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Protection of Metals and Physical Chemistry of Surfaces
Protection of Metals and Physical Chemistry of Surfaces
INVESTIGATION METHODS
FOR PHYSICOCHEMICAL SYSTEMS
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
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
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
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
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