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Calculated Solubility of Trivalent Iron and Aluminum in Oxalic Acid Solutions

At 25 °C.

Article  in  Canadian Metallurgical Quarterly · October 2001

DOI: 10.1179/cmq.2001.40.4.421

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 421

Canadian Metallurgical Quarterly, Vol 40, No 4 pp 421-432, 2001

@ Canadian Institute of Mining, Metallurgy and Petroleum
Published by Canadian Institute of Mining, Metallurgy and Petroleum
Printed in Canada. All rights reserved

CALCULATED SOLUBILITY OF TRIVALENT IRON AND

ALUMINUM IN OXALIC ACID SOLUTIONS AT 25°C.
E. CHRISTODOULOU, D. PANIAS and I. PASPALIARIS

National Technical University of Athens (NTUA), Department of Mining and Metallurgical Engineering,
Section of Metallurgy and Materials Technology, Laboratory of Metallurgy,
9 Heroon Polytechniou Str" Zografou Campus, 15780 Athens, Greece

(Received October, 2000; in revised form May, 2001)

Abstract - Based on the principle of thennodynamic equilibrium, the solubility curves of trivalent iron
and aluminum at 25°C are presented and used as a guide for the prediction and understanding of the
chemistry of these metal ions in oxalic acid solutions. The present paper proposes a framework derived
from equilibrium thennodynamic data that was fonnulated to qualitatively correlate and predict the triva-
lent iron and aluminum species distribution in the Fe3+-A13+ - H2C204- H20 system for oxalic acid con-
centrations varying between 1 and 10-6M. The paper also advocates the use of graphical representations
to visualise the importance of different appearing species in the system under study as a function of pH
and oxalic acid concentration.

Resume - La solubilite au 25°C d' ions ferriques et aluminium dans de solutions d'acide oxalique a
ete caIculee et representee graphiquement, pour mieux comprendre et predire la chimie de ces deux ions
metalliques dans Ie millieu oxalique, Cet article propose un cadre, derive des donnees d' equilibre
thennodynamique, pour correler et predire la distribution des especes ferriques et aluminium au systeme
Fe3+_AI3+- H2C204- H20, pour des concentrations d' acide oxalique entre 1et 10-6M. Les avantages des
representations graphiques pour visualiser I'apparition de differentes especes et leur importance relative
en fonction du pH et de la concentration d' ions oxalates sont aussi discutes dans cet article.

INTRODUCTION ject of a mass balance relation. This led to the principle of

Solubility information is of particular interest in areas such
as chemical processing, development and use of analytical
methods, prediction of the ecological impact of chemicals
and assessment of transport and distribution problems with
organic and inorganic species. Therefore, guidelines are
needed that will allow solubility and partition behaviour of
chemical species to be estimated without recourse to exper-
iments.
The basic principle on which the detailed study of
chemical equilibrium and the solubility determination of Fe
and Al in the Fe3+ - A13+ - H2C204 - H20 system was based
was the existence of an equilibrium constant and its specif-
ic algebraic form for each of the system's component.
However, equilibrium constants alone were not enough to
determine the set of simultaneous equations to be solved.
Additional relations were obtained from mass balances on
each component of the system through the law that each
element that appears in a number of species forms the sub-
the calculation of the total amount of the i component
which should be equal to the sum of all the various species
in which the i component existed in the system.
A mathematical formalism was developed for the cal-
culation of Fe(III) and Al solubility assuming that the solu-
tion was saturated in the Fe(III) and Al hydroxides and thus
the ion products equal the solubility products of the above
hydroxides. The most appealing features of the applied
technique were that a few input parameters were needed
and the effects of a change in input conditions could be
foreseen. However, the technique relies heavily on the
assumption of equilibrium and on the validity and com-
pleteness of the equilibrium constants used. Also the tech-
nique is directly correlated to the quality of the underlying
thermodynamic database.
The equilibrium constants of formation reactions were
defined through a detailed bibliographic search of the most
popular existing databases [1,2] and other sources [3-12].

CANADIAN METALLURGICAL QUARTERLY

422 E. CHRISTODOULOU, D. PANIAS and I. PASPALIARIS
All obtained equilibrium data refer to zero ionic strength
and 25°C. It is well known that the ionic strength at the
equilibrium will set the values of the activity coefficients
which appear in the determination of the various equilibri-
um formation constants. The formation constants are
important since concentrations enter the mass balances. In
the present study, no ionic strength corrections were made
because for rough calculations and very dilute solutions,
activity coefficients can simply be assumed to be unity and
activities could be set equal to concentrations. This led to a
qualitative and not quantitative approach of the equilibrium
of the system. On the other hand, the qualitative approach
was imposed due to the system's complexity, the numerous
simultaneous equations that occur and most of all, to the
lack of equilibrium data for all the formation constants at
several ionic strengths. However it is necessary to note that
the qualitative approach would match a quantitative one for
the cases of very dilute oxalate solutions (10-4to 10-6M).
Finally, from an engineering point of view, the main advan-
tage of this thermodynamic equilibrium study is the reduc-
tion of experimental effort for qualitative speciation mod-
eling of the Fe3+- A13+- HZCZ04- HzO system as soon as
direct experimental measurements are purely operational
[13] due to the complexity of the system.
EQUILIBRIUM AND MASS BALANCE
CALCULATIONS
Description of the Fe3+- A13+- HZCZ04-HzO System
In order to determine the equilibrium and solubility dia-
grams of the Fe3+-A13+-HzCz04-HzO system, the following
generalized steps were followed [9,14]:
1. Establishing the nature of all the species present in the
solution.
Table I - Equilibrium constants of formation reactions for hydroxo-Al and oxalato-Al complexes
(25°C, zero ionic strength).
Eq.No. Reactions in the A!3+-HzCZ04-HzO
System
A13+(aq)+ HzO =Al(OH)z+(aq) + H+(aq)
2 A13+(aq)+ 2HzO = Al(OHh +(aq)+ 2H+(aq)
3 A13+(aq)+ 3HzO = Al(OH)(aq) + 3H+(aq)
4 A13+(aq)+ 4HzO = Al(OH):;(aq) + 4H+(aq)
CANADIAN METALLURGICAL QUARTERLY
2. Finding the equilibrium constants relating to the con-
centrations of the various species. These were determined
from literature data and are listed in Tables I and II.
3. Determining enough other relations so that there are
as many independent equations as unknowns. These
include mass balance and the total concentration of each
component to the solution.
4. Solving the system of n simultaneous equations for
all n unknowns.
The Fe3+ - A13+- HZCZ04 -HzO ternary system can be
described by the following binary subsystems: Fe3+ -
HZCZ04, A13+- HZCZ04, Fe3+ -HzO and A13+-HzO.
A13+- HzO and Fe3+- HzO Systems
The trivalent Al and Fe ions in aqueous solutions can be
found in the form of simple Al or Fe(III) ions, complex
mononuclear A13+- OH or Fe3+- OH ions and complex
polynuclear A13+ - OH or Fe3+ - OH ions. These subsys-
tems in equilibrium can be described from Equations 1
to 15 and 22 to 27 in Tables I and II respectively.
A13+- HZCZ04 and Fe3+ -HZCZ04 Systems
The CzO/- ion has two oxygen atoms with unshared
pairs of electrons. This makes the ion a strong com-
plexing agent. In the presence of Al and Fe(III) ions, the
oxalate ions have the ability to form chelate complexes.
Equations 16 to 21 and 28 to 31 in Tables I and II respec-
tively describe the possible ion formation in the A13+-
HZCZ04and Fe3+- HZCZ04systems.
Formation Constant Values Reference
*K,=10-5.o, [1-6,11]
* z--10-9.30 [2-5]
* 3-
-10-15 [ 1-6]
*4=IO-zz.8z [3-6, 13]
 CALCULATED SOLUBILITY OF TRIVALENT IRON AND ALUMINUM IN OXALIC ACID SOLUTIONS AT 25°C. 423

Table I - Equilibrium constants of formation reactions for hydroxo- AI and oxalato- AI complexes
(25°C, zero ionic strength).

Formation Constant Values Reference

5 2AI3+(aq)+ 2H20 = AI2(OH)i+(aq) + 2H+(aq) '22=10-7.60 [4.6, 13]

6 3AI3+(aq)+ 4H20 = AI3(OH)+(aq) + 4H+(aq) '34=1O-13.9 [3,4]

7 7AI3+(aq)+ 17H20 = A17(OH):;(aq) + 17H+(aq) . 7.17=1O-s9.48 [ 12]

8 13A13+(aq)+ 32H20 = A113(OH);(aq) + 32H+(aq) . 13.32

=10-107.47 [ 12]

9 13A13+(aq)+ 28H20 = A11304(OH):(aq) + 32H+(aq) . 13.24

=10-98.7 [3-4]

10 5AI3+(aq)+ 12H20 =Als(OH)i;(aq) + 12H+(aq) . S.12

=10-43.41 [ 12]

11 6AI3+(aq)+ 15H20 = A16(OH)ft(aq) + 15H+(aq) . 6.IS=1O-S3.78 [ 12]

12 14A13+(aq)+ 34H20 =A114(OH):(aq) + 34H+(aq) . 14.34

=10-113.14 [ 12]

13 8A13+(aq)+ 20H20 = A18(OH)i;(aq) + 20H+(aq) . 8.20-

-10-69.82 [ 12]

14 9AI3+(aq)+ 23H20 =A19(OH)i;(aq) + 23H+(aq) . 9.23=10-80.14 [ 12]

15 1OA13+(aq)+ 24H20 = A11O(OH):(aq) + 24H+(aq) . 10.24

=10-81.18 [ 12]

16 AI3+(aq)+ H2C204(aq) = AlHC20+(aj) + H+(aq) 'Ks=104.71 [5]

17 A13+(aq)+ H2C204(aq) = AIC20:(aj) + 2H+("'I) 'K6=229.09 [5]

18 Al 3+ ("'I)+ 2H2C204(aq) =Al (r

C204 2(aj) +4H + ("'I) '=295 .12 [5]

19 t
Al 3+("'I)+ 3H2C204(aq) =Al (C204 3 ()aj +6H + ("'I) 'K8=2.14 [5]

20 3Al3+(aq) +3H2C204(aq) + 3H20(aq) =A13(OH)3(C204 )3("'1)+ 9H+(aq) '=5.25 . 1O-S [5]

21 2Al 3+ ("'I) +4H2C204(aq) +2H20(aq) =A12(OH )2(C204 t-

4("'1)+ 10H +("'I) 'KIO=1.38 . 10-6 [5]

CANADIAN METALLURGICAL QUARTERLY

-- --
424 E. CHRISTODOULOU, D. PANIAS and I. PASPALIARIS

Table II - Equilibrium constants of formation reactions for hydroxo- Fe (III) and oxalato- Fe(III) complexes
(25°C, zero ionic strength).

Eq.No. Formation constant values Reference

22 **K,=1O-2.19 [2-4, 9]

23 ** 2--1O-s.67 [2-4, 9]

24 ** 3--10-13.60 [2]

25 **4=1O-21.6O [2-4, 9]

26 ** 22=1O-2.9s [2-4, 9]

27 ** 34=10-6.3 [2,9]

28 **Ks=1.89 . lOs [7,8]

29 **K6=8.71 . 103 [8]

30 **K7=1.89 . lOs [8]

31 **Ks=1.34 . 104 [8]

According to the above equations of the binary subsys-

tems, the molar concentrations of all the species present in
the solution can be defined from the expressions of their (36)
formation constants:

(32) (37)

(33) (38)

32
7+ * 3+ \3 ~ +
(34) [
AI\3(OH)32 ]= ~13.32 [Al ] II[H ] (39)

32
7+ * 3+ 13 ~ +
(35) [
AI\304(OH)24 ]= ~13.24 [Al ] IIH[ ] (40)

CANADIAN METALLURGICAL QUARTERLY

CALCULATED SOLUBILITY OF TRIVALENT IRON AND ALUMINUM IN OXALIC ACID SOLUTIONS AT 25°C. 425

(41) (56)

(42) (57)

* 34
8+ 3+ 14 ~ +
[Al14 (OH )34 ] = ~14.34 [Al ] II[H ] (43) (58)

(44) (59)

(45)
(60)

24
6+ * 3+ 10 +
[AIIO(OH )24 ]= ~1O.24 [Al ] /[H ] (46)
(61)

(47)
(62)

On the other hand, oxalic acid as a diprotic acid has two

ionization constants, given in Table III [8]. In oxalic acid
solutions, molecules of oxalic acid (H2C204)and its ions
(HC204-, CP/), coexist in equilibrium. The molar con-
centrations of these ions can be defined from the expres-
sions of their ionization constants:

(63)

(64)

Supposing that the solution is saturated in iron (III)

and aluminum hydroxides Fe(OH)3 and AI(OH)3 respec-
tively, the ion products equal the solubility products. In
that case, the molar concentrations of ferric and aluminum
ions become simple functions of pH and are defined as
(53) follows:

(54)

(55)

CANADIAN METALLURGICAL QUARTERLY

---------------
 426 E. CHRISTODOULOU, D. PANIAS and I. PASPALIARIS

Table III - Ionisation constants of oxalic acid (25 DC,zero ionic strength).

~C204 ionisation reactions Formation constant values Reference

H2C204 = H+ + HC204- Kal = 5.6 10-2 [8]

HC204-= H++ C20/" Ka2= 6.2 IO-s [8]

where Kw represents the dissociation constant of water and The total iron (III) concentration (Felol) denotes the
has a value of 10-14at 25 DC, solubility of trivalent iron in molar units and is determined
as the sum of all the iron containing species (Equation 68):
KSP(FC)
= 3 .10-39(25 DC) [10]

=
KSP(Al) 3.5 . 10-34(25 dc) [10]. Fe101=[Fe3+]+[FeOHz+]+[Fe(OH)~]
The analytical molar concentration of oxalic acid (Cox) +[Fe(OH);] + 2[Fez(OH)~+]
in the solution can be expressed as follows: (68)
+3[Fe3(OH)~+]+[FeHCzO~+]
Cox =[HZCZ04] =[HCZ04] +[CzO~-]+[FeHCzO~+]
+[FeCzO:] + [Fe(CZ04);] + [Fe(CZ04)~-]
+[ FeCzO: ] + 2[ Fe( CzO 4)~ ] + 3[ Fe( CzO 4 ):- ]
Respectively, the total aluminum concentration (Altot)'
denoting the solubility of aluminum in molar units is
+[AIHCzO~+]+ [AICzO:] + 2[ AI(Cz04)~] (67) expressed by Equation 69

{AI(Cz04):- ]+3[ AI3(OH)3(Cz04)3]

AIIOI=[Ae+ ]+[AIOHz+ ]+[AI(OH);]

+4[Alz(OH)z(Cz04):- ] +[AI(OH)~] + [AI(OH);] + 2[Alz(OH)~+]

The mathematical system of Equations 32-67 consists of +3[AI3(OH)~+]+ 7[AI7(OH):;] + 13[AII3(OH)~;]

thirty-five independent equations and thirty-seven
unknowns. Thus, the values of two unknowns, the analyti- +13[AI1304(OH)~: ]+5[AIs(OH);;]
cal concentration of oxalic acid and the pH of the solution (69)
have to be set in order to obtain a mathematical solution. +6[AI6(OH);;] + 14[AI14(OH)~:]+ 8[AI8(OH)~;]
The above system of equations cannot be solved analyti-
cally because it is too complicated. Therefore, it is solved +9[AI9(OH)~;] + IO[AllO(OH)~:]+ [AIHCzO~+]
by the use of a computer program using the capabilities of
MathCad 8.0 software. The solution of the mathematical +[AICzO:] + [AI(Cz04);] + [Al(CZ04)~-]
system always involves only one real positive root for each
set of realistic positive values of Coxand pH. Although real +3[AI3(OH)3(Cz04)3] + 2[Alz(OH)z(CZ04):-]
negative and imaginary roots are also calculated, they are
rejected as they do not have any meaning in nature.

Eq.No. Fe(III) species % Fe(III) species quotient (x I00)

1 Fe3+ ao = [Fe3+]! FelOI
2 Fe(OH)n (3-n) an = [Fe(OH)n(3-n)]!FelOI n=1,2,3,4
3 FeiOH)Z4+ <1z2 = 2[FeiOH)24+]! FelOI
4 Fe3(OH)/+ a34 = 3[Fe3(OH)4s+]! FelOI
5 FeHC2O/+ as = [FeHC20/+]! FelOI
6 y= 1,2,3
Fe(Cp4)y ay = [Fe(Cp4\]! Fetol

CANADIAN METALLURGICAL QUARTERLY

----- -------------------
 CALCULATED SOLUBILITY OF TRIVALENT IRON AND ALUMINUM IN OXALIC ACID SOLUTIONS AT 25°C. 427

The concluded mathematical system was solved by setting major areas where significant solubility differences are
the values of the two independent factors, oxalic acid con- observed: the high acidic, the high alkaline and the inter-
centration (Cox)and pH, ranging from 1-10-6M and 0-14, mediate area.
respectively.

The results are shown in Figures 1 to 6. The solubility
diagrams of Fe(Ill) and Al are shown in Figures 1 and 2,
respectively. The speciation diagrams of all possible
hydroxo and oxalato species of Fe(Ill) and Al are shown in
Figures 3, and 5 and Figures 4 and 6, respectively. The per-
cent individual species quotients presented in Figures 3 to
6 are defined in Tables IV and V.
RESULTS AND DISCUSSION
Figures 1 and 2 present the solubility plots for Fe(ITI)
and AI, respectively in the form of log [Fetot] and
log[Altot] versus pH for oxalate concentration ranging
from 1 to 10-6M. The major observation derived from
Figures 1 and 2 is that the solubility curves of Fe(ITI) and
-
Al in the Fe3+ - A13+ H2C204-H20 system expose three
High Acidic Area
The high acidic area in the case of Fe(Ill) solubility curves
extends to pH 1 while in the case of Al to pH 2.5. In this
area, Fe(Ill) and Al solubility are independent of the oxalic
acid concentration and equal the Fe(Ill) and Al solubility in
the absence of oxalic acid. Figures 3 and 5 show that in the
acidic pH area the major Fe(Ill) and Al species in the solu-
tion are hydroxo species while oxalato species (Figures 4
and 6) are not yet formed. This can explain the fact that the
solubility of Fe(Ill) and Al are independent of the oxalic
acid concentration.
Intermediate Area
This area refers to the 1-11 pH range for Fe(Ill) and 2.5-10
pH range for AI. This area can be divided into three indi-

Eq.No. Al species % Al species quotient (xI00)

A13+ (,(o = [A13+]/Al tot

2 Al(OH)n (3-n) (,(n = [Al(OH)n (3-n)]/Altot n=1,2,3,4
3 A12(OH)24+ (,(22= 2[AliOH)24+]/ Altot

4 A13(OH)/+ (,(34= 3 [A13(OH)/+]/ Altot

5 AliOH) 1/+ (,(7.17= 7 [AliOH) 1/+]1 Altot

6 Al 13(OH)3/+ =
(,(13.32 13[AlI3(OH)327+]/ Altot

7 Al 1304(OH)247+ (,(13.24= 13 [AI 130iOH)2/+]/ Altot

8 AliOH)I/+ =
(,(S.12 5[Als(OH)I/+]/ Altot
9 A16(OH)I/+ (,(6.1S= 6[A16(OH)i/+]I Altot
10 Al,iOH)34S+ (,(14.34= 14[Al1iOH)34S+]/ Altot

11 AlS(OH)204+ (,(S.20 = 8 [Als(OH)204+]/ Altot

12 A19(OH)234+ (,(9.23= 9[A19(OH)234+]/ Altot

13 AllO(OH)246+ =
(,(10.24 IO[AllO(OH)2/+]/ Altot

14 AlHCP/+ (,(s = [AIHCp/+]I Altot

15 Al(CP4)y (,(y = [Al(CP4\]/ Altot y=6,7,8

16 AIlOH)3(C204)2 (,(9 = 3[AIlOH)3(CP4)2]/ Altot
17 A12(OH)iCP 4)4- (,(10 =2[A12(OH)iCP4)/"]/ Altot

CANADIAN METALLURGICAL QUARTERLY

428 E. CHRISTODOULOU, D. PANIAS and I. PASPALIARIS

6.0
Intermediate Area 1=1 MH,c,o.
Region ll: In this region, the solubility of both metals
4.0 2 =10-' MH,c,o. increases slightly or remains constant as the pH increases at
3 =10-' MH,c,o.
2.0 4 =10-'
5 =10-'
MH,c,o.
MH,c,o.
a given oxalic acid concentration. The higher the oxalic
0.0 6=10-' MH,c,o. acid concentration, the higher the Fe(III) and Al solubility
RegionII 7 =10-' MH,C,O.
-2.0
Region III
in the solution. In this region, there are no Fe(III)-hydroxo
-4.0 complexes as seen in Figure 3. The dominating species are
-6.0 the Fe(III)-oxalato complexes (Figure 4). FeHCp/+,
-8.0 Fe(CZ04)z-and Fe(CZ04)33-are the most important ones.
Region II, in the case of Fe(III) solubility curves, starts
-10.0
with the gradual transformation of FeHCzO4z+ and
-12.0
0 6 10 II 12 Fe(CZ04) - species to Fe(CZ04)/- and ends when
pH Fe(CP4)?- is the only Fe(III)-bearing species in the solu-
tion.
Fig. 1. Fe(III) solubility in the Fe3+-AP+-H2CP4-HP system as a func-
tion of pH and oxalic acid concentration. On the other hand, regarding AI, the dominating species
in that pH range are the oxalato-Al complexes (Figure 6)
and especially the AICP/, AI(CP4)z- AI/OH)3(CP4)3
I
and AI(CP4)/- species. Region II starts with the gradual
6.0 Intermediate Area : Ar'::'~ne
transformation of AICP/, Al(CP4)z- and AI3(OH)3(Cz04)3
:
I
Area

4.0 I
I
to AI(CP4)/- and AIz(OH)iC 04)44- and ends when
I

~ 2.0
RegionII
<~ 0.0
Region
'j -2.0
-4.0
-6.0
-8.0
I 6
pH
Fig. 2. AI solubility in the Fe3+-AI3+-H2C204-H20 system as a function
of pH and oxalic acid concentration.
vidual sub-areas: Regions I, II and III. The main character-
istic of the intermediate area is that Fe(III) and Al solubili-
ty are strongly dependent on oxalic acid concentration in
the solution.
Region I: In this region and at a given oxalic acid con-
centration, Fe(III) and Al solubility decrease as the pH
increases. The higher the oxalic acid concentration, the
smaller the decrease on Fe(III) and Al solubility. At a given
pH value the solubility of both metals increases as the oxal-
ic acid concentration increases. In this region the Fe(III)-
hydroxo and AI-hydroxo complexes are gradually decom-
posed and the major part of both metals is complexed with
oxalic acid as seen in Figures 4 and 6. This transformation
is more evident as the oxalic acid concentration increases.
Therefore, the solubility of both metals results in decreas-
ing functions of pH and increasing functions of oxalic acid
concentration. The end of Region I coincides with the
beginning of the Fe(Cp4)/- and Al(CP4)/- complex ions
formation as seen in Figures 4 and 6. The formation of these
complex ions starts at lower pH values as the oxalic acid
concentration in the solution increases. For this reason, the
width of Region I increases as the oxalic acid concentration
decreases.
I
I
Al(CP4)/- and Alz(OH)z(CP4)}= become the only Al-
I
I bearing species in the solution (Figure 5).
I
III:
I
I
I
The width of Region II for the solubility curves of both
I metals decreases as the oxalic acid concentration decreas-
es. The width disappears for concentration of oxalates
lower than 10-5M. Finally, the broadening of the curves can
10 II
be attributed to the high chelating capacity of oxalic acid
and especially to the wide stability area of the complex ions
Fe(Cp4)/-' Al(CP4)33- and AliOH)iCP4)44-.
Region lll: In this region, the solubility of Fe(III) and Al
decreases sharply as the pH increases and finally reaches
the values of the corresponding solubility in non-oxalate
aqueous solutions. The decomposition of Fe(CZ04)33-,
Al(CP4)/- and Alz(OH)z(CP4)44-ions takes place as the
pH increases and an amount of Fe(III) and Al is complexed
as hydroxo complexes (Figures 3 and 6). Therefore, Fe(III)
and Al solubility decrease rapidly as the pH increases.
The end of Region III coincides with the rapid forma-
tion of hydroxo-Fe(III) and hydroxo-Al complexes which
become the only Fe(III) and Al species in the solution
(Figures 3 and 5). For this reason, the Fe(III) and Al solu-
bility curves approach the corresponding ones for aqueous
solutions in the absence of oxalic acid. This approach
occurs at lower pH values as the oxalic acid concentration
decreases.
High Alkaline Area
This area in the case of Fe(III) refers to pH> II and in the case
of Al to pH> 1O. Fe(III) and Al solubility in the high alkaline
area are independent of oxalic acid concentration and are
attributed to the existence ofhydroxo-Fe(III) and hydroxo-AI
complexes which are the only Fe(III) and Al bearing species
in the solution, respectively (Figures 3 and 5).

CANADIAN METALLURGICAL QUARTERLY

 CALCULATED SOLUBILITY OF TRIVALENT IRON AND ALUMINUM IN OXALIC ACID SOLUTIONS AT 25°C. 429

;: 1M
;:
-.!!100
" .!i 100
§. 90
\"Fe(OH)4-
g 90
""
~ 80 ~ 80 ~Fe(OH)4-
170
.; 60
1 70
S 50
~ 60
S 50
~ 40 '"
'"' 40
".; 30 ~ 30
i: 20
...
£10 Fe(OH)" ~ 20
£10
~ 0 ~ 0
o 4 10 12 14
4 6 10 12 14
pH o
pH

to-'M ;;<II lO-3M

;:
.!i 100 ~ 100
§""
90
\... Fe(OH).
g.90 '-Fe(OH)..
:rJ 80 .~ 80
.~ 70 ~ 70
~ 60 ~ 60
§' 50 == 50
;: 40 ;f. 40
30
.; 30
~ 20 ~ 20
.a 10
rFe(OH)"
~r Fe(OHhO
~10
.c 0 "'-- 2 0
10 12 14
~ 0 4 6 10 12 14 ~
pH pH

Fig. 3. Speciation diagram of hydroxo-Fe(III) complexes as a function of pH for oxalic acid concentration I, 10-1, 10-2 and 1O-3M,respectively.

tM to-1M
. 100 . 100
§90 §"" 90
Fe(C,04h3-
:; 80 80
'"
"270
60
.21
i: 70
...
60
I \ I \LFeHC,o.,. \rFe(C,04h3-

5' 50 S 50
40
;:40
". 30 g 30
20
<;;20
to 10
0 0
0 8 10 12 14 0 2 4 6 8 10 12 14
pH pH

to-'M ;;<II lO-3M

. 100 100
g90 g. 90
80 :!i 80 - -'-"'-"'1')''''
. 70 .;;;
<II 70 \/ \ I \rFe(C20.h3-
60 60
§ 50 -
= 40
50
40
.; 30 l 30
]
.. 20
<= 20
OJ
10 OJ 10
0 ..
<= 0
0 10 12 14 0 2 4 6 8 10 12 14
pH pH

Fig. 4. Speciation diagram of oxalato-Fe(III) complexes as a function of pH for oxalic acid concentration I, 10-1, 10-2 and 1O-3M,respectively.

CANADIAN METALLURGICAL QUARTERLY

430 E. CHRISTODOULOU, D. PANIAS and I. PASPALIARIS

1M 10.IM
;:
.~ 100
§... 90
\...AI(OH)4-
\. AI(OHk ~ 80

- .~
Co 70
Q 60
S 50

"..
~ 40
".. ~ 30
...
....
~ 20 Ah(OH)z4+
.c ~IO
1:11
r AI(OH))O
4 6 8 10 12 14 1:11 0
~

pH o 6 8 10 12 14
pH
10.2M 10-3M
;: c
.~ ~
="
'-AI(OH)4-
" 100
...
'"
;. 90
.. ~ 80
.~ i
-~ ~60
70

;. 50
;;:: 40
".. .." 30
".. AIJ(OH)z4+ "E 20
...
.c.... rA1(OH))O ~IO
......
1:11 ~ 00 10 12 14
6 8 10 12 14
pH pH

Fig. 5. Speciation diagram of hydroxo-AI complexes as a function of pH for oxalic acid concentration I, 10-1, 10-2 and 1O-3M, respectively.

10-1M
1M
;;
. 100 ;:100L2'
90
g90
... 80
80
. 70 70
60 160
§ 50 50
40 40
30 ] 30
... 20 Ah(OH),(C204)4- !i 20 I I \ J \ ...---+ Ah(OH)z(C204)4-
10 1:11 10
1:11 0 0
0 2 12 14 0 2 4 6 8 10 12 14
pH
pH

..= lO.3M
10.2M ..
.§ 100 100
goo So 90
80 80
. 70 . 70
60 60
§ 50 == 50
40 040
< 30
30
] 20 Ah(OH),(C204)4- 20L , ,\ I \\ .r----Ah(OHh(C204)44-
S to .!!
..
10
1:110 .. 0
0 2 4 6 8 10 12 14 c 0 2 4 6 8 10 12 14
pH pH

Fig. 6. Speciation diagram of oxalato-AI complexes as a function of pH for oxalic acid concentration I, 10-1, 10-2 and 1O-3M,respectively.

CANADIAN METALLURGICAL QUARTERLY

 CALCULATED SOLUBILITY OF TRIVALENT IRON AND ALUMINUM IN OXALIC ACID SOLUTIONS AT 25°C. 431

Table VI - Fe(III) and AI solubility values in pH 3 for that reason, the alkaline conditions cannot be recommend-
various oxalic acid concentrations. ed for controllable partial precipitation. Figure 7 visualises
the variations in Fe(III) and Al solubility in pH 3 as a func-
Acidic pH range tion of oxalic acid concentration. As shown, the solubility
Variables of Al is almost 10 g.L-I while Fe(III) solubility varies
pH3 between 1.7-43 ppm for all studied oxalic acid concentra-
tions.
Oxalic acid
10-1 10-2 10-3 4.5

concentration (M) 4.0

Al

3.5f pH3
Fe(III) solubility 43 ppm 5.7 ppm 2 ppm 1.7 ppm E 3.0
0-
0-
2.5
OJ
Al solubility 12 g.L-I 10 g.L-l 9.8 g-L-I 9.75 g-L-I ;;
2.0
.§.
." 1.5
.9
1.0

Comparison Between Fe(III) and Al Solubility Curves - 0.5

Partial Precipitation 0.0

-6 -5 -4 -3 -2 -I
The comparison of Figures 1 and 2 concludes that Al is log [H,C,O.. MI

more soluble than Fe(III) in the system under study. As the

oxalic acid concentration decreases, both Fe(III) and Al
become less soluble. On the other hand, the Fe(III) solubil-
ity is affected by the oxalates in a wider pH range than the
Al solubility as soon as the stability region of the Fe(III)-
oxalate species in the solution is wider than the AI-oxalate
corresponding ones (Figures 4 and 6).
The observed solubility differences between Fe(III) and
Al were used to effect their chemical separation through
partial precipitation. This was accomplished mostly by the
precipitation of one metal ion while the other was left most-
ly in the solution according to the solubility curves. On that
point, the maximum degree of separation was achieved
under given conditions.
Figures 1 and 2 show that the solubility differences for
Fe(III) and Al at given oxalate concentrations are strong in
both the acidic (pH<6) and alkaline (pH>8) pH range. In
between these pH values, the solubility differences are not
very distinct and partial precipitation is rather impossible.
One additional criterion used for the selection of narrow
specific pH ranges where partial precipitation could be
applied successfully, regards not only the pH ranges where
simple differences in the solubility values appear but also
the pH ranges where the solubility of the one metal is
extremely low while at the same time the solubility of the
other metal remains high. If this criterion is not met, then
the partial precipitation would not be operational as soon as
both metals could precipitate uncontrollably at the same
time. For that reason, the proposed pH ranges for partial
precipitation meet the requirements of the above criteria.
Regarding the acidic pH range, pH values in the range
2.5-3.5 satisfy the above criteria (Table VI). In the alkaline
pH range high Fe(III) and Al solubility differences are
detected but the solubility of both metals is very low. For
Fig. 7. Fe(III) and Al solubility values in the Fe3+-AI3+-H2Cp.-HP sys-
tem at pH 3 as a function of oxalic acid concentration.
A general conclusion claimed from the study is that effi-
cient partial precipitation of Fe(III) in the presence of Al
can be implemented in the acidic pH region and particular-
ly in pH 2.5-3.5.
CONCLUSIONS
The major conclusions derived from the study on the
Fe(III) and Al solubility curves for oxalic acid solutions
with concentrations varying between 1 and 10-6M at 25 °C
are as follows:
1) Fe(III) exhibits lower solubility than Al in the studied
oxalic acid solutions.
2) The solubility curves for both metals introduce three
major areas in the acidic, alkaline and intermediate pH
regions. Also, the intermediate area can be subdivided into
three sub-areas with similar characteristics for both metals.
The solubility of Fe(III) and Al is strongly dependent on the
oxalic acid concentration in the intermediate pH area, while
in the high acidic and high alkaline region they approach
the corresponding solubility values for non-oxalate aque-
ous solutions.
3) Partial precipitation of Fe(III) in the presence of Al is
theoretically possible especially in pH 2.5-3.5 where
Fe(III) and Al present major differences in their solubility
values. This could lead to an operational method for sepa-
rating these metals from oxalic acid solutions with varying
concentrations.

CANADIAN METALLURGICAL QUARTERLY

 432 E. CHRISTODOULOU, D. PANIAS and I. PASPALIARIS

ACKNOWLEDGEMENT 6. G.A. Parks, American Mineralogist, 1972, vol. 57, pp. 1163-
1189.

The author wishes to thank the Hellenic Republic States 7. L. Vincze and S. Papp, J. Photochemistry, 1987, vol. 36, pp.
Scholarship Foundation. 289-296.

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4. W. Stumm and J.J. Morgan, Aquatic Chemistry: An
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9. J.E Pankow, Aquatic Chemistry Concepts, 1991, Lewis
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10. J.e. Bailar, T. Moeller, J. Kleinberg, e.O. Guss, M.E.
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