Wat. Res. Vol. 28, No. 10, pp.

21 1994
Copyright © 1994 Elsevier Science Ltd
Pergamon Printed in Great Britain. All rights reserved
0043-1354/94 $7.00 + 0.00

HYDROXIDE PRECIPITATION OF COMPLEXED METALS

O. Ti5NAY@ and N. I. KABDA¶.I
Department of Environmental Engineering, Istanbul Technical University, i.T.Ü., ln9aat Fakültesi,
80626, Maslak, Istanbul, Turkey

(First received April 1993; accepted in revised form January 1994)

Abstract—ln this study, theoretical analysis of the complexed metal treatment by conventional hydroxide
precipitation is made. The analysis is aimed to evaluate the mechanism of ligand-sharing effect of metals which
are added to wastewater to ensure effective removal of complexed heavy metals. Theoretical expression of the
analysis is made using phase diagrams. Cadmium, copper and nickel are selected as heavy metals. EDTA, NTA
and succinic acid are selected as organic complex formers of different strengths. Calcium is used as the ligand
binding agent. Theoretical solutions are made for, single metal—single ligand system and several metal and
ligand combinations in the closed system and single metal—single ligand in the open system. Theoretical
solutions are interpreted considering the solubility, stability and ionization constants and their relative
magnitudes. Experimental studies are conducted to check the theoretical predictions. Result indicate that high
pH precipitation is applicable to the cases where organic ligand can be effectively bound by calcium or any
other coagulant or pH adjustment agent thus freeing the heavy metal to form hydroxide or carbonate solids.
Theoretical diagrams can be used to predict the favorable conditions for precipitation and as a guide to determine
the operating conditions.

Key words—Complexed metals, complexation, high pH precipitation, hydroxide precipitation,

solubilization, cadmium, copper, nickel, lime
INTRODUCTION
Heavy metals have long been known to be toxic to
human beings and to aquatic life. Their relatively newly
recognized effects such as bioconcentration have
stimulated the research efforts to rationalize the removal
mechanisms of the treatment systems which have been
commonly employed as well as to seek new and efficient
methods of treatment e.g. magnetic separation (Tamaura
et al., 1991; Patterson, 1985). Conventional methods of
heavy metal treatment in general perform satisfactorily
to meet direct discharge requirements. Hydroxide
precipitation is the most common method on the basis of
its performance, ease of operation and cost. Although,
sulfide precipitation has many advantages over
hydroxide precipitation, such as higher efficiencies
almost regardless of wastewater character, far less pH
dependency, it finds limited application because of
hazardous nature of the sludge produced, cost, and
operational difficulties. One important advantage of the
sulfide precipitation, however, is that the complexed
metals can be effectively removed due to much lesser
solubility of metal sulfides than that of hydroxides (US
EPA, 1982). Complexed metals, on the other hand,
cannot be efficiently removed by the hydroxide
precipitation and restrict the reliability and common
application of this process. Complexed metals are the
form of metals which are bound to strong complex
formers, mostly organic ligands, which keep them in
solution. This definition, although clear enough, does not
provide a basis for the differentiation of complexed
metals from those of free or weakly complexed metals.
The key point here is the "strength" which is rather a
relative measure of the binding preference of the ligand
of concern to the metal ions existing in the solution. This
complicates the definition of the complexed metals and
generalization of the methods by which the extent of the
applicability of hydroxide precipitation to complexed
metals are predicted. This is why neither a technological
basis nor effluent limitations are defined for complexed
metals while they are generally considered as a separate
subcategory of the metal finishing category (US EPA,
1982). There have been methods suggested for
complexed metal treatment such as high pH
precipitation, reduction at low pH followed by
precipitation, though their basis and applicability have
not been developed (US EPA, 1982). Therefore, these
methods are not assumed to be as "proven" technologies
on which the discharge standards are based. The
definition of complexed metals subcategory is rather
loose in that many of the organic and inorganic complex
formers that may exist in metal fishing wastewaters i.e.
phosphates, succinic acid do not exert significant effect
on the solubility of the heavy metals to necessitate a
modification of regular hydroxide precipitation. On the
other hand, some strong organic complex formers can be
effectively coped with, if the hydroxide precipitation
application incidentally meets the conditions to favor the
precipitation of the metals. Therefore, the rationale of the
complexed metals definition lies in the assessment of
wastewater quality in relation to the treatment
technology.
The theoretical basis of the hydroxide precipitation is
well known. However, the expression of the
performance of hydroxide precipitation has been on a
statistical basis due to the number of factors involved in
the process and the complexity of the way they affect
(US EPA, 1982). Following the recent developments, the
theoretical limits of the system have been evaluated to
define more stringent standards where applicable (Tünay

N. I.
2118 O. TÜNAY and
et al., 1991). The complexed metals wastewater class is importance in pollution control. The solubility
the most important exception in that its responses to controlling solid phase in the solutions is the hydroxides
hydroxide precipitation cannot be simply predicted. except the cadmium for which carbonate precipitation is
This paper attempts to theoretically analyze the also considered in closed and open system solutions.
complexed metal precipitation by conventional Theoretical solutions are made for; single metal—
hydroxide precipitation. Since the lime is the most single ligand, two metals—single ligand, single metal—
common agent for pH adjustment, emphasis is given to two ligands, in closed systems and single metal—single
calcium as the ligand-sharing metal. Theoretical study is ligand in the open system.
based on phase diagrams. Experimental studies are Hydroxocomplex species of the metals which play
conducted to check the accuracy of the theoretical important role in the solubilization are taken from the
predictions. pertinent literature (Sillen and Martell, 1964, 1971;
Kolthoff et al., 1979; Snoeyink and Jenkins, 1980). All
hydroxocomplex species which have been proved to
THEORETICAL APPROACH exist in the solution are taken into account. The stability
constants are also taken from the literature considering
Solubility of metals in the presence of complex proper ionic strengths (25 0 C, I: 0—0. l). Metal organic
formers can be studied using phase diagrams. The ligand complexes and their stability constants are also
construction of phase diagrams requires the solution of a determined in a similar way. Tables l, 2 and 3 outline
set of equations whose number equals the number of complex species and their stability constants and
species existing in the solution. Each phase diagram solubility products as they are used in the theoretical
represents the composition of the components involved solutions.
in the system depending on a selected variable. pH, as Solutions are made for the metal ions not
the master variable in acidbase systems and pH-related accompanied by anions, in other words the solutions
precipitation reactions is mostly the choice of variable. represent the solubilities which result in when the solid
Phase diagrams provide a means of representing the phase is equilibrated with water, base and organic
solubility—pH relations, solubility of species with ligands in acid form. Consequently, the
respect to one another and assessment of the critical
Table l. Solubility productsa and hydroxocomplex stability constantsa
points such as optimum pH. In this paper, theoretical
studies are based on pH—metal solubility diagrams. Constants for
There are more than 50 organic complex formers being hydroxide
used in metal finishing processes (US EPA, 1982). Many compounds Cd
K sob
of these organic ligands are also used in various 19.66
industrial applications. These ligands exist in 4.3 6.0
3.36
wastewaters singly or in combination with varying 7.7
concentrations. The composition of metal ions in the 10.3 (-
solution also varies in wide concentration ranges. 12.0 4.22)
Determination of the solubility of a metal requires the 10.48
construction of a phase diagram for the specified solution 1333 4.9 7.18
4.4
composition. However, the magnitude of the shift in the
solubility with respect to ligand-free solution can be 34.83 20.42
assessed by the diagrams for the metals of concern if the 24.2
ligands are sorted into groups which are defined by a
Logarithmic.
considering the stability constants of ligand—metal
complexes as well as their interrelation with other For carbonate.
components of precipitation system. This interpretation
is also useful for the understanding of the main
mechanisms controlling the precipitation (Kabdasll,
1990).
Organic ligands selected for the theoretical solutions
are EDTA, NTA and succinic acid all of which are of
common usage in metal finishing and other industries.
The stability of the complexes formed by EDTA, NTA
and succinic acid with heavy metals studied are
representative of strong, medium and weak complexes,
respectively. The stability constants together with the
selected concentrations delineate the competition
between ligands for the metals. The concentrations of the
ligands are selected to reflect the solubilization effects
which also serve to assess the scope of the definition of
complexed metals subcategory. Cadmium, nickel and
copper are selected for the solutions considering their
different ranges of hydroxide solubility and their
common coexistence with the ligands as well as their
 Hydroxide precipitation of complexed metals 2119
a
Table 2. Stability and ionization constants of organic ligands

Organic ligand Stability constant Cadmium Copper Nickel Calcium

EDTA
K ML
H4L I .99 16.46 18.79 18.6210.59
KMHI
H3L 2.67 3.40 5.58 3.23.18
ML.H 6.16
H2L
K MLOH2.410.26
ML,OH NTA

H3L
1.97
H2L 10.0 12.96 1 1.266.41
2.59
4.6 3.3 4.73.43
9.81
Succinic
acid 12.0 9.6112.0
MLOH,H

H2L 5.20 2.1 1.6 2.6 1.2

3.98
aLogarithmic. pH
3 46
Fig. l. Cu—EDTA (10 - M system solubilities with
this approach reflect the higher solubilities and the different anions existing in solution.
general character of the graphs are not significantly
As pointed out above the solubility of Cd is mainly due
affected at low and medium concentrations of the anion
to the major species CdL 2 - and Cd precipitation can be
and can be taken as general references for solubility
carried out if the concentration of this complex is
evaluations. Figure l , shows the solution of Cu—
reduced. This reduction can be provided if another metal
EDTA—Ca system with different concentrations of and
competes for the ligand and shares a part of it. However,
S02
the competing metal must be environmentally acceptable
and common as a reactive as well as being an effective
THEORETICAL SOLUTIONS competitor.
The alternatives of the metals are determined to be
Figure 2, shows the response of complexed metal to
Mg2 + Mn 2 + Fe2 + Fe 3 + and Ca 2 + A study conducted
hydroxide precipitation in comparison with
to find out the applicability of these cations indicated that
uncomplexed metal where only NaOH is used for pH
Fe 3 + is not effective due to low solubility. Fe2 + and Mn
adjustment in the Cd—EDTA system. Evaluation of the 2 + are readily oxidizable at high pH. Mg2 + is not soluble
species distribution at each pH indicates that the major
at high pH, however can be used instead of Ca2 + when
species increasing the complexed metal solubility is
the alkalinity is high. Ca2 * is determined to be the most
CdL2 - (CdEDTA) whose concentration is practically
effective ligand-binding agent (Tünay et al., 1993).
unaffected by pH. NaL 3 -, on the other hand, is a very
Figure 3, shows the Cd—EDTA—Ca systems at
weak complex whose concentration can become
different ligand concentrations. Ligand binding effect of
comparable with that of CdL2 - only after pH 13. Then
Ca becomes significant beginning approximately the
the behaviour of Cd complexed with EDTA is a good
optimum pH of Cd and Cd concentrations then decline
example of why hydroxide precipitation does not work
rather steeply for higher ligand concentrations and meet
with complexed metals.
3
hydroxide solid line. These intersection points are
important since they represent the

14
2120 O. TÜNAY and
pH
Fig. 2. Cd-EDTA -Na system (symbols for experimental
results: this study A without EDTA; with EDTA; Patterson's
study (1977) without EDTA).
 Hydroxide precipitation of complexed metals 2121
N
M EDTA .
1 acid NTA

O 10-2
o 3

4 8 10 12 13 14

5
6
7
8 9 10 Il 12 13 14
pH
Fig. 3.system (symbols for experimental results: M EDTA; M
EDTA; Awithout EDTA).
return to ligand-free conditions. Although these points
can be calculated theoretically or determined on the
graphs, the following approximation for Cd—EDTA
system is helpful for rapid estimation
[CdL2-]
o (l) [CaL 2 -]
At the intersection point the [CdL- ] ratio is generally
less than 0.01. By applying this ratio for 10 346 M ligand
the intersection point pH is found as 12.07 which is close
enough to the exact value of 12. l. Derivation of equation
(l) is based on the fact that [Ca2 +] value can be
approximated from the combination of electroneutrality
equation and mass balance on ligand and by neglecting
the minor terms.
Cadmium phase diagrams for NTA and succinic acid
are given in Fig. 4. Ligand binding effect of calcium
becomes significant at lower pH values in the
pH
Fig. 4. Cd—NTA Ca and Cdsuccinic acid-Ca systems.
case of NTA as compared to EDTA. The decrease in
the solubility with increasing pH is gradual. For Cd—
NTA—Ca system with the same approximation as
above the following ratio is obtained
(2)
In the case of succinic acid, however, ligand effects for
all calculated concentrations, are almost totally
eliminated as the optimum pH is reached.
Figure 5 shows and Ni-NTA-Ca
systems. Although solubility product of nickel
hydroxide is smaller than that of cadmium, its response
to EDTA and Ca binding of the ligand is similar to
cadmium system because of the higher stability constant
of NiL2 - as compared to CdL2 . On the other hand, the
response of the Cu—EDTA—Ca system shown in Fig.
6, is a steeper decrease in the solubility after the
optimum pH and the system returns to hydroxide phase
at a comparatively lower pH. The optimum pH of nickel
is close to copper. Therefore, the change in the response
is owing to much lower solubility of copper hydroxide
while the magnitude of stability constants of CuL2 - and
Nil- 2 - is the same. A comparison of Ni—NTA—Ca and
systems shows that the effect of NTA on the Ni
solubility decreases sharply with increasing pH while
the decrease in Cd solubility is rather gradual. However,
shape of the curves are similar for both metals and
systems turn back to hydroxide solubility as their
optimum pH values are exceeded about one pH unit.
This response is predictable since the stability constants
for CdL2 - and NiL2 - are comparable and nickel
hydroxide has a lower solubility. Cu—NTA—Ca
system responses are similar to nickel, however, the
effect of NTA can be compensated at lower pH values
due to low solubility of copper hydroxide. The ratios of
the stability constants of ligand—Ca to ligand heavy
O. TÜNAY and I. KABDA}LI
metal are of similar values for both EDTA and NTA. compensation with Ca ions are similar in character for
Therefore, the ligand-induced solubility especially Cu and Ni whose solubility products are
comparable, and solubilities sharply decrease beginning
0 2 76 M optimum pH of the metals. For higher solubilities as in
2
0 10 -3 46 M the case of Cd, solubility compensation by ligand-
sharing effect of Ca, is gradual with increasing pH. The
effect of ligand concentration on the solubility becomes
very small at the points of intersection. Therefore, a
selected pH value within the neighborhood of
intersection points for a metal— ligand system can be a
measure of the beginning of the free metal hydroxide
precipitation.
The effect of more than one ligand on solubility can
3 be explained using the above approach. Figure 7, shows
the combined effect of EDTA and NTA on Cd solubility
4 when is used as a pH adjustment agent. When both
EDTA and NTA exist at 10 -346 M the effect is a good
5 example of the competition between the ligands for the
metals. At low pH values the ligand-binding capability of
6 Ca is negligible due to the low concentration. Before the
optimum pH of Cd, at pH 10 and lower, Cd solubility is
7
approximately the sum of the two solubility values
provided
8 9 10 Il 12 13
pH M

Fig. 5. Ni EDTAXa and Ni NTA Ca systems (symbols for

- 10 3 46 M EDTA - 10 3 46 M NTA
_3_46
0 10 276 M @ 10-3 10 M EDTA
10 346

10 4 45 EDTA - 10-3 M NTA

46 M

-4
2
experimental results of Ni—EDTA-CA system:
EDTA; EDTA).
2 3

3 4

4
5
5
6
6

7 8 9 10 12 13 14

pH
8
Fig. 7. Ca system.
9
by the two ligands when they singly exist. At pH 10
major complexes of Ca, CaL2 - (10 665 M) and CaL-(lO 442
5 6 7 8 9 10 12 13 14
M), however, have higher concentrations than those
pH obtained in single ligand cases (CaL2 -: CaL-: 10 -48 ). At
Fig. 6. Cu-EDTA-Ca and systems. pH I l, EDTA becomes the major ligand determining Cd
solubility. At this pH the distribution of ligands to metals
roxide precipitation of complexed metals 2123 10 M EDTA
(CdL 2 -: 10 -348 M; CdL-: 10 -483 M) is well reflected by 2
10 M EDTA
the stability and ligand ionization constants. Ni - EDTA
Lower ionization constants decrease both CdL2 and
CaL 2 - concentration while CaL/CdL ratio is less affected.
If we re-calculate the species distribution of NTA
system assuming that only the pK3 of
NTA is changing from 9.81 to 15; at pH Il and 10 -346 M
ligand concentration, the values of CdLi and Calai will be
respectively 10 548 M and 10 -4 -23 M as compared to NTA 3
system which yields 10 -466M and 10 -349 M for CdL
and CaL respectively, while the Cal: /CdL- ratios are 4
approximately 15 and 18 for NTA and hypothetical L3
ligand cases respectively. In the case of EDTA—Cd—Ca
5
system the above ratio is approximately 0.1 due to 00 o
relatively higher stability constant of CdL2 - than that of 6
CaL2 -. Then if EDTA and NTA are mixed at the same
concentration of 10 -3 •46 M at pH Il the CaL2 -/CdL2 -
7
ratio is 0.06 and CdL2 - concentration is comparable with
that of EDTA single ligand system. NTA binding at pH Il
7 8 9 10 12 13
has Cal. - (CdL ratio of 22.4 which yields a lower but
again a comparable concentration (the ratio is 14.8) of pH
CdL with that of NTA single ligand system. Therefore, Fig. 9. Nickel phase diagram for
beginning pH Il Cd solubility is practically identical with (symbols for experimental results
that of Cd—EDTA—Ca system. Another combination of system: 010 346 M EDTA:
shown in Fig. 7 is Cd solubility in 10 -445 M EDTA and 10
-3 M NTA mixture which represents the case where
strong ligand has lower concentration while the weak ever, beginning pH 10 the graph follows a way in
one is of higher concentration. At pH 10, high solubility between 10 M NTA and M EDTA single ligand graphs,
of Cd (10 -3 •03 M) is mainly owing to high at pH I I concentration of CdEDTA (CdL 2 : 10 -45 M)
concentrations of CdNTA (CdL ) complex (10 -3 •06 M) and CdNTA (CdL : M) become approximately the same.
and the Cd solubility is far above the single ligand EDTA Figures 8 and 9 show two metals, Cd and Ni and one
M case (10 44 M). How- ligand EDTA system where pH adjustment is with
At pH 9 nickel solubility is less than that of
O C) -4 M EDTA Ni—EDTA system, The competition between the metals
10 45 can be represented by the ratio
Cd
[CdL2 ] K SO,Cd KS.Cd
Cd
(3)
- [NiL 2 -] K SO,Ni KS.Ni
N. K
M M EDTA
EDTA
- EDTA
2

8 9 10 13 14

pH 8 9 10 Il 12 13 14
Fig. 8. Cadmium phase diagrams for Cd Ni- EDTA Ca system pH
(symbols for experimental results
of M EDTA; M
Fig. 10. and
systems.
EDTA).
O. TÜNAY and I. KABDA}LI
hand, free calcium concentration depends mainly on
the total ligand concentration and pH as explained in
the derivation of equation (l). At the same pH, [Ca2 +]
is determined by total ligand concentration. Therefore,
[Ca2 +] will be the same in Cd-Ni-EDTA and Cd—
EDTA systems. Total calcium in solution is also almost
the same as in Cd—EDTA system only slight
difference at pH I I being due to sharing the ligand with
nickel.
which yields 10 1 1 being independent of pH. This ratio
indicates that Cd solubility in the metals mixture will be
less affected as compared to Cd—EDTA system, while
nickel solubility is reduced. Therefore the ligand sharing
is a result of combined effect of stability constants and
solubility products. Here, although the stability constant
of NiEDTA (NiL2 - ) is bigger than that of Cd—EDTA,
the lower solubility of makes Ni less soluble than
single ligand case and higher concentration of Cd2v
results in Cd—EDTA complexation. In the abovc
system let Cd' be a hypothetical metal taken instead of
nickel with a hydroxide solubility very close to Cd and
having the stability constant of Cd'L (with EDTA) 10 1862
which is equal to that of NiL 2 . Here the ratio of
and this significant differ-
cnce decreases the Cd solubility to an extent which
practically equals, at almost all pH values, the Cd
solubility when no ligand exists. However, the Cd'
solubility varies in a way similar to that of Cd in single
metal•ingle ligand system. At pH I l , the difference
between Ni solubility in single metal and two metals
cases reduces in parallel with the decrease in NiL2
concentration, however, this reduction does not affect
the Cd solubility significantly. On the other
Closed system, (Exp, pts) Open system, (Exp. pts)
8 9 10 12 13 14
without EDTA (A) - without EDTA (A)
Figure 10 shows system. Since
the stability constants of CdNTA (CdL- ) and NiNTA
(NiL- ) are comparable and Cd hydroxide solubility is
much higher than that of nickel, Cd solubility graph is
practically the same as Cd—Ca—NTA system. Nickel,
on the other hand, has lower solubilities at lower pH
values and the solubil-
pH
Fig. I I . Carbonate precipitation in open and closed systems.
ity returns to the level that of Ni—Ca—NTA
system at pH l l .
Carbonate precipitation of cadmium is effective at
high alkalinities. Figure I l shows carbonate— hydroxide
precipitation phase boundaries at 1000 mg/l CaC03
alkalinity. When 10 -346 M EDTA exists and pH
adjustment is with NaOH and Cd solubility is almost
constant.
In such a case metals with high carbonate solubility
can be used to carry out the ligand sharing function. In
the open system, carbonate ion reaches very high
concentrations, if the pH is increased with NaOH. If I(F
A6 M EDTA exists in this system cadmium solubility
decreases beginning pH 12 due to huge amount of Na+
added to the system for carbonate balancing which
combines the ligand and then very low cadmium
concentrations may be obtained (Fig. I l ).
EXPERIMENTAL
Materials and Methods
and solids are obtained by precipitation of CdC12
and NiC12 respectively. NaOH is used for precipitation.
Dissolved ions are removed by washing with distilled water
and degree of removal is checked by chloride determination.
All chemicals used are reagent grade. Millipore 0.45 um
membrane filters are used for filtration. pH measurements are
with Metrohm Herisau Model E 510 pH meter. Rank Hilger
Atomspeck H5150 model Atomic Absorption
Spectrophotometer is used for metal measurements. All
determinations are according to Standard Methods (APHA,
1989).
Procedure
250 ml beakers are used for the experiments. Distilled water
used in the experiments is type Il as defined in Standard
Methods (APHA, 1989). Titriplex Il (acid form of EDTA) and
NaOH, or NaŽC03 are added on solid hydroxides. Closed
system experiments are continued for 24 h with pH control.
The samples are overlaid with a layer of paraffin of
approximately 0.5 cm thickness immediately after addition of
reactives to ensure closed system conditions. Then the mixture
is filtered and filtrates are acidified with nitric acid and stored
for measurements. Open system experiments are allowed to
continue for I week,
RESULTS
Results of cadmium precipitation experiments in the
system with NaOH and lime and with and without
EDTA arc given in Figs 2 and 3 respectively. Cadmium
precipitation in the systems with no ligand yields points,
which although lower than predicted, follow the general
character of theoretical line. The difference would be
due to the values of solubility product and stability
constants selected. On the other hand, the experimental
roxide precipitation of complexed metals
points obtained in another study by Patterson (1977) for
Cd-NaOH system provide a better fit as seen in Fig. 2.
However, the theoretical predictions are accurate enough
for most of the purposes. Experimental points of the
systems with EDTA and have the same degree of fit and
trace the same shape as of the theoretical solubility lines.
In case of EDTA—Na system the points are on the
theoretical line. A similar fit is obtained for carbonate
precipitation of Cd— EDTA—Na in closed system (Fig.
I l) and in the open system with equilibrium alkalinity
(Fig. I l ). Figure 5 shows the Ni—EDTA—Ca system
with experimental points where even a better fit is
obtained. Solubilities in system with
experimental points are shown in Figs 8 and 9.
Experimental fit especially in Fig. 9 indicates the
validity of the theoretical approach even in such
complex systems.
CONCLUSIONS
Hydroxide precipitation is, although other methods
have been developed, still the most common and
effective method of treatment for heavy metals.
Complexed metals are becoming common not only in
the metal finishing industry but also in many other
industrial branches such as electronics, mining, etc. The
concentrations of organic ligands in the wastewaters also
tend to increase. These developments necessitate the
definition of the limits of complexed metal treatment by
conventional hydroxide preicipitation application.
Theoretical assessment of metal solubility in
wastewaters may not provide very accurate results,
however, especially if the species and their
thermodynamic constants are interrelated with solution
characteristics and carefully evaluated, this approach
provides a basis by which the practical applications can
be adequately managed. Complexed metals treatment by
chemical precipitation which is neither theoretically nor
practically well defined is a suitable case for the
application of the above approach.
Results of the theoretical evaluation delineated in this
study can be summarized as follows:
Phase diagrams provide a means to assess the general
character of the metal—ligand mixtures. The extent of
the effects of ligands on the metal solubility can be
determined within an acceptable range of accuracy
provided that realistic constants can be defined for the
case of concern. Literature data as well as the
experimental studies conducted in this study verify this.
Theoretical basis of the complexed metal
precipitations at high pH is the ligand sharing effect of
the base used for the pH adjustment. For the bases whose
metal ion has negligible ligand binding capacity such as
NaOH, high pH precipitation is not meaningful. The
criteria for the cation to be effective are; the pH-
solubility curve must have a minimum and this
minimum should be close enough to the optimum pH of
the heavy metal to provide a low solubility at applicable
high pH values. In some cases where low solubilities can
be obtainable within a wider pH range, carbonate
precipitation may be applicable.
2125
The shape of the heavy solubility
curves obtained in this study are suitable for
interpolation to provide a quick reference for solubility
assessment at different ligand concentrations. This
approach can be extended to obtain graphs for each
metal with calcium and with different ligands which are
represented by stability constants of different
magnitude.
Solubility graphs can also be used as a basis for the
definition of complexed metals subcategory. The pH
interval employed in hydroxide precipitation of socalled
common metals is generally between 8 and I l . Then this
pH interval or upper limit of this interval can be taken as
a measure to define the complexed metals. For instance,
if the solubility line of a metal—ligand—Ca system
coincides with metal hydroxide solubility before pH I l
this system can be considered within the common metals
subcategory provided that lime is used in the treatment.
If the solubility of the metal turns back to hydroxide
solubility after pH I l then the system is considered as
complexed metal which requires high pH application for
effective treatment. This would call for new standards to
be defined.
Of course the selection of appropriate pH levels
requires a thorough evaluation of the all potential
combinations. Equation (l) in general form can be used
to determine the required pH for obtaining ligand-free
precipitation efficiency. Some ligands i.e. succinic acid
has considerable effect on solubility at low pH, however,
they are of no importance at high pH. Similarly, many of
the organic ligands can be classified as having negligible
effect on solubility in the hydroxide precipitation or in
other words excluded from the complexed metals
subcategory by defining upper concentration levels.
Operating conditions of complexed metal
precipitation can be determined using the diagrams.
Relative efficiencies of the metal removals can be
predicted especially in case of mixtures. In some cases
selective removal of a certain metal may be realized by
adding appropriate metals or bases. The amount of
chemicals required for precipitation can also be
determined.
In the high pH precipitation mode ligands which are
harmful in many ways are released to environment with
the treated water. Ligands in the effluent, however, are
to a great extent bound into a single compound i.e. CaL
which being in this form or with proper modification in
the structure can be removed or recovered, if appropriate
methods of treatment can be developed.
REFERENCES
APHA, AWWA and WPCF (1989) Standard Methods for the
Examination of Water and Wastewater, 17th Edn, Am. Publ.
Hlth Assoc., Am. Wat. Works Assoc. and Wat. Pollut.
Control Fedn, Washington, D.C.
Kabdasll N. I. (1990) The treatment of complexed heavy
metals by hydroxide precipitation method, M.Sc. thesis,
Istanbul Technical University (in Turkish).
Kolthoffl. M. and Elving P. J. (1979) Treatise on Analytical
Chemistry, Vol. 2, Part I. Wiley Interscience, N.Y.
Patterson J. W. (1985) Industrial Wastewater Treatment
Technology, 2nd Edn. Butterworth, London.
N.
O. TÜNAY and I. KABDA}LI
Patterson J. W. , Allen H. E. and Scala J. J. (1977) Carbonate
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