Synthesis of C-4-hydroxy-3-methoxyphenylcalix[4]resorcinarene and its application as adsorbent for lead(II), copper(II) and chromium(III)

Article abstract of DOI:10.1246/bcsj.20180323

This study aims to synthesize C-4-hydroxy-3-methoxyphenylcalix[ 4]resorcinarene and investigate the kinetics of its application as an adsorbent for lead(II), copper(II) and chromium( III) ions. The interaction between this adsorbent and these metal ions was also studied. In this work, C-4-hydroxy- 3-methoxyphenylcalix[4]resocinarene was synthesized from vanillin and resorcinol as a light red solid in 84% yield, and its ability to adsorb the metal ions was conducted in a batch system. The kinetics and interaction of the adsorbent with these metal ions were analyzed by FAAS spectrometry and FT-IR respectively. The optimum pH values of this adsorbent to adsorb Pb(II), Cu(II) and Cr(III) ions were determined to be 5.48, 5.70 and 4.50 respectively. The adsorption rate order of these metal ions onto adsorbent was found to be Pb(II) > Cu(II) > Cr(III). The competitive adsorption of these heavy metal ions was also investigated. FT-IR spectra showed the presence of interaction between Pb(II) and the adsorbent, but no such interaction was observed between the adsorbent and Cr(III) or Cu(II). Further studies based on the ¹HNMR and UV spectra of the free and metal ion loaded adsorbents confirmed the presence of interaction between the adsorbent and all metal cations.

Full text of DOI:10.1246/bcsj.20180323

Document type: Article
Synthesis of C-4-Hydroxy-3-methoxyphenylcalix[4]resorcinarene and Its
Application as Adsorbent for Lead(II), Copper(II) and Chromium(III)
Jumina,*1 Dwi Siswanta,1 Kira Nofiati,1 Arif Cahyo Imawan,1 Yoga Priastomo,1 and Keisuke Ohto2
1Department of Chemistry, Faculty of Mathematics and Natural Science, Universitas Gadjah Mada,
Sekip Utara Yogyakarta 55281, Indonesia
2Department of Chemistry and Applied Chemistry, Faculty of Science and Engineering, Saga University,
1-Honjo, Saga 840-8502, Japan
E-mail: jumina@ugm.ac.id
Received: October 22, 2018; Accepted: January 15, 2019; Web Released: January 24, 2019
Jumina
Jumina received his PhD degree in Organic Chemistry from University of New South Wales, Sydney,
Australia in 1997. He has been working as a lecturer in the Department of Chemistry, Faculty of Mathematics
and Natural Science, Universitas Gadjah Mada, Yogyakarta-Indonesia since 1989 and was appointed as a
full professor at the same department in 2008. His research field is organic synthesis with particular interest
in drug development and medicinal chemistry, and environmental chemistry.
Abstract
1. Introduction
This study aims to synthesize C-4-hydroxy-3-methoxyphen-
ylcalix[4]resorcinarene and investigate the kinetics of its
application as an adsorbent for lead(II), copper(II) and chro-
mium(III) ions. The interaction between this adsorbent and
these metal ions was also studied. In this work, C-4-hydroxy-
3-methoxyphenylcalix[4]resocinarene was synthesized from
vanillin and resorcinol as a light red solid in 84% yield, and
its ability to adsorb the metal ions was conducted in a batch
system. The kinetics and interaction of the adsorbent with these
metal ions were analyzed by FAAS spectrometry and FT-IR
respectively. The optimum pH values of this adsorbent to
adsorb Pb(II), Cu(II) and Cr(III) ions were determined to be
5.48, 5.70 and 4.50 respectively. The adsorption rate order of
these metal ions onto adsorbent was found to be Pb(II) >
Cu(II) > Cr(III). The competitive adsorption of these heavy
metal ions was also investigated. FT-IR spectra showed the
presence of interaction between Pb(II) and the adsorbent, but
no such interaction was observed between the adsorbent and
Cr(III) or Cu(II). Further studies based on the 1H NMR and UV
spectra of the free and metal ion loaded adsorbents confirmed
the presence of interaction between the adsorbent and all metal
cations.
Heavy metals form a group of metal elements with atomic
mass between 63.5 and 200.6 g mol and density greater than
¹1
5 g cm¹3. Some of the elements in this group are required as
micronutrients by most living organisms including humans.
However, the excess of these heavy metals in the environment
can cause environmental pollution as well as many health
problems.1 Lead is one of the very harmful heavy metals that
can damage the lipid membrane and chlorophyll of plants and
influence the photosynthetic process.2 Another example is
chromium that is very harmful to humans because of its weak
membrane permeability, which allows its ionic form to diffuse
into human cells and cause molecular stress. On the other hand,
copper can cause liver damage, anemia and intestinal irritation.3
In spite of the harmfulness of these heavy metals to orga-
nisms, some of them are still being used in various industries.
Thus, heavy metal waste distribution cannot be avoided.4
Researchers worldwide are investigating ways to reduce or
eliminate heavy metals in the environment. These include
chemical precipitations (e.g. hydroxide, sulfide, and heavy
metal chelating precipitation),5,6 ion exchange7 and adsorption
(e.g. active carbon and carbon nanotube).8-13 Calixarene is a
stable macromolecule with unique geometric structure likes
flower vases or crowns. Thus, calixarenes can be developed as
adsorbents,14-18 solvent extraction agents,19 host molecules,20
UVabsorbers21 and catalysts.22 The adsorbent property is really
attractive because of its effectiveness and simple operation.13
In this study, C-4-hydroxy-3-methoxyphenylcalix[4] resor-
cinarene (Figure 1) was synthesized from vanillin and resorci-
Keywords: C-4-Hydroxy-3-methoxyphenylcalix[4] resorcinarene
Heavy metal Adsorption
j
j
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© 2019 The Chemical Society of Japan | 825

OCH3
HO
Table 1. pH values of the solutions for the adsorption
process
HO
OH
OCH3
OH
Metal Ion
pH Values
HO
OH
Pb(II)
Cu(II)
Cr(III)
3.19; 4.43; 5.16; 5.48 and 5.99
3.31; 3.87; 4.54; 5.11; 5.45; 5.70 and 5.97
2.48; 3.54; 3.94; 4.50 and 5.11
HO
OH
H3CO
HO
OH
Table 2. Adsorbent Dosage Variations
HO
OH
H3CO
Metal Ion
Adsorbent Mass (g)
Figure 1. Chemical structure of synthesized C-4-hydroxy-
3-methoxyphenylcalix[4]resorcinarene.
Pb(II)
Cu(II)
Cr(III)
0.005; 0.010; 0.020; 0.050; 0.080; 0.100 and 0.150
0.015; 0.050; 0.080; 0.100 and 0.120
0.005; 0.010; 0.050; 0.800; 0.100 and 0.125
nol and then applied as a heavy metal adsorbent. Since both
raw materials are abundantly found in nature, this adsorbent
can be produced in high quantity at low-cost. Furthermore, its
adsorption kinetics and behaviour with lead, copper, and
chromium ions have been investigated by using mathematical
equations reported by Santosa.23 The analysis of the interaction
between these heavy metal ions and adsorbent was carried out
by means of FT-IR spectroscopy. The effect of pH value and
the competitor ion in the adsorption process of the correspond-
ing heavy metals onto adsorbent was also conducted.
as listed in Table 1. These solutions were shaken for 2 h and
then filtered. Blank solutions (solution without the adsorbent)
with the corresponding metal ion and pH values were also
prepared. Determination of the metal ion concentration was
carried out using FAAS.
Adsorption Rate of Pb(II), Cu(II) and Cr(III). C-4-
Hydroxy-3-methoxyphenylcalix[4]resorcinarene (50 mg) as
adsorbent was mixed with different solutions containing Pb(II)
(18 ppm, 10 mL), Cu(II) (8 ppm, 10 mL) or Cr(III) (8 ppm,
10 mL). These solutions were then stirred for different period of
time (i.e. 15, 30, 60, 90 and 150 min) at optimum pH values.
The blank solutions were also treated in the same way as the
test solutions. Metal ion concentrations were determined by
using FAAS.
2. Experimental
Materials.
Vanillin, resorcinol, p-toluenesulfonic acid,
Cr(NO)3¢9H2O, pH 4 buffer, pH 7 buffer, NaOH, HNO3 and
1000 ppm standard solutions of Pb(NO3)2 and Cu(NO3)2 were
purchased from Merck Millipore as analytical grade reagents.
Instrumentation.
Instruments used to characterize the
Adsorption Isotherm of Pb(II), Cu(II) and Cr(III).
Solutions of Pb(II) (18 ppm, 10 mL), Cu(II) (8 ppm, 10 mL)
or Cr(III) (8 ppm, 10 mL) were mixed with the adsorbent in
varied concentrations (Table 2) and these solutions were then
shaken at the predetermined optimum pH and time. The blank
solutions were also treated by the same procedure as the test
solutions. Metal ions concentrations were determined by using
FAAS.
Adsorption of Two Mixed Metal Ions. Adsorbent (100
mg) was mixed with the solutions with two metal ions at
pH 4.5. The concentration of one of the metal ions in the solu-
tion was fixed while the other one was varied. These solutions
were shaken and then filtered. The metal ion concentrations
were determined by using FAAS.
Study of the Bonding between Pb(II), Cu(II) and Cr(III).
Adsorbent (100 mg) was mixed individually with solutions of
Pb(II) (50 ppm), Cu(II) (50 ppm) or Cr(III) (50 ppm), and these
solutions were then filtered. The precipitate was dried and ana-
lyzed using FT-IR spectroscopy. The spectra of the precipitate
were compared to that of the free adsorbent spectrum to study
the binding of metal ions onto this adsorbent.
synthesized products are melting point instrument (Electro-
thermal 9100), FT-IR (Fourier transform infrared) spectrometer
(Shimadzu-Prestige 21), liquid-mass spectrometry chromatog-
raphy (LC-MS Waters HPLC-SQD MS M3100) and NMR
spectrometers (NMR, JEM JNMECA 500 MHz and Agilent
CNMR 400 MHz). Flame atomic absorption spectroscopy
(FAAS, Perkin Elmer) was used to determine the concentration
of metal in solution.
Synthesis of C-4-Hydroxy-3-methoxyphenylcalix[4]resor-
ci narene. Resorcinol (5.50 g; 0.05 mol) was dissolved in
75 mL of 98% ethanol, and to this solution was added vanillin
(7.60 g, 0.05 mol). After the dissolution of the mixture, HCl
(1 mL, 37%) was added dropwise. The mixture was then stirred
and heated at reflux for 20 h. The mixture was allowed to cool
to rt before distilled water was added until precipitation
formed. FTIR (KBr, ¯; cm¹1): (-OH) 3394, (Csp3 -H) 2970,
(C=C aromatic) 1612 and 1512, (C-H) 1427, (-CH3) 1373,
(C-O) 1280. 1H NMR (DMSO-d6; 500 MHz) ¤ (ppm): 3.52
(12 H, s, Ph-O-CH3), 5.40 (4H, s, CH(Ph)3), 6.07 (4H, s, Ph
(resorcinol)), 6.13 (4H, s, Ph (vanillin)), 6.30 (4H, d, Ph
(vanillin), 6.32 (4H, s, Ph (resorcinol)), 6.35 (4H, d, Ph
(vanillin)), 6.37 (4H, s, Ph (vanillin)), 8.47 (4H, s, Ph-OH).
LCMS [M]+: 730 (m/z).
3. Results and Discussion
Effect of Equilibrium pH Value. It was found that the
solution pH greatly affects the adsorption of Pb(II), Cu(II) and
Cr(III) as shown in Figure 2.
Effect of Equilibrium pH on the Adsorption of Pb(II),
Cu(II) and Cr(III). C-4-Hydroxy-3-methoxyphenyl-calix[4]
resorcinarene (50 mg) as an adsorbent was mixed with different
solutions containing Pb(II) (18 ppm, 10 mL), Cu(II) (8 ppm,
10 mL) or Cr(III) (8 ppm, 10 mL) solution at various pH values
Increasing the pH value of solution means that the solution
¹
was poor in H+ ion concentration but rich in OH ion, thus
it could lead to the formation of a salt of the phenolic adsor-
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© 2019 The Chemical Society of Japan

3
2.5
2
If ª0 and ª1 are the portion of empty and occupied binding
sites on adsorbent ª0 þ ª1 ¼ 1, k1 and k are adsorption and
ꢀ1
desorption constants and follow Langmuir isotherm adsorption,
the adsorption-desorption (rads and rdes) is given as:
1.5
1
rads ¼ k1ª0CA
¼ k1ð1 ꢀ ª1ÞCA
ð2Þ
ð3Þ
rdes ¼ kꢀ1ª1
when the equilibrium reached, rads ¼ rdes
0.5
0
,
2
4
6
k1ð1 ꢀ ª1ÞCA ¼ kꢀ1ª1
-0.5
Initial pH of Solution
k1
ª1 ¼
ð1 ꢀ ª1ÞCA
ð4Þ
Pb(II)
Cu(II)
Cr(III)
k
ꢀ1
k1
Figure 2. The effect of equilibrium pH value on adsorption
of Pb(II), Cu(II) and Cr(III) ions onto the adsorbent.
If
¼ K (adsorption-desorption constant), the eq (4) become:
k
ꢀ1
ª1 ¼ Kð1 ꢀ ª1ÞCA or
KCA
1.7
1.5
1.3
1.1
0.9
0.7
ª1 ¼
ð5Þ
1 þ KCA
Substitution eq (5) to eq (2), the adsorption rate (rads) yields:
ꢀ
k1CA
ꢁ
KCA
rads ¼ k1 1 ꢀ
CA or
1 þ KCA
rads
¼
ð6Þ
1 þ KCA
Adsorption rate defined as the decreasing amount of species A
(CA) rate in solution, then:
2
52
102
152
Cr(III)
Contact Time (min)
Cu(II)
dCA
dt
k1CA
rads ¼ ꢀ
¼
Pb(II)
1 þ KCA
ꢀ dCA ꢀ KCAdCA ¼ k1CAdt
dCA
Figure 3. The concentration of adsorbed Pb(II), Cu(II) and
Cr(III) ions onto adsorbent versus contact time at optimum
pH values.
ꢀ
ꢀ KdCA ¼ k1dt
CA
dCA
CA
þ KdCA ¼ ꢀk1dt
ð7Þ
ð8Þ
bent C-4-hydroxy-3-methoxyphenylcalix[4]resorcinarene, with
a negative charge on its oxygen atoms. This negative charge
can strongly attract metal ions through ionic bonding, thus the
increase in pH tends to increase the amount of metal ions
adsorbed onto adsorbent until it is saturated and the concen-
tration of adsorbed ion plateaues out. The pH values at which
the adsorbent reached saturation for Pb(II), Cu(II) and Cr(III)
were determined to be 5.99, 5.70 and 4.50 respectively.
Adsorption Rate of Pb(II), Cu(II) and Cr(III). The effect
of contact time between the adsorbent and the solution with the
corresponding metal ions is shown in Figure 3. The curve
pattern of the concentration of adsorbed metal ion versus time
was similar for all tested ions. The rapid adsorption was ob-
served at the initial stage (0-40 min) and then it plateaued out.
It suggested that at the initial stage of adsorption, active sites
of the adsorbent were unoccupied and the tested metal ions
have easily interacted with it. However, after 40 min adsorption
reached steady state due to equilibrium.
After the integration of eq 7, the expression becomes:
ln CA þ KCA ¼ ꢀk1t þ Y
At t = 0, the concentration of species A in solution (CA) is the
same as the initial concentration (CA0), and the K parameter
does not exist before the adsorption process takes place, then:
Y ¼ ln CA0
Substitution Y value at eq 9 to eq 8,
ð9Þ
ln CA þ KCA ¼ ꢀk1t þ ln CA0 or
CA0
ln
¼ k1t þ KCA
ð10Þ
CA
Equation 10 divided by CA, then the following expression is
obtained:
CA0
lnð C
CA
Þ
t
A
¼ k1
þ K
ð11Þ
CA
The adsorption kinetics of these metal ions onto adsorbent
was carried out by using mathematics modelling reported by
Santosa [23]. The adsorption equilibrium of these metal ions is
shown in eq 1, where A and P are the metal ions and C-4-
hydroxy-3-methoxyphenylcalix[4]resorcinarene as the adsorb-
ent, respectively.
If the straight line can be obtained from plot [ln(CA0/CA)]/
CA versus t/CA, slope and intercept are k1 (adsorption constant)
and K. The results of this analysis are shown in Figures 4-6
and show the constant values k for Pb(II), Cu(II) and Cr(III) ion
to be 12.90, 6.90 and 3.80 © 10¹3 min respectively. The
¹1
order of the adsorption rate of these metal ions onto adsorbent
was Pb(II) > Cu(II) > Cr(III). This result was consistent with
A þ P ꢀ A*P
ð1Þ
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15.7
10.7
5.7
9.7
8.7
7.7
6.7
5.7
4.7
3.7
2.7
1.7
0.7
y = 0.0129x + 3.8263
R² = 0.9115
0.7
45
245
445
645
t/CA x 104
Figure 4. ln(Co/CA)/CA versus t/CA plot for adsorption of
0
0.05
0.1
0.15
Cr(III)
Pb(II).
Adsorbent Mass (g)
Cu(II)
Pb(II)
1.9
1.7
1.5
Figure 7. The effect of adsorbent dosage variation on the
amount (mmol) of adsorbed metal ions onto the adsorbent.
100.7
80.7
60.7
40.7
20.7
0.7
1.3
y = 0.0069x + 0.5801
1.1
R² = 0.9256
0.9
0.7
20
70
120
170
t/CA x 104
Figure 5. ln(Co/CA)/CA versus t/CA plot for adsorption of
Cu(II).
0
0.05
0.1
0.15
Cr(III)
1
0.95
0.9
Adsorbent Mass (g)
Cu(II)
Pb(II)
0.85
0.8
0.75
0.7
0.65
0.6
0.55
0.5
Figure 8. The effect of adsorbent dosage variation on the
amount (mmol per mmol adsorbent) of adsorbed metal ions
onto the adsorbent.
y = 0.0038x + 0.6591
R² = 0.6304
the hydrogen bonding mechanism between the hydrated metal
ions and the phenolic oxygen atoms of the adsorbent. As the
phenolic oxygen atoms of the adsorbent are capable of forming
hydrogen bonds with all hydrated metal ions, hence poor
selectivity of the adsorbent was observed. The flexibility of the
conformation of the adsorbent is another factor for the occur-
rence of low selectivity of the adsorbent. Incorporation of
certain functional groups such as amides or esters on the
structure of the adsorbent is perhaps useful for future studies
aiming to increase the selectivity of the adsorbent.
Effect of Adsorbent Dosage on the Adsorption of Pb(II),
Cu(II) and Cr(III). The effect of the adsorbent dosage on
the adsorption of Pb(II), Cu(II) and Cr(III) is exhibited in
Figures 7-8.
Figure 7 shows that the amount of adsorbed Pb(II) ion
increases with the increasing adsorbent mass from 0.005 g (can
adsorb 2.54 © 10¹4 mmol of Pb(II)) to 0.05 g (can adsorb
4.60 © 10¹4 mmol of Pb(II)). Further addition of the adsorbent
dosage did not increase the amount of adsorbed Pb(II). The
addition of adsorbent dosage also did not affect the amount of
5
25
45
65
85
t/CA x 104
Figure 6. ln(Co/CA)/CA versus t/CA plot for adsorption of
Cr(III).
the rate constants for water exchange on aqua metal ions
proposed by Eigen.24 It also suggested that the greater the
radius of the metal ion (i.e. Pb(II): 133 pm, Cu(II): 87 pm,
Cr(III): 73 pm), the more rapid its adsorption because a metal
ion with a larger radius will have a smaller degree of hydration
which can affect its mobility to the adsorbent. Nonetheless, the
value of R2 (Figure 6) for the adsorption of Cr(III) was only
relatively low (R2 = 0.6304) which implied that the adsorption
of Cr(III) under the set condition did not comply very well with
the Santosa equation.
From Figures 2 and 3, it was observed that the selectivity of
the prepared adsorbent was still not satisfied. However, this
work revealed simultaneous adsorption of some heavy metals
(Pb(II), Cu(II), Cr(III)) which was remarkable. This was due
to the adsorption process, which perhaps mainly depends on
adsorbed Cr(III) (5.17 © 10¹4 mmol and Cu(II) (8.48 © 10
mmol) ions onto the adsorbent. Thus, Figure 7 showed that the
adsorbent dosage was not proportional to the amount of metal
ion adsorbed onto the adsorbent.
¹4
828 | Bull. Chem. Soc. Jpn. 2019, 92, 825–831 | doi:10.1246/bcsj.20180323
© 2019 The Chemical Society of Japan

100
90
80
70
60
50
40
30
20
10
0
100
90
80
70
60
50
40
30
20
10
0
mol Cr(III)/mol Cu(II)
mol Pb(II)/mol Cr(III)
Figure 11. The effect of Cu(II) competitor ion on the
adsorption of Cr(III) ion.
Figure 9. The effect of Cr(III) competitor ion on the
adsorption of Pb(II) ion.
100
90
80
70
60
50
40
30
20
10
0
100
90
80
70
60
50
40
30
20
10
0
mol Pb(II)/mol Cu(II)
mol Cr(III)/mol Pb(II)
Figure 10. The effect of Cu(II) competitor ion on the
adsorption of Pb(II) ion.
Figure 12. The effect of Pb(II) competitor ion on the
adsorption of Cr(III) ion.
Figure 8 describes the effect of adsorbent dosage on the
adsorbed metal ion for each mmol of calix[4]resorcinarene unit
in the adsorbent. As described on Figure 7, Figure 8 also
showed that adsorbent dosage was not proportional to the
amount of metal ion adsorbed onto the adsorbent. This phe-
nomenon was predicted to have occurred by the aggregation of
adsorbent as the increase of adsorbent dosage decreases the
surface area of the active sites of adsorbent.
Effect of Cr(III) and Cu(II) as Competitor Ions on the
Adsorption of Pb(II) Ion. The effects of Cr(III) and Cu(II) as
competitor ions on the adsorption of Pb(II) are exhibited in
Figure 9 and 10 respectively.
The figures clearly show that the presence of Cr(III) and
Cu(II) ions in the adsorption process can greatly decrease the
amount of adsorbed Pb(II) ion. The presence of Cr(III) and
Cu(II) ions with the same amount of Pb(II) ion can reduce the
amount of Pb(II) adsorbed onto the adsorbent by 32 and 22%
respectively. Moreover, the further addition of these competitor
ions decreases the amount of adsorbed Pb(II) further.
Effect of Cu(II) and Pb(II) as Competitor Ions on the
Adsorption of Cr(III) Ion. The effect of Cu(II) and Pb(II) as
competitor ions on the adsorption of Cr(III) ion are exhibited
in Figure 11 and Figure 12 respectively. Figure 11 shows that
the presence of 6.30 © 10¹4 mmol Cu(II) ion or 0.38 times the
amount of Cr(III) did not affect the Cr(III) adsorption. The
decrease of the Cr(III) adsorption was observed when the
amount of Cu(II) was beyond 9.40 © 10¹4 mmol or 0.54 times
of Cr(III) amount.
¹4
On the other hand, the presence of 1.90 © 10¹4, 2.90 © 10
and 4.8 © 10¹4 mmol Pb(II) ion had a small effect on Cr(III)
adsorption (Figure 12). The decreasing trend of Cr(III) adsorp-
tion was clearly observed when the amount of Pb(II) was
beyond 9.60 © 10¹4 mmol or 0.53 times the Cr(III) amount.
The presence of Pb(II) ion with the same amount of Cr(III)
greatly reduced the amount of adsorbed Cr(III) to 28.8%,
however the presence of Cu(II) ion with the same amount of
Cr(III) only slightly decreased the adsorbed Cr(III) to 76.7%.
This phenomenon can occur because the hydration degree
of these competitor ions is less than that of Cr(III), thus the
mobility of these competitor ions is faster than Cr(III). The
presence of these competitor ions can affect the amount of
adsorbed Cr(III). In addition, because the hydration degree of
Pb(II) is greatly lower than Cr(III), the presence of Pb(II) can
greatly affect the amount of the adsorbed Cr(III).
Effect of Pb(II) and Cr(III) as Competitor Ions on the
Adsorption of Cu(II) Ion. The effects of Pb(II) and Cr(III)
as competitor ions on the adsorption of Cu(II) are exhibited
in Figure 13 and Figure 14 respectively. It is evident from
Figure 13 that the presence of Pb(II) ion can greatly affect the
amount of Cu(II) adsorbed onto adsorbent even in small quan-
tity (0.18 times the Cu(II) amount), while Figure 14 depicts
that the presence of Cr(III) did not significantly affect the
Bull. Chem. Soc. Jpn. 2019, 92, 825–831 | doi:10.1246/bcsj.20180323
© 2019 The Chemical Society of Japan | 829

100
80
60
40
20
0
mol Cu(II)/mol Pb(II)
Figure 13. The effect of Pb(II) competitor ion on the
adsorption of Cu(II) ion.
100
80
60
40
20
0
Figure 15. FT-IR spectra of free adsorbent (A), adsorbent-
Cu(II) (B), adsorbent-Pb(II) (C) and adsorbent-Cr(III) (D).
mol Cu(II)/mol Cr(III)
Figure 14. The effect of Cr(III) competitor ion on the
adsorption of Cu(II) ion.
amount of adsorbed Cu(II) even in large quantity (1.39 times
of Cu(II) amount). This phenomenon can happen because the
hydration degree of Cu(II) is lower than that of Cr(III) but
greater than that of Pb(II), so the mobility of Cu(II) was more
rapid than Cr(III) but less rapid than Pb(II). Thus, the presence
of Pb(II) ion can greatly affect the amount of adsorbed Cu(II),
but the presence of Cr(III) did not affect the amount of
adsorbed Cu(II) significantly.
Figure 16. 1H NMR spectra of the free adsorbent (A),
adsorbent-Cr(III) (B), adsorbent-Cu(II) (C), and adsorbent-
Pb(II) (D).
Spectroscopic Study of the Complexes of Pb(II), Cu(II)
and Cr(III) with C-4-Hydroxy-3-methoxyphenylcalix[4]
Resorcinarene. The spectroscopic study on the complexes
of Pb(II), Cu(II) and Cr(III) ions with the adsorbent C-4-
hydroxy-3-methoxyphenylcalix[4]resorcinarene was carried
out by comparing the FT-IR spectra of the free adsorbent with
the metal-loading adsorbents. The comparison of the FT-IR
spectra of the adsorbent with and without loaded metal ion is
exhibited in Figure 15. It showed that the FT-IR spectrum of
the free adsorbent was different from the FT-IR spectrum of the
adsorbent with loaded Pb(II) ion, with a shift of -OH stretching
Wavelength (nm)
¹1
¹1
frequency from 3394 cm (A) to the 3386 cm (C). It can be
deduced that the Pb(II) ion strongly interacted with the OH
moiety on the adsorbent resulting in a change in its OH fre-
quency. However, this shift was not observed clearly in the case
of Cu(II) or Cr(III) ions, indicating that a weak interaction of
Cu(II) and Cr(III) with the OH groups of the adsorbent.
Figure 17. UV-Vis spectra of the free adsorbent (A),
adsorbent-Cr(III) (B), adsorbent-Cu(II) (C), and adsorb-
ent-Pb(II) (D).
1
the free adsorbent exhibited a broadened H NMR spectrum
1
A study using H NMR (Figure 16) gave more evidence for
which may be attributed by the existence of mobile conforma-
tion of the molecule, the metal ion loaded adsorbents all
the interaction between the adsorbent and the metal ions. While
830 | Bull. Chem. Soc. Jpn. 2019, 92, 825–831 | doi:10.1246/bcsj.20180323
© 2019 The Chemical Society of Japan

1
showed sharper H NMR spectra which implied the existence
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metal ion loaded adsorbents all displayed the same maximum
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4. Conclusions
C-4-Hydroxy-3-methoxyphenylcalix[4]resorcinarene
has
been successfully synthesized and applied as an adsorbent of
heavy metals Pb(II), Cu(II) and Cr(III). The optimum adsorp-
tion pH values on this adsorbent for Pb(II), Cu(II) and Cr(III)
ion were determined to be 5.48, 5.70 and 4.50 respectively. The
order of the adsorption rate of these metal ions onto adsorbent
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¹3
¹1
12.90 © 10¹3; 6.90 © 10 and 3.80 ©10¹3 min for Pb(II),
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1
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The authors deeply thank the Directorate of Research and
Development, The Ministry of Research, Technology, and
Higher Education, The Republic of Indonesia for its financial
support for this research through Penelitian Strategis Nasional
Institusi (PSNI) Research Grant budget year 2018.
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Bull. Chem. Soc. Jpn. 2019, 92, 825–831 | doi:10.1246/bcsj.20180323
© 2019 The Chemical Society of Japan | 831