B51
per in glycine solutions. First, the thermodynamics of copper complexation in aqueous glycine solutions are analyzed, and potentialpH diagrams for the copper-glycine-water system are presented. Experimental measurements of the polarization behavior of copper in
glycine solutions of different compositions are then reported. This
behavior is discussed in terms of the relevant potential-pH diagrams.
Potential-pH Diagrams
Potential-pH diagrams are conventially plotted with pH on the
horizontal axis, and potential on the vertical axis. Consider a generalized reduction reaction involving n electrons
aA mH ne bB dH2O
[2]
{A}a {H}m
2.303 RT
log
b
d
nF
{B} {H 2 O}
volts
[3]
[4]
{B}b {H 2 O}d
{A}a {H}m
[5]
{B}b {H 2 O}d
G o
a
2.303 RT
{A}
[6]
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B52
Cu(H2NCH2COO)
2 . These are referred to as CuHL , CuL , CuL2,
and CuL
,
respectively.
2
Table I lists the standard Gibbs free energies of formation of
species in the copper-water-glycine system.13 Cupric hydroxide,
Cu(OH)2, was not considered because it is less stable than cupric
oxide.4 Standard Gibbs free energies of formation have not been tabulated for all the copper-glycine complexes identified above. The
stabilities of these were deduced using the association constants presented in Table II.12 Table III shows all thermodynamically meaningful reactions between the species in the copper-water-glycine system, along with the equations of each equilibrium line, calculated
using the data provided in Tables I and II, and Eq. 3 or 6.
Figure 2 shows potential-pH diagrams plotted from the equilibria
in Table III at various combinations of total glycine activity {LT} and
total dissolved Cu activity {CuT}. The lines identified as 1 to 4 correspond to the equations of the same number in Table III. Figure 2
demonstrates that copper metal is oxidized to form copper(II) glycinate species, either CuHL2, CuL, or CuL2, over a wide range of
pH. The copper(I) glycinate complex CuL
2 only appears when LT is
much higher than CuT (diagrams b and c), such that the line for
reduction of CuL
2 to elemental copper is below the line for reduction of CuL2 to CuL
2 . It is notable that glycine appears in the anionic form at much lower pH values when complexing copper than it
does in the free form. Table II and Fig. 1 show that free glycine only
predominates as an anion above pH 9.778 and predominates in the
zwitterionic form between pH 2.35 and 9.778. The anionic form of
glycine clearly forms more stable copper complexes than does the
zwitterionic form, which would be expected since the former is
State
Gof (kJ/mol)
H
OH
H2O
H2
O2
Cu
Cu2
Cu
CuO
Cu2O
CuO22
HCuO2
H2L
HL
L
CuL
Aqueous
Aqueous
Liquid
Gas
Gas
Aqueous
Aqueous
Solid
Solid
Solid
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
Aqueous
0
117.244
237.129
0
0
49.98
65.49
0
129.7
146.0
183.6
258.5
384.061
370.647
314.833
298.2
capable of bidentate chelation, while the latter can only give monodentate coordination through the carboxylate group. CuHL2,
which contains the zwitterion, predominates only when the total
glycine activity exceeds 1.94 102. Anionic hydrolyzed Cu(II)
species appear at high pH, and their predominance regions are unaffected by glycine. A very narrow region appears for HCuO
2 at
106 M {CuT}, along with CuO2
2 , whereas at higher {CuT} only
CuO22 appears. The stability regions of cupric oxide, CuO, and
cuprous oxide, Cu2O, expand with increasing CuT, and contract with
increasing LT.
It must be emphasized that potential-pH diagrams only provide
information about thermodynamic equilibrium and infer nothing
about the kinetics of reactions. Moreover, although underlying metals might be passive in regions where oxides predominate, they need
not be; passivation requires coherent, adherent oxide films with low
conductivity. Nevertheless, potential-pH diagrams have proved useful in elucidating the electrochemistry of copper in various aqueous
media.1,5,6,14,15
Experimental
Reagents and solutions.Glycine (>99%) was obtained from
Acros Organics Co. Reagent grade cupric nitrate hemipentahydrate
was purchased from Fisher Scientific Co. Electrolyte solutions were
prepared using doubly distilled water, and their pH was adjusted to
0.1 units using NaOH or HNO3 (both reagent grade from Fisher
Scientific Co.). The electrolyte was either aerated or deaerated before use. For aeration, breathing (medical) air was purged into the
electrolyte through a porous gas disperser for 18 h. The pH was adjusted with NaOH after aeration, to correct for absorption of CO2.
For deaeration, ultrapure nitrogen gas (99.999% N2) was sparged for
24 h; this did not affect the pH.
L H HL
HL H H2L
Cu2 L CuL
Cu2 2L CuL2
Cu 2L CuL
2
CuL H CuHL2
Label
KL1
KL2
KML1
BML2
BmL2
KML3
log K or log B
09.778
02.350
08.570
15.640
10.100
02.920
(I 0).0
(I 0).0
(I 0).0
(I 0).0
(I 0.2)
(I 0.1)
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B53
Reaction
O2 4H 4e 2H2O
2H 2e H2
HL H H2L
L H HL
Cu2 H2L CuHL2 H
CuL H CuHL2
Cu2 HL CuL H
CuL HL CuL2 2H
CuL2 e CuL
2
CuO2
2 H HCuO2
CuL
2 e Cu 2L
2Cu2 H2O 2e Cu2O 2H
2CuL H2O 2e Cu2O 2HL
Cu2O 2H 4L 2CuL
2 2H2O
2CuL2 2H2O 2e Cu2O 2H 4L
2CuL2 2H2O 2H 2e Cu2O 4HL
2CuO22 6H 2e Cu2O 3H2O
2CuO22 4H 2e Cu 2H2O
2HCuO
2 4H 2e Cu2O 3H2O
CuO 2H 2L CuL2 H2O
Equilibrium line
E 1.229 0.0591 pH
E 0.0591 pH
pH 2.350 log{HL}/{H2L}
pH 9.778 log{L}/{HL}
pH 0.649 log{H2L} log {CuHL2}/{Cu2}
pH 2.920 log{CuL}/{CuHL2}
pH 1.219 log{HL} log{CuL}/{Cu2}
pH 2.710 log{HL} log{CuL2}/{CuL}
E 0.167 0.0591 log{CuL2}/{CuL
2}
pH 13.12 log{CuO22}/{HCuO
2}
E 0.472 0.0591pH
E 0.641 0.0591pH
E 0.339 0.0295 log{Cu2}
E 0.358 0.0295 pH 0.0295 log{CuHL2} 0.0295 log{H2L}
E 0.288 0.0295 log{CuHL2} 0.0295 log{HL}
E 0.375 0.0295 pH 0.0295 log{CuL} 0.0295 log{HL}
E 0.455 0.0591 pH 0.0295 log{CuL2} 0.0591 log{HL}
E 0.126 0.0295 log{CuL2} 0.0591 log{L}
E 1.077 0.1182 pH 0.0591 log{CuL
2 } 0.0591 log{HL}
pH 9.32 log{CuL
2 } 2 log{L }
E -0.722 0.0591 pH 0.0591 log{CuL2} 0.1182 log{L}
E 0.438 0.0591 pH 0.0591 log{CuL2} 0.1182 log{HL}
E 2.562 0.1773 pH 0.0591 log{CuO2
2 }
E 1.506 0.1182pH 0.0591 log{CuO2
2 }
E 1.783 0.1182 pH 0.0591 log{HCuO
2}
pH 11.495 0.5 log{CuL2} log{L}
pH 16.05 0.5 log{CuO2
2 }
pH 18.979 log{CuO2
2 }
Linear polarization resistance measurements were used to estimate the current densities (iOC) at EOC. In these experiments, the electrode was scanned at 0.2 mV/s from 40 mV below EOC to 40 mV
above. A plot of overpotential () from EOC vs. current density (i)
should be linear near EOC, and the slope of such a plot gives the polarization resistance, Rp. iOC is inversely proportional to Rp16,17
ioc
ac
2.303(a c ) Rp
[8]
where a and c are the absolute values of anodic and cathodic Tafel
constants, respectively. Cathodic Tafel constants could seldom be
determined reliably from the potentiodynamic scans. For copper dissolution in aerated solutions, c was assumed to be 0.06 V/decade
while the cathodic reaction in deaerated solutions was assumed to be
limited by concentration polarization (c V/decade). The error
in determining iOC with estimated Tafel constants has been shown to
be within the experimental scatter.18
Results and Discussion
Polarization studies were made in aqueous solutions of 102 M
glycine with 105 M cupric nitrate, and 101 M glycine with 104 M
cupric nitrate. Figures 2a and b are the potential-pH diagrams for
these solution chemistries. Table IV shows EOC and iOC for each group
of experiments, at each pH.
Figure 3 shows the effect of pH from 9 to 12 on the polarization
behavior of the copper electrode rotating at 1000 rpm in deaerated
102 M glycine with 105 M cupric nitrate aqueous solutions. The
polarization behavior given in Fig. 3 is reasonably consistent with
the potential-pH diagram shown in Fig. 2a, which predicts that CuL2
should predominate at pH 9 and 10 above potentials 106 and
154 mV, respectively. On polarizing anodically from EOC, copper
dissolves actively at pH 9 and 10, with no evidence of passivation.
Despite the similarity in rest potential at pH 9 and 10, iOC increased
by a factor of about three on increasing the pH from 9 to 10. As the
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B54
[9]
[10]
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B55
Table IV. Open-circuit potential, current densities, and absolute values of Tafel constants of copper in aqueous Cu(NO3)2-glycine solutions.
Solution
pH
EOC
(mV, SHE)
iOC
(A/m2)
A
mV/decade
C
mV/decade
09
10
11
12
09
10
11
12
9
10
11
12
09
10
11
12
131
137
223
254
018
042
059
063
107
212
217
258
061
101
128
142
4.87 103
1.47 102
8.56 103
6.63 103
1.32 101
3.14 101
2.43 101
1.63 101
3.15 102
4.43 102
4.61 102
2.78 102
5.16 101
9.75 101
1.62
9.60 101
60
40
60
60
50
50
50
50
50
60
60
40
60
60
60
50
Large
Large
Large
Large
60
60
60
60
Large
Large
Large
Large
60
60
60
60
to 150 mV higher, while the current densities are one to two orders
of magnitude greater. Over most of the potentials scanned, the
cathodic current densities were about two orders of magnitude higher than those observed under deaerated conditions at the same over-
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B56
potentials (Fig. 3). The higher potentials and currents reflect cathodic reduction of oxygen
The open-circuit potentials are clearly mixed potentials, with modest anodic dissolution of the copper electrode at the steady state.
Active corrosion of copper by oxygen in aqueous glycine solutions
has been reported earlier.15
At pH 9 and 10, the anodic polarization curves for copper are
very similar in Fig. 3 and 4. The passivation behavior exhibited at the
higher pH values is also similar, except that no minor passive region
was seen at about 80 mV at pH 12, because under aerated conditions the net current was cathodic at this potential.
Figure 2b suggests that the solubility region of copper extends to
higher pH at {CuT} 104 and {LT} 101. No Cu2O is predicted below pH 11.3, and CuO is only expected above pH 12.5. Figure 5 shows the effect of pH from 9 to 12 on the polarization behavior of a copper electrode rotating at 1000 rpm in deaerated 101 M
glycine with 104 M cupric nitrate aqueous solutions. EOC and iOC
values at each pH are shown in Table IV. The polarization curves
given in Fig. 5 agree reasonably well with Fig. 2b, which predicts
that CuL2 would form on oxidation of copper at pH 9, while CuL2-
O2 2H2O 4e 4 OH
[11]
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B57
References
1. J. van Muylder, in Comprehensive Treatise of Electrochemistry, J. OM. Bockris,
B. E. Conway, E. Yeager, and R. E. White, Editors, Vol. 4, p. 1, Plenum Press, New
York (1981).
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