ISSN 20702051, Protection of Metals and Physical Chemistry of Surfaces, 2010, Vol. 46, No. 5, pp. 615–619.

© Pleiades Publishing, Ltd., 2010.

Original Russian Text © E.G. Vinokurov, 2010, published in Fizikokhimiya Poverkhnosti i Zashchita Materialov, 2010, Vol. 46, No. 5, pp. 543–547.

INVESTIGATION METHODS
FOR PHYSICOCHEMICAL SYSTEMS

Thermodynamic Probability Model of Ligand Selection in Solutions

Designed for Electrodeposition of Alloys and Multivalent Metals
E. G. Vinokurov
Mendeleev Russian University of Chemical Technology, 9 Miusskaya pl., Moscow, 125047 Russia
email: vin@muctr.ru
Received July 10, 2009

Abstract—In this work, we created a thermodynamic probability model of ligand selection in solutions for
the electrodeposition of alloys. A forecast was made for complex compounds for the electrodeposition of
Cu–Co and Sn–Zn alloys and potential electrochemical synthesis of Cu–Co alloy from the solutions
based on ammonia and glutamate complexes and Sn–Zn alloy from solutions containing fluoride com
plexes was experimentally confirmed.
DOI: 10.1134/S2070205110050205

INTRODUCTION The general scheme of alloy electrodeposition can

be described by the following equations:
The application of complex compounds in electro
[ AL n]z A + nAe − → A + nL L,
z
chemistry assumes, e.g., the solution of the problem of (1)
the targeted ligand selection for new solutions in the [BL m]zB + nBe − → B + mL L. (2)
z
electrodeposition of alloys of any composition and
structure as well as multivalent metals. Only the gen Reactions (1) and (2) may be accompanied by
eral approaches [1–6], which enable one to approxi reduction of hydroxonium ions or water molecules as
mately estimate the probable codeposition of metals follows:
with significantly different electrode potentials. The 2H3O + + 2e − → H 2 + 2H 2O, (3)
detailed analysis of the model assumptions for the − −
description and forecast of alloy electrodeposition is 2H 2O + 2e → H 2 + OH . (4)
given in [7]. –
The accumulation of ОН ions in the nearelec
Based on thermodynamics, the authors of [8] cre trode layer at insufficient stability of complexes
ated the physicochemical model for selection of formed by A and B metal ions yields various hydroxo
ligands (L) in the solution for electrodeposition of complexes and eventually A and B hydroxides that
multivalent metals, which enabled to develop the decelerates or terminates reactions (1) and (2). There
chromiumplating electrolyte with respect to the sta fore, the reduction rate of water molecules should not
bility constants of Cr(III) and Cr(II) complexes. To exceed some critical value.
create new solutions for electrodeposition of alloys, Based on the provisions and assumptions described
the authors of [9] also suggested the probability ligand in [8, 9], we formulated the following logical terms in
selection model, the adequacy of which was confirmed selection of ligand for new solutions of A and B metal
with the known experimental results. The goal of this complexes for electrodeposition of A–B alloy.
work is to make the thermodynamic probability ligand A ligand should form complexes with A and B
selection model in design of new solutions for elec metal ions with the stability constants (β) as follows:
trodeposition of alloys or multivalent metals 1. they exceed those of relevant hydroxocomplexes,
i.e.,
RESULTS AND DISCUSSION ⎧⎪l o g βA( AL n) > l o g β1( AOH)
⎨  
Modeling. To make the ligand selection model of ⎩⎪l o g β B( BL m) > l o g β1( BOH )
the solution for electrodeposition of A–B alloy, con or
sider electrodeposition of two metals A and B, pro
⎧l o g βA( AL n) l o g β1( AOH )
vided that the standard electrode potentials of
⎪⎪ >
A nA(aq)|A and B nB(aq)|B electrodes are E A and E B, ⎨
nA nA
(5)
 
respectively ( E A > E B), and the activities of all the ⎪l o g βB( BL m) > l o g β1( BOH )
components of this electrochemical system are 1. ⎪⎩ nB nB

615
616 VINOKUROV

logβ°A or
nA ⎧l o g βn( AL n) pSР [ A( OH ) nA]
а' b' c'
⎪⎪ <
nA nA
⎨ 
(8)
b ⎪l o g β n( BL m) < pSР [ B ( OH ) nB]
г ⎪⎩ nB nB
4) they yield a specific logarithm of the stability
c constant of complexes with A nA, ions, which exceeds
the same value for BnB [9] by more than 1.5 times, i.e.,
Ω l o g βA ≥ 1.5 l o g βB . (9)
nA nB
а Therefore, the ligand in question should simulta
neously satisfy all the aforementioned conditions as
expressed by combination of the mathematical
descriptions (5, 7, 8, 9) of all the conditions into the
set of inequalities (a–d):
⎧ ⎧l o g βA(AL n) l o g β1(AOH)
logβ°В
⎪⎪ > ( а)
nВ ⎪⎨⎪ nA nA
⎪ ⎪l o g βB(BL m) l o g β1(BOH)
Fig. 1. Scheme for graphical solution of inequality (10) and ⎪⎪ > ( а' )
identification of permissible range Ω of specific logarithms ⎪⎩ nB nB
of stability constants of A and B metal ion complexes, from ⎪ ⎧l o g βA(AL n)
whose solutions A–B alloy can be electrochemically
⎪ ⎪ < F (E A − EH2O) ( b)
deposited.
⎪ ⎨ ⎪ n A 2.3RT
⎪ ⎪l o g βB(BL n)
⎨ ⎪ < F (EB − EH2O) (b ')
2. they ensure standard electrode potentials E[AL n] ⎪ ⎩ nB 2.3RT (10)
of reaction (1) and E[BL m] of reaction (2), which will be ⎪ ⎧l o g β(AL ) pSР[A(OH)n ]
⎪⎪ A n
< A
(c )
more positive than the electrode potential EH2O, being ⎪ ⎪ nA n A

EH 2O or standard electrode potential of water molecule ⎪ ⎨l o g β(BL ) pSР[B(OH)n ]

⎪⎪ B m
< B
(c ')
reduction or starting potential of water molecule
⎪⎩ ⎪ n B n B
active discharge E*, i.e., ⎪l o g β
A ≥ l o g βB
⎧⎪E[AL n] > E H2O ⎪ 1.5 . ( d)
⎨  (6) ⎩ nA nB
⎪⎩E[BL m] > E H2O This set of inequalities (10) makes the thermody
namic probability model in selection of ligands for
or, expressing E  and E  through the standard
[AL n] [BL m]
electrodeposition of A−B alloy from the solutions con
taining complexes of the two relevant metals (A and B).
electrode potential of reaction A nA(aq) + nAe − ↔ A Substituting the numerical values of the constants
and BnB(aq) + nBe − ↔ В and complex stability con to this set of inequalities (10) solving the same by
stants, and, upon simple transformations, deriving:  
graphical method in l o g β A – l o g βB coordinates, we
⎧l o g βA( AL n)
< F ( E A − E H 2O)
nA nB
⎪⎪ nA 2.3 RT obtain the permissible range Ω (Fig. 1) of the stability
⎨ 
(7) constant logarithms for complexes of A and B metal
⎪l o g β B( BL n) < F ( E  − E ) ions that satisfy all of the ligand selecting conditions
⎪⎩ nB 2.3 RT
B H 2O (or maximum possible number thereof). The solution
of set (10) is the range of logβ values from log β A, min to
3. they are lower than the solubility product (SP) of
the relevant metal hydroxides (this provides selection of log β A, max , for complexes of metal ions A from
such ligand, which does not impair decontamination of log β B, min to log β B, max for complexes of metal ions B.
sewage water at the stage of neutralization), i.e.,
Comparison of Simulation Results with Experimen
⎧⎪l o g βn(AL n) < pSР[A(OH)nA] tal Data. The forecast thermodynamic probability
⎨ 
model was experimentally tested for the example of
⎪⎩l o g β n(BL m) < pSР[B(OH)nB] electrodeposition of Cu–Co and Sn–Zn alloys.

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 46 No. 5 2010

 THERMODYNAMIC PROBABILITY MODEL 617

Table 1. Solubility products of some metal hydroxides, elec According to our model forecast, the electrodepo
trode potentials of reactions with these metal ions or water sition of the Cu–Co alloy is impossible from the solu
molecules tion of relevant metal ethylenediaminetetraacetates.
Nevertheless, there are references [10] to the compo
Values for some metal ions sition of the ethylenediaminetetraacetate electrolyte
Parameter (pH < 4) for the electrodeposition of Cu–Co alloy.
Cu Co Sn Zn Electrochemical deposition of alloy from this solution
is possible due to the formation of Cu(II) and Co(II)
protonated ethylenediaminetetraacetate complexes.
pSP[M(OH)2] 19.1 14.8 26.2 16.9 This assumption is confirmed with the calculated dis
tribution of complexes at various ðÍ, results of experi
 2+ , V
EM 0.337 –0.277 –0.136 –0.736 ments [10], and forecast because the point for proto
M nated ethylenediaminetetraacetate (Hedta) com
plexes is significantly closer to the permissible range Ω
EH 2O, V –0.826 than the point for ethylenediaminetetraacetate (edta)
(this value was used in simulation complexes (Fig. 2). We know the electrodeposition of
for Cu–Co alloy) alloy from solutions of Cu(II) and Co(II) pyrophos
phate [11] and glycinate [12] complexes, as well as
E*, V –1.2 from solutions that contain both ammonia and tartrate
(this value was used in simulation ions as ligands [13]. In the latter case, we can hardly
for Sn–Zn alloy) refer to the prevailing type of complexes.
The model forecast evidences probable elec
trodeposition of alloy from solutions containing, for
example, Cu(II) and Co(II) ammonia and glutamate
The substitution of the constants and physical complexes. For experimental confirmation of the
parameters from Table 1 to set of inequalities (10) and model forecast, we studied the electrodeposition of
solution thereof by graphical method resulted in the Cu–Co alloy from copper and cobalt sulfate solution
permissible range for specific logarithms of stability with and without ammonia or sodium glutamate
constants of copper and cobalt (Fig. 2a) and tin and (Glut).
zinc (Fig. 2b) complexes, the solutions of which can Electrolysis of the solutions containing no ammo
be used to produce the relevant alloys by electrodepo nia or sodium glutamate provides pure copper deposi
sition. tion. The cathode deposits containing 11–34 at % Co
were produced by electrolysis of solutions containing
Our comparison of stability constants of some cop Cu(II) and Co(II) ammonia complexes (Table 2).
per(II) and cobalt (II) complexes (dots in Fig. 2a) However, the electrolysis of the same solutions for sev
showed that, with the exception of cobalt and copper eral days yielded the cathode deposits that contain
sulfate and ethylenediaminetetraacetate complexes, almost no cobalt. Most likely, this is due to air oxygen
all of the data fall in the range Ω and the complexes in oxidizing Co(II) ammonia complexes into Co(III) as
question can be used for electrodeposition of Cu–Co is evidenced by the platinum indicator electrode
alloy. potential in solution 1 (Table 2) shifting to positive val

Table 2. Composition of solution containing Cu(II) and Co(II) ammonia complexes and cathode current density affecting co
balt contents in cathode deposits

Cobalt contents, at % Co)

No. Solution composition (mol/l) Current density, A/dm2
in cathode deposit

1 CuSO4 – 0.2
CoSO4 – 0.2
2.0 11
(NH4)2SO4 – 0.7
NH3 – 1.7
2 CuSO4 – 0.3 2.0 31
CoSO4 – 0.5
(NH4)2SO4 – 1.4 2.5 34
NH3 – 3.4

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 46 No. 5 2010

618 VINOKUROV

а' c' b' (а)

20 b 100

15 d
logβ(CuIILm)/nCu(II)

xCo, xZn, at %
2Glut
2en
10 c 50
4NH3

edta
Ω 1
Hedta
5
P2O7
а
2
SO4
0 5 10
logβ(CoIILm)/nCo(II) (b) 0 1 2 3
20 а' b' d i, A/dm2
b
Fig. 3. Contents of Co share in Cu–Co alloy (1) and Zn in
15 Sn–Zn (2) alloy vs. current density for electrolysis of solu
logβ(SnLm)/nSn

tions: (1) 0.25 MCuSO4 + 0.3 М CoSO4 + 1.65 M sodium

c glutamate, pH 5; (2) 0.2 M SnCl2 + 0.5 M ZnSO4 +
Ω 3OH 1.45 M NaF + 0.68 M NaCl + 0.45 M HCl + 0.24 M
edta CH3COONa + 4 g/l OC20.
10 P2O7
SnF3
ZnF,

Tart [14]. The studies of the current density affecting the

а alloy composition and current efficiency (CE) of elec
5 trodeposition from the solutions, the composition of
0 5 10
logβ(ZnLm)/nZn
Fig. 2. Graphical identification of permissible range Ω of
specific logarithms of stability constants of Cu(II) and
Co(II) complexes, whose solutions can be used for elec
trodeposition of Cu–Co alloy (a) and Sn(II) and Zn(II)
complexes, whose solutions can be used for electrodeposi
tion of Sn–Zn alloy (b): a–d correspond to symbols of
inequalities in set (10), dots denote experimental loga
rithms of stability constants of complexes with the follow
ing ligands: pyrophosphate ion (Р2О7), tartrate ion (Tart),
glutamate ion (Glut), ethylenediamine (en), ethylenedi
aminetetraacetate (edta or Hedta), fluoride ion (F), sulfate
ion (SO4), hydroxide ion (OH), and ammonia (NH3).
Numbers at symbols of ligands denote their number in the
coordination sphere.
ues during exposure of this solution as follows (time, h
is the potential, V): 0–0.17, 12–0.25, 24–0.29, 48–
0.33, 144–0.39. The impossible electrodeposition of
the alloy from the solution containing Co(III) and
Cu(II) ammonia complexes is due to the prevailing
reduction of Co(III) complexes and copper metal
deposition.
The electrochemical deposition of alloy is also pos
sible from the solution of Cu(II) and Co(II) glutamate
complexes, which are barely oxidized by air oxygen
which is specified in the note to Fig. 3, showed that, if
the current density increases from 0.5 to 3.0 A/dm2,
the alloy CE decreases from 100 to 50%, but the
20 amount of cobalt in the alloy does not change signifi
cantly. For example, in electrodeposition of alloy from
a solution of pH 5 containing 0.25 M CuSO4 + 0.3 М
CoSO4 + 1.65 M sodium glutamate an increase in the
current density from 0.5 to 3 A/dm2 decreases the portion
fo Co in the alloy from 40 to 35 at % (Fig. 3, curve 1).
Our comparison of stability constants of Sn(II) and
Zn(II) complexes (dots in Fig. 2b) shows that almost
all of the data fall within the range Ω and the studied
complexes can be used for the electrodeposition of
Sn–Zn alloy. Indeed, we know that the wellstudied
electrodeposition of alloy from the solutions, e.g.,
Sn(II) and Zn(II) pyrophosphate [15, 16] and tartrate
[17] complexes. Note that the fulfillment of ine
qualities (a) and (a’) in set (10) is not binding
because, in some cases, e.g., in the electrodeposi
tion of the Sn–Zn alloy, the formation of hydroxo
complexes can promote accelerated electron transfer
and the electrodeposition of metals and alloys. In this
case, the model forecast is evidence of the probable
electrodeposition of alloy from the solution of Sn(II)
and Zn(II) fluoride complexes.
For the experimental confirmation of the model
forecast, we conducted the electrochemical deposi
tion of Sn–Zn alloy at various current densities from
the solution containing 0.2 Ì SnCl2 + 0.5 М ZnSO4 +

PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 46 No. 5 2010

 THERMODYNAMIC PROBABILITY MODEL
1.45 M NaF + 0.68 M NaCl + 0.45 M HCl + 0,24 M
CH3COONa + 4 g/l OC20. If the current density
increases from 0.5 to 2 A/dm2, the portion of zinc in
the deposited alloy increases from 16 to 42 at % (Fig. 3,
curve 2), and the current efficiency is near 100%.
As the object for construction of forecasting models
in selection of ligands for electrodeposition of alloys,
we can also consider electrodeposition of individual
metal from the solutions containing multivalent metal
ions, e.g., Cr(III) and Cr(II), Fe(III) and Fe(II), etc.
For these objects of simulation, A corresponds to
metal atom М produced by electrode reaction at a
more positive standard electrode potential and B cor
responds to the atom of same metal M produced by the
electrode reaction at a more negative standard elec
trode potential. The advantage of this object of study is
absolutely no formation of solid solutions or chemical
compounds in electrodeposition of metal, while elec
trodeposition of even A−B alloy, which is character
ized with the state diagram of eutectic type in equilib
rium conditions, may form supersaturated solid solu
tion, which cannot always be accounted quantitatively
in the course of simulation.
Based on the principles of thermodynamics and
integrated in the thermodynamic probability model,
the physiochemical model enabled one to use the sta
bility constants of Cr(III) and Cr(II) complexes to
select ligands for chromiumplating solutions based
on Cr(III) complexes. Similar studies for estimating
the probability forecast and physicochemical model
were carried out for electrochemical iron deposition
from solutions of Fe(III) and Fe(II) complexes and,
based on the forecast of these models, sulfosalicylic
acid was suggested as the ligand [18].
As is confirmed for the example of the electrodepo
sition of multivalent metals, the trustworthiness and
adequacy of both physicochemical and probability
models integrated into the thermodynamic probability
model enabled one to also consider it to be adequate
with respect to the electrodeposition of multivalent
metals rather than alloys only.
Therefore, we suggested the thermodynamic prob
ability model in selection of ligands to be used in the
solutions for electrodeposition of alloys. This thermo
dynamic probability model enables one to identify the
permissible range of stability constants (β) of the com
plexes containing ions of two metals A and B and,
thus, to forecast the composition of the complexes,
whose solution can be used for electrodeposition of
alloys. We experimentally confirmed the model fore
cast of the probable electrochemical deposition of
Cu–Co alloy from a solution containing copper and
cobalt ammonia or glutamate complexes and Sn–Zn
alloy from the solution containing fluoride complexes
of the relevant metals.
PROTECTION OF METALS AND PHYSICAL CHEMISTRY OF SURFACES Vol. 46 No. 5 2010
619
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