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Research: Science and Education

Predominance Diagrams, a Useful Tool for the Correlation


of the Precipitation–Solubility Equilibrium
with other Ionic Equilibria1
Constantino Fernández Pereira,* Manuel Alcalde, Rosario Villegas, and José Vale
E.S. Ingenieros Industriales, Departamento de Ingeniería Química y Ambiental, Universidad de Sevilla, E-4102 Sevilla,
Spain; *pereira@esi.us.es

Aqueous ionic equilibria have certain aspects in com- corresponds to the elemental equilibrium that links the two
mon, which has led some authors to develop a unified treat- members of the donor–acceptor pair. In the precipitation
ment of them (1–4). Although it is in analytical chemistry equilibrium, and in ideal conditions, the equilibrium con-
and aquatic chemistry textbooks (5–11) where the similarity stant is called the solubility product constant, or Ksp.2
among the ionic equilibria—acid–base and redox in most
cases—has been emphasized the most, the idea pursued by Mm X d (s) mM(aq) + d X(aq)
the authors of this article is to facilitate learning of aqueous m
K sp = [ M] [ X ]
d (1)
ionic equilibria at the introductory level and to show that,
although they appear to be different, they share an underly- In other words, Mm Xd (s) is a ligand donor, whether it
ing pattern. Thus, although most general chemistry courses be M or X. Besides, as SSIC is a salt, the symbol M stands
present the ionic reactions separately, we think that it is of for the cation (the metal) and thus X is the anion.
interest pedagogically to study them together as this leads to The acceptance potential is defined as the negative of
an overall view of these reactions. the logarithm of the equilibrium constant divided by the
The similarities between the acid–base and redox reac- number of exchanged particles.
tions are quite clear: both of them can be interpreted as par-
ticle exchange reactions (of protons or electrons, respectively). 1 pK sp
APM = − log K sp = (2)
Complexation and precipitation equilibria can be viewed d d
similarly if we consider that complexes and sparingly soluble
ionic compounds (SSICs) act as ligand donors, and that this The lower Ksp is, the higher the APM; then M has a high
ligand is a molecule, either neutral or electrically charged. tendency to accept particles (X in this case), so it is a strong
Precipitation equilibria have quite a few things in common acceptor.
with complexation equilibria and, thus, an SSIC can be seen In acid–base equilibrium, the AP is the pKa (3), while
as a sparingly soluble coordination compound. The precipi- in the redox equilibrium, at 25 ⬚C, AP ⫽ E⬚兾0.059 V (4),
tation equilibrium is always heterogeneous and the ligand is where E⬚ is the standard reduction potential.
a cation or an anion.
The unified treatment is based on viewing the ionic re- Definition of Predominance Intervals
actions mentioned above as producing an exchange of par- The treatment also proposes a graphic resolution of the
ticles (X) between a donor and an acceptor of two conjugate equilibrium problems using predominance diagrams or
pairs, and the particles are protons (H⫹), electrons (e᎑) or chemical-species distribution diagrams (12) and predomi-
ligands (L): nance intervals. Predominance diagrams are linear diagrams
that use (the negative of ) the logarithm of the concentration
Donor 1 + Acceptor 2 Donor 2 + Acceptor 1 (activity) of the exchanged particle, pX (pH, pe or pL), as
the variable:
This study presents the application of the unified treat-
ment to the precipitation–solubility equilibrium and describes
the usefulness of the predominance interval diagrams for solv-
ing solubility problems.

The Significance of Acceptance Potential in Precipitation From the Ksp determined above in eq (1) the following
expression can be obtained:
Definition of Acceptance Potential
As the main tool unifying the equilibria, the treatment 1 1
APM − pX = log (3)
defines the term acceptance potential (AP), which refers to d [M]m
an exchange of particles for a conjugate donor–acceptor pair;
this term is related to the pair’s particle release (dissociation) and that yields three possibilities:
constant (2). The AP receives this name because it measures
the tendency to accept particles in a conjugate pair, charac- pX < APM ⇒ [ M] < 1
terizes each pair and makes easier comparisons between pairs.
pX > APM ⇒ [ M] > 1
The tendency of the pair’s donor to yield particles comes
from the value of the dissociation or instability constant that pX = APM ⇒ [ M] = 1

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Research: Science and Education

In precipitation, the predominance diagram has a some- Exchange Reactions in Precipitation


what different meaning from that when the donor and ac- and Precipitate Redissolution
ceptor are dissolved species. In this case, the donor is a solid
(supposedly a pure solid with activity equal to 1), so in the An ionic compound that is sparingly soluble in water,
predominance zone (predominance interval) of the acceptor MmXd, can be dissolved by adding an acceptor (a cation or
(M, in this case), its concentration (activity) is greater than anion) that belongs to a pair with an AP greater than its own:
1, while for the predominance interval of the donor, the con-
centration of the acceptor is always less than 1. MmXd (s) mM(aq) + d X(aq)
As was mentioned above, the SSIC is the particle do- nN(aq) + aX(aq) Nn Xa(s)
nor, but the role of the acceptor (and that of the particle), 1 M X s + n N aq
and consequently the AP of the pair, are left undefined until d m d( ) a ( ) m
d M( aq ) + 1 a N n X a (s )
a second conjugated pair is introduced. The pairs that are
compared have to have something in common, so they have
m
to be salts with the same cation or anion; the common cat- K sp, M = [M] [ X ]d
ion or anion, then, is the exchanged particle and the other
ion is the acceptor. Thus, for example, Ag2S(s) can be com- 1 1
=
pared to AgI(s) so that S2−(aq) and I−(aq) act as acceptors of K sp,N [ N ] [ X ]a
n

Ag+(aq) (the exchanged particle); or it can be compared to


m m (4)
HgS(s), where Ag+(aq) and Hg2+(aq) are two possible accep- [ M] d [ M] d [ X ] d K sp,M
tors for S2−(aq). K = n
= n
=
[N] a [N] a [ X ] a Ksp, N
Exercise 1
The solubility product constant of silver sulphate is
1.5 × 10᎑5. K = 10 ( APN − APM )

Ag2SO4(s) + −
2Ag (aq) + SO42 (aq) pK sp,N pK sp, M
since: APN = and APM = .
pK sp = 4.8 a d
The extension of the reaction thus depends on the dif-
The acceptance potential of the pair Ag2SO4(s)/Ag+(aq) ference between APs and can be easily visualized if the pre-
in exchange reactions involving SO42− is thus: dominance intervals of the implicated species are represented
on a common pX scale (2). Therefore, if a solution contains
pK sp Cd(IO3)2(s) and Ag+, which do not have a common interval
APAg = = 4.8 or zone of predominance (one is predominant for pIO3 values
1
less than 3.8 while the other predominates for pIO3 values

while the acceptance potential for the pair Ag2SO4(s)/SO42−


(aq) in exchange reactions involving Ag+ is:

pK sp
APSO4 = = 2.4
2

The AP always measures the tendency to accept particles


from a pair (from the acceptor of the pair). In precipitation,
this means the tendency to form a precipitate, that is, the
degree of insolubility of the sparingly soluble ionic com-
pound. The predominance interval diagram is thus a solu-
bility (insolubility) diagram, such that the pair with the
greatest AP will correspond to the least soluble compound.
Figure 1 shows the values of the APs for some of the main
sparingly soluble metallic iodates, which allows their respec- Figure 1. Acceptance potentials (AP = pKsp/n) of sparingly soluble
tive solubilities to be compared (13). iodates.

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Research: Science and Education

Table 1. Comparison of Logarithmic Forms Saturated Solutions and Existence Intervals


among Aqueous Ionic Equilibria
If the solubility equilibrium for MmXd exists, then:
Ionic Equilibria Types Logarithmic Expressions
MmXd (s) mM(aq) + d X(aq)
1 1 1 m
Solubility–Precipitation
pX (lim) =
d
pK sp −
d
log
C Mm
K sp = [ M] [ X ]d
MmXd (s) 1 1
= APsolubility − log but:
d C Mm
[M ]m [ X ]d < K sp
pH = pK a − log
[acid ]
[base ] can also occur, in which case the solution will not be satu-
Acid–Base rated and there will be no equilibrium.
= APacidity − log
[acid ] For a total concentration of M equal to CM, the limit
[base ] for the equilibrium existence is reached when:

pe =
1
pK redox −
1
log
[reductant ] [ M] = CM
d d [oxidant ] and
Redox
1 [reductant ]
= AP −
d
log
[oxidant ] [ M]m [ X ]d = K sp = [C M ]
m
[ X ]d
From that, the pX value that establishes the existence limit
pX =
1
pK −
1
log
[ donor ] for the solid can be obtained:
General
d d [acceptor ] 1
1 [ donor ] K sp d
= AP − log [ X ](lim) = (5)
d [acceptor ] C Mm

1 1 1
pX (lim) = pKsp − log
d d C Mm
1 1 (6)
= APM − log
greater than 7.5) and thus cannot coexist stably, the exchange d C Mm
reaction of IO3᎑ will progress until one of the reactants (the
limiting reactant) is exhausted (K >>1): When the concentration of X (the exchanged particle)
is put in logarithmic form, it is easier to see the agreement
1 Cd IO (s) + Ag+ (aq)
( ) with other similar expressions in the other types of equilib-
2 3 2
rium (2–4), although in precipitation, as the donor is always
AgIO3(s) + 1 2 Cd 2 +(aq) the SSIC, its molar concentration is replaced by its activity,
K = 10 7.5 − 3.8 = 103.7 >> 1 which is always equal to one (Table 1).
If this value is represented on a pX scale, we get the ex-
istence interval for the solid, that is, the range of pX where
the solid exists.

which forms AgIO3(s), while the solid Cd(IO3)2 ends up dis-


appearing if Ag⫹(aq) is present in excess. Likewise, if the exchanged particle is M and its acceptor
However, in a solution with Ag(IO3)(s) and Cd2⫹(aq) is X, then the value of pM that establishes the existence limit
(with a common interval in between 3.8–7.5 pIO3 values) of the solid is:
there will be virtually no exchange (K << 1): 1 1 1
pM(lim) = pKsp − log
m m C Xd
1 1 (7)
= APX − log
m C Xd

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Research: Science and Education

which, if is represented on a pM scale, would yield: Fractional Precipitation and Ion Separation
One interesting, practical application of the existence
diagrams relates to the procedure for separating cations or
anions known as fractional precipitation, in which anions or
cations that form sparingly soluble compounds with a com-
In order to understand the usefulness of the existence mon component are separated based on their different solu-
interval and to become familiar with its use, students can bilities.
imagine that they have a certain concentration of a metal, Exercise 3
M, in solution (CM) and add increasing amounts of a soluble
Consider a solution that contains the cations
iodate (NaIO3) dropwise. In this case, the [IO3− ] increases,
and this implies moving from right to left on the above dia- Ba2⫹ 2.0 ⫻ 10᎑2 M
gram: Ag⫹ 2.5 ⫻ 10᎑2 M
Ca2⫹ 1.0 ⫻ 10᎑3 M
La3⫹ 3.0 ⫻ 10᎑3 M
Study the separation of these cations by means of fractional
precipitation in the form of iodates.
As soon as pIO3 (lim) ([IO3− ](lim)) is reached, according to the Data
above equation for pX(lim) , and only at that moment, the first The solubility product constants, Ksp (pKsp) are (13):
solid particle will appear (the iodate of the metal, M(IO3)m).
Ba(IO3)2: 4.01 ⫻ 10᎑9 (8.40)
Until then all of the metal will be dissolved and no solid will
AgIO3: 3.17 ⫻ 10᎑8 (7.50)
exist:
Ca(IO3)2: 6.47 ⫻ 10᎑6 (5.19)
La(IO3)3: 7.50 ⫻ 10᎑12 (11.12)
Although these considerations are often far from the con-
ditions that really exist (14), if we assume that no secondary
species (complexes or dissolved undissociated molecules) form
If the iodate concentration continues to increase and becomes from the atoms in the precipitate and that hydrolysis reac-
greater than pIO3 (lim), more and more solid metallic iodate tions are unimportant, that is, if there are no competing equi-
forms, and the concentration of the free metal, M, in the libria (15–16), the separation conditions are deduced from
solution becomes smaller and smaller. In other words, to the the existence intervals of the precipitates.
left of pIO3 (lim), equilibrium is achieved, that is, the solu- The existence intervals of the different M(IO3)m iodates
tion is saturated, while to the right of it, the solution is un- are obtained by replacing the concentrations of the different
saturated: cations, CM, in the Ksp expression, which, in logarithmic form,
gives:
1 1 1
pIO3 M(lim) = pK sp − log
m m CM
1 1 (8)
= AP − log
m CM
Exercise 2
If 0.010 mol of Ag2SO4(s) is added to a liter of water, and, represented on a pIO3 scale, are:
the existence limit for the solid (for CAg ⫽ 2.0 ⫻ 10᎑2 M ),
according to the concentration of SO42− (exchanged particle),
is:
+ −
Ag2SO4(s) 2Ag (aq) + SO42 (aq)
pK sp = 4.8

1 1 1
pSO4(lim) = pK sp − log
1 1 C Ag2
= 4.8 + 2 log (0.02 ) = 1.4

Thus, the first thing that can be clearly seen is the order of
precipitation (from right to left): 1 Ag⫹, 2 Ba2⫹, 3 La3⫹ and

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Research: Science and Education

Table 2. Comparative Examples of Fractional Precipitation by Species’ Concentration

Molar Ion Concentrations (C) and Fraction of Metal Precipitated (Pr)


When the Condition of Saturation Is Attained For:

Species Initial Molar 1 AgIO3 2 Ba(IO3)2 3 La(IO3)3 4 Ca(IO3)2


Concentration

C Pr C Pr C Pr C Pr

pIO3᎑ 5.9 3.3 2.9 1.1

IO3᎑ 1.3 ⫻ 10 ᎑6
5.0 ⫻ 10 ᎑4
1.3 ⫻ 10 ᎑3
7.9 ⫻ 10᎑2

Ag⫹ 2.5 ⫻ 10᎑2 2.5 ⫻ 10᎑2 0.0 6.3 ⫻ 10᎑5 99.7 2.5 ⫻ 10᎑5 99.9 4.0 ⫻ 10᎑7 99.998

00Ba2⫹ 2.0 ⫻ 10᎑2 2.0 ⫻ 10᎑2 0.0 2.0 ⫻ 10᎑2 0.0 2.5 ⫻ 10᎑3 87.5 6.4 ⫻ 10᎑7 99.997
3⫹ ᎑3 ᎑3 ᎑3 ᎑3 ᎑8
00La 3.0 ⫻ 10 3.0 ⫻ 10 0.0 3.0 ⫻ 10 0.0 3.0 ⫻ 10 0.0 1.5 ⫻ 10 99.999

00Ca2⫹ 1.0 ⫻ 10᎑3 1.0 ⫻ 10᎑3 0.0 1.0 ⫻ 10᎑3 0.0 1.0 ⫻ 10᎑3 0.0 1.0 0.0

4 Ca2⫹; that is, the silver iodate first, as it is the least soluble, while at point 6 , [La 3⫹] = 7.5 × 10 ᎑9 M (and Pr La ⫽
and then the other precipitates start to form in the order in- 99.99975%).
dicated above. We can see that the order of precipitation does In practical terms, precipitation is usually considered com-
not correspond to the increasing order of the respective Ksp plete (a quantitative precipitation) when 99.9% of the metal
constants. Let us remember that we can really compare solu- has precipitated, that is, when 0.1% of the original amount of
bility products in a semiquantitative manner only if there are the ion remains dissolved. In the case above, we have:
the same number of terms in the solubility product relation-
ship (that is why different stoichiometric ratios were chosen
for this example). It is the solubility rather than the solubility 1 1 1
pIO3 = pK sp − log
product constant that must be compared (16). 3 3 La 3 +
Apart from the order, we can also know the separation
possibilities in the conditions indicated. For that, students 1 1
have to understand that to the left of the pIO3 (lim) there is = AP − log = 1. 9
3 3 × 10 −6
always a solid, but also that some non-precipitated metal will
always be left, although the further to the left we go, the less
dissolved metal there will be. The question arises: When can
we be sure that all of the metal has precipitated? The answer
is never. There will always be something left, no matter how
little. Thus, for example, for the previous system with CLa ⫽
3.0 ⫻ 10᎑3 M we have:

With regard to the problem under consideration in this


section, Table 2 shows the concentrations of the species
present at the moment in which the saturation of each of
the solids is produced upon adding the soluble iodate.
Thus, in these conditions at point 5 , the amount of lan- Until an iodate concentration of 1.3 ⫻ 10᎑6 (pIO3 ⫽
thanum in solution is: 5.9) is reached, the solution is not saturated in any compound
and all of the species are dissolved. When Ba2⫹ (pIO3 ⫽ 3.3)
begins to precipitate, 99.7% of Ag⫹ has already precipitated.
K sp 7.5 × 10 −12
La 3 + = = = 7.5 × 10 − 6 When La3⫹ (pIO3 ⫽ 2.9) begins to precipitate, 99.9% of
− −2 3 Ag⫹ and 87.5% of Ba2⫹ have precipitated. Finally, when Ca2⫹
IO3 (10 ) (pIO3 ⫽ 1.1) begins to precipitate, 99.998% ⬇ 100% of
that is, the percentage of lanthanum precipitated will be: Ag⫹, 99.997% ⬇ 100% of Ba2⫹ and 99.999% ⬇ 100% of
La3⫹ have precipitated.
La 3 + In other words, in these conditions, the only complete
Pr La = 100% − × 100% = 99.75% (quantitative) separation is that of Ca2⫹, which manages to
C La separate from the other three ions. Apart from that, Ag⫹ sepa-

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Research: Science and Education

rates from Ca2⫹ and La3⫹, and, although the quantitative pre- 2. Vale, J.; Pereira, C. F.; Alcalde, M. J. Chem. Educ. 1993, 70,
cipitation limit is not strictly achieved, in practical terms it 790–795.
also separates from Ba2⫹. La3⫹ and Ba2⫹ are not able to sepa- 3. Fernández Pereira, C.; Alcalde, M.; Vale, J. Chem. Educator
rate from each other. [Online] 1996, 1 (6), 1; DOI 10.1333/s00897970073a.
4. Fernández Pereira, C.; Vale, J.; Alcalde, M. Chem. Educator [On-
Conclusions line] 2003, 8 (1), 15–21; DOI 10.1333/s00897020641a.
5. Charlot, G. Chimie Analytique Generale, Part I; Masson: Paris, 1967.
In this paper, we describe an application of the unified
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New York, 1966.
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Horwood: Chichester, UK, 1976.
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9. Stumm, W.; Morgan, J. E. Aquatic Chemistry. An Introduction
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Emphasizing Chemical Equilibria in Natural Waters; Wiley
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Interscience: New York, 1981.
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Notes
Aquatic Chemistry; Wiley Interscience: New York, 1993.
1. Part of this paper was presented at the XXVI Latin American 12. Rojas–Hernández, A.; Ramírez, M. T.; González, I. J. Chem.
Chemistry Congress held in Salvador, Brazil, 30 May–2 June 2004. Educ. 1995, 72, 1099.
2. For the sake of simplicity, the ionic charges of M and X have 13. Lide, D. R. Handbook of Chemistry and Physics, 85th ed.; CRC
been omitted. Press: Boca Raton, FL, 2004.
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