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

2117-2124, 1994
~ Pergamon 0043-1354(94)E0023-Y
Copyright © 1994ElsevierScience Ltd
Printed in Great Britain.All rights reserved
0043-1354/94$7.00+ 0.00

H Y D R O X I D E PRECIPITATION OF C O M P L E X E D METALS

O. TUNAY@ and N. I. KABDA~;LI@

Department of Environmental Engineering, Istanbul Technical University, I.T.O., In~aat Fakiiltesi,
80626, Maslak, Istanbul, Turkey

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

Abstract--In 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 analysisis 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, singlemetal-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 solution. This definition, although clear enough, does

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 dis-
charge requirements. Hydroxide precipitation is the
most common method on the basis of its perform-
ance, ease of operation and cost. Although, sulfide
precipitation has many advantages over hydroxide
precipitation, such as higher efficiencies almost re-
gardless of wastewater character, far less pH depen-
dency, 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 com-
plexed metals can be effectively removed due to much
lesser solubility of metal sulfides than that of hydrox-
ides (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
not provide a basis for the differentiation of com-
plexed 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 com-
plexed 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 subcate-
gory of the metal finishing category (US EPA, 1982).
There have been methods suggested for complexed
metal treatment such as high pH precipitation, re-
duction 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. phos-
phates, 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 precipi-
tation application incidentally meets the conditions

2117
2118 O. T1]NAYand N. 1. KABDA~LI

to favor the precipitation of the metals. Therefore, mechanisms controlling the precipitation (Kabda~h,
the rationale of the complexed metals definition lies 1990).
in the assessment of wastewater quality in relation to Organic ligands selected for the theoretical sol-
the treatment technology. utions are EDTA, NTA and succinic acid all of which
The theoretical basis of the hydroxide precipitation are of common usage in metal finishing and other
is well known. However, the expression of the per- industries. The stability of the complexes formed by
formance of hydroxide precipitation has been on a EDTA, NTA and succinic acid with heavy metals
statistical basis due to the number of factors involved studied are representative of strong, medium and
in the process and the complexity of the way they weak complexes, respectively. The stability constants
affect (US EPA, 1982). Following the recent develop- together with the selected concentrations delineate
ments, the theoretical limits of the system have been the competition between ligands for the metals. The
evaluated to define more stringent standards where concentrations of the ligands are selected to reflect
applicable (Tfinay et al., 1991). The complexed metals the solubilization effects which also serve to assess the
wastewater class is the most important exception in scope of the definition of complexed metals subcate-
that its responses to hydroxide precipitation cannot gory. Cadmium, nickel and copper are selected for
be simply predicted. the solutions considering their different ranges of
This paper attempts to theoretically analyze the hydroxide solubility and their common coexistence
complexed metal precipitation by conventional hy- with the ligands as well as their importance in
droxide precipitation. Since the lime is the most pollution control. The solubility controlling solid
common agent for pH adjustment, emphasis is given phase in the solutions is the hydroxides except the
to calcium as the ligand-sharing metal. Theoretical cadmium for which carbonate precipitation is also
study is based on phase diagrams. Experimental considered in closed and open system solutions.
studies are conducted to check the accuracy of the Theoretical solutions are made for; single
theoretical predictions. metal-single ligand, two metals-single ligand, single
metal-two ligands, in closed systems and single
metal-single ligand in the open system.
THEORETICAL APPROACH Hydroxocomplex species of the metals which play
important role in the solubilization are taken from
Solubility of metals in the presence of complex the pertinent literature (Sillen and Martell, 1964,
formers can be studied using phase diagrams. The 1971; Koithoff et al., 1979; Snoeyink and Jenkins,
construction of phase diagrams requires the solution 1980). All hydroxocomplex species which have been
of a set of equations whose number equals the proved to exist in the solution are taken into account.
number of species existing in the solution. Each phase The stability constants are also taken from the liter-
diagram represents the composition of the com- ature considering proper ionic strengths (25°C, I:
ponents involved in the system depending on a 0-0.1). Metal organic ligand complexes and their
selected variable, pH, as the master variable in acid- stability constants are also determined in a similar
base systems and pH-related precipitation reactions way. Tables 1, 2 and 3 outline complex species and
is mostly the choice of variable. Phase diagrams their stability constants and solubility products as
provide a means of representing the solubility-pH they are used in the theoretical solutions.
relations, solubility of species with respect to one Solutions are made for the metal ions not ac-
another and assessment of the critical points such as companied by anions, in other words the solutions
optimum pH. In this paper, theoretical studies are represent the solubilities which result in when the
based on pH-metal solubility diagrams. There are solid phase is equilibrated with water, base and
more than 50 organic complex formers being used in organic ligands in acid form. Consequently, the
metal finishing processes (US EPA, 1982). Many of
these organic ligands are also used in various indus- Table I. Solubility products a and hydroxocomplex stability
constants a
trial applications. These ligands exist in wastewaters
C o n s t a n t s for
singly or in combination with varying concentrations.
hydroxide compounds Cd Cu Ni
The composition of metal ions in the solution also
Kso -13.93 -19.66 -17.19
varies in wide concentration ranges. Determination K~o -11.18 -- --
of the solubility of a metal requires the construction //11 4.3 6.0 3.36
of a phase diagram for the specified solution compo- fl21 (K32) 7.7 -- ( - 7.0)
fl~t(K33) 10.3 (-4.99) (-4.22)
sition. However, the magnitude of the shift in the f141 (K34) 12.0 (-4.09) --
solubility with respect to ligand-free solution can be flsI 11.36
fl6t 10.48 -- --
assessed by the diagrams for the metals of concern if flt2 4.9 7.18 4.4
the ligands are sorted into groups which are defined fl:2 -- 17.11 --
by considering the stability constants of ligand-metal fl33 -- 20.42
fl43 -- 34.83 --
complexes as well as their interrelation with other fl,~ 24.2 -- 27.58
components of precipitation system. This interpret- aLogarithmic.
ation is also useful for the understanding of the main bFor c a r b o n a t e .
 Hydroxide precipitation of complexed metals 2119

Table 2. Stabilityand ionizationconstantsa of organic ligands

Organic ligand Stability constant Cadmium Copper Nickel Calcium
EDTA

H4L 1.99 K ML
M.L 16.46 18.79 18.62 10.59
H 3L 2.67 KML,HMHI" 3.40 5.58 3.2 3.18
H2L 6.16 Kwr,o
HML°H -- 2.4 -- --
HL 10.26
NTA

H3L 1.97 K M,L

ML 10.0 12.96 11,26 6.41
H2L 2.59 KML,LM2L 4.6 3.3 4.7 3.43
HL 9.81 ~L
K MLOH.H 12.0 9.61 12.0 --
Succinic acid

H2L 5.20 K ML
M,L 2.1 1.6 2.6 1.2
HL 3.98
~Logarithmic.

this approach reflect the higher solubilities and the
general character of the graphs are not significantly
affected at low and medium concentrations of the
anion and can be taken as general references for
solubility evaluations. Figure 1, shows the solution of
C u - E D T A - C a system with different concentrations
of C1- and SO4:-.
THEORETICAL SOLUTIONS
Figure 2, shows the response of complexed metal
to hydroxide precipitation in comparison with un-
complexed metal where only NaOH is used for pH
adjustment in the C d - E D T A system. Evaluation of
the species distribution at each pH indicates that the
major species increasing the complexed metal solubil-
ity is CdL 2 (CdEDTA) whose concentration is
practically unaffected by pH. NaL 3-, on the other
hand, is a very weak complex whose concentration
can become comparable with that of CdL 2- only
after pH 13. Then the behaviour of Cd complexed
with EDTA is a good example of why hydroxide
precipitation does not work with complexed metals.
3 --
As pointed out above the solubility of Cd is mainly
due to the major species CdL 2- and Cd precipitation
can be carried out if the concentration of this com-
plex is reduced. This reduction can be provided if
another metal competes for the ligand and shares a
part of it. However, the competing metal must be
environmentally acceptable and common as a reac-
tive as well as being an effective competitor.
The alternatives of the metals are determined to be
Mg 2+, Mn 2+, Fe 2+, Fe 3÷ and Ca 2÷. A study con-
ducted to find out the applicability of these cations
indicated that Fe 3÷ is not effective due to low solubil-
ity. Fe :÷ and Mn 2÷ are readily oxidizable at high pH.
Mg 2÷ is not soluble at high pH, however can be used
instead of Ca 2÷ when the alkalinity is high. Ca 2+ is
determined to be the most effective ligand-binding
agent (Tiinay et aL, 1993).
Figure 3, shows the C d - E D T A - C a systems at
different ligand concentrations. Ligand binding effect
of Ca becomes significant beginning approximately
the optimum pH of Cd and Cd concentrations then
decline rather steeply for higher ligand concen-
trations and meet hydroxide solid line. These intersec-
tion points are important since they represent the

IF.
4 -- ,

'(\ \ \ /
/ 2 • (D 10-3'46 M E D T A /

.= .~ 3

o
o e-
7 -- /~ \ ' with no anion
"7 (~/- ' \ / Q 2500mg11CI-
8 - \ / ® 500 el- 6 - -

® 5o0
I I* I I I I
9 I 1 I I I I 9 10 11 12 13 14
9 10 11 12 13 14
pH
pH
Fig. 2. Cd-EDTA-Na system (symbols tbr experimental
Fig. 1. Cu-EDTA (10 34oM ) ~ a system solubilities with results: this study • without EDTA; • with EDTA;
different anions existing in solution. Patterson's study (1977) • without EDTA).
2120 O. TONAY and N. I. KABDA~;LI

(~) 10 -2.76 M EDTA

case of NTA as compared to EDTA. The decrease in
-- (~) 10-3.46 M EDTA the solubility with increasing pH is gradual. For
C d - N T A - C a system with the same approximation as
~" 2
above the following ratio is obtained
o /
.o 3 [CdL ] Ksl 2Kso,cd[H + ]2
®o ~ " [ C a L - ] = K s , 2 / Kw ~' (2)

o
4 ~ K w k [ - ~ + CT.c )
r.,a

5 In the case of succinic acid, however, ligand effects

o
i for all calculated concentrations, are almost totally
I I I I*
8 9 10
pH
Fig. 3. Cd-EDTA-Ca system (symbols for experimental
results: O10 346M EDTA; 1110 -4.45 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
C d - E D T A system is helpful for rapid estimation
[CdL 2~ ] Ks1
[CaL:-] KsZK2w(2_~]
+Kw
At the intersection point the [CdL 2 ]/[CaL 2 ] ratio is
generally less than 0.01. By applying this ratio for
10 -3.46 M ligand the intersection point pH is found as
12.07 which is close enough to the exact value of 12.1.
Derivation of equation (1) is based on the fact that
[Ca 2+ ] value can be approximated from the combi-
nation 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
- - Succinic acid
C) 1 M
(~) I O - ' M
(~) IO-2M
eliminated as the optimum pH is reached.
Figure 5 shows N i - E D T A - C a and N i - N T A - C a
I I I systems. Although solubility product of nickel hy-
11 12 13 14 droxide 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 con-
stant of NiL 2- as compared to CdL 2-. On the other
hand, the response of the C u - E D T A - C a 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
Kso.cd[H+]2 stability constants of CuL 2 and NiL 2 is the same.
CT.C)" (l)
A comparison of N i - N T A - C a and C d - N T A - C a
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. How-
ever, 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 con-
stants for CdL 2- and NiL 2 are comparable and
nickel hydroxide has a lower solubility. C u - N T A ~ S a
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 metal are of similar values for both EDTA
NTA
and NTA. Therefore, the ligand-induced solubility
(~) 10-2"76M
(~) 10_3.46M 1 ( D 10-276M
0 10-445M 2 (~) 10-3"46M

3
e.
8 4
@"" ~ 5
"7
_ W
~ 6
5
Xkq,\\\/ .,
I I I 1 I t I I
6 -- 7 S 9 10 11 12 IS 14
I I [ I I I pH
10 11 12 13 14
Fig. 5. Ni EDTA~Ca and Ni NTA-Ca systems (symbols
pH for experimental results of Ni--EDTA-CA system:
Fig. 4. Cd-NTA Ca and Cd-succinic acid-Ca systems. O10-346M EDTA; 1 1 0 - 4 4 5 M EDTA).
 Hydroxide precipitation of complexed metals 2121
1
(D 10-2"76M by the two ligands when they singly exist. At pH 10
2 -- major complexes of Ca, CaL 2- (10-6'65M) and
C) (~) 10-3,46 M
CaL-(10-442M), however, have higher concen-
3 trations than those obtained in single ligand cases
\-'~"~ ~ "x~'~N EDTA ( C a L 2 - : 10-68; C a L - : 10-48). At pH 11, EDTA
4 X (i) _ \:~.X~X - - NTA / becomes the major ligand determining Cd solubility.
5 At this pH the distribution of ligands to metals
8 (CdL:-: 10 -3.48 M; CdL-: 10 -4.83 M) is well reflected
6 by the stability and ligand ionization constants.
7 Lower ionization constants decrease both CdL 2-
I and CaL 2- concentration while CaL/CdL ratio is less
8 affected. If we re-calculate the species distribution of
NTA (10-3~)-Cd-Ca system assuming that only the
9
[ I I I I I I I I I pK 3 of NTA is changing from 9.81 to 15; at pH 11
6 7 8 9 10 II 12 13 14 a n d 10-346M ligand concentration, the values of
pH CdL 3 and CaLf will be respectively 10 548M and
10 -4.23 M as compared to NTA system which yields
Fig. 6. C u - E D T A - C a and Cu NTAqZa systems.
10-466M and 10 -3'49 M for CdL- and CaL respect-
ively, while the C a L - / C d L - ratios are approximately
compensation with Ca ions are similar in character 15 and 18 for NTA and hypothetical L3 ligand cases
for especially Cu and Ni whose solubility products respectively. In the case of EDTA-Cd-Ca system the
are comparable, and solubilities sharply decrease above ratio is approximately 0.1 due to relatively
beginning optimum pH of the metals. For higher higher stability constant of CdL 2 than that of
solubilities as in the case of Cd, solubility compen- CaL 2-. Then if EDTA and NTA are mixed at the
sation by ligand-sharing effect of Ca, is gradual with same concentration of 10 -3.46 M at pH 11 the
increasing pH. The effect of ligand concentration on CaL: /CdL 2- ratio is 0.06 and CdL 2- concentration
the solubility becomes very small at the points of is comparable with that of EDTA single ligand
intersection. Therefore, a selected pH value within system. NTA binding at pH 11 has CaL-/CdL ratio
the neighborhood of intersection points for a metal- of 22.4 which yields a lower but again a comparable
ligand system can be a measure of the beginning of concentration (the ratio is 14.8) of CdL with that of
the free metal hydroxide precipitation. NTA single ligand system. Therefore, beginning pH
The effect of more than one ligand on solubility can 11 Cd solubility is practically identical with that of
be explained using the above approach. Figure 7, Cd-EDTA-Ca system. Another combination shown
shows the combined effect of EDTA and NTA on Cd in Fig. 7 is Cd solubility in 10 -4.45 M EDTA and
solubility when Ca(OH)2 is used as a pH adjustment 10-3 M NTA mixture which represents the case where
agent. When both EDTA and NTA exist at 10 -3.46M, strong ligand has lower concentration while the weak
the effect is a good example of the competition one is of higher concentration. At pH 10, high
between the ligands for the metals. At low pH values solubility of Cd (10 -3.03 M) is mainly owing to high
the ligand-binding capability of Ca is negligible due concentrations of CdNTA ( C d L ) complex
to the low concentration. Before the optimum pH of (10-3°6M) and the Cd solubility is far above the
Cd, at pH 10 and lower, Cd solubility is approxi- single ligand EDTA 10 -4.45 M case (10 4.4 M). How-
mately the sum of the two solubility values provided
(~) 10 - 3 . 4 6 M E D T A
-- - - 10 - 4 . 4 5 M E D T A - 10 - 3 M N T A
® -4.4 M /
L -- -- 10 - 3 . 4 6 M E D T A - 10 - 3 . 4 6 M N T A

1 ...... 10-346 M EDTA

10 - 3 ' 4 6 M N T A
\ - - C d - N i - E O T A
/
2
- 40

~
e- 4
8
8 4 2I 5

6
rl i i i I i i
6
8 9 10 11 12 13 14
I I I I I I
8 10 11 12 13 14 pH
pH Fig. 8. Cadmium phase diagrams for Cd N i - E D T A - C a
system (symbols for experimental results of
Fig. 7. C d - E D T A - N T A - C a system. C d - N i - E D T A - C a : O10 3.46M EDTA; 1104.45 M EDTA).
2122 O. TONAY a n d N . I. KABDA~LI

Q 10-3"46 M E D T A I --
(T) 10 -2.76 M N T A
O 10-4"45 M E D T A
(~) 10-3'46M N T A
Ni - EDTA 2
- - Cd- Ni- EDTA ~~~ 3~, 10-4"45
N T AMc /d /

O ~3
e-
?,
t-
g
4 od
_o
i
g s
\ /
"7 6 _\ ® /
I I I I I [
8 9 10 11 12 13

pH I I [ I I I I
8 9 10 II 12 13 14
Fig. 9. Nickel phase diagram for Cd Ni-EDTA~Ca system
(symbols for experimental results of Cd Ni-EDTA-Ca pH
system: O10 346M EDTA: II10 445M EDTA).
Fig. 10. Cd-NTA-Ca and Ni NTA~Ca systems.

hand, free calcium concentration depends mainly on

ever, beginning pH 10 the graph follows a way in
between 10 3.46M NTA and 10 346M EDTA single
ligand graphs, at pH 11 concentration of CdEDTA
(CdL 2 : 10 45M) and CdNTA (CdL : 10 -438 M )
become approximately the same.
Figures 8 and 9 show two metals, Cd and Ni and
one ligand EDTA system where pH adjustment is
with Ca(OH) 2. At pH 9 nickel solubility is less than
that of Ni-EDTA system. The competition between
the metals can be represented by the ratio
[CdL 2 ] _ Kso,cd Ks,cd
(3)
[NiL 2 ] Kso.NiKs.Ni
which yields 10~t being independent ofpH. 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 lig-
and sharing is a result of combined effect of stability
constants and solubility products. Here, although the
stability constant of NiEDTA (NiL 2- ) is bigger than
that of Cd-EDTA, the lower solubility of Ni(OH) 2
the total ligand concentration and pH as explained in
the derivation of equation (1). At the same pH,
[Ca-'+ ] is determined by total ligand concentration.
Therefore, [Ca 2+ ] will be the same in C d - N i - E D T A
and Cd-EDTA systems. Total calcium in solution is
also almost the same as in Cd-EDTA system only
slight difference at pH 11 being due to sharing the
ligand with nickel.
Figure 10 shows Cd-Ni~Ca-NTA 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-
Closed system, (Exp, pts) Open system, (Exp, pts)
.... without EDTA (A) - - - without E D T A (4)
10-3-46 M EDTA (o) - - 10 -3.46 M E D T A (O)
/
3 -- ,"

makes Ni less soluble than single ligand case and ~__ o-, ~_o__ __ -,- ~ J 7
higher concentration of Cd :+ results in Cd-EDTA 4 - , <-.-'/
complexation. In the above system let Cd' be a
hypothetical metal taken instead of nickel with a ~ 5-
hydroxide solubility very close to Cd and having the •~ ,~ • \
stability constant of Cd'L (with EDTA) l018-62which 6-- \ ~' & \
is equal to that of NiL 2-. Here the ratio of
, /
[CdL 2 ]/[Cd'L 2 ] is 10TM and this significant differ- 7 -- \ .'
ence decreases the Cd solubility to an extent which \
practically equals, at almost all pH values, the Cd i 8 -- '\
solubility when no ligand exists. However, the Cd'
solubility varies in a way similar to that of Cd in 9 - s \ CdCO,{s) / "
single metal-single ligand system. At pH 11, the
difference between Ni solubility in single metal and
8 10 I1 12 13 14
two metals cases reduces in parallel with the decrease
in NiL 2 concentration, however, this reduction does pH
not affect the Cd solubility significantly. On the other Fig. 11. Carbonate precipitation in open and closed systems.
 Hydroxide precipitation of complexed metals
ity returns to the level that of Ni~Ca-NTA system at
pH 11.
Carbonate precipitation of cadmium is effective
at high alkalinities. Figure 11 shows carbonate-
hydroxide precipitation phase boundaries at
1000 mg/l CaCO 3 alkalinity. When 10-3'46 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 10 346M EDTA exists in this system
cadmium solubility decreases beginning pH 12 due to
huge amount of Na + added to the system for carbon-
ate balancing which combines the ligand and then
very low cadmium concentrations may be obtained
(Fig. 11).
EXPERIMENTAL
Materials and Methods
Cd(OH)2 and Ni(OH)2 solids are obtained by precipi-
tation of CdC12 and NiCI2 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. Milli-
pore 0.45/am 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 measure-
ments. 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 II as defined in
Standard Methods (APHA, 1989). Titriplex II (acid form
of EDTA) and NaOH, Ca(OH)2 or Na2CO3 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 1
week.
RESULTS
Results of cadmium precipitation experiments in
the system with NaOH and lime and with and
without EDTA are 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 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 Ca(OH)2 have the same degree of
fit and trace the same shape as of the theoretical
2123
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. 11) and in the
open system with equilibrium alkalinity (Fig. 11).
Figure 5 shows the Ni-EDTA~2a system with
experimental points where even a better fit is ob-
tained. Solubilities in C d - N i - E D T A - C a 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 waste-
waters also tend to increase. These developments
necessitate the definition of the limits of complexed
metal treatment by conventional hydroxide preicipi-
tation application.
Theoretical assessment of metal solubility in
wastewaters may not provide very accurate results,
however, especially if the species and their thermo-
dynamic 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 treat-
ment by chemical precipitation which is neither theor-
etically 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 precipi-
tations 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.
The shape of the heavy metal-ligand-Ca solubility
curves obtained in this study are suitable for interp-
2124 O. TUNAY and N. I. KABDA~LI
olation 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 so-
called common metals is generally between 8 and 11.
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 hy-
droxide solubility before pH 11 this system can be
considered within the common metals subeategory
provided that lime is used in the treatment. If the
solubility of the metal turns back to hydroxide solu-
bility after pH i 1 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 (1) 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 precipi-
tation 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 environ-
ment 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.
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