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Adsorption of Benzoic Acid and Its Derivatives to

Swollen Chitosan Beads
a a a a
Tomoyo Mitani , Tetsuya Yamashita , Chiho Okumura & Hiroshi Ishii
a
Department of Chemical Science and Engineering, Tokyo National College of
Technology, 1220-2 Kunugida, Hachioji, Tokyo 193, Japan
Published online: 12 Jun 2014.

To cite this article: Tomoyo Mitani, Tetsuya Yamashita, Chiho Okumura & Hiroshi Ishii (1995) Adsorption of Benzoic Acid
and Its Derivatives to Swollen Chitosan Beads, Bioscience, Biotechnology, and Biochemistry, 59:5, 927-928, DOI: 10.1271/
bbb.59.927

To link to this article: http://dx.doi.org/10.1271/bbb.59.927

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 Biosci. Biotech. Biochem., 59 (5), 927--928, 1995
Note
Adsorption of Benzoic Acid and Its Derivatives to Swollen Chitosan Beads
Tomoyo MITANI, Tetsuya YAMASHITA, Chiho
Department of Chemical Science and Engineering, Tokyo National College of Technology, 1220-2 Kunugida, Hachioji,
Tokyo 193, Japan
Received September 30, 1994
The adsorption of benzoic acid and its derivatives to swollen chi-
tosan beads increased with decreasing pKa value, except for those
compounds having a hydroxyl group in the aromatic ring. The hy-
droxyl group had the ability to stimulate adsorption, this effect
being stronger than that of pKas. The presence of glucose and meth-
anol also stimulated the adsorption of benzoic acid.
Chitosan is a promising adsorbent to remove heavy metals and
Downloaded by [University of North Texas] at 07:04 22 November 2014
organic compounds from water and wastewater. There have been
many investigations on the adsorption characteristics of heavy
metals to chitosan.l - 6) However, few investigations have been
done on the contribution of the structure of organic compounds
to the adsorption characteristics. Organic acids such as benzoic
acid and its derivatives are suitable compounds for studying the
adsorption characteristics to chitosan, because of their simple
chemical structures. In the present paper, we report the effects of
the pKa value of benzoic acid and its derivatives on the adsorp-
tion to swollen chitosan beads, and the effect of the hydroxyl
group of adsorbates and coexisting compounds on the adsorption
characteristics.
Swollen chitosan beads were prepared from 7 wt% chitosan
flakes (84% degree of deacetylation, presented by Katakura Chik-
karin Co.) dissolved in 7% acetic acid. The resultant viscous solu-
tion was debubbled under vacuum, and dropped into an alkaline
coagulating solvent (H20~MeOH-NaOH 4: 5: I wt/wt) to pre-
pare highly swollen chitosan beads of 2.5 mm in average diameter,
and with an average water content of 92% (wt/wt). The beads
were collected and washed thoroughly with distilled water.
The adsorbates used were p-aminobenzoic acid, anisic acid, ben-
-c
[R
20
.9 10
:.2
u .e::
..... 5 ~0
ClJ
~ E
'0 2 a::
01
.......
15
E
~ 0.5
I
0-
0.2
20 50 100 500
Coo (}Jmolll )
Fig. 1. Adsorption Isotherms of Benzoic Acid and Its Derivatives.
C I ' equilibrium concentration; q,. equilibrium adsorption amount. O. benzoic acid;
/::::.. salicylic acid; O. methyl benzoate.
OKUMURA, and Hiroshi ISHII
zoic acid, 3,5-dihydroxybenzoic acid, 3,5-dinitrobenzoic acid, gal-
lic acid, p-hydroxybenzoic acid, methyl benzoate, m-nitrobenzoic
acid, and salicylic acid. p-Aminobenzoic acid and gallic acid were
used after being recrystallized from acetone and hot water, re-
spectively, while the others were used without purification.
One gram of swollen chitosan beads and 19 ml of the prescribed
concentration of an adsorbate were placed in a 100-mt stoppered
Erlenmeyer flask. The flask was shaken at 150 oscillations/min
in a water bath maintained at 30 ± 0.1 °C for 3 h. It had been
previously confirmed that 3 h was a long-enough period to reach
adsorption equilibrium. After shaking, the solution was filtered
through glass fiber (Toyo GS25). The concentration of organic
compound in the filtrate was measured by a UV spectrophotom-
eter (Nihon Bunko UVDEC-I) at 254 nm. The percentage re-
moval of the adsorbate was calculated from the concentration of
the filtrate. All the experiments were run without controlling the
pH value of the buffer solution.
Figure 1 shows the adsorption isotherms of benzoic acid, salicylic
acid, and methyl benzoate. The isotherms obey the Freundlich-type
equation, the amount adsorbed decreasing in the order of benzoic
acid> salicylic acid> methyl benzoate. The free carboxyl group of
salicylic acid partially forms hydrogen bonds to ortho-OH,7) so
that the adsorption of salicylic acid was less than that of benzoic
acid. For methyl benzoate, it is considered that methylation of
the carboxyl group that is capable of binding to chitosan caused
the lowest adsorption. Thus, it is suggested that the free carboxyl
group of benzoic acid and its derivatives plays an important role
100
.6
6
.6
7
"'7
50
ell
o~----~------~----~
2.0 3.0 4.0 5.0
pKa.
Fig. 2. Relationship between the pKa values for Benzoic Acid Derivatives
and the Removal (0;;)) by Swollen Chitosan Beads.
The initial concentration of each adsorbate was IOOllmol/1. (I) p-aminobenzoic acid;
(2) 3.5-dinitrobenzoic acid; (3) m-nitrobenzoic acid; (4) benzoic acid; (5) anisic acid;
(6) 3.5-dihydroxybenzoic acid; (7) gallic acid; (8) p-hydroxybenzoic acid; (9) salicylic
acid.
NII-Electronic Library Service
 928 T. MITANI et at.

100~------------------~
in the adsorption to chitosan. The binding site of chitosan to the
carboxyl group may be mainly an amino group, as is the case with
heavy metal ions.
It is necessary to note that there are some binding sites besides
the carboxyl group in benzoic acid and its derivatives because, as
shown in Fig. I, methyl benzoate could be adsorbed to chitosan
in spite of having no free carboxyl group.
Figure 2 shows the relationship between the percentage removal
of adsorbates and the pKa value. Except for those compounds
having a hydroxyl group in the aromatic ring, the smaller the pKa
value, the larger the percentage removal. This result also suggests
the participation of a dissociated carboxyl group in the binding
of benzoic acid derivatives to chitosan.
The compounds having a hydroxyl group, p-hydroxybenzoic
acid, 3,5-dihydroxybenzoic acid, and gallic acid, showed higher
percentage removal than expected from their pKa values. Figure
3 shows the change of percentage removal with the increase in
OL-----L----'----~
number of hydroxyl groups in the aromatic ring of benzoic acid
o
Downloaded by [University of North Texas] at 07:04 22 November 2014

2 3 derivatives. The percentage removal increases markedly with in-

creasing number of hydroxyl groups. It is evident that the hydroxyl
Number of OHgroups group has a function for stimulating the adsorption of benzoic
Fig. 3. Relationship between the Number of Hydroxyl Groups of acid derivatives to chitosan, and that this function is stronger than
Benzoic Acid Derivatives and the Removal (%) by Swollen Chitosan the effect of dissociation of the carboxyl group. On the other hand,
Beads. the percentage removal of salicylic acid was different from the
The initial concentration of each adsorbate was 100/.tmol/1. (1) benzoic acid; (2) expected values as shown in Figs. 2 and 3. This may be ascribable
p-hydroxybenzoic acid; (3) 3,5-dihydroxybenzoic acid; (4) gallic acid; (5) salicylic to intramolecular hydrogen bonding between OH and COOH of
acid.
salicylic acid.
Figure 4 shows the effects of coexisting compounds having
100 hydroxyl groups on the removal of benzoic acid by chitosan. The
percentage removal reached its maximum at a concentration of
about 2 mmoljl for both glucose and methanol. It is concluded
that the presence of glucose and methanol brings about stimula-
80 tion of the adsorption of benzoic acid to chitosan beads. The same
-
~
0
0
results were obtained for the benzoic acid derivatives tested in this
study. Further work is necessary to interpret these results.
ili> 60
0 References
E I) R. A. A. Muzzarelli and R. Rocchetti, Ta/anta, 21, l137~ll43 (1974).
<IJ
a::: 40 2) C. A. Eiden, C. A. Jewell, and J. P. Wightman, l. Appl. Po/ym. Sci.,
25, 1587~ 1599 (1980).
3) J. M. Nieto, C. P. Covas, and J. D. Bosque, Carbohydrate Po/ym.,
r 18, 22l~224 (1992).
ot 4) c. P. Covas, L. W. Alvarez, and W. A. Monal, l. Appl. Po/ym. Sci.,
0 5 10 15 20 46, l147~1150 (1992).
5) J. R. Deans and B. G. Dixon, Wat. Res., 26, 469-472 (1992).
Glucose & methanol (mmoll[)
6) K. Inoue, Y. Baba, and K. Yoshizuka, Bull. Chern. Soc. lpn., 66,
Fig. 4. Effects of Glucose and Methanol on the Removal (%) of Benzoic 2915~292l (1993).

Acid by Swollen Chitosan Beads. 7) B. D. Pearson, in "Intermediate Organic Chemistry," translated by

The initial concentration of benzoic acid was 100 /.tmol/1. 0, glucose; /:", methanol. M. Hirota, Tokyo Kagaku Dojin, 1973, p. 138.

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