22] A.A. El-Nasser, R.V. Parish, J. Chem. Soc., Dalton Trans.
(1999) 3463
[23] S. Brunauer, P. Emett, E. Teller, J. Am. Chem. Soc. 60 (1938)
309.
[24] S. Roca, C. Airoldi, J. Chem. Soc., Dalton Trans. (1997) 2517.
[25] L.M. Nunes, C. Airoldi, Thermochim. Acta 328 (1999) 416.
[26] H.A. Flaschka, EDTA Titration, An Introduction to Theory and
Practice, 2nd edn., Pergamon Press, Oxford, 1967.
[27] M.R.M.C. Santos, C. Airoldi, J. Colloid Interface Sci. 183
(1996) 416.
[28] L.N.H. Arakaki, C. Airoldi, Polyhedron 19 (2000) 367.
[29] J.G.P. Espnola, J.M.P. Freitas, S.F. Oliveira, C. Airoldi, Col-
loids Surf. A 87 (1994) 33.
View publication stats
[30] C.J. Brinker, G.W. Scherer, Sol Gel Science The Physics and
Chemistry of Sol Gel Processing, Academic Press, New York,
1990.
[31] C. Bresson, M.J. Menu, M. Darliguenave, Y. Dartiguenave, J.
Chem. Res. M (1998) 1919.
[32] C.A. Fyfe, Y. Zhang, P. Aroca, J. Am. Chem. Soc. 114 (1992)
3252.
[33] G.E. Maciel, D.W. Sindorf, J. Am. Chem. Soc. 102 (1980) 7606.
[34] D.W. Sindorf, G.E. Maciel, J. Am. Chem. Soc. 105 (1983) 3767.
[35] A.R. Cestari, C. Airoldi, J. Thermal Anal. 44 (1995) 79.
[36] A.S. Gonc alves, C. Airoldi, Polyhedron 8 (1989) 2901.
[37] C. Airoldi, A.S. Gonc alves, Colloids Surf. 28 (1987) 199.
[38] C. Airoldi, L.M. Nunes, Langmuir 16 (2000) 29.
[39] Y. Marcus, Ions Solvation, Wiley, UK, 1985.
[40] C. Airoldi, E.F.C. Alcantara, J. Chem. Thermodyn. 27 (1995)
623.
[41] O.A.C. Monteiro Jr., C. Airoldi, J. Colloid Interface Sci. 212
(1999) 212.
[42] C. Airoldi, A.P. Chagas, Coord. Chem. Rev. 119 (1992) 29.