Beruflich Dokumente
Kultur Dokumente
Department of Chemical Technology, Seoul National University, Kwanak-Gu, Seoul, 151-742, Korea
and 2UNESCO Centre for Membrane Science and Technology, The University of
New South Wales, Sydney 2052, Australia
INTRODUCTION
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EXPERIMENTAL
4.9 meq/gc
2.9 meq/gc
7.8 meq/gc
Beckett, 1987, all the values are of peak maximum in ow eldow fractionation method.
Jucker and Clark, 1994, potentiometric titration data.
c
Thorn, 1989, 13 C NMR data.
b
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s
2
s 2p 1 10pKa H
2
Using the m and s, calculated by nonlinear regression
method, average dissociation, a (=dissociated functional
group/total functional group), can be obtained at any pH.
The calcium binding property was investigated by the
potentiometric measurement (Dempsey and O'Melia,
1983). Calcium selective ion electrode (AES602, Activion)
was used.
Fig. 3. Calcium complexation with humic acid as a function of pH (100 mg/l of humic acid).
Zeta-potential of nanolter
The zeta-potential of MPF34 membrane was
measured with pH and was shown in Fig. 5. The
zeta-potential of unused membrane was positive for
all pHs in the absence of humic acid. However,
when the zeta-potential was measured in the presence of humic acid, it was found to be mostly
negative except at pH 4.5. This phenomenon can be
attributed to the adsorption of negatively charged
humic acid on the positively charged membrane surface. It was assumed that the zeta-potential of
membrane surface would be more negative in the
actual nanoltration process of humic acid because
of the adsorption and deposition of humic acid on
membrane surface.
Flux and humic acid adsorption
Nanoltration of humic acid solution was performed to investigate the eect of charge of humic
acid and membrane surface on the fouling of nanolter. As shown in Fig. 6, signicant ux decline
was observed in the presence of the calcium ion
during the nanoltration of humic acid compared
with that of ultrapure water. On the other hand,
ux decline was not observed in the absence of the
calcium ion.
Except for the case of zero calcium concentration
the ux showed a distinct trend with pH regardless
of calcium concentrations (Fig. 6). The average ux
increased with pH and reached maximum value and
then decreased again. It is worth noting that this
phenomenon is coincident with the trend of
adsorbed humic acid shown in Fig. 7. The amount
of adsorbed humic acid at each pH was mostly
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4.24
3.84
6.49 meq/g
26 meq/g
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Fig. 8. Mechanism of humic acid adsorption. (a) Van der Waals force and electrostatic repulsion and
(b) bridging of calcium ion between negatively charged functional groups.
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EDTA is a strong chelating agent and the complex formation constant with calcium ion, Kf, is
5.01 1010 (Cristian, 1994). It can chelate an equivalent amount of calcium ion at alkaline conditions
and reduce the free calcium ion concentration in
solution.
Theoretically EDTA can bind the equivalent
amount of calcium ion above pH 7 if there is no
competing chelating agent as shown in Fig. 13.
However, humic acid is another chelating agent
for the calcium ion, although weaker than EDTA.
The capacity for calcium binding of humic acid
has a maximum of 2 meq/g at pH 10 as shown in
Fig. 3, while that of EDTA is 6.8 meq/g at the
same pH. Consequently most of the calcium ion is
expected to exist as CaEDTA complex rather than
CaHA.
CONCLUSIONS
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Beckett R., Jue Z. and Gidding J. C. (1987) Determination of molecular weight and distributions of
fulvic and humic acids using ow eld-ow fractionation. Environ. Sci. & Technol. 23, 394.
Cameron R. S., Thornton B. K., Swift R. S. and Posner
A. M. (1972) Molecular weight and shape of humic acid
from sedimentation and diusion measurements on fractionated extracts. J. Soil Sci. 23, 394.
Cornel P. K., Summers R. S. and Roberts P. V. (1986)
Diusion of humic acid in dilute aqueous solution.
J. Colloid Interface Sci. 110(1), 149164.
Cristian, G. D. (1994) Analytical Chemistry. John Wiley
and Sons, New York, pp. 250268.