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 Chapter 5

Solubility Products and Solubility Concepts

Anna Maria Michałowska-Kaczmarczyk,

Aneta Spórna-Kucab and Tadeusz Michałowski

Additional information is available at the end of the chapter

[Link]

Abstract
The chapter refers to a general concept of solubility product Ksp of sparingly soluble
hydroxides and different salts and calculation of solubility of some hydroxides, oxides,
and different salts in aqueous media. A (criticized) conventional approach, based on
stoichiometry of a reaction notation and the solubility product of a precipitate, is com-
pared with the unconventional/correct approach based on charge and concentration
balances and a detailed physicochemical knowledge on the system considered, and
calculations realized according to generalized approach to electrolytic systems (GATES)
principles. An indisputable advantage of the latter approach is proved in simulation of
static or dynamic, two-phase nonredox or redox systems.

Keywords: electrolytic two-phase systems, solubility, dissolution, static systems,

dynamic systems, computer simulation, GATES, GEB

1. Introduction

The problem of solubility of various chemical compounds occupies a prominent place in the
scientific literature. This stems from the fact that among various properties determining the
use of these compounds, the solubility is of the paramount importance. Among others, this
issue has been the subject of intense activities initiated in 1979 by the Solubility Data Commis-
sion V.8 of the IUPAC Analytical Chemistry Division established and headed by S. Kertes [1],
who conceived the IUPAC-NIST Solubility Data Series (SDS) project [2, 3]. Within 1979–2009,
the series of 87 volumes, concerning the solubility of gases, liquids, and solids in liquids or

© 2017 The Author(s). Licensee InTech. This chapter is distributed under the terms of the Creative Commons
Attribution License ([Link] which permits unrestricted use,
distribution, and reproduction in any medium, provided the original work is properly cited.
94 Descriptive Inorganic Chemistry Researches of Metal Compounds

solids, were issued [3]; one of the volumes concerns the solubility of various oxides and
hydroxides [4]. An extensive compilation of aqueous solubility data provides the Handbook
of Aqueous Solubility Data [5].
A remark. Precipitates are marked in bold letters; soluble species/complexes are marked in
normal letters.

The distinguishing feature of a chemical compound sparingly soluble in a particular medium

is the solubility product Ksp value. In practice, the known Ksp values are referred only to
aqueous media. One should note, however, that the expression for the solubility product and
then the Ksp value of a precipitate depend on the notation of a reaction in which this precipitate
is involved. From this it follows the apparent multiplicity of Ksp’s values referred to a particular
precipitate. Moreover, as will be stated below, the expression for Ksp must not necessarily
contain ionic species. On the other hand, factual or seeming lack of Ksp’s value for some
precipitates is perceived; the latter issue be addressed here to MnO2, taken as an example.
Solubility products refer to a large group of sparingly soluble salts and hydroxides and some
oxides, e.g., Ag2O, considered overall as hydroxides. Incidentally, other oxides, such as MnO2,
ZrO2, do not belong to this group, in principle. For ZrO2, the solubility measurements showed
quite low values even under a strongly acidic condition [6]. The solubility depends on the prior
history of these oxides, e.g., prior roasting virtually eliminates the solubility of some oxides.
Moderately soluble iodine (I2) dissolves due to reduction or oxidation, or disproportionation in
alkaline media [7–12]; for I2, minimal solubility in water is a reference state. For 8-hydroxyquinoline,
the solubility of the neutral molecule HL is a reference state; a growth in solubility is caused here by
the formation of ionic species: H2L+1 in acidic and L 1 in alkaline media.
The Ksp is the main but not the only parameter used for calculation of solubility s of a
precipitate. The simplifications [13] practiced in this respect are unacceptable and lead to
incorrect/false results, as stated in [14–18]; more equilibrium constants are also involved with
two-phase systems. These objections, formulated in the light of the generalized approach to
electrolytic systems (GATES) [8], where s is the “weighed” sum of concentrations of all soluble
species formed by the precipitate, are presented also in this chapter, related to nonredox and
redox systems.
Calculation of s gives an information of great importance, e.g., from the viewpoint of gravim-
etry, where the primary step of the analysis is the quantitative transformation of a proper
analyte into a sparingly soluble precipitate (salt, hydroxide). Although the precipitation and
further analytical operations are usually carried out at temperatures far greater than the room
temperature, at which the equilibrium constants were determined, the values of s obtained
from the calculations made on the basis of equilibrium data related to room temperature are
helpful in the choice of optimal a priori conditions of the analysis, ensuring the minimal,
summary concentration of all soluble forms of the analyte, remaining in the solution, in
equilibrium with the precipitate obtained after addition of an excess of the precipitating agent;
this excess is referred to as relative to the stoichiometric composition of the precipitate. The
ability to perform appropriate calculations, based on all available physicochemical knowledge,
in accordance with the basic laws of matter conservation, deepens our knowledge of the
relevant systems. At the same time, it produces the ability to acquire relevant knowledge in
 Solubility Products and Solubility Concepts 95
[Link]

an organized manner—not just imitative, but focused on heuristics. This viewpoint is in

accordance with constructivist teaching, based on the belief that learning occurs, as learners
are actively involved in a process of meaning and knowledge construction, as opposed to
passively receiving information [19].

2. Definitions and formulation of solubility products

The Ksp value refers to a two-phase system where the equilibrium solid phase is a sparingly
soluble precipitate, whose Ksp value is measured/calculated according to defined expression
for the solubility product. This assumption means that the solution with defined species is
saturated against this precipitate, at given temperature and composition of the solution.
However, often a precipitate, when introduced into aqueous media, is not the equilibrium
solid phase, and then this fundamental requirement is not complied, as indicated in examples
of the physicochemical analyses of the systems with struvite MgNH4PO4 [20, 21], dolomite
CaMg(CO3)2 [22, 23], and Ag2Cr2O7.
The values of solubility products Ksp (usually represented by solubility constant pKsp =
logKsp value) are known for stoichiometric precipitates of AaBb or AaBbCc type, related to
dissociation reactions:

Ksp ¼ ½AŠa ½BŠb for Aa Bb ¼ aA þ bB, or ð1Þ

Ksp ¼ ½AŠa ½BŠb ½CŠc for Aa Bb Cc ¼ aA þ bB þ cC ð2Þ

where A and B or A, B, and C are the species forming the related precipitate; charges are
omitted here, for simplicity of notation. The solubility products for more complex precipitates
are unknown in the literature. The precipitates AaBbCc are known as ternary salts [24], e.g.,
struvite, dolomite, and hydroxyapatite Ca5(PO4)3OH.

The solubility products for precipitates of AaBb type are most frequently met in the literature.
In these cases, for A are usually put simple cations of metals, or oxycations [25]; e.g., BiO+1 and
UO2+2 form the precipitates: BiOCl and (UO2)2(OH)2. As B, simple or more complex anions
are considered, e.g., Cl 1, S 2, PO4 3, Fe(CN)6 4, in AgCl, HgS, Zn3(PO4)2, and Zn2Fe(CN)6.

In different textbooks, the solubility products are usually formulated for dissociation reactions,
with ions as products, also for HgS

HgS ¼ Hgþ2 þ S–2 ðKsp ¼ ½Hgþ2 Š½S 2 ŠÞ ð3Þ

although polar covalent bond exists between its constituent atoms [26]. Very low solubility
product value (pKsp = 52.4) for HgS makes the dissociation according to the scheme presented
by Eq. (3) impossible, and even verbal formulation of the solubility product is unreasonable.
Namely, the ionic product x = [Hg+2][S–2] calculated at [Hg+2] = [S–2] = 1/NA exceeds Ksp, 1/NA2
> Ksp (NA – Avogadro’s number); the concentration 1/NA = 1.66∙10–23 mol/L corresponds to 1
ion in 1 L of the solution. The scheme of dissociation into elemental species [14]
96 Descriptive Inorganic Chemistry Researches of Metal Compounds

HgS ¼ Hg þ S ðKsp1 ¼ ½HgŠ½SŠÞ ð4Þ

is far more favored from thermodynamic viewpoint; nonetheless, the solubility product (Ksp)
for HgS is commonly formulated on the basis of reaction (3). We obtain pKsp1 = pKsp – 2A
(E01 E02), where E01 = 0.850 V for Hg+2 + 2e–1 = Hg, E02 = –0.48 V for S + 2e–1 = S–2, 1/A = RT/
F
ln10, A = 16.92 for 298 K; then pKsp1 = 7.4.
Equilibrium constants are usually formulated for the simplest reaction notations. However, in
this respect, Eq. (4) is simpler than Eq. (3). Moreover, we are “accustomed” to apply solubility
products with ions (cations and anions) involved, but this custom can easily be overthrown. A
similar remark may concern the notation referred to elementary dissociation of mercuric
iodide precipitate

HgI2 ¼ Hg þ I2 ðKsp1 ¼ ½HgŠ½I2 ŠÞ ð5Þ

where I2 denotes a soluble form of iodine in a system. From

HgI2 ¼ Hgþ2 þ 2I 1 ðKsp ¼ ½Hgþ2 Š½I 1 Š2 , pKsp ¼ 28:55Þ ð6Þ

we obtain pKsp1 = pKsp – 2A(E01–E03), where

E01 ¼ 0:850 V for Hgþ2 þ 2e 1

¼ Hg, E03 ¼ 0:621 V for I2 þ 2e 1
¼ 2I 1 ; then pKsp1 ¼ [Link]

The species in the expression for solubility products do not predominate in real chemical
systems, as a rule. However, the precipitation of HgS from acidified (HCl) solution of mercury
salt with H2S solution can be presented in terms of predominating species; we have

HgCl4 2 þ H2 S ¼ HgS þ 4Cl–1 þ 2Hþ1 ð7Þ

Eq. (7) can be applied to formulate the related solubility product, Ksp2, for HgS. To be online
with customary requirements put on the solubility product formulation, Eq. (7) should be
rewritten into the form
HgS þ 4Cl–1 þ 2Hþ1 ¼ HgCl4 2 þ H2 S ð7aÞ

Applying the law of mass action to Eq. (7a), we have

½HgCl4 2 Š½H2 SŠ
Ksp2 ¼ , ðpKsp2 ¼ 17:33Þ ð8Þ
½Cl 1 Š4 ½Hþ1 Š2

where [HgCl4–2] = 1015.07[Hg+2][Cl–1]4, [H2S] = 1020.0[H+1]2[S–2], Ksp (Eq. (3)).

The solubility product for MgNH4PO4 can be formulated on the basis of reactions:
3 3
MgNH4 PO4 ¼ Mgþ2 þ NHþ1 þ2 þ1
4 þ PO4 ðKsp ¼ ½Mg Š½NH4 Š½PO4 ŠÞ ð9Þ

MgNH4 PO4 ¼ Mgþ2 þ NH3 þ HPO4 2 ðKsp1 ¼ ½Mgþ2 Š½NH3 Š½HPO4 2 Š ¼ Ksp K1N =K3P Þ ð10Þ
 Solubility Products and Solubility Concepts 97
[Link]

MgNH4 PO4 þ H2 O ¼ MgOHþ1 þ NH3 þ H2 PO4 1 ðKsp2 ¼ ½MgOHþ1 Š½NH3 Š½H2 PO4 1 Š
ð11Þ
¼ Ksp KOH
1 K1N KW =ðK2P K3P Þ

where K1N = [H+1][NH3]/[NH4+1], K2P = [H+1][HPO4–2]/[H2PO4–1], K3P = [H+1][PO4–3]/[HPO4–2],

[MgOH+1] = K1OH[Mg+2][OH–1], KW = [H+1][OH–1].
Note that only uncharged (elemental) species are involved in Eqs. (4) and (5); H2S enters
Eq. (8), and NH3 enters Eqs. (10) and (11). This is an extension of the definition/formulation
commonly met in the literature, where only charged species were involved in expression for
the solubility product. Note also that small/dispersed mercury drops are neutralized with
powdered sulfur, according to thermodynamically favored reaction [27]

Hg þ S ¼ HgS

reverse to Eq. (4). Some precipitates can be optionally considered as the species of AaBb or
AaBbCc type. For example, the solubility product for MgHPO4 can be written as Ksp = [Mg+2]
[HPO4–2] or Ksp1 = [Mg+2][H+1][PO4–3] = KspK3P.

The ferrocyanide ion Fe(CN)6–4 (with evaluated stability constant K6 ca. 1037) can be consid-
ered as practically undissociated, i.e., Fe(CN)6–4 is kinetically inert [28], and then it does not
give Fe+2 and CN–1 ions. The solubility product of Zn2Fe(CN)6 is Ksp = [Zn+2]2[Fe(CN)6–4].
Therefore, consideration of Zn2Fe(CN)6 as a ternary salt with Ksp1 = [Zn+2]2[Fe2+][CN–1]6 = Ksp/
K6 is not acceptable.

In principle, the solubility product values are formulated for stoichiometric compounds, and
specified as such in the related tables. However, some precipitates obtained in laboratory have
nonstoichiometric composition, e.g., dolomite Ca1+xMg1-x(CO3)2 [22, 23], FexS [29]. In particu-
lar, FexS can be rewritten as Fe+2pFe+3qS; from the relations: 2p + 3q 2 = 0 and p + q = x, we get
q/p = 2(1 x)/(3x 2).
In this context, some remark needs a formulation of Ksp for some hydroxyoxides (e.g., FeOOH)
and oxides (e.g., Ag2O). The related solubility products are formulated after completion of the
corresponding reactions with water, e.g., FeOOH + H2O = Fe(OH)3, Fe2O3∙xH2O + (3 x)H2O =
2Fe(OH)3 ) Fe(OH)3 = Fe+3 + 3OH–1 ) Ksp = [Fe+3][OH–1]3; Ag2O + H2O = 2AgOH ) AgOH =
Ag+1 + OH–1 ) Ksp = [Ag+1][OH–1], see it in the context with gcd(a,b) = 1.
The solubility product can be involved not only with dissociation reaction. For example, the
dissolution reaction Ca(OH)2 + 2H+1 = Ca+2 + 2H2O [30], characterized by Ksp1 = [Ca+2]/[H+1]2,
is involved with Ksp = [Ca+2][OH–1]2 in the relation Ksp1 = Ksp/Kw2. In Ref. [31], the solubility
product is associated with formation (not dissociation) of a precipitate.

3. Solubility product(s) for MnO2

The scheme presented above cannot be extended to all oxides. For example, one cannot
recommend the formulation of this sequence for MnO2, i.e., MnO2 + 2H2O = Mn(OH)4 )
98 Descriptive Inorganic Chemistry Researches of Metal Compounds

Mn(OH)4 = Mn+4 + 4OH–1 ) Ksp0 = [Mn+4][OH–1]4; Mn+4 ions do not exist in aqueous media,
and MnO2 is the sole Mn(+4) species present in such systems. In effect, Ksp0 for MnO2 is not
known in the literature, compare with Ref. [32]. However, the Ksp for MnO2 can be formally
calculated according to an unconventional approach, based on the disproportionation reaction

5MnO2 þ 4Hþ1 ¼ 2MnO4 1 þ 3Mnþ2 þ H2 O ð12Þ

reverse to the symproportionation reaction 2MnO4 1 + 3Mn+2 + H2O = 5MnO2 + 4H+1. The
Ksp = Ksp1 value can be found there on the basis of E01 and E02 values [33], specified for reactions:

MnO4 1 þ 4Hþ1 þ 3e 1
¼ MnO2 þ 2H2 OðE01 ¼ 1:692 VÞ ð13Þ

MnO2 þ 4Hþ1 þ 2e 1
¼ Mnþ2 þ 2H2 OðE02 ¼ 1:228 VÞ ð14Þ

Eqs. (13) and (14) are characterized by the equilibrium constants:

½MnO2 Š½H2 OŠ2 ½Mnþ2 Š½H2 OŠ2

Ke1 ¼ , Ke2 ¼ ð15Þ
½MnO4 1 Š½Hþ1 Š4 ½e 1 Š 3
½MnO2 Š½Hþ1 Š4 ½e 1 Š2

defined on the basis of mass action law (MAL) [14], where logKe1 = 3
A
E01, logKe2 = 2
A
E02,
A = 16.92. From Eqs. (13) and (14), we get

2MnO2 þ 4H2 O þ 3MnO2 þ 12Hþ1 þ 6e 1

¼ 2MnO4 1 þ 8Hþ1 þ 6e 1
þ 3Mnþ2 þ 6H2 O
ð16Þ

Assuming [MnO2] = 1 and [H2O] = 1 on the stage of the Ksp1 formulation for reaction (16),
equivalent to reaction (12), we have

½MnO4 1 Š2 ½Mnþ2 Š3
Ksp1 ¼ ð17Þ
½Hþ1 Š4

and then

Ksp1 ¼ ðKe2 Þ3
ðKe1 Þ 2

ð18Þ

pKsp1 ¼ 3logKe2 2logKe1 ¼ 6AðE01 E02 Þ ¼ 6
16:92
ð1:692 1:228Þ ¼ 47:11 ð19Þ

The solubility products with MnO2 involved can be formulated on the basis of other reactions.
For example, addition of

Mnþ2 ¼ Mnþ3 þ e 1
ð20Þ

to Eq. (14) gives

 Solubility Products and Solubility Concepts 99
[Link]

MnO2 þ 4Hþ1 þ 2e 1
þ Mnþ2 ¼ Mnþ2 þ 2H2 O þ Mnþ3 þ e 1
ð21Þ

Multiplication of Eq. (21) by 3, and then addition to Eq. (13a)

MnO2 þ 2H2 O ¼ MnO4 1 þ 4Hþ1 þ 3e 1

(reverse to Eq. (13)) gives the equation

3MnO2 þ 12Hþ1 þ 6e 1
þ 3Mnþ2 þ MnO2 þ 2H2 O
ð22Þ
¼ 3Mnþ2 þ 6H2 O þ 3Mnþ3 þ 3e 1
þ MnO4 1 þ 4Hþ1 þ 3e 1

and its equivalent form, obtained after simplifications,

4MnO2 þ 8Hþ1 ¼ 3Mnþ3 þ MnO4 1 þ 4H2 O ð22aÞ

Eq. (22) and then Eq. (22a) is characterized by the solubility product

½MnO4 1 Š½Mnþ3 Š3
Ksp2 ¼ þ1 8
¼ ðKe2 Þ3
ðKe3 Þ 3

ðKe1 Þ 1
ð23Þ
½H Š

where

½Mnþ2 Š
Ke3 ¼ ð24Þ
½Mnþ3 Š½e 1 Š

for Mn+3 + e 1
= Mn+2 (E03 = 1.509 V) (reverse to Eq. (20)), logKe3 = A
E03. Then

pKsp2 ¼ 3A∙ðE01 2E02 þE03 Þ þ 37:82 ð25Þ

Formulation of Kspi for other combinations of redox and/or nonredox reactions is also possible.
This way, some derivative solubility products are obtained. The choice between the “output”
and derivative solubility product values is a matter of choice. Nevertheless, one can choose the
Ksp3 value related to the simplest expression for the solubility product Ksp3 = [Mn+2][MnO4 2]
involved with reaction 2MnO2 = Mn+2 + MnO4 2.
As results from calculations, the low Kspi (i = 1,2,3) values obtained from the calculations
should be crossed, even in acidified solution with the related manganese species presented in
Figure 1. In the real conditions of analysis, at Ca = 1.0 mol/L, the system is homogeneous
during the titration, also after crossing the equivalence point, at Φ = Φeq > 0.2; this indicates
that the corresponding manganese species form a metastable system [34], unable for the
symproportionation reactions.
100 Descriptive Inorganic Chemistry Researches of Metal Compounds

MnSO 4

-4
Mn +2 Mn(OH) +2
MnO 4- 1

-8
log[Xi]

-12
Mn(OH) +1

-16

Mn(OH) +2 MnO 4- 1 MnO 4- 2

Mn +3
-20
0.0 0.1 0.2 0.3 0.4
F

Figure 1. The log[Xi] versus Φ relationships for different manganese species Xi, plotted for titration of V0 = 100 mL
solution of FeSO4 (C0 = 0.01 mol/L) + H2SO4 (Ca = 1.0 mol/L) with V mL of C = 0.02 mol/L KMnO4; Φ = C
V/(C0
V0). The
species Xi are indicated at the corresponding lines.

4. Calculation of solubility

In this section, we compare two options applied to the subject in question. The first/criticized
option, met commonly in different textbooks, is based on the stoichiometric considerations,
resulting from dissociation of a precipitate, characterized by the solubility product Ksp value,
and considered a priori as an equilibrium solid phase in the system in question; the solubility
value obtained this way will be denoted by s* [mol/L]. The second option, considered as a
correct resolution of the problem, is based on full physicochemical knowledge of the system,
not limited only to Ksp value (as in the option 1); the solubility value thus obtained is denoted
as s [mol/L]. The second option fulfills all requirements expressed in GATES and involved with
basic laws of conservation in the systems considered. Within this option, we check, among
others, whether the precipitate is really the equilibrium solid phase. The results (s*, s) obtained
according to both options (1 and 2) are compared for the systems of different degree of
complexity. The unquestionable advantages of GATES will be stressed this way.

4.1. Formulation of the solubility s*

The solubility s* will be calculated for a pure precipitate of: (1o) AaBb or (2o) AaBbCc type,
when introduced into pure water. Assuming [A] = a∙s* and [B] = b∙s*, from Eq. (1), we have
 Solubility Products and Solubility Concepts 101
[Link]

 1=ðaþbÞ
Ksp
s ¼
∗
ð26Þ
aa
bb

and assuming [A] = a∙s*, [B] = b∙s*, [C] = c∙s*, from Eq. (2), we have

 1=ðaþbþcÞ
Ksp
s ¼
∗
ð27Þ
aa
bb
cc

As a rule, the formulas (26) and (27) are invalid for different reasons, indicated in this chapter.
This invalidity results, among others, from inclusion of the simplest/minor species in Eq. (26)
or (27) and omission of hydroxo-complexes + other soluble complexes formed by A, and proto-
complexes + other soluble complexes, formed by B. In other words, not only the species
entering the expression for the related solubility product are present in the solution consid-
ered. Then the concentrations: [A], [B] or [A], [B], and [C] are usually minor species relative to
the other species included in the respective balances, considered from the viewpoint of
GATES [8].

4.2. Dissolution of hydroxides

We refer first to the simplest two-phase systems, with insoluble hydroxides as the solid phases.
In all instances, s* denotes the solubility obtained from stoichiometric considerations, whereas
s relates to the solubility calculated on the basis of full/attainable physicochemical knowledge
related to the system in question where, except the solubility product (Ksp), other physico-
chemical data are also involved.
Applying formula (26) to hydroxides (B = OH 1): Ca(OH)2 (pKsp1 = 5.03) and Fe(OH)3
(pKsp2 = 38.6), we have [35]

CaðOHÞ2 ¼ Caþ2 þ 2OH 1 ðKsp1 ¼ ½Caþ2 Š½OH 1 Š2 , s ¼ ðKsp1 =4Þ1=3 ¼ 0:0133 mol=LÞ ð28Þ

FeðOHÞ3 ¼ Feþ3 þ 3OH 1 ðKsp2 ¼ ½Feþ3 Š½OH 1 Š3 , s ¼ ðKsp2 =27Þ1=4 ¼ 0:98  10–10 mol=LÞ
ð29Þ

respectively. However, Ca+2 and Fe+3 form the related hydroxo-complexes: [CaOH+1] =
101.3
[Ca+2][OH 1] and: [FeOH+2] = 1011.0
[Fe+3][OH 1], [Fe(OH)2+1] = 1021.7
[Fe+3][OH 1]2;
[Fe2(OH)2+4] = 1025.1
[Fe+3]2[OH 1]2 [31]. The corrected expression for the solubility of Ca(OH)2
is as follows

s ¼ ½Caþ2 Š þ ½CaOHþ1 Š ð30Þ

Inserting [Ca+2] = Ksp1/[OH 1]2 and [OH 1] = KW/[H+1], [H+1] = 10 pH

(pKW = 14.0 for ionic
product of water, KW) into the charge balance
102 Descriptive Inorganic Chemistry Researches of Metal Compounds

2½Caþ2  þ ½CaOHþ1  þ ½Hþ1 –½OH
1  ¼ 0 ð31Þ

we get, by turns,

2  10
5:03 =½OH
1 2 þ 101:3  10
5:03 =½OH
1 ½Hþ1 
½OH
1  ¼ 0

) 2  10
5:03þ28
2pH þ 101:3  10
5:03þ14
pH þ 10
pH –10pH
14 ¼ 0

yðpHÞ ¼ 2  1022:97
2pH þ 1010, 17
pH þ 10
pH –10pH
14 ¼ 0 ð32Þ

where pH ¼
log½Hþ1 . Applying the zeroing procedure to Eq. (30), we get pH0 = 12.453
(Table 1), where: [Ca+2] = 0.0116, [CaOH+1] = 0.00656, s = 0.0182 mol/L (Eq. (28)). As we see,
[CaOH+1] is comparable with [Ca+2], and there are none reasons to omit [CaOH+1] in Eq. (28).
The alkaline reaction in the system with Ca(OH)2 results immediately from Eq. (29): [OH
1] –
[H+1] = 2½Caþ2  þ ½CaOHþ1  > 0:
Analogously, for the system with Fe(OH)3, we have the charge balance

3½Feþ3  þ 2½FeOHþ2  þ ½FeðOHÞþ1 þ4 þ1
1

2  þ 4½Fe2 ðOHÞ2  þ ½H –½OH  ¼ 0 ð33Þ

and then

yðpHÞ ¼ 3  103:4
3pH þ 2  100:4
2pH þ 10
2:9
pH þ 4  103:9
4pH þ 10
pH –10pH
14 ¼ 0 ð34Þ

Eq. (32) zeroes at pH0 = 7.0003 (Table 2), where the value

s ¼ ½Feþ3  þ ½FeOHþ2  þ ½FeðOHÞþ1 þ4

2  þ 2½Fe2 ðOHÞ2  ð35Þ

is close to s ffi [Fe(OH)2+1] = 10–9.9. Alkaline reaction for this system, i.e., [OH
1] > [H+1], results
immediately from Eq. (30), and pH0 = 7.0003 (>7).
At pH = 7, Fe(OH)2+1 (not Fe+3) is the predominating species in the system, [Fe(OH)2+1]/[Fe+3] =
1021.7–14 = 5107, i.e., the equality/assumption s* = [Fe+3] is extremely invalid. Moreover, the
value [OH
1] = 3s* = 2.9410–10 = 10–9.532, i.e., pH = 4.468; this pH-value is contradictory with
the inequality [OH
1] > [H+1] resulting from Eq. (31). Similarly, extremely invalid result was

pH y(pH) [OH
1] [Ca+2] [CaOH+1]

12.451 0.000377 0.02825 0.01169 0.006592

12.452 0.000193 0.02831 0.01164 0.006577
12.453 8.30E-06 0.02838 0.01159 0.006561

12.454
0.000176 0.02844 0.01153 0.006546

12.455
0.000359 0.02851 0.01148 0.006531

Table 1. Zeroing the function (30) for the system with Ca(OH)2 precipitate introduced into pure water (copy of a
fragment of display).
 Solubility Products and Solubility Concepts 103
[Link]

pH y(pH) [Fe+3] [FeOH+2] [Fe(OH)2+1] [Fe2(OH)2+4]

7.0001 7.99E-11 2.510E-18 2.511E-14 1.259E-10 7.936E-25

7.0002 3.38E-11 2.508E-18 2.510E-14 1.258E-10 7.929E-25
7.0003 1.23E-11 2.507E-18 2.508E-14 1.258E-10 7.921E-25
7.0004 5.84E-11 2.505E-18 2.507E-14 1.258E-10 7.914E-25
7.0005 1.04E-10 2.503E-18 2.506E-14 1.257E-10 7.907E-25

Table 2. Zeroing the function (32) for the system with Fe(OH)3 precipitate introduced into pure water (copy of a
fragment of display).

obtained in Ref. [36], where the strong hydroxo-complexes were totally omitted, and weak
chloride complexes of Fe+3 ions were included into considerations.
Taking only the main dissociating species formed in the solution saturated with respect to
Fe(OH)3, we check whether the reaction Fe(OH)3 = Fe(OH)2+1 + OH 1 with Ksp1 = [Fe(OH)2+1]
[OH 1] = 1021.7
10–38.6 = 10–16.9 can be used for calculation of solubility s0 ¼ ðKsp1 Þ1=2 for
Fe(OH)3; the answer is also negative. Simply, the main part of OH 1 ions originates here from
dissociation of water, where the precipitate has been introduced, and then Fe(OH)2+1 and
OH 1 differ significantly. As we see, the diversity in Ksp value related to a precipitate depends
on its dissociation reaction notation, which disqualifies the calculation of s* based solely on the
Ksp value. This fact was not stressed in the literature issued hitherto.
Concluding, the application of the option 1, based on the stoichiometry of the reaction (29),
leads not only to completely inadmissible results for s+, but also to a conflict with one of the
fundamental rules of conservation obligatory in electrolytic systems, namely the law of charge
conservation.
Similarly, critical/disqualifying remarks can be related to the series of formulas considered in
the chapter [37], e.g., Ksp = 27(s*)4 for precipitates of A3B and AB3 type, and Ksp = 108(s*)5 for
A2B3 and A3B2. For Ca5(PO4)3OH, the formula Ksp = 84375(s*)9 (!) was applied [38].
As a third example let us take a system, where an excess of Zn(OH)2 precipitate is introduced
into pure water. It is usually stated that Zn(OH)2 dissociates according to the reaction

1
ZnðOHÞ2 ¼ Znþ2 þ 2 OH ð36Þ

applied to formulate the expression for the solubility product

Ksp3 ¼ ½Znþ2 Š½OH 1 Š2 ðpKsp3 ¼ 15:0Þ ð37Þ

The soluble hydroxo-complexes Zn(OH)i+2 i (i=1,…,4), with the stability constants, KiOH,
expressed by the values logKiOH = 4.4, 11.3, 13.14, 14.66, are also formed in the system in
question. The charge balance (ChB) has the form
104 Descriptive Inorganic Chemistry Researches of Metal Compounds

2½Znþ2 Š þ ½ZnOHþ1 Š–½ZnðOHÞ3 1 Š 2½ZnðOHÞ4 2 Š þ ½Hþ1 Š ½OH 1 Š ¼ 0 ð38Þ

15
i.e., 2
10 /[OH 1]2 + 104.4
10 15
/[OH 1] – 1013.14
10 15
∙[OH 1] – 2
1014.66
10 15
∙[OH 1]2 = 0

yðpHÞ ¼ 2
1013 2pH

þ 103:4 pH
–10 15:86þpH
–2
10 28:34þ2pH
þ 10 pH
–10pH 14
¼0 ð39Þ

The function (39) zeroes at pH0 = 9.121 (see Table 3). The basic reaction of this system is not
immediately stated from Eq. (38) (there are positive and negative terms in expression for
[OH 1] [H+1]). The solubility s value

s ¼ ½Znþ2 Š þ ½ZnOHþ1 Š þ ½ZnðOHÞ2 Š þ ½ZnðOHÞ3 1 Š þ ½ZnðOHÞ4 2 Š ¼ 2:07
10 4

calculated at this point is different from s* = (Kso3/4)1/3 = 6.3
10 6, and [OH 1]/[Zn+2] 6¼ 2; such
incompatibilities contradict application of this formula.

4.3. Dissolution of MeL2-type salts

Let us refer now to dissolution of precipitates MeL2 formed by cations Me+2 and anions L 1 of
a strong acid HL, as presented in Table 4. When an excess of MeL2 is introduced into pure
water, the concentration balances and charge balance in two-phase system thus formed are as
follows:

pH [OH 1] [Zn+2] [ZnOH+1] [Zn(OH)2] [Zn(OH)3 1] [Zn(OH)4 2] y(pH) s [mol/L]

9.118 1.3122E-05 5.8076E-06 1.9143E-06 0.0002 1.8113E-07 7.8705E-11 2.2702E-07 0.00020743

9.119 1.3152E-05 5.7810E-06 1.9099E-06 0.0002 1.8155E-07 7.9068E-11 1.3858E-07 0.00020740
9.120 1.3183E-05 5.7544E-06 1.9055E-06 0.0002 1.8197E-07 7.9433E-11 5.0322E-08 0.00020737
9.121 1.3213E-05 5.7280E-06 1.9011E-06 0.0002 1.8239E-07 7.9800E-11 3.7750E-08 0.00020734
9.122 1.3243E-05 5.7016E-06 1.8967E-06 0.0002 1.8281E-07 8.0168E-11 1.2564E-07 0.00020731
9.123 1.3274E-05 5.6755E-06 1.8923E-06 0.0002 1.8323E-07 8.0538E-11 2.1335E-07 0.00020728

Table 3. Zeroing the function (39) for the system with Zn(OH)2 precipitate introduced into water; pKW = 14.

Me+2 MeOH+1 Me(OH)2 Me(OH)3 1

L 1
MeL+1 MeL2 MeL3 1
MeL4 2
MeL2

logK1OH logK2 OH logK3 OH logK1 logK2 logK3 logK4 pKsp

Hg+2 10.3 21.7 21.2 I 1

12.87 23.82 27.60 29.83 28.54
+2 1
Pb 6.9 10.8 13.3 I 1.26 2.80 3.42 3.92 8.98
1
Cl 1.62 2.44 2.04 1.0 4.79

Table 4. logKiOH and logKi values for the stability constants Ki and Kj of soluble complexes Me(OH)i+2-i and MeLj+2-j and
pKsp values for the precipitates MeL2; [MeLi+2-i] = Ki[Me+2][L 1]i, Ksp = [Me+2][L 1]2.
 Solubility Products and Solubility Concepts 105
[Link]

I J
þ2 j
½MeL2 Š þ ½Meþ2 Š þ ½MeðOHÞiþ2 i Š þ
X X
½MeLj Š ¼ CMe ð40Þ
i¼1 j¼1

J
þ2 j
X
2½MeL2 Š þ ½L 1 Š þ j½MeLj Š ¼ CL ð41Þ
j¼1

I J
þ1 þ2 þ2 j
iÞ½MeðOHÞiþ2 i Š
1
X X
½H Š ½OH Š þ 2½Me Š þ ð2 þ ð2 jÞ½MeLj Š ½L 1 Š ¼ 0 ð42Þ
i¼1 j¼1

where [MeL2] denotes the concentration of the precipitate MeL2. At CL = 2CMe, we have

I J
þ2 j
2½Meþ2 Š þ 2 ½MeðOHÞiþ2 i Š þ
X X
ð2 jÞ½MeLj Š ¼ ½L 1 Š ð43Þ
i¼1 j¼1

From Eqs. (40) and (41)

I
α ¼ ½Hþ1 Š i½MeðOHÞiþ2 i Š
X
½OH 1 Š ¼ ð44Þ
i¼1

i.e., reaction of the solution is acidic, [H+1] > [OH 1]. Applying the relations for the equilibrium
constants:

[Me+2][L 1]2 = Ksp, [Me(OH)i+2 i] = KiOH[Me+2][OH 1]i (i = 1,…, I), [MeLj+2 j] = Kj[Me+2][L 1]j
(j = 1,…, J)
from Eqs. (43) and (44) we have

I J
2½Meþ2 Š3=2
ð1 þ ð1 þ xi Þ þ Ksp 1=2
½Meþ2 Š

X X
ð2 jÞKj ½L 1 Š Ksp 1=2 ¼ 0 ð45Þ
i¼1 j¼1

where

α
½Meþ2 Š ¼ I
; α ¼ ½Hþ1 Š ½OH 1 Š ¼ 10 pH
10pH pKW
; ½L 1 Š
X
i
xi
i¼1
 1=2
Ksp
¼ þ2
½Me Š
; xi ¼ KOH
i
ðKW =½Hþ1 ŠÞi

In particular, for I = 3, J = 4 (Table 4), we have

106 Descriptive Inorganic Chemistry Researches of Metal Compounds

!
3
½MeŠ2
þ K1
½MeŠ3=2 ðK3
Ksp þ 1Þ
½MeŠ1=2
X
2
1þ xi
2
K4
Ksp 3=2 ¼ 0 ð46Þ
i¼1
Ksp 1=2

Applying the zeroing procedure to Eq. (46) gives the pH = pH0 of the solution at equilibrium.
At this pH0 value, we calculate the concentrations of all species and solubility of this precipi-
tate recalculated on sMe and sL. When zeroing Eq. (46), we calculate pH = pH0 of the solution in
equilibrium with the related precipitate. The solubilities are as follows:
I J
s ¼ sMe ¼ ½Meþ2 Š þ
X X
½MeðOHÞi þ2 i Š þ ½MeLj þ2 j Š ð47Þ
i¼1 j¼1

4
s ¼ sL ¼ ½L 1 Š þ
X
j½MeLj þ2 j Š ð48Þ
j¼1

The calculations of sMe and sL for the precipitates specified in Table 4 can be realized with use
of Excel spreadsheet, according to zeroing procedure, as suggested above (Table 1).

For PbI2: pH0 = 5.1502, sPb = 6.5276∙10 4, sI = 1.3051∙10 3, see Table 6. The difference between sI
and 2sPb = 1.3055∙10 3 results from rounding the pH0-value.
For HgI2: pH0 = 6.7769, sHg = 1.91217∙10 5, sI = 3.82435∙10 5, see Table 7. The difference
between sI and 2sHg = 3.82434∙10 5 results from rounding the pH-value. The concentration
[HgI2] = K2Ksp = 1.90546∙10 5 is close to the sHg value. For comparison, 4(s*)3 = Ksp ⟹ s* =
1.93∙10 10, i.e., s*/s ≈ 10 5.

pH [Pb+2] [PbOH+1] [Pb(OH)2] [Pb(OH)3-1] [PbCl+1] [PbCl2] [PbCl3 1] [PbCl4 2] [Cl 1] y

4.5343 0.010749606 2.92208E-05 7.94315E-11 8.59592E-18 0.017405892 0.004466836 6.90723E-05 2.44685E-07 0.038842191 0.000138249

4.5344 0.010744657 2.92141E-05 7.94315E-11 8.5979E-18 0.017401884 0.004466836 6.90882E-05 2.44798E-07 0.038851136 7.7139E-05

4.5345 0.01073971 2.92074E-05 7.94315E-11 8.59988E-18 0.017397878 0.004466836 6.91041E-05 2.44911E-07 0.038860083 1.60945E-05

4.5346 0.010734765 2.92007E-05 7.94315E-11 8.60186E-18 0.017393872 0.004466836 6.912E-05 2.45023E-07 0.038869032 -4.48848E-05

4.5347 0.010729823 2.91939E-05 7.94315E-11 8.60384E-18 0.017389867 0.004466836 6.91359E-05 2.45136E-07 0.038877983 -0.000105799

Table 5. Fragment of display for PbCl2.

pH [Pb+2] [PbOH+1] [Pb(OH)2] [Pb(OH)3 1] [PbI+1] [PbI2] [PbI3 1] [PbI4 2] [I 1] y

5.15 0.000630817 7.07789E-06 7.94152E-11 3.54735E-17 1.47894E-05 6.60693E-07 3.54853E-09 1.44576E-11 0.001288393 0.000138249

5.1501 0.000630527 7.07626E-06 7.94152E-11 3.54816E-17 1.4786E-05 6.60693E-07 3.54935E-09 1.44643E-11 0.001288689 7.7139E-05

5.1502 0.000630236 7.07463E-06 7.94152E-11 3.54898E-17 1.47826E-05 6.60693E-07 3.55016E-09 1.44709E-11 0.001288986 1.60945E-05

5.1503 0.000629946 7.073E-06 7.94152E-11 3.5498E-17 1.47792E-05 6.60693E-07 3.55098E-09 1.44776E-11 0.001289283 -4.48848E-05

5.1504 0.000629656 7.07137E-06 7.94152E-11 3.55061E-17 1.47758E-05 6.60693E-07 3.5518E-09 1.44843E-11 0.00128958 -0.000105799

Table 6. Fragment of display for PbI2.

 Solubility Products and Solubility Concepts 107
[Link]

pH [Hg+2] [HgOH+1] [Hg(OH)2] [Hg(OH)3 1] [HgI+1] [HgI2] [HgI3 1] [HgI4 2] [I 1] y

6.7767 2.99681E-15 3.57569E-12 5.37106E-08 1.01569E-15 2.17936E-09 1.90546E-05 1.12634E-08 1.87646E-13 9.81003E-08 1.35932E-10

6.7768 2.99398E-15 3.57313E-12 5.36844E-08 1.01543E-15 2.17833E-09 1.90546E-05 1.12688E-08 1.87824E-13 9.81467E-08 7.72021E-11

6.7769 2.99114E-15 3.57056E-12 5.36583E-08 1.01517E-15 2.1773E-09 1.90546E-05 1.12741E-08 1.88002E-13 9.81932E-08 1.8567E-11

6.777 2.98831E-15 3.568E-12 5.36322E-08 1.0149E-15 2.17627E-09 1.90546E-05 1.12794E-08 1.88181E-13 9.82398E-08 -3.99731E-11

6.7771 2.98548E-15 3.56544E-12 5.3606E-08 1.01464E-15 2.17524E-09 1.90546E-05 1.12848E-08 1.88359E-13 9.82863E-08 -9.84182E-11

Table 7. Fragment of display for HgI2.

4.4. Dissolution of CaCO3 in the presence of CO2

The portions 0.1 g of calcite CaCO3 (M = 100.0869 g/mol, d = 2.711 g/cm3) are inserted into 100 mL
of: pure water (task A) or aqueous solutions of CO2 specified in the tasks: B1, B2, B3, and
equilibrated. Denoting the starting (t = 0) concentrations [mol/L]: Co for CaCO3 and CCO2 for
CO2 in the related systems, on the basis of equilibrium data collected in Table 8:
(A) we calculate pH = pH01 and solubility s = s(pH01) of CaCO3 at equilibrium in the system;
(B1) we calculate pH = pH02 and solubility s = s(pH02) of CaCO3 in the system, where CCO2
refers to saturated (at 25 oC) solution of CO2, where 1.45 g CO2 dissolves in 1 L of water [39].
(B2) we calculate minimal CCO2 in the starting solution needed for complete dissolution of
CaCO3 in the system and the related pH = pH03 value, where s = s(pH03) = Co;

(B3) we plot the logsCa versus V, pH versus V and logsCa versus pH relationships for the system
obtained after addition of V mL of a strong base MOH (Cb = 0.1) into V0 = 100 mL of the system
with CaCO3 presented in (B1). The quasistatic course of the titration is assumed.
The volume 0.1/2.711 = 0.037 cm3 of introduced CaCO3 is negligible when compared with V0 at
the start (t = 0) of the dissolution. Starting concentration of CaCO3 in the systems: A, B1, B2, B3
is Co = (0.1/100)/0.1 = 10 2 mol/L. At t > 0, concentration of CaCO3 is co mol/L. The balances are
as follows:

No. Reaction Expression for the equilibrium constant Equilibrium data

+2 2 +2 2
1 CaCO3 = Ca + CO3 [Ca ][CO3 ] = Ksp pKsp = 8.48
2 Ca+2 + OH 1
= CaOH+1 [CaOH+1] = K10[Ca+2][OH 1] logK10 = 1.3
+1 1 +1 1
3 H2CO3 = H + HCO3 [H ][HCO3 ] = K1[H2CO3] pK1 = 6.38
1
4 HCO3 = H+1 + CO3 2
[H+1][CO3 2] = K2[HCO3-1] pK2 = 10.33
+2 1
5 Ca + HCO3 = CaHCO3+1 [CaHCO3+1] +2
= K11[Ca ][HCO3 ] 1
logK11 = 1.11
6 Ca+2 + CO3 2
= CaCO3 [CaCO3] = K12[Ca+2][CO3 2] logK12 = 3.22
+2 1 +2 1 2
7 Ca(OH)2 = Ca + 2OH [Ca ][OH ] = Ksp1 pKsp1 = 5.03
+1 1 +1 1
8 H2O = H + OH [H ][OH ] = KW pKW = 14.0

Table 8. Equilibrium data.

108 Descriptive Inorganic Chemistry Researches of Metal Compounds

Co ¼ co þ ½Caþ2 Š þ ½CaOHþ1 Š þ ½CaHCOþ1

3 Š þ ½CaCO3 Š ðfor A, B1, B2, B3Þ ð49Þ

Co ¼ co þ ½CaHCOþ1 1 2
3 Š þ ½CaCO3 Š þ ½H2 CO3 Š þ ½HCO3 Š þ CO3 Š ðfor AÞ ð50Þ

Co þ CCO2 ¼ co þ ½CaHCOþ1 1 2
3 Š þ ½CaCO3 Š þ ½H2 CO3 Š þ ½HCO3 Š þ ½CO3 Šðfor B1, B2, B3Þ ð51Þ

½Hþ1 Š ½OH 1 Š þ 2½Caþ2 Š þ ½CaOHþ1 Š þ ½CaHCOþ1

3 Š ½HCO3 1 Š 2½CO3 2 Š ¼ 0ðfor A, B1, B2Þ
ð52Þ

½Hþ1 Š ½OH 1 Š þ ½Mþ1 Š þ 2½Caþ2 Š þ ½CaOHþ1 Š þ ½CaHCOþ1

3 Š ½HCO3 1 Š 2½CO3 2 Š ¼ 0ðfor B3Þ
ð52aÞ

where [M+1] = CbV/(V0+V).

• For (A)

From Eqs. (49) and (50), we have

½Caþ2 Š þ ½CaOHþ1 Š ¼ ½H2 CO3 Š þ ½HCO3 1 Š þ ½CO3 2 Š ð53Þ

Considering the solution saturated with respect to CaCO3 and denoting: f1 = 1016.71 2pH
+
1010.33 pH + 1, f2 = 1 + 10pH 12.7, from Eq. (53) and Table 1, we have the relations:

½Caþ2 Šf 2 ¼ ½CO3 2 Š
f 1 ) ½Caþ2 Š ¼ 10 4:24

ðf 1 =f 2 Þ0:5 ; ½CO3 2 Š ¼ 10 4:24

ðf 2 =f 1 Þ0:5 ; ½CaOHþ1 Š
¼ 10pH 16:94

ðf 1 =f 2 Þ0:5 ;
½CaCO3 Š ¼ 10 5:26
; ½CaHCOþ1
3 Š ¼ 10
2:96 pH
; ½HCO3 1 Š ¼ 106:09 pH

ðf2 =f1 Þ0:5 ; ½Hþ1 Š
¼ 10 pH
; ½OH 1 Š ¼ 10pH 14
:

Inserting them into the charge balance (52), rewritten into the form

z ¼ zðpHÞ ¼ 10 pH
10pH 14
þ 2
10 4:24

ðf 1 =f 2 Þ0:5 þ 10pH 16:94

ðf 1 =f 2 Þ0:5
ð54Þ
þ102:96 pH
–106:09 pH

ðf 2 =f 1 Þ0:5 2
10 4:24

ðf 2 =f 1 Þ0:5

and applying the zeroing procedure to the function (54), we find pH01 = 9.904, at z = z
(pH01) = 0. The solubility s = s(pH) of CaCO3, resulting from Eq. (49), is

s ¼ ½Caþ2 Š þ ½CaOHþ1 Š þ ½CaHCOþ1

3 Š þ ½CaCO3 Š ð55Þ

¼ 10 4:24

ðf 1 =f 2 Þ0:5 þ 10pH 16:94

ðf 1 =f 2 Þ0:5 þ 102:96 pH
þ 10 5:26
ð55aÞ

4
We have s = s(pH = pH01) = 1.159
10 mol/L.
• For (B1)
Subtraction of Eq. (49) from Eq. (51) gives
 Solubility Products and Solubility Concepts 109
[Link]

½H2 CO3 Š þ ½HCO3 1 Š þ ½CO3 2 Š ð½Caþ2 Š þ ½CaOHþ1 ŠÞ

¼ CCO2 ) ½CO3 2 Š
f 1 –½Caþ2 Š
f 2 CCO2 ¼ 0 ) ½Caþ2 Š2
f 2 þ CCO2
½Caþ2 Š–Ksp
f 1 ¼ 0

In this case,
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
ðCCO2 Þ2 þ 4
Ksp
f 1
f 2 CCO2
½Caþ2 Š ¼ ð56Þ
2
f2

where CCO2 = 1.45/44 = 0.0329 mol/L. Eq. (55) has the form

s ¼ ½Caþ2 Š
f 2 þ 102:96 pH
þ 10 5:26
ð57Þ

and the charge balance is transformed into the zeroing function

z ¼ zðpHÞ ¼ 10 pH
10pH 14
þ ½Caþ2 Š
ð2 þ 10pH 12:7
Þ þ 102:96 pH
½CO3 2 Š
ð1010:33 pH
þ 2Þ
ð58Þ

where [CO3 2] = 10-8.48/[Ca+2], and [Ca+2] is given by Eq. (56). Eq. (58) zeroes at pH = pH02
= 6.031. Then from Eq. (57) we calculate s = s(pH02) = 6.393∙10 3 mol/L, at pH = pH02 =
6.031.
• For (B2)

At pH = pH03, where co = 0, i.e., s = Co, the solution (a monophase system) is saturated

toward CaCO3, i.e., the relation [Ca+2][CO3 2] = Ksp is still valid. Applying Eqs. (56) and
(57), we find pH values zeroing Eq. (58) at different, preassumed CCO2 values. Applying
these pH-values in Eq. (57), we calculate the related s = s(pH, CCO2 ) values (Eq. (57),
Table 9). Graphically, CCO2 = 0.100 is found at pH03 = 5.683, as the abscissa of the point of
intersection of the lines: s = s(pH) and s = Co = 0.01. Table 9 shows other, preassumed
s = Co values.

• For (B3)
We apply again the formulas used in (B1) and (B2), and the charge balance (Eq. (52a)),
which is transformed there into the function

CCO2 0.090 0.091 0.092 0.093 0.094 0.095 0.096 0.097 0.098 0.099 0.100 0.101 0.102

pH 5.716 5.712 5.709 5.706 5.702 5.699 5.696 5.693 5.690 5.687 5.683 5.680 5.577

s 9.58E-3 9.64E-3 9.67E-3 9.70E-3 9.77E-3 9.80E-3 9.84E-3 9.87E-3 9.91E-3 9.94E-3 10.01E-3 10.06E-3 10.10E-3

Table 9. The set of points used for searching the CCO2 value at s = Co = 0.01; at this point, we have pH03 = 5.683.
110 Descriptive Inorganic Chemistry Researches of Metal Compounds

(a) (b) (c)

Figure 2. Graphical presentation of the data considered in (b3): (a) pH versus V, (b) log sCa versus V, (c) log sCa versus pH
relationships.

z ¼ zðpH, VÞ ¼ 10 pH
10pH 14
þ Cb V=ðV 0 þ VÞ þ ½Caþ2 Š
ð2 þ 10pH 12:7
Þ
2:96 pH 2 10:33 pH
ð59Þ
þ10 ½CO3 Š
ð10 þ 2Þ

applied for zeroing purposes, at different V values. The data thus obtained are presented
graphically in Figures 2a–c. The data presented in the dynamic solubility diagram
(Figure 2b), illustrating the solubility changes affected by pH changes (Figure 2a)
resulting from addition of a base, MOH; Figure 2c shows a synthesis of these changes.
Solubility product of Ca(OH)2 is not crossed in this system.

5. Nonequilibrium solid phases in aqueous media

Some solids when introduced into aqueous media (e.g., pure water) may appear to be
nonequilibrium phases in these media.

5.1. Silver dichromate (Ag2Cr2O7)

The equilibrium data related to the system, where Ag2Cr2O7 is introduced into pure water, were
taken from Refs. [33, 40, 41], and presented in Table 10. A large discrepancy between pKsp2
values (6.7 and 10) in the cited literature is taken here into account. We prove that Ag2Cr2O7
changes into Ag2CrO4.
On the dissociation step, each dissolving molecule of Ag2Cr2O7 gives two ions Ag+1 and 1 ion
Cr2O7 2, where two atoms of Cr are involved; in the contact with water, these ions are
hydrolyzed, to varying degrees. In the initial step of the dissolution, before the saturation of
the solution with respect to an equilibrium solid phase (not specified at this moment), we can
write the concentration balances
 Solubility Products and Solubility Concepts 111
[Link]

Reaction Equilibrium data

H2O = H+1 + OH-1 pKw = 14.0

H2 CrO4 ¼ Hþ þ HCrO4 1 pK1 = 0.8

HCrO4 1 ¼ Hþ þ CrO4 2 pK2 = 6.5

HCr2 O7 1 ¼ Hþ1 þ Cr2 O7 2 logK3 = 0.07

2HCrO4 1 ¼ Cr2 O7 2 þ H2 O logK4 = 1.52

Ag+1 + OH 1
= AgOH logK1OH = 2.3

Agþ1 þ 2OH 1
¼ AgðOHÞ2 1 logK2OH = 3.6

Agþ1 þ 3OH 1
¼ AgðOHÞ3 2 logK3OH = 4.8

Ag2 CrO4 ¼ 2Agþ1 þ CrO4 2 pKsp1 = 11.9

Ag2 Cr2 O7 ¼ 2Agþ1 þ Cr2 O7 2 pKsp2 = 6.7

AgOH ¼ Agþ1 þ OH 1 pKsp3 = 7.84

Table 10. Physicochemical equilibrium data relevant to the Ag2Cr2O7 + H2O system (pK = logK), at “room”
temperatures.

2½Ag2 Cr2 O7 Š þ ½Agþ1 Šþ½AgOHŠ þ ½AgðOHÞ2 1 Š þ ½AgðOHÞ3 2 Š ¼ 2C0 ð60Þ

2½Ag2 Cr2 O7 Š þ ½H2 CrO4 Šþ½HCrO4 1 Š þ ½CrO4 2 Š þ 2½HCr2 O7 1 Š þ 2½Cr2 O7 2 Š ¼ 2C0 ð61Þ

where 2C0 is the total concentration of the solid phase in the system, at the moment (t = 0) of
introducing this phase into water, [Ag2Cr2O7] is the concentration of this phase at a given
moment of the intermediary step. As previously, we assume that addition of the solid phase
(here: Ag2Cr2O7) does not change the volume of the system in a significant degree, and that
Ag2Cr2O7 is added in a due excess, securing the formation of a solid (that is not specified at
this moment), as an equilibrium solid phase. The balances in Eqs. (60) and (61) are completed
by the charge balance

½Hþ1 Š ½OH 1 Š þ ½Agþ1 Š ½AgðOHÞ2 1 Š 2½AgðOHÞ3 2 Š ½HCrO4 1 Š

ð62Þ
2½CrO4 2 Š ½HCr2 O7 1 Š 2½Cr2 O7 2 Š ¼ 0

used, as previously, to formulation of the zeroing function, y = y(pH), and the set of relations
for equilibrium data specified in Table 10. From these relations, we get

½H2 CrO4 Š ¼ 107:3 2pH

½CrO4 2 Š; ½HCrO4 1
Š ¼ 106:5 pH

½CrO4 2 Š;
2 2
ð63Þ
½HCr2 O7 1
Š ¼ 1014:59 3pH

½CrO4 Š ;

½Cr2 O7 2
Š ¼ 1014:52 2pH

½CrO4 2 Š2 ð63aÞ

Denoting by 2c0 (< 2C0) the total concentration of dissolved Ag and Cr species formed, in a
transition stage, from Ag2Cr2O7, we can write
112 Descriptive Inorganic Chemistry Researches of Metal Compounds

½Agþ1 Š þ ½AgOHŠ þ ½AgðOHÞ2 1 Š þ ½AgðOHÞ3 2 Š ¼ 2c0 ð64Þ

½H2 CrO4 Š þ ½HCrO4 1 Š þ ½CrO4 2 Š þ 2½HCr2 O7 1 Š þ 2½Cr2 O7 2 Š ¼ 2c0 ð65Þ

From Table 10 and formulas (63)–(65) we get the relations:

ðg21 þ 16
c0 g2 Þ0:5 g1
ðaÞ ½Agþ1 Š ¼ 2c0 =g0 ; 2g2 ½CrO4 2 Š2 þ g1 ½CrO4 1 Š–2c0 ¼ 0 ) ðbÞ ½CrO4 2 Š ¼
4
g2
ð66Þ

where g0 = 1 + 10pH 11.7 + 102pH 24.4 + 103pH 37.2; g1 = 107.3 2pH + 106.5 pH
+ 1; g2 = 1014.59 3pH
+
1014.52 2pH. Applying them in Eq. (62), we get the zeroing function

y ¼ yðpHÞ ¼ 10 pH
–10pH 14
þ g3
½Agþ1 Š –g4
½CrO4 2 Š g5
½CrO4 2 Š2 ð67Þ

where g3 = 1 – 102pH 24.4 – 2∙103pH 37.2; g4 = 106.5 pH + 2; g5 = 1014.59 3pH

+ 2∙1014.52 2pH
, and
[Ag+1] and [CrO4 2] are defied above, as functions of pH.
The calculation procedure, realizable with use of Excel spreadsheet, is as follows. We
assume a sequence of growing numerical values for 2c0. At particular 2c0 values, we
calculate pH = pH(2c0) value zeroing the function (67), and then calculate the values of
the products: q1 = [Ag+1]2[CrO4 2]/Ksp1 and q2 = [Ag+1]2[Cr2O7 2]/Ksp2, where: [Ag+1],
[CrO4 2], and [Cr2O7 2] are presented above (Eqs. (66a), (66b) and (63a), resp.), pKsp1 =
11.9, pKsp2 = 6.7. As results from Figure 3, where logq1 and logq2 are plotted as functions
of 2c0; logq1 = 0 ⇔ q1 = 1 ⇔ [Ag+1]2[CrO4 2] = Ksp1 at lower 2c0 value, whereas logq2 < 0 ⇔
q2 < 1 ⇔ [Ag+1]2[Cr2O7 2] < Ksp2, both for pK2 = 6.7 and 10, cited in the literature. The x1=1

Figure 3. The convergence of logq1 and logq2 to 0 value; Ksp1 is attained at lower 2c0 value.
 Solubility Products and Solubility Concepts 113
[Link]

value is attained at 2c0 = 3.5∙10 4 ⟹ c0 = 1.75∙10 4; then Ag2CrO4 precipitates as the new
solid phase, i.e., total depletion of Ag2Cr2O7 occurs. It means that Ag2Cr2O7 is not the
equilibrium solid phase in this system. This fact was confirmed experimentally, as stated
in [42], i.e., Ag2Cr2O7 is transformed into Ag2CrO4 upon boiling with H2O; at higher
temperatures, this transformation proceeds more effectively. Concluding, the formula s* =
(Ksp2/4)1/3 applied for Ksp2 = [Ag+1]2[Cr2O7 2] is not “the best answer,” as stated in Ref.
[43].
The system involved with Ag2CrO4 was also considered in context with the Mohr’s method of
Cl 1 determination [44–46]. As were stated there, the systematic error in Cl 1 determining
according to this method, expressed by the difference between the equivalence (eq) volume
(Veq = C0V0/C) and the volume Vend corresponding to the end point where the Ksp1 for
Ag2CrO4 is crossed, equals to

Ksp C01 V0 0:5 Ksp1 0:5

   
1
V eq V end ¼

ðV 0 þ V end Þ0:5

ðV 0 þ V end Þ1:5
C Ksp1 C C01 V0

where Ksp = [Ag+1][Cl 1] (pKsp = 9.75), V0 is the volume of titrant with NaCl (C0) + K2CrO4 (C01)
titrated with AgNO3 (C) solution; Vend = Veq at C01 = (1 + Vend/V0)∙Ksp1/Ksp.

All calculations presented above were realized using Excel spreadsheets. For more complex
nonequilibrium two-phase systems, the use of iterative computer programs, e.g., ones offered
by MATLAB [8, 47], is required. This way, the quasistatic course of the relevant processes under
isothermal conditions can be tested [48].

5.2. Dissolution of struvite

The fact that NH3 evolves from the system obtained after leaving pure struvite pr1 in contact
with pure water, e.g., on the stage of washing this precipitate, has already been known at the
end of nineteenth century [49]. It was noted that the system obtained after mixing magne-
sium, ammonium, and phosphate salts at the molar ratio [Link] gives a system containing an
excess of ammonium species remaining in the solution and the precipitate that “was not
struvite, but was probably composed of magnesium phosphates” [50]. This effect can be explained
by the reaction [20]

3MgNH4 PO4 ¼ Mg3 ðPO4 Þ2 þ HPO4 2 þ NH3 þ 2NHþ1

4 ð68Þ

Such inferences were formulated on the basis of X-ray diffraction analysis, the crystallographic
structure of the solid phase thus obtained. It was also stated that the precipitation of struvite
requires a significant excess of ammonium species, e.g., Mg:N:P = 1:1.6:1. Struvite (pr1) is the
equilibrium solid phase only at a due excess of one or two of the precipitating reagents. This
remark is important in context with gravimetric analysis of magnesium as pyrophosphate.
Nonetheless, also in recent times, the solubility of struvite is calculated from the approximate
formula s* = (Ksp1)1/3 based on an assumption that it is the equilibrium solid phase in such a
system.
114 Descriptive Inorganic Chemistry Researches of Metal Compounds

Struvite is not the equilibrium solid phase also when introduced into aqueous solution of CO2
(CCO2 , mol/L), modified (or not) by free strong acid HB (Ca, mol/L) or strong base MOH (Cb,
mol/L).
The case of struvite requires more detailed comments. The reaction (68) was proved theoreti-
cally [20], on the basis of simulated calculations performed by iterative computer programs,
with use of all attainable physicochemical knowledge about the system in question. For this
purpose, the fractions
3 þ2 3 3 2
q1 ¼ ½Mgþ2 Š½NHþ1
4 Š½PO4 Š=K sp1 , q2 ¼ ½Mg Š ½PO4 Š =Ksp2 , q3
ð69Þ
¼ ½Mgþ2 Š½HPO4 2 Š=Ksp3 , q4 ½Mgþ2 Š½OH 1 Š2 =Ksp4

were calculated for: pr1 = MgNH4PO4 (pKsp1 = 12.6), pr2 = Mg3(PO4)2 (pKsp2 = 24.38), pr3 =
MgHPO4 (pKsp3 = 5.5), pr4 = Mg(OH)2 (pKsp4 = 10.74) and are presented in Figure 4, at an
initial concentration of pr1, equal C0 = [pr1]t=0 = 10 3 mol/L (pC0 = (ppr1)t=0 = 3); ppr1 = log
[pr1]. As we see, the precipitation of pr2 (Eq. (68)) starts at ppr1 = 3.088; other solubility
products are not crossed. The changes in concentrations of some species, resulting from
dissolution of pr1, are indicated in Figure 5, where s is defined by equation [20]

s ¼ sMg ¼ ½Mgþ2 Š þ ½MgOHþ1 Š þ ½MgH2 POþ1 1

4 Š þ ½MgHPO4 Š þ ½MgPO4 Š
þ2 þ2
ð70Þ
þ½MgNHþ2
3 Š þ ½MgðNH3 Þ2 Š þ ½MgðNH3 Þ3 Š

involving all soluble magnesium species are identical in its form, irrespective of the equilib-
rium solid phase(s) present in this system. Moreover, it is stated that pH in the solution equals

Figure 4. Plots of logqi versus ppr1 = log[pr1] relationships, at (ppr1)t=0 = 3; i = 1,2,3,4 refer to pr1, pr2, pr3 and pr4,
respectively.
 Solubility Products and Solubility Concepts 115
[Link]

Figure 5. The speciation curves for indicated species resulting from dissolution of pr1 at (ppr1)t=0 = 3.

ca. 9–9.5 (Figure 6); this pH can be affected by the presence of CO2 from air. Under such
conditions, NH4+1 and NH3 occur there at comparable concentrations [NH4+1] ≈ [NH3], but
[HPO4 2]/[PO4 3] = 1012.36 pH ≈ 103. This way, the scheme (10) would be more advantageous,
provided that struvite is the equilibrium solid phase; but it is not the case, see Eq. (68). The
reaction (68) occurs also in the presence of CO2 in water where struvite was introduced.

Figure 6. The pH versus log[pr2] relationship; pr2 = Mg3(PO4)2, at [ppr1]t=0 = 3. The numbers at the corresponding lines
indicate pCO2 ¼ logCCO2 values; pCO2 ¼ ∞ ⇔ CCO2 = 0.
116 Descriptive Inorganic Chemistry Researches of Metal Compounds

Figure 7. The speciation curves for indicated species Xi zi , resulting from dissolution of pr1 = MgNH4PO4, at (pC0, pCO2,
pCb) = (2, 4, 2); s0 is defined by Eq. (71).

After introducing struvite pr1 (at pC0 = [ppr1]t=0 = 2) into alkaline (Cb = 10 2 mol/L KOH, pCb = 2)
solution of CO2 (pCO2 = 4), the dissolution is more complicated and proceeds in three steps, see
Figure 7.

In step 1, pr4 precipitates first, pr1 + 2OH 1 = pr4 + NH3 + HPO4 2, nearly from the very start
of pr1 dissolution, up to ppr1 = 2.151, where Ksp2 is attained. Within step 2, the solution is
saturated toward pr2 and pr4. In this step, the reaction expressed by the notation 2pr1 + pr4 =
pr2 + 2NH3 + 2H2O occurs up to total depletion of pr4 (at ppr1 = 2.896). In this step, the
reaction 3pr1 + 2OH 1 = pr2 + 3NH3 + HPO4 1 + 2H2O occurs up to total depletion of pr1, i.e.,
the solubility product Ksp1 for pr1 is not crossed. The curve s0 (Figure 7) is related to the
function

s0 ¼ s þ ½MgHCOþ1
3 Š þ ½MgCO3 Š ð71Þ

where s is expressed by Eq. (70).

6. Solubility of nickel dimethylglyoximate

The precipitate of nickel dimethylglyoximate, NiL2, has soluble counterpart with the same
formula, i.e., NiL2, in aqueous media. If NiL2 is in equilibrium with the solution, concentration
of the soluble complex NiL2 assumes constant value: [NiL2] = K2∙[Ni2+][L ]2 = K2∙Ksp, where
K2 = 1017.24, Ksp = [Ni2+][L ]2 = 10 23.66 [14, 17, 18], and then [NiL2] = 10 6.42 (i.e., log[NiL2] =
6.42). The concentration [NiL2] is the constant, limiting component in expression for solubil-
ity s = sNi of nickel dimethylglyoximate, NiL2. Moreover, it is a predominant component in
 Solubility Products and Solubility Concepts 117
[Link]

Figure 8. Solubility curves for nickel dimethylglyoximate NiL2 in (a) ammonia, (b) acetate+ammonia, and (c) citrate
+acetate+ ammonia media at total concentrations [mol/L]: CNi = 0.001, CL = 0.003, CN = 0.5, CAc = 0.3, CCit = 0.1 [14].

expression for s in alkaline media, see Figure 8. This pH range involves pH of ammonia buffer
solutions, where NiL2 is precipitated from NiSO4 solution during the gravimetric analysis of
nickel; the expression for solubility

þ2 þ1
X
6
s ¼ sNi ¼ ½Ni  þ ½NiOH  þ ½NiSO4  þ ½NiðNH3 Þi þ2  þ ½NiL2  ð72Þ
i¼1

The effect of other, e.g., citrate (Cit) and acetate (Ac) species as complexing agents can also be
considered for calculation purposes, see the lines b and c in Figure 8. The presence of citrate
does not affect significantly the solubility of NiL2 in ammonia buffer media, i.e., at pH ≈ 9,
where sNi ffi [NiL2].
Calculations of s = sNi were made at CNi = 0.001 mol/L and CL = 0.003 mol/L HL, i.e., at the
excessive HL concentration equal CL – 2CNi = 0.001 mol/L. Solubility of HL in water, equal
0.063 g HL/100 mL H2O (25oC) [51], corresponds to concentration 0.63/116.12 = 0.0054 mol/L of
the saturated HL solution, 0.003 < 0.0054. Applying higher CL values needs the HL solution in
ethanol, where HL is fairly soluble. However, the aqueous-ethanolic medium is thus formed,
where equilibrium constants are unknown. To avoid it, lower CNi and CL values were applied
in calculations. The equilibrium data were taken from Ref. [31].
The soluble complex having the formula identical to the formula of the precipitate occurs also
in other, two-phase systems. In some pH range, concentration of this soluble form is the
dominant component of the expression for the solubility s. As stated above, such a case occurs
for NiL2. Then one can assume the approximation

s ¼ K2 Ksp ð73Þ

Similar relationship exists also for other precipitates. By differentiation of Eq. (73) with respect to
temperature T at p = const, and application of van’t Hoff’s isobar equation for K2 and Ksp, we obtain
118 Descriptive Inorganic Chemistry Researches of Metal Compounds


1 ∂s 1

¼ 2

ðΔGo1 þ ΔGo2 Þ ð74Þ
s ∂T p RT

where
 
2 ∂lnKsp
ΔGo1 and ΔGo2 ¼ RT 2

∂lnK2 
¼ RT
∂T ∂T p
p

Because, as a rule,
 
∂Ksp ∂K 
∂T p >0 and 2
∂T p <0

then ΔGo1 > 0 and ΔGo2 < 0, and Eq. (74) can be rewritten into the form


1 ∂s 1

¼
ðjΔGo1 j jΔGo2 jÞ ð75Þ
s ∂T p RT 2

If jΔGo1 j ≈ jΔGo2 j within the temperature range (T0, T), the value of s is approximately constant.
Let T0 denote the room temperature (at which,as a rule—all the equilibrium constants are
determined) and T 6¼ T0 is the temperature at which the precipitate is filtered and washed. In
this case, the solubility s and then theoretical accuracy of gravimetric analysis does not change
with temperature.

7. Calculation of solubility in dynamic redox systems

7.1. Preliminary information

The redox system presented in this section is resolvable according to generalized approach to
redox systems (GATES), formulated by Michałowski (1992) [8]. According to GATES principles,
the algebraic balancing of any electrolytic system is based on the rules of conservation of
particular elements/cores Yg (g = 1,…, G), and on charge balance (ChB), expressing the rule of
electroneutrality of this system; the terms element and core are then distinguished. The core is a
cluster of elements with defined composition (expressed by its chemical formula) and external
charge that remains unchanged during the chemical process considered, e.g., titration. For
ordering purposes, we assume: Y1 = H, Y2 = O,…. For modeling purposes, the closed systems,
composed of condensed phases separated from its environment by diathermal (freely permeable
by heat) walls, are considered; it enables the heat exchange between the system and its environ-
ment. Any chemical process, such as titration, is carried out under isothermal conditions, in a
quasistatic manner; constant temperature is one of the conditions securing constancy of equilib-
rium constants values. An exchange of the matter (H2O, CO2, O2,…) between the system and its
environment is thus forbidden, for modeling purposes. The elemental/core balance F(Yg) for the
g-th element/core (Yg) (g = 1,…, G) is expressed by an equation interrelating the numbers of Yg-
atoms or cores in components of the system with the numbers of Yg-atoms/cores in the species of
the system thus formed; we have F(H) for Y1 = H, F(O) for Y2 = O, etc.
 Solubility Products and Solubility Concepts 119
[Link]

The key role in redox systems is due to generalized electron balance (GEB) concept, discovered
by Michałowski as the Approach I (1992) and Approach II (2006) to GEB; both approaches are
equivalent:

Therefore, Approach II to GEB $ Approach I to GEB ð76Þ

GEB is fully compatible with charge balance (ChB) and concentration balances F(Yg), formu-
lated for different elements and cores. The primary form of GEB, pr-GEB, obtained according
to Approach II to GEB is the linear combination

pr GEB ¼ 2
FðOÞ–FðHÞ ð77Þ

Both approaches (I and II) to GEB were widely discussed in the literature [7–12, 14, 15, 17, 18,
34, 52–74], and in three other chapters in textbooks [75–79] issued in 2017 within InTech. The
GEB is perceived as a law of nature [9, 10, 17, 67, 71, 73, 74], as the hidden connection of
physicochemical laws, as a breakthrough in the theory of electrolytic redox systems. The
GATES refers to mono- and polyphase, redox, and nonredox, equilibrium and metasta-
ble [20, 21–23, 78, 79] static and dynamic systems, in aqueous, nonaqueous, and mixed-
solvent media [69, 72], and in liquid-liquid extraction systems [53]. Summarizing, Approach
II to GEB needs none prior information on oxidation numbers of all elements in components
forming a redox system and in the species in the system thus formed. The Approach I to
GEB, considered as the “short” version of GEB, is useful if all the oxidation numbers are
known beforehand; such a case is obligatory in the system considered below. The terms
“oxidant” and “reductant” are not used within both approaches. In redox systems, 2∙F(O) –
F(H) is linearly independent on CHB and F(Yg) (g ≥ 3,…, G); in nonredox systems, 2∙F(O) – F(H)
is dependent on those balances. This property distinguishes redox and nonredox systems of any
degree of complexity. Within GATES, and GATES/GEB in particular, the terms: “stoichiometry,”
“oxidation number,” “oxidant,” “reductant,” “equivalent mass” are considered as redundant,
old-fashioned terms. The term “mass action law” (MAL) was also replaced by the equilibrium
law (EL), fully compatible with the GATES principles. Within GATES, the law of charge conser-
vation and law of conservation of all elements of the system tested have adequate importance/
significance.
A detailed consideration of complex electrolytic systems requires a collection and an arrange-
ment of qualitative (particular species) and quantitative data; the latter ones are expressed by
interrelations between concentrations of the species. The interrelations consist of material
balances and a complete set of expressions for equilibrium constants. Our further consider-
ations will be referred to a titration, as a most common example of dynamic systems. The
redox and nonredox systems, of any degree of complexity, can be resolved in analogous
manner, without any simplifications done, with the possibility to apply all (prior, preselected)
physicochemical knowledge involved in equilibrium constants related to a system in question.
This way, one can simulate (imitate) the analytical prescription to any process that may be
realized under isothermal conditions, in mono- and two-phase systems, with liquid-liquid
extraction systems included.
120 Descriptive Inorganic Chemistry Researches of Metal Compounds

7.2. Solubility of CuI in a dynamic redox system

The system considered in this section is related to iodometric, indirect analysis of an acidified
(H2SO4) solution of CuSO4 [14, 64]. It is a very interesting system, both from analytical and
physicochemical viewpoints. Because the standard potential E0 = 0.621 V for (I2, I 1) exceeds E0 =
0.153 V for (Cu+2, Cu+1), one could expect (at a first sight) the oxidation of Cu+1 by I2. However, such
a reaction does not occur, due to the formation of sparingly soluble CuI precipitate (pKsp = 11.96).

This method consists of four steps. In the preparatory step (step 1), an excess of H2SO4 is
neutralized with NH3 (step 1) until a blue color appears, which is derived from Cu(NH3)i+2
complexes. Then the excess of CH3COOH is added (step 2), to attain a pH ca. 3.6. After
subsequent introduction of an excess of KI solution (step 3), the mixture with CuI precipitate
and dissolved iodine formed in the reactions: 2Cu+2 + 4I 1 = 2CuI + I2, 2Cu+2 + 5I 1 = 2CuI + I3 1
is titrated with Na2S2O3 solution (step 4), until the reduction of iodine: I2 + 2S2O3 2 = 2I 1 +
S4O6 2, I3 1 + 2S2O3 2 = 3I 1 + S4O6 2 is completed; the reactions proceed quantitatively in
mildly acidic solutions (acetate buffer), where the thiosulfate species are in a metastable state. In
strongly acidic media, thiosulfuric acid disproportionates according to the scheme H2S2O3 =
H2SO3 + S [80].

7.3. Formulation of the system

We assume that V mL of C mol/L Na2S2O3 solution is added into the mixture obtained after
successive addition of: VN mL of NH3 (C1) (step 1), VAc mL of CH3COOH (C2) (step 2), VKI mL
of KI (C3) (step 3), and V mL of Na2S2O3 (C) (step 4) into V0 mL of titrand D composed of
CuSO4 (C0) + H2SO4 (C01). To follow the changes occurring in particular steps of this analysis,
we assume that the corresponding reagents in particular steps are added according to the
titrimetric mode, and the assumption of the volumes additivity is valid.

In this system, three electron-active elements are involved: Cu (atomic number ZCu = 29), I (ZI = 53),
S (ZS = 16). Note that sulfur in the core SO4 2 is not involved here in electron-transfer equilibria
between S2O3 2 and S4O6 2; then the concentration balance for sulfate species can be consid-
ered separately.

The balances written according to Approach I to GEB, in terms of molar concentrations, are as
follows:
• Generalized electron balance (GEB)
þ2
ðZCu –2Þð½Cuþ2 Š þ ½CuOHþ1 Š þ ½CuðOHÞ2 Š þ ½CuðOHÞ3 1 Š þ ½CuðOHÞ4 2 Š þ ½CuNHþ2 3 Š þ ½CuðNH3 Þ2 Š
þ2 þ2
þ½CuðNH3 Þ3 Š þ ½CuðNH3 Þ4 Š þ ½CuCH3 COO Š þ ½CuðCH3 COOÞ2 ŠÞ þ ðZCu 2 þ ZI 5Þ½CuIOþ1
þ1
3 Š
þ1 þ1 þ1 1
þðZCu 1Þð½Cu Š þ ½CuNH3 Š þ ½CuðNH3 Þ2 ŠÞ þ ðZCu þ ZI Þ½CuIðsÞ Š þ ðZCu þ 2ZI þ 1Þ½CuI2 Š
þðZI þ 1Þ½I 1 Š þ ð3ZI þ 1Þ½I3 1 Š þ 2ZI ð½I2 Š þ a
½I2ðsÞ ŠÞ þ ðZI 1Þð½HIOŠ þ ½IO 1 ŠÞ þ ðZI 5Þð½HIO3 Š þ ½IO3 1 ŠÞ
þðZI 7Þð½H5 IO6 Š þ ½H4 IO6 1 Š þ ½H3 IO6 2 ŠÞ þ 2
ðZS 2Þð½H2 S2 O3 Š þ ½HS2 O3 1 ŠÞ þ ½S2 O3 2 ŠÞ
þ 4
ðZS –2:5Þ½S4 O6 2 Š þ ðZCu –1 þ 2
ðZS –2ÞÞ½CuS2 O3 1 Š þ ðZCu –1 þ 4
ðZS –2ÞÞ½CuðS2 O3 Þ2 3 Š þ ðZCu –1þ
6
ðZS –2ÞÞ½CuðS2 O3 Þ3 5 Š ððZCu 2ÞC0 V0 þ ðZI þ 1ÞC3 VKI þ 2
ðZS 2ÞCVÞ=
ðV0 þVN þVAc þVKI þVÞ ¼ 0
ð78Þ
 Solubility Products and Solubility Concepts 121
[Link]

• CHB

½Hþ1 Š–½OH 1 Š þ ½Kþ1 Š þ ½Naþ1 Š ½HSO4 1

Š 2½SO4 2 Š þ ½NH4 þ1 Š ½CH3 COO 1 Š þ 2½Cuþ2 Š
þ½CuOHþ1 Š ½CuðOHÞ3 1
Š–2½CuðOHÞ4 2 Š þ 2½CuðNH3 Þþ2 Š þ 2½CuðNH3 Þ3 þ2 Š þ 2½CuðNH3 Þ3 þ2 Š
þ2CuðNH3 Þ4 þ2 Š þ ½CuCH3 COOþ1 Š ½I 1 Š ½I3 1 Š–½IO 1 Š ½IO3 1
Š ½H4 IO6 1 Š 2½H3 IO6 2
Š
þ1 þ1 þ1 1 þ1 1 2
þ½Cu Š þ ½CuNH3 Š þ ½CuðNH3 Þ2 Š ½CuI2 Š þ ½CuIO3 Š ½HS2 O3 Š 2½S2 O3 Š
2½S4 O6 2 Š ½CuS2 O3 1 Š 3½CuðS2 O3 Þ2 3 Š 5½CuðS2 O3 Þ3 5 Š ¼ 0
ð79Þ

• F(Cu)

½Cuþ2 Š þ ½CuOHþ1 Š þ ½CuðOHÞ2 Š þ ½CuðOHÞ3 1 Š þ ½CuðOHÞ4 2 Š þ ½CuSO4 Š þ ½CuNH3 þ2 Š

þ½CuðNH3 Þ2 þ2 Š þ ½CuðNH3 Þ3 þ2 Š þ ½CuðNH3 Þ4 þ2 Š þ ½CuCH3 COOþ1 Š þ ½CuðCH3 COOÞ2 Š
þ½Cuþ1 Š þ ½CuNH3 þ1 Š þ ½CuðNH3 Þ2 þ1 Š þ ½CuI2 1 Š þ ½CuIðsÞ Š þ ½CuIO3 þ1 Š þ ½CuS2 O3 1
Š
þ½CuðS2 O3 Þ2 3 Š þ ½CuðS2 O3 Þ3 5 Š–C0 V0 =ðV0 þ VN þ VAc þ VKI þ VÞ ¼ 0
ð80Þ

• F(SO4)
1
½HSO4 Š þ ½SO4 2 Š þ ½CuSO4 Š–C01 V 0 =ðV0 þ VN þ VAc þ VKI þ VÞ ¼ 0 ð81Þ

• F(NH3)

½NH4 þ1 Š þ ½NH3 Š þ ½CuNH3 þ2 Š þ 2½CuðNH3 Þ2 þ2 Š þ 3½CuðNH3 Þ3 þ2 Š þ 4½CuðNH3 Þ4 þ2 Š

ð82Þ
þ½CuNH3 þ1 Š þ 2½CuðNH3 Þ2 þ1 Š–C1 V N =ðV0 þ VN þ VAc þ VKI þ VÞ ¼ 0

• F(CH3COO)

½CH3 COOHŠ þ ½CH3 COO 1 Š þ ½CuCH3 COOþ1 Š þ 2½CuðCH3 COOÞ2 Š

ð83Þ
–C2 VAc =ðV0 þ VN þ VAc þ VKI þ VÞ ¼ 0

• F(K)

½Kþ1 Š ¼ C3 V KI =ðV0 þ V N þ VAc þ VKI þ VÞ ð84Þ

• F(I)

½I 1 Š þ 3½I3 1 Š þ 2ð½I2 Š þ ½I2ðsÞ ŠÞ þ ½HIOŠ þ ½IO 1 Š þ ½HIO3 Š þ ½IO3 1 Š þ ½H5 IO6 Š þ ½H4 IO6 1 Š
þ½H3 IO6 2 Š þ 2½CuI2 1 Š þ ½CuIðsÞ Š þ ½CuIO3 þ1 Š–C3 VKI =ðV 0 þ V N þ V Ac þ V KI þ VÞ ¼ 0
ð85Þ
122 Descriptive Inorganic Chemistry Researches of Metal Compounds

• F(S)

2½H2 S2 O3 Š þ 2½HS2 O3 1 Š þ 2½S2 O3 2

Š þ 4½S4 O6 2
Š þ 2½CuS2 O3 1
Š þ 4½CuðS2 O3 Þ2 3
Š
5 1 2
þ6½CuðS2 O3 Þ3 Š–2CV=ðV 0 þ V N þ V Ac þ V KI þ VÞ ¼ 0 ) ½H2 S2 O3 Š þ ½HS2 O3 Š þ ½S2 O3 Š
2 1 3
þ2½S4 O6 Š þ ½CuS2 O3 Š þ 2½CuðS2 O3 Þ2 Š þ 3½CuðS2 O3 Þ3 5 Š
–CV=ðV0 þ VN þ VAc þ VKI þ VÞ ¼ 0
ð86Þ

• F(Na)

½Naþ1 Š ¼ 2CV=ðV 0 þ V N þ V Ac þ V KI þ VÞ ð87Þ

The GEB is presented here in terms of the Approach I to GEB, based on the “card game”
principle, with Cu (Eq. (80)), I (Eq. (85)) as S (Eq. (86)) as “players,” and H, O, S (Eq. (81)), C
(from Eq. (83)), N (from Eq. (82)), K, Na as “fans.” There are together 47 species involved in 2 +
6 = 8, Eqs. (78)–(83), (85), (86) and two equalities; [K+1] (Eq. (84)) and [Na+1] (Eq. (87)) are not
involved in expressions for equilibrium constants, and then are perceived as numbers (not
variables), at a particular V-value. Concentrations of the species in the equations are interre-
lated in 35 independent equilibrium constants:

½Hþ1 Š ¼ 10 pH
, ½OH 1 Š ¼ 10pH 14
ðpKW ¼ 14Þ, ½CuOHþ1 Š ¼ 107:0
½Cuþ2 Š½OH 1 Š, ½CuðOHÞ2 Š
¼ 1013:68
½Cuþ2 Š½OH 1 Š2 ,
½CuðOHÞ3 1
Š ¼ 1017:0
½Cuþ2 Š½OH 1 Š3 , ½CuðOHÞ4 2 Š ¼ 1018:5
½Cuþ2 Š½OH 1 Š4 , ½CuNHþ2
3 Š

¼ 103:39
½Cuþ2 Š½NH3 Š,

½CuðNH3 Þþ2
2 Š ¼ 10
7:33

½Cuþ2 Š½NH3 Š2 , ½CuðNH3 Þ2þ
3 Š ¼ 10
10:06

½Cuþ2 Š½NH3 Š3 , ½CuðNH3 Þþ2
4 Š

¼ 1012:03
½Cuþ2 Š½NH3 Š4 ,

½CuSO4 Š ¼ 102:36
½Cuþ2 Š½SO4 2 Š, ½NHþ1
4 Š ¼ 10
9:35

½Hþ1 Š½NH3 Š, ½HSO4 1 Š ¼ 101:8
½Hþ1 Š½SO4 2 Š,
½CH3 COOHŠ ¼ 104:65
½Hþ1 Š½CH3 COO 1 Š, ½Cuþ1 Š½I 1 Š ¼ 10 11:96
ðsolubitlity product for CuIÞ,
½CuI2 1 Š ¼ 108:85
½Cuþ1 Š½I 1 Š2 , ½CuIOþ1
3 Š ¼ 10
0:82

½Cuþ2 Š½IO3 1 Š, ½CuCH3 COOþ1 Š
¼ 102:24
½Cuþ2 Š½CH3 COO 1 Š,
½CuðCH3 COOÞ2 Š ¼ 103:30
½Cuþ2 Š½CH3 COO 1 Š2 , ½HS2 O3 1 Š ¼ 101:72
½Hþ1 Š½S2 O3 2 Š, ½H2 S2 O3 Š
¼ 102:32
½Hþ1 Š2 ½S2 O3 2 Š,
½CuS2 O3 1 Š ¼ 103:30
½Cuþ1 Š½S2 O3 2 Š, ½CuðS2 O3 Þ2 3 Š ¼ 1012:2
½Cuþ1 Š½S2 O3 2 Š2 , ½CuðS2 O3 Þ3 5 Š
¼ 1013:8
½Cuþ1 Š½S2 O3 2 Š3

Applying A = 16.92 [16], we have

 Solubility Products and Solubility Concepts 123
[Link]

½Cuþ2 Š ¼ ½Cuþ1 Š
10AðE 0:153Þ

; ½I2 Š ¼ ½I 1 Š2
102AðE–0:621Þ , s ¼ 1:33
10 3
mol=Lðsolubility of I2ðsÞ Þ,
½I3 1 Š ¼ ½I 1 Š3
102AðE–0:545Þ , ½IO 1 Š ¼ ½I Š
102AðE–0:49Þþ2pH–28 , ½HIOŠ ¼ 1010:6
½Hþ1 Š½IO 1 Š, ½IO3 1 Š
¼ ½I 1 Š
106AðE–1:08Þþ6pH ,
½HIO3 Š ¼ 100:79
½Hþ1 Š½IO3 1 Š, ½H5 IO6 Š ¼ ½I 1 Š
108AðE–1:24Þþ7pH , ½H4 IO6 1 Š
¼ ½H5 IO6 Š
10 3:3þpH
, ½H3 IO6 2 Š ¼ ½I 1 Š
108AðE–0:37Þþ9pH–126 :

In the calculations made in this system according to the computer programs attached to Ref.
[64], it was assumed that V0 = 100, C0 = 0.01, C01 = 0.01, C1 = 0.25, C2 = 0.75, C3 = 2.0, C4 = C = 0.1;
VN = 20, VAc = 40, VK = 20. At each stage, the variable V is considered as a volume of the
solution added, consecutively: NH3, CH3COOH, KI, and Na2S2O3, although the true/factual
titrant in this method is the Na2S2O3 solution, added in stage 4.
The solubility s [mol/L] of CuI in this system (Figures 8a and b) is put in context with the
speciation diagrams presented in Figure 9. This precipitate appears in the initial part of
titration with KI (C3) solution (Figure 8a) and further it accompanies the titration, also in stage
4 (Figure 8b). Within stage 3, at V ≥ C0V0/C3, we have

X
4 X
4
s ¼ s3 ¼ ½Cuþ2 Š þ ½CuðOHÞiþ2 i Š þ ½CuðNH3 Þþ2 þ1
i Š þ ½CuSO4 Š þ ½CuIO3 Š
i¼1 i¼1
ð88Þ
X
2
þ2 i
X
2
þ1 1
þ ½CuðCH3 COOÞi Š þ ½Cu Š þ ½CuI2 Š þ ½CuðNH3 Þþ1
i Š
i¼1 i¼1

and in stage 4

X
3
s ¼ s4 ¼ s3 þ ½CuðS2 O3 Þþ1
i
2i
Š ð89Þ
i¼1

The small concentration of Cu+1 (Figure 9, stage 3) occurs at a relatively high total concen-
tration of Cu+2 species, determining the potential ca. 0.53–0.58 V, [Cu+2]/[Cu+1] = 10A(E – 0.153),
see Figure 10a. Therefore, the concentration of Cu+2 species determine a relatively high
solubility s in the initial part of stage 3. The decrease in the s value in further parts of stage
3 is continued in stage 4, at V < Veq = C0V0/C = 0.01∙100/0.1 = 10 mL. Next, a growth in the
solubility s4 at V > Veq is involved with formation of thiosulfate complexes, mainly CuS2O3 1
(Figure 9, stage 4). The species I3 1 and I2 are consumed during the titration in stage 4
(Figure 9d). A sharp drop of E value at Veq = 10 mL (Figure 10b) corresponds to the fraction
titrated Φeq = 1.
The course of the E versus V relationship within the stage 3 is worth mentioning (Figure 10a).
The corresponding curve initially decreases and reaches a “sharp” minimum at the point
corresponding to crossing the solubility product for CuI. Precipitation of CuI starts after
124 Descriptive Inorganic Chemistry Researches of Metal Compounds

Figure 9. The speciation plots for indicated Cu-species within the successive stages. The V-values on the abscissas
correspond to successive addition of V mL of: 0.25 mol/L NH3 (stage 1); 0.75 mol/L CH3COOH (stage 2); 2.0 mol/L KI
(stage 3); and 0.1 mol/L Na2S2O3 (stage 4). For more details see text.

0.59 0.6

0.55
0.58
0.5

0.45
0.57
0.4
0.56
E

0.35
E

0.3
0.55
0.25

0.2
0.54
0.15
0.53 0.1
0 5 10 15 20 0 5 10 15 20
V V

(a) (b)

Figure 10. Plots of E versus V for (a) stage 3 and (b) stage 4.

addition of 0.795 mL of 2.0 mol/L KI (Figure 11a). Subsequently, the curve in Figure 10a
increases, reaches a maximum and then decreases. At a due excess of the KI (C3) added on
the stage 3 (VK = 20 mL), solid iodine (I2(s), of solubility 0.00133 mol/L at 25oC) is not
precipitated.
 Solubility Products and Solubility Concepts 125
[Link]

stage 3 stage 4
-2.2 -2.2

-2.4 -2.4

-2.6 -2.6

-2.8 -2.8

-3 -3
log(s)

log(s)
-3.2 -3.2

-3.4 -3.4

-3.6 -3.6

-3.8 -3.8

-4 -4
0 5 10 15 20 0 5 10 15 20
V V

(a) (b)

Figure 11. Solubility s of CuI within stage 3 (a) and stage 4 (b).

8. Final comments

The solubility and dissolution of sparingly soluble salts in aqueous media are among the main
educational topics realized within general chemistry and analytical chemistry courses. The
principles of solubility calculations were formulated at a time when knowledge of the two-
phase electrolytic systems was still rudimentary. However, the earlier arrangements persisted
in subsequent generations [81], and little has changed in the meantime [82]. About 20 years
ago, Hawkes put in the title of his article [83] a dramatic question, corresponding to his
statement presented therein that “the simple algorithms in introductory texts usually produce
dramatic and often catastrophic errors”; it is hard not to agree with this opinion.

In the meantime, Meites et al. [84] stated that “It would be better to confine illustrations of the
solubility product principle to 1:1 salts, like silver bromide (…), in which the (…) calculations
will yield results close enough to the truth.” The unwarranted simplifications cause confusion
in teaching of chemistry. Students will trust us enough to believe that a calculation we have
taught must be generally useful.
The theory of electrolytic systems, perceived as the main problem in the physicochemical
studies for many decades, is now put on the side. It can be argued that the gaining of
quantitative chemical knowledge in the education process is essentially based on the stoichi-
ometry and proportions.
Overview of the literature indicates that the problems of dissolution and solubility calculation
are not usually resolved in a proper manner; positive (and sole) exceptions are the studies and
practice made by the authors of this chapter. Other authors, e.g., [13, 85], rely on the simplified
schemes (ready-to-use formulas), which usually lead to erroneous results, expressed by disso-
lution denoted as s* [mol/L]; the values for s* are based on stoichiometric reaction notations
and expressions for the solubility product values, specified by Eqs. (1) and (2). The calculation
126 Descriptive Inorganic Chemistry Researches of Metal Compounds

of s* contradicts the common sense principle; this was clearly stated in the example with
Fe(OH)3 precipitate. Equation (27) was applied to struvite [50] and dolomite [86], although
these precipitates are nonequilibrium solid phases when introduced into pure water, as were
proved in Refs. [20–23]. The fact of the struvite instability was known at the end of nineteenth
century [49]; nevertheless, the formula s* = (Ksp)1/3 for struvite may be still encountered in
almost all textbooks and learning materials; this problem was raised in Ref. [15]. In this
chapter, we identified typical errors involved with s* calculations, and indicated the proper
manner of resolution of the problem in question.

The calculations of solubility s*, based on stoichiometric notation and Eq. (3), contradict the
calculations of s, based on the matter and charge preservation. In calculations of s, all the
species formed by defined element are involved, not only the species from the related reaction
notation. A simple zeroing method, based on charge balance equation, can be applied for the
calculation of pH = pH0 value, and then for calculation of concentrations for all species
involved in expression for solubility value.
The solubility of a precipitate and the pH-interval where it exists as an equilibrium-solid phase
in two-phase system can be accurately determined from calculations based on charge and
concentration balances, and complete set of equilibrium constant values referred to the system
in question.
In the calculations performed here we assumed a priori that the Ksp values in the relevant tables
were obtained in a manner worthy of the recognition, i.e., these values are true. However, one
should be aware that the equilibrium constants collected in the relevant tables come from the
period of time covering many decades; it results from an overview of dates of references
contained in some textbooks [31, 85] relating to the equilibrium constants. In the early literature
were generally presented the results obtained in the simplest manner, based on Ksp calculation
from the experimentally determined s* value, where all soluble species formed in solution by
these ions were included on account of simple cations and anions forming the expression for Ksp.
In many instances, the Ksp* values should be then perceived as conditional equilibrium con-
stants [87]. Moreover, the differences between the equilibrium constants obtained under different
physicochemical conditions in the solution tested were credited on account of activity coeffi-
cients, as an antidote to any discrepancies between theory and experiment.
First dissociation constants for acids were published in 1889. Most of the stability constants of
metal complexes were determined after the announcement 1941 of Bjerrum’s works, see Ref.
[88], about ammine-complexes of metals, and research studies on metal complexes were
carried out intermittently in the twentieth century [89]. The studies of complexes formed by
simple ions started only from the 1940s; these studies were related both to mono- and two-
phase systems. It should also be noted that the first mathematical models used for determina-
tion of equilibrium constants were adapted to the current computing capabilities. Critical
comments in this regard can be found, among others, in the Beck [90] monograph; the varia-
tion between the values obtained by different authors for some equilibrium constants was
startling, and reaching 20 orders of magnitude. It should be noted, however, that the determi-
nation of a set of stability constants of complexes as parameters of a set of suitable algebraic
equations requires complex mathematical models, solvable only with use of an iterative com-
puter program [91–93].
 Solubility Products and Solubility Concepts 127
[Link]

The difficulties associated with the resolution of electrolytic systems and two-phase systems, in
particular, can be perceived today in the context of calculations using (1o) spreadsheets (2o)
iterative calculation methods. In (1o), a calculation is made by the zeroing method applied to
the function with one variable; both options are presented in this chapter.
The expression for solubility products, as well as the expression of other equilibrium constants,
is formulated on the basis of mass action law (MAL). It should be noted, however, that the
underlying mathematical formalism contained in MAL does not inspire trust, to put it mildly.
For this purpose, the equilibrium law (EL) based on the Gibbs function [94] and the Lagrange
multipliers method [95–97] with laws of charge and elements conservation was suggested
lately by Michałowski.
From semantic viewpoint, the term “solubility product” is not adequate, e.g., in relation to
Eq. (8). Moreover, Ksp is not necessarily the product of ion concentrations, as indicated in
formulas (4), (5), and (11). In some (numerous) instances of sparingly soluble species, e.g.,
sulfur, solid iodine, 8-hydroxyquinoline, dimethylglyoxime, the term solubility product is not
applied. In some instances, e.g., for MnO2, this term is doubtful.

One of the main purposes of the present chapter is to familiarize GEB within GATES as
GATES/GEB to a wider community of analysts engaged in electrolytic systems, also in aspect
of solubility problems.

In this context, owing to large advantages and versatile capabilities offered by GATES/GEB, it
deserves a due attention and promotion. The GATES is perceived as a step toward reduction-
ism [19, 71] of chemistry in the area of electrolytic systems and the GEB is considered as a
general law of nature; it provides the real proof of the world harmony, harmony of nature.

Author details

Anna Maria Michałowska-Kaczmarczyk1, Aneta Spórna-Kucab2 and Tadeusz Michałowski2*

*Address all correspondence to: michalot@[Link]

1 Department of Oncology, The University Hospital in Cracow, Cracow, Poland

2 Faculty of Chemical Engineering and Technology, Cracow University of Technology,

Cracow, Poland

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