Supporting Information

Spreadsheet methodology for the calculation of equilibrium diagrams

including precipitation reactions and formation of mixed ligand and
polynuclear hydroxo complexes

Ulrich Briones-Guerash S. a, Arturo García-Mendoza b, Julio C. Aguilar-Cordero a*

a Departamento de Química Analítica, Facultad de Química, Universidad Nacional

Autónoma de México, Ciudad de México, C.P. 04510, México.

b Facultad de Estudios Superiores, Cuautitlán, Universidad Nacional Autónoma de México,

Cuautitlán Izcalli, Edo. de México, C.P. 54714, México.

Derivation of redox potential under non-standard conditions

Consider the following redox half-reaction:

with (SI i)

where the standard redox potential, 𝐸0𝑂𝑥/𝑅𝑒𝑑 , is the spontaneity parameter for reaction (SI i).
Outside standard conditions, equilibrium redox potential (𝐸) can be determined with the
Nernst equation at 25 ° C of the corresponding redox pair:

(SI 1)

Where 𝑎𝑖 denotes the activity of the “i” species.

An alternative representation of the redox equilibria SI i is given by the following expression

of an equilibrium constant (𝐾) for the formation of the 𝑅𝑒𝑑 species (1):

(SI 2)

Where [e-] stands for the activity of the electrons at the electrode-electrolyte interfase.
Remembering that at dilute solutions the activity is approximately equal to the molar
concentration (𝑎𝑖 → []𝑖 ) for soluble species and to unity for pure solids (𝑎𝑖 → 1), if we consider:

(SI 3)

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and:

(SI 4)

Then, the logarithmic form of expression (SI 2) is:

(SI 5)

Expression SI 5 is analogous to the Henderson-Hasselbalch equation, in such a way that

electrons are the exchanged particles in redox reactions and protons are the exchanged
particles in acid-base reactions. Now, if we remember that:

(SI 6)

And:

(SI 7)

Then, we can find that the parameters 𝑝𝑒 and 𝑝𝑒 are simply a measurement of the
corresponding redox potentials normalized by 0.059 V, instead of a measurement of the
concentration of “free electrons”:

(SI 8)

(SI 9)

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However, if 𝑅𝑒𝑑 is a solid species, speciation problems arise when we want to consider the
amount of substance of this species in terms of the redox potential in the mass balance
equation. To address this issue, we can define a mixed equilibrium constant, 𝐾∗ , as follows:

(SI 10)

where the term 𝑛𝑅𝑒𝑑 /𝑉 stands for the amount of substance of the 𝑅𝑒𝑑 solid species in a
system of volume 𝑉 (please, do not confuse the symbol for volume with the unit volt used
in equations SI 1, SI 8, SI 9 and SI 16).

Now, if as proposed by Rodríguez de San Miguel (2), we identify the activity of the 𝑅𝑒𝑑 solid
species, 𝑎𝑅𝑒𝑑 , as equal to its fraction of species, 𝜑𝑅𝑒𝑑 , 𝑎𝑅𝑒𝑑 = 𝜑𝑅𝑒𝑑 , with:

(SI 11)

and considering that:

(SI 12)

then by combining equations SI 10-11 and considering equation SI 2, one finds that:

(SI 13)

Where:

(SI 14)

The modified equilibrium constant 𝐾∗ allows one to consider the restrictions imposed on
the system by the total amount of substance of the redox species, and lets one calculate

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the distribution of soluble and solid species outside standard conditions ([ ]𝑖 ≠ 1 𝑀) by using
the modified redox spontaneity parameters 𝑝𝑒 ∗ and 𝐸∗ , related by:

(SI 15)

(SI 16)

Equations SI 13 and SI 15-16 imply that for standard conditions (CT = 1 mol L-1), 𝐾∗ =𝐾,
𝑝𝑒 ∗ = 𝑝𝑒 and 𝐸∗ =𝐸0 .

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Distribution and predominance zone diagrams calculated with MEDUSA software

A-Cu(II) B-Cu(II)

Figure 1 B-Cu(II)

C and D-Cu(II) E-Cu(II)

Figure 1 E-Cu(II)

A and B-Cu(I) C-Cu(I)

D and E-Cu(I)

Figure SI 1. Distribution diagrams obtained with MEDUSA software using data from Table
1 and experimental conditions from Table 2 of the article.

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A B

Figure SI 2. Predominance diagrams obtained with MEDUSA software using data from
Table 1 and experimental conditions from Table 2 of the article.

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Statistics about the application in the classroom

General instructions for students: answer the following questions considering the
corresponding diagram or spreadsheet.

Table SI 1. Figure 3A corresponds to the log(S’corr) vs pH diagram at multi-buffered

conditions of CZn, [C2O42-’] and [En’] equal to 0.001 mol/L each.
Students
that
Diagram
Question answer
employed
correctly
(%)
The precipitation percentage of Zn(II) at a pH of 6 is equal
to:
a) 99.3 %
Figure 3A 96.4
b) 99.9 %
c) 93.5 %
d) 89.2 %
The pH interval at which the precipitation percentage of
Zn(II) it is equal to or above 99.5 % is:
a) 3.63<pH<7.86
Figure 3A 94.6
b) 7.93<pH<14.0
c) 2.25<pH<6.42
d) 9.53<pH<12.57
Using the spreadsheet that you created for the
construction of Figure 3A, determine the minimum
required value of [En’] to completely dissolve the Zn(II) at a
pH of 8:
- a) 0.038 mol/L 91.1
b) 0.054 mol/L
c) 0.027 mol/L
d) 0.047 mol/L
The pH value at which the solid species ZnC2O4 and
Zn(OH)2 coexist is:
a) 9.1
Figure 3A 96.4
b) 10.7
c) 5.5
d) 8.0
The maximum precipitation percentage of Zn(II) in the form
of Zn(OH)2(s) is:
a) 96.2 %
Figure 3A 96.4
b) 98.5 %
c) 99.9 %
d) 90.3 %

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Table SI 2. Figure 3B correspond to the pL’ vs pH diagram at multi-buffered conditions of

CZn, [C2O42-’] and [En’] equal to 0.001 mol/L each.
Students
that
Diagram
Question answer
employed
correctly
(%)
Determine the pH interval where the species ZnL 2 2+ is
unstable at a pL’ value of 3.8:
a) 4.1<pH<14
Figure 3B 91.1
b) 1.9<pH<14
c) 2.8<pH<14
d) 1.4<pH<14
If the solution has a pL’ value of 2, the species distribution
as a function of pH is:

Figure 3B 94.6

The predominance zones of the species ZnC2O4(s) and ZnL2 2+

are separated by a curve defined by the following expression:
a) (𝑙𝑜𝑔𝛽 − 𝑙𝑜𝑔𝛽 )/2
Figure 3B b) 𝑙𝑜𝑔𝛽 /2 94.6
c) 𝑝𝐾 ,
d) 𝑝𝐾 ,
Indicate which of the following options is the correct
representative equilibria at a pH equal to 12.5, if an 1,10-
ortophenantroline (L) solution is gradually added to a Zn(II)
solution:
Figure 3B a) 𝑍𝑛(𝑂𝐻) ( ) + 2𝐻𝐿 ⇌ 𝑍𝑛𝐿 + 2𝐻 𝑂 94.6
b) 𝑍𝑛𝐶 𝑂 ( ) + 3𝐿 ⇌ 𝑍𝑛𝐿 + 𝐶 𝑂
c) 𝑍𝑛(𝑂𝐻) + 3𝐿 ⇌ 𝑍𝑛𝐿 + 3𝑂𝐻
d) 𝑍𝑛(𝐸𝑛) + 3𝐻 + 3𝐿 ⇌ 𝑍𝑛𝐿 + 3𝐻𝐸𝑛

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Table SI 3. Figures 4A and B correspond to the E vs pH diagrams at multi-buffered

conditions of (A) CPb=1x10-4 mol/L and [L’]=0.01 mol/L, (B) CPb=1.0 mol/L and [SO42-’]=0.5
mol/L.
Students
that
Diagram
Question answer
employed
correctly
(%)
Indicate the pH interval at which the ampholyte species,
Pb3O4, is not stable:
a) 0<pH<7.2
Figure 4A 94.5
b) 7.2<pH<14
c) 9.8<pH<14
d) 0<pH<9.8
At a pH equal to 9, the representative reduction half-
reaction of Pb3O4 to Pb(II) is:
a) 𝑃𝑏 𝑂 ( ) + 2𝑒 + 2𝐻 + 2𝐻 𝑂 ⇌ 3𝑃𝑏(𝑂𝐻) ( )
Figure 4A b) 𝑃𝑏 𝑂 ( ) + 2𝑒 + 8𝐻 + 6𝐿 ⇌ 3𝑃𝑏𝐿 + 4𝐻 𝑂 90.9
c) 𝑃𝑏 𝑂 ( ) + 2𝑒 + 5𝐻 𝑂 ⇌ 3𝑃𝑏(𝑂𝐻) + 𝐻
d) 𝑃𝑏 𝑂 ( ) + 2𝑒 + 8𝐻 + 9𝐿 ⇌ 3𝑃𝑏𝐿 + 4𝐻 𝑂
The predominant species at pH=3 and E=0.25 V/SHE it is:
a) 𝑃𝑏𝐿
Figure 4A b) 𝑃𝑏(𝑂𝐻) ( ) 98.2
c) 𝑃𝑏(𝑂𝐻)
d) 𝑃𝑏𝐿
Considering that the electromotive force (emf) of an
electrochemical cell corresponds to the difference E cathode-
Eanode, the electrochemical cell with an emf of
approximately 2 V is the one that has a cathode, anode,
Figure 4B and electrolyte, respectively, consisting of: 78.2
a) Pb plate, PbO2 plate and 0.5 mol/L H2SO4
b) PbO2 plate, Pb plate, and 0.5 mol/L H2SO4
c) Pb plate, Pb3O4 plate, and 0.5 mol/L H2SO4
d) Pb3O4 plate, Pb plate, and 0.5 mol/L H2SO4
If the electrolyte of the electrochemical cell from the
previous question is substituted by a solution of 0.1 mol/L
KNO3 at pH=4, it is expected that:
a) The E°’ value of the redox pair Pb(IV)/Pb(II) decreases
and the one from the redox pair Pb(II)/Pb increases
Figure 4B 7.3
b) The E°’ value of the redox pair Pb(IV)/Pb(II) increases
and the one from the redox pair Pb(II)/Pb decreases
c) The E°’ value of the redox pair Pb(IV)/Pb(II) decreases
and the one from the redox pair Pb(II)/Pb remains equal
d) None of the above

Selected bibliography on chemical equilibrium constants data

There are many different sources for reliable equilibrium constants and standard electrode
potential values, and some of them include critically selected stability constants. For data

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on the hydrolysis of metal ions, the book Hydrolysis of Metal Ions, edited by Paul L. Brown
and Christian Ekberg (Brown, P. L., Ekberg, C., eds., Hydrolysis of Metal Ions, Wiley‐VCH,
2016) is a comprehensive treatise on theory, methods and thermodynamic data on the
formation of hydrolysis products of metal ions. The International Union of Pure and Applied
Chemistry (IUPAC) has a series of compilations of chemical equilibrium constants (Bjerrum,
J., Schwarzenbach, G., Sillén, L.G., Stability Constants for Metal-ion Complexes. Part I.
Special Publication 6, Chemical Society, London., UK (1957); Bjerrum, J., Schwarzenbach,
G., Sillén, L.G., Stability Constants for Metal-Ion Complexes. Part II. Special Publication 7,
Chemical Society, London, UK (1958); Sillén, L. G., Martell, A. E., Smith, R. M., Stability
Constants of Metal Complexes. Special Publication No. 17, Chemical Society, London, UK
(1964); Sillén, L.G., Högfeldt, E., Martell, A. E., Smith, R. M., Stability Constants
Supplement No. 1, Special Publication No. 25, Chemical Society, London, UK (1971);
Högfeldt, E., Stability Constants of Metal-ion Complexes. Part A. Inorganic Ligands. IUPAC
Chem. Data Series No. 21, Pergamon Press, Oxford, UK (1982); Perrin, L. D., Stability
Constants of Metal-ion Complexes. Part B. Organic Ligands. IUPAC Chem. Data Set No. 22,
Pergamon Press, Oxford, UK (1979)). The US National Institute of Standards and
Technology (NIST) has collected in digital form (NIST Standard Reference Database 46,
discontinued. A simple database search program created by Dr. Naoyuki Hatada from the
Department of Materials Science and Engineering, Kyoto University, may be downloaded
for 64-bit Windows versions in https://n-hatada.github.io/stability-constant-
explorer/english.html) data found in six volumes edited by Robert M. Smith and Arthur E.
Martell between 1974 and 1989 (Martell, A.E., Smith, R.M., 1974. Critical Stability
Constants. Volume 1: Amino Acids. Plenum Press, New York, p. 469; Smith, R.M., Martell,
A.E., 1975. Critical Stability Constants. vol. 2. Amines. Plenum Press, New York, p. 415;
Martell, A.E., Smith, R.M., 1976. Critical Stability Constants. Volume 3: Other Organic
Ligands. Plenum Press, New York, p. 495; Smith, R.M., Martell, A.E., 1977. Critical Stability
Constants. Volume 4: Inorganic Complexes. Plenum Press, New York, p. 257; Martell, A.E.,
Smith, R.M., 1982. Critical Stability Constants. Volume 5: First Supplement. Plenum Press,
New York, p. 604; Smith, R.M., Martell, A.E., 1989. Critical Stability Constants. Volume 6:
Second Supplement. Plenum Press, New York, p. 643). Finally, standard electrode potential
values may be obtained from sources such as Bard, A. J., Parsons, B., Jordon, J., eds.
Standard Potentials in Aqueous Solutions, Dekker: New York, 1985; Milazzo, G.; Caroli, S.;
Sharma, V. K. Tables of Standard Electrode Potentials, Wiley: London, 1978; Swift, E. H.;
Butler, E. A. Quantitative Measurements and Chemical Equilibria, Freeman: New York,
1972 and in the Encyclopedia of Electrochemistry of the Elements edited by Allen J. Bard
and published by Marcel Dekker from 1973 to 1986. Other sources of thermodynamic and
equilibrium constants values can be found in (3).

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References
(1) Inczédy, J., The Use of Electron Activity Concept in the Calculation of Oxidation
Reduction Equilibria. Period. Polytech. Chem. Eng. 1970, 14(2), 131-139.

(2) Rodríguez de San Miguel, E., A New Model for the Full Inclusion of Precipitation
Reactions in the General Ionic Equilibrium Framework of Homogeneous Solutions
Based on the Fraction of Species Concept in Heterogeneous Systems. J. Appl. Solut.
Chem. Model. 2018, 7, 39-51.

(3) Hummel, W., Filella, M., Rowland, D., Where to find equilibrium constants? Sci. Total
Environ. 2019, 692, 49–59.

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