Russian Journal of Coordination Chemistry, Vol. 31, No. 1, 2005, pp. 14–18. Translated from Koordinatsionnaya Khimiya, Vol.

31, No. 1, 2005, pp. 17–21.

Original Russian Text Copyright © 2005 by Vinokurov, Demidov, Bondar’.

Physicochemical Model for Choosing Complexes

for Chromium-Plating Solutions Based on Cr(III) Compounds
E. G. Vinokurov*, A. V. Demidov*, and V.V. Bondar’**
* Mendeleev University of Chemical Technology, Miusskaya pl. 9, Moscow, 125190 Russia
** All-Russia Institute of Scientific and Technical Information, Baltiiskaya ul. 14, Moscow, Russia
Received December 4, 2003

Abstract—A prognostic physicochemical model for choosing complexes for chromium-plating solutions is
constructed on the basis of a combination of the thermodynamic principles and data on the kinetics of some
electrochemical reactions. It is shown that high-quality chromium coating can be produced from solutions of
Cr(III) complexes, whose logarithm of stability constants ranges from 10 to 20, and the logarithm of stability
constants of Cr(II) complexes formed in electrolysis ranges from 7 to 10. The influence of the nature of ligands
on chromium electrodeposition is studied. Using the model proposed, a chromium-plating solution based on a
chromium(III) malonate complex is developed. This solution makes it possible to produce high-quality coatings
in a wide interval of current densities.

INTRODUCTION The purpose of this work is to construct a physico-

When developing new solutions containing Cr(III)
compounds for the electrodeposition of chromium
coatings, many researchers proposed amino [1], carb-
oxylic [2], dicarboxylic [3–5], and hydroxycarboxylic
[6] acids and some other compounds [7] forming com-
plexes with Cr3+. However, with a diversity of chro-
mium complexes, it is difficult to choose ligands for
developing “trivalent” chromium-plating solutions.
The studies of chromium electrodeposition from
solutions of the chromium complexes [8–10] revealed
no direct relationship between the stability of the
Cr(III) complexes formed, the cathodic polarization,
and the formation of coatings, whereas the influence of
ligands on chromium electrodeposition is explained by
specific properties of passivation layers on the cathode
surface. At the same time, the rate of electroreduction
Cr3+ + e– Cr2+ at a mercury electrode correlates
with the spectral characteristics of some Cr(III) com-
plexes [11]. The authors of [12] attempted to find a rela-
tioanship between the addition of complexones in low
concentrations (2 g/l, ~10–2 mol/l) to chromium-plating
solutions (containing Cr3+, HCOO–, (NH4)2SO4, and
H3BO3 in concentrations 0.4, 0.66, 1.5, and 0.65 mol/l,
respectively) and the stability of complexes formed. It
is recommended in [6, 12, 13] to use ligands binding
Cr3+ ions into complexes of moderate stability in chro-
mium-plating solutions. However, no quantitative char-
acteristics of the complexes or ligands are reported.
When choosing ligands, the stability of the Cr(II) com-
plexes, which are intermediate species in the reduction
of the Cr3+ ions to the metal, is not considered, as a rule,
probably, because these data on the Cr(II) complexes
are scarce.
chemical model that can be used to choose the Cr(III)
complexes taking into account their constants of forma-
tion and stability constants of the Cr(II) complexes and
select ligands for chromium-plating solutions.
EXPERIMENTAL
Electrolysis was carried out in a solution of compo-
sition KCr(SO4)2, 0.2 mol/l; H3BO3, 1.0 mol/l; Na2SO4,
1.0 mol/l. A ligand in a concentration providing the
complete substitution of water molecules in the coordi-
nation sphere of Cr3+ ions was added to the solution.
Mono- and polybasic acids were sources of ligands in
solutions for chromium electrodeposition. The required
concentration of the ligand was calculated with account
of its assumed dentate number (d) and coordination
number of the Cr3+ ions equal to six
6
c L = --- c Cr .
d
After all components were mixed, the solutions
were heated and stored at 70–80°ë for 20 min, then
cooled and stored for 2 days such that complex forma-
tion is complete. This procedure made it possible to
attain a quasi-equilibrium state and reproducible results
of electrodeposition [14]. The required pH values were
achieved using H2SO4 or NaOH solutions. The elec-
trodeposition of coatings was carried out in an interval
of pH 1.5–3.5 with an increment of 0.5 at room temper-
ature and current densities from 2 to 60 A/dm2 with tita-
nium dioxide–iridium anodes. The electrolysis time
was 5–15 min, which made it possible to obtain coat-
ings 0.5–2 µm thick.

1070-3284/05/3101-0014 © 2005 Pleiades Publishing, Inc.

 PHYSICOCHEMICAL MODEL FOR CHOOSING COMPLEXES 15

RESULTS AND DISCUSSION

 log β n° ( Cr L n ) > log β m° ( Cr A m )
3+ 3+

Physicochemical model for choosing ligands for  (5)

chromium-plating solutions. The physicochemical
model for choosing ligands was constructed on the
basis of a combination of the thermodynamic principles
and known data on the kinetics of some electrochemi-
cal reactions.
The physicochemical model for choosing ligands in
the development of complex electrolytes for chromina-
tion should take into account the stepwise reduction of
Cr3+ ions to the metal with the formation of stable ions
of intermediate valence. The general scheme of this
 log β °n ( Cr L n ) > log β °m ( Cr A m ).
2+ 2+
2. A ligand should form with Cr3+ and Cr2+ ions the
complexes, whose stability constants are higher than
those of the corresponding hydroxo complexes.
This condition can be described mathematically by
the following system of inequalities:
 log β °n ( Cr L n ) > log β °1 ( Cr OH )
3+ 3+
 (6)
 log β °n ( Cr L n ) > log β °1 ( Cr OH ).
2+ 2+

process in the absence of the coordination sphere rear-

rangement can be described as follows: 3. A ligand should form with Cr2+ ions a complex,
whose stability provides the standard electrode poten-
[Cr3+Ln]3 + nz + e– [Cr2+Ln]2 + nz, (1)
tial E ° 2+ of reaction (2) with a positive value higher
[ Cr L n ]
[Cr2+Ln]2 + nz + 2e– Cr + nLz, (2)
than the potential of the beginning of active discharge
where z is the charge of the ligand. of water molecules E*.
Hydroxonium ions and water molecules are reduced This condition can be written as an inequality
simultaneously with the reduction of the chromium
complexes E °[ Cr2+ L ] > E*. (7)
n

2H3O+ + 2e– H2 + 2H2O, (3) Let us express E °[ Cr2+ L ] in terms of the standard elec-
n

2H2O + 2e– H2 + 2OH–. (4) trode potential of the reaction Cr2+ + 2e– Cr and a
stability constant of a discharging complex
A model for choosing ligands cannot be constructed
when thermodynamic principles are used only, because 2.3RT
E °[ Cr2+ L ] = E °Cr2+ – --------------- log β °n ( Cr L n )
2+
the standard electrode potential of reaction (2) is more (8)
n 2F
negative than the potentials of reactions (3) and (4),
indicating that the electrodeposition of chromium is and insert this expression into inequality (7). After sim-
thermodynamically impossible. ple transformations, we have
The accumulation of éç– ions in the near-electrode 2F
log β °n ( Cr L n ) < --------------- ( E °Cr2+ – E* ).
2+
layer together with an insufficient stability of the Cr3+ (9)
2.3RT
and Cr2+ complexes brings about the formation of vari-
ous hydroxo complexes and, finally, chromium hydrox- Since the complexes are reduced in several steps
ides, as a result of which the reduction of the chromium (formation of stable ions of intermediate valence), we
complexes in reaction (2) terminates. Therefore, the can formulate another condition.
rate of reduction of water molecules should not be 4. A ligand should form with Cr3+ and Cr2+ ions
higher than some critical value determined by the rate complexes, whose stability provides the standard elec-
of reduction of the Cr3+ and Cr2+ complexes. The
kinetic stability of water molecules during their reduc- trode potential E °[ Cr3+ L ]/ [ Cr2+ L ] of reaction (1) such that
n n
tion was characterized further by the potential of the it is more positive than the potential of the beginning of
beginning of active reduction of water molecules (E*), active discharge of water molecules E*.
which was found as a potential that conventionally The mathematical formulation of this condition can
divided the polarization curve of hydrogen evolution be written as an inequality
into two regions of high and low resistance to the
charge transfer. E °[ Cr3+ L ]/ [ Cr2+ L ] > E*. (10)
n n
The concepts presented above make it possible to
formulate the following rules of choosing ligands for Let us express E °[ Cr3+ L ]/ [ Cr2+ L ] in terms of the stan-
n n
solutions containing chromium complexes.
dard electrode potential of the reaction Cr3+ + e–
1. A ligand should form with Cr3+ and Cr2+ ions the Cr2+ and the stability constant of the complexes
complexes, whose stability constant (β) is higher than
β °n ( Cr L n )
those of complexes (predominant in the solution) with 2+
2.3RT
anions of a salt (Az) and/or a supporting electrolyte. E° 3+ 2+
[ Cr L n ]/ [ Cr L n ]
°
= E Cr3+ /Cr2+ + --------------- log ---------------------------
β °n ( Cr L n )
F 3+
The mathematical expression of this condition can
be described by the following system of inequalities: (11)

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 31 No. 1 2005

16 VINOKUROV et al.

and insert this expression into inequality (10) 2.3RT

E °Cr3+ L = E °Cr3+ – --------------- log β °n ( Cr L n )
3+
(15)
log β °n ( Cr L n ) < log β °n ( Cr L n )
2+ 3+ n 3F

F (12) and insert this expression into inequality (14)

– --------------- ( E °Cr3+ /Cr2+ – E* ).
2.3RT
Taking into account a certain probability of dis-
charge of the [Cr3+ Ln] complexes with a simultaneous
transfer of three electrons, one can formulate one more
condition.
5. A ligand should form with Cr3+ ions a complex,
whose stability provides the standard electrode poten-
tial E °[ Cr3+ L ] of the reaction
n
[Cr3+Ln]3 + z + 3e– Cr + nLz, (13)
such that it is more positive than the potential of the
beginning of active discharge of water molecules E*.
The mathematical formulation of this condition can
also be written as an inequality
E °Cr3+ L > E*.
n
3F
log β °n ( Cr L n ) < --------------- ( E °Cr3+ – E* ).
3+
(16)
2.3RT
The choice of a ligand that does not aggravate sew-
age purification is also very important for the develop-
ment of solutions for metal electrodeposition. If it is
assumed that heavy metal hydroxides (in our case,
Cr(OH)3) are formed at the first step of sewage neutral-
ization by the reagent method, then the following con-
dition can be formulated.
6. A ligand should form with Cr3+ ions a complex,
whose stability constant is lower than the solubility
product (SP) of chromium hydroxide.
The mathematical formulation of this condition is
expressed by an inequality
(14) log β °n ( Cr L n ) < pSP ( Cr ( OH ) 3 ).
3+
(17)

Let us express E °Cr3+ L through the standard elec- Since the proposed ligand should simultaneously
n meet all above requirements, this can be expressed by
trode potential of the reaction Cr3+ + 3e– Cr and the uniting all mathematical equation (6), (9), (12), (16),
stability constant of a reducing complex and (17) into a system of inequalities

  log β n° ( Cr L n ) > log β 1° ( Cr OH )

3+ 3+
(‡)

  log β °n ( Cr 2+ L n ) > log β °1 ( Cr 2+ OH ) ( a' )

 2F
 log β °n ( Cr L n ) < -------------- - ( E °Cr2+ – E* )
2+
(b)
 2.3RT
 F (18)
 log β °n ( Cr L n ) < log β °n ( Cr L n ) – --------------- ( E °Cr3+ /Cr2+ – E* ) ( c )
2+ 3+

 2.3RT
 3F
 log β °n ( Cr 3+ L n ) < --------------
- ( E ° 3+ – E* ) (d )
 2.3RT Cr

 log β n° ( Cr L n ) < pSP ( Cr ( OH ) 3 )
3+
(e)

Numerical simulation. After the values of some
physical magnitudes presented in Table 1 are inserted
into the system of inequalities (18) and the latter is
solved by the graphical method, a region Ω (figure) of
admissible values of logarithms of stability constants of
chromium complexes of different valence is obtained
that meet all (or almost all) requirements for choosing
ligands. The solution of the system is an interval of logβ
values for the Cr(III) complexes from 10 ( log β min ) to
20 ( log β max ) and for the Cr(II) complexes an interval
from 7 to 9.8.
Since the stability constants for some chromium
complexes are unknown, it seems reasonable to deter-
mine boundaries of both the stability constants and
characteristics of the ligand, for instance, an exponent
of the dissociation constant (K) of protonated ligand.
In [17], we presented equations relating the stability
constants of the Cr(II) and Cr(III) complexes to the sum
of exponents of dissociation constants of protonated
forms of the ligands
log β °1 ( Cr L ) = a Z ( Σ p K m ) .
Z
(19)
The parameters of the Panteleon–Ecka equation (λZ)
log β °n = n log β °1 – λ Z n ( n – 1 ) (20)
were also determined in this work to calculate the sta-
bility constants of the Cr(II) and Cr(III) complexes with
n bidentate ligands (n = 2, 3), where Z is the valence of
the chromium ions, and aZ and λZ are proportionality

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 31 No. 1 2005

 PHYSICOCHEMICAL MODEL FOR CHOOSING COMPLEXES 17

Table 1. Logarithms of stability constants of the Cr3+ and cients aZ and λZ for the corresponding chromium com-
Cr2+ hydroxo complexes, the solubility product exponent for plexes into Eq. (21), we find the boundary conditions
Cr(III) (pSP), the standard electrode potentials of the reac- for ΣpKm: (ΣpKm)max = 9.2 and (ΣpKm)min = 5.4, which
tions involving chromium ions (E°), and the potential of ac-
tive reduction of water molecules (E*) is an obligatory requirement for choosing ligands for
chromium-plating solutions.
Parameter Value References Comparison of the results of simulation with
experimental data. For experimental checking, we
log β °1 (Cr3+OH) 10.0 [15] chose ligands satisfying the boundary conditions and
overstepping them (Table 2). An admissible interval of
log β °1 (Cr2+OH) ~7 [15] current densities of the electrodeposition of high-qual-
ity coatings (∆i) was determined at pH 2 in solutions
pSP(Cr(OH)3) 30.2 [15]
containing the ligands chosen.
E °Cr3+ /Cr2+ , V –0.41 [15] The results obtained were used to verify the pro-
posed model. The plot of ∆i vs. logβ for the correspond-
E °Cr3+ , V –0.744 [15] ing coordinatively saturated Cr(III) complexes is pre-
sented in the figure (curve f). This plot has a maximum,
E °Cr2+ , V –0.914 [15] whose position corresponds to the Ω region. The widest
interval of current densities is observed for the elec-
E*, V –1.2 [16] trodeposition of chromium from a solution of the chro-
mium malonate complexes. When using the ligands
that form complexes with Cr3+ ions, whose stability
coefficients. In Eqs. (19) and (20), a2 = 0.53, λ2 = 0.57 constants are beyond the upper ( log β max = 20) and
and a3 = 0.88, λ3 = 0.69. To find ΣpKm, we solved a sys-
tem of Eqs. (19) and (20) lower ( log β min = 10) boundaries of the Ω region, the
admissible interval of current densities narrows
log β °n [ Cr L n ] λ Z
Z
sharply, and chromium deposition even stops com-
ΣpK m = ---------------------------------
- + ----- ( n – 1 ). (21) pletely in some cases of the indicated conditions.
n aZ
Thus, our studies confirmed the validity of the
Inserting log β max , log β min for the coordinatively model developed for choosing Cr(III) complexes and
saturated complexes (n = 3) and the values of coeffi- selecting ligands for chromium-plating solutions con-

Table 2. Exponents of dissociation constants of the protonated ligands, logarithms of stability constants of the coordinately
saturated Cr(III) complexes, minimally and maximally admissible current densities, and the range of current densities for the
deposition of high-quality chromium coatings
pK1 ΣpKn logβ imin, imax, ∆i,
Protonated ligand c, mol/l pH
[15] [15] [17] A/dm2 A/dm2 A/dm2
–
HS O 4 0.6 1.94 1.94 1.4 2 0
Formic acid 0.6 3.75 3.75 5.76 1.5 17.6 21.0 3.4
2.0 10.6 13.2 2.6
2.5 9.1 10.9 1.8
Lactic acid 0.6 3.83 3.83 6.0 2.5 3.5 5.5 2.0
Oxalic acid 0.6 1.19 5.20 9.6 1.5 6.8 11.3 4.5
2.0 2.4 5.9 3.5
2.5 2.5 4.1 1.6
3.0 1.5 3.5 2.0
Nitrilotriacetic acid 0.4 1.89 14.11 12.3 1.5 6.8 12.2 5.4
2.0 2.4 7.5 5.1
2.5 2.1 6.7 4.6
Malonic acid 0.6 2.80 8.50 18.3 1.5 13.5 47.6 34.1
2.0 6.5 13.3 6.8
2.5 4.5 11.1 6.5
3.0 4.5 6.1 1.6
Trilon B 0.2 2.0 23.0 26.5 2.0 0

RUSSIAN JOURNAL OF COORDINATION CHEMISTRY Vol. 31 No. 1 2005

18 VINOKUROV et al.
logβ0n (Cr2+Ln) ∆i, A/dm2
12 15
a d c e
10 b
8 Ω 10
a'
6 f
4 5
2
0 5. Edigaryan, A.A. and Polukarov, Yu.M., Zashch. Met.,
0 5 10 15 20 25 30 35
logβ0n (Cr3+Ln)
Graphical determination of the admissible region Ω for log-
arithms of stability constants of the coordinatively saturated
chromium complexes of different valence: a–e correspond
to the numbers of inequalities in system (18), and f is the
plot of the range of admissible current densities of the elec-
trodeposition of high-quality chromium coatings at pH 2 vs.
logβ of the coordinatively saturated chromium(III) com-
plexes.
taining Cr(III) complexes and made it possible to draw
the following conclusions. Based on the analysis of
chemical and electrochemical processes that can occur
during electrodeposition of chromium from solutions
of the Cr(III) complexes, we proposed a physicochem-
ical model for choosing complexes and, correspond-
ingly, ligands for chromium-plating solutions. It was
shown that high-quality chromium coatings can be
obtained from solutions of the Cr(III) complexes for
which logβ range from 10 to 20 and logβ of the Cr(II)
complexes formed in electrolysis range from 7 to 10.
The influence of the ligand nature on the process of
chromium electrodeposition was established. The
physicochemical model was experimentally confirmed.
Using the proposed model and the results of experi-
RUSSIAN JOURNAL OF COORDINATION CHEMISTRY
mental verification, we developed a chromium-plating
solution containing the chromium(III) malonate com-
plex that makes it possible to produce high-quality
coatings in a wide range of current densities.
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