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Kavner Etal 09a
Kavner Etal 09a
Kavner Etal 09a
Chemical Geology
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / c h e m g e o
a r t i c l e i n f o a b s t r a c t
Article history: Electron-transfer related isotope fractionation may produce large stable isotope geochemical signatures as a
Accepted 25 April 2009 result of a variety of Earth processes, including biology, chemical weathering, fluid–rock interactions, and
Editor: ESNL deep Earth redox reactions. In the laboratory, isotope fractionation at a charged electrode has been observed
for electroplating of Fe and Zn; however these can arise from a variety of effects besides the electron transfer
Keywords: process. Here, we examine the effect of mass transport on observed isotope fractionation during
Electrochemistry potentiostatic electroplating of iron. We examine the observed isotope fractionation as a function of the
Redox ratio of the observed plating current to the mass-transport limited current (the Cottrell current). When the
Diffusion electroplating experiments are run at currents greater than the Cottrell current, the observed fractionation
Stable isotope fractionation
is ~− 1.15(± 0.40) ‰, and the extent of fractionation shows a tendency to decrease with increasing plating
Fe stable isotopes
rate. When electroplating experiments are run at currents below the Cottrell current, observed fractionations
are strongly dependent on the plating rate, with a maximum value of δ56Fe = − 4.8. The data set demon-
strates that mass transport to the electrode tends to attenuate a large fractionation factor associated with
other, non-mass transport, processes at the electrode.
© 2009 Elsevier B.V. All rights reserved.
0009-2541/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.chemgeo.2009.04.018
132 A. Kavner et al. / Chemical Geology 267 (2009) 131–138
solution chemistry and its changes as the electrode surface is ap- drop across that interface; l is the length scale over which that voltage
proached. Finally, an isotope effect due electron transfer has been drop takes place; and uj is the mobility—which has units of velocity/
hypothesized in two previous papers (Kavner et al., 2005; Kavner electric field or cm/s per V/cm or cm2 s− 1 V− 1.
et al., 2008). The mobility is derived by considering the force balance between
Our goal in this paper is to examine how isotope fractionation viscous drag and electric field on a charged species in a viscous fluid.
occurs during mass-transport-limited electron transfer processes. We At equilibrium, this balance is written as:
derive an isotope-sensitive version of the Cottrell equation, which
describes electrochemical reaction rates in the diffusion-limited zj ee = 6πηrmj ð5Þ
regime (Bard and Faulkner, 1980). We use this theory to interpret a
series of new experiments showing isotope fractionation during iron where ε is electric field, η is the viscosity of the fluid, r is the radius of
electrodeposition under a variety of experimental conditions. particle, and v is its velocity. The mobility is defined at this
equilibrium, as uj = vj/ε, where the velocity is the terminal velocity.
2. Mass transport at an electrode
j zj j e
uj = ð6Þ
Mass transfer to a charged electrode is governed by convection, 6πηr
electromigration, and diffusion of the ion species to the surface of the
electrode. For simplicity, we only examine the one-dimensional Substituting Eq. (6) back into Eq. (4) yields a current due to
problem. We assume that the electrode is an infinite plane, and all electromigration equal to:
behavior takes place as a function of distance from the electrode.
Although these simplifying assumptions may introduce some quanti- 2
j zj j FAeCj ΔE
tative errors, they should not change the basic qualitative isotope im;j = : ð7Þ
6πlηr
behavior of these systems. This section follows the development
as presented by a standard electrochemistry textbook (Bard and
Faulkner, 1980). The steady state, one-dimensional version of the The only isotope-dependent term in this equation is related to the
equation governing mass transport to an electrode is known as the concentration of each species Cj. Therefore, although electromigration
Nernst–Planck equation, where total flux is equal to contributions may change the overall flux to an electrode, it does not cause any
from convection, electromigration, and diffusion, and is given by: additional isotope fractionation that is not already due to other factor
affecting relative isotope compositions, such as diffusion, evolution of
zF Au ACj ðxÞ reservoir, and/or electrochemical processes.
Jj ðxÞ = Cj mðxÞ − DC − Dj ð1Þ
RT j j Ax Ax
2.2. Diffusion at an electrode
where Jj(x) is the flux of species j to the electrode; Cj is the con-
centration of species j; ν(x) is the viscosity; Dj is the diffusivity of The one-dimensional diffusion equation for a planar electrode is:
species j; ∂φ/∂x is the electric field, z is the number of electrons
transferred in a single reaction (2 for the Fe+2 + 2e− = Fe reaction), AC0 ðx; t Þ A2 C0 ðx; t Þ
T is temperature, R is the ideal gas constant, and F is Faraday's = D0 ð8Þ
At Ax2
constant, equal to 96,485 Coulombs/mol. This equation can be recast
with each flux term written as currents: The initial condition assumes that the concentration near the
electrode is identical to the bulk solution; i.e. Cj(x = 0, t = 0) = Cj,0,
−zFJj ðxÞ = itotal = iconvection + ielectromigration + idiffusion ð2Þ
where C0 is the starting concentration in the reservoir. For mass-
transport limited processes at an electrode, the concentration at the
where Ji(x) is the flux of species j at distance x (units: s− 1 cm− 2), and
electrode surface is established by the boundary condition Cj (x = 0,
the current i is related to the flux via the Faraday equivalent between
t N 1) = 0 which is equivalent to assuming that at the electrode, the
current and concentration zF; and the terms on the right hand sides of
aqueous species is immediately reduced. Finally, we assume that the
Eqs. (1) and (2) represent currents due to convection, electromigra-
reservoir is large compared with the amount of plated material, and
tion, and diffusion. Since mass transport by convection cannot
therefore Cj(x N N 0, all t) = Cj,0. As will be seen in the next section, we
generate isotope fractionation by itself, it will not be considered
have designed our experiments to plate out only small amounts of the
here. In the following two sub-sections, we consider isotope effects of
total ion in solution to satisfy this boundary condition.
both electromigration and diffusion to a charged electrode.
The solution to this differential equation with these boundary
conditions for mass-transport-limited electrochemical reactions pro-
2.1. Electromigration at an electrode
vides the current-time response at an electrode, and is known as the
Cottrell equation (Bard and Faulkner, Section 5.2.1).
For simplicity, we assume the electric field varies linearly away
from the electrode. The electromigration current is proportional to the pffiffiffiffiffiffi
nFA D0
electric field, with only concentration and mobility, uj, as proportion- iðt Þ = id ðt Þ = pffiffiffiffiffi ð9Þ
ality constants: πt
Jj = uj cj e ð3Þ where id(t) is the rate-limiting current, also known as the “Cottrell
current”; and A is the electrode area. When reaction rates are
The current due to electromigration can then be written as: significantly larger than the Cottrell current, then mass transport to
the electrode is the rate-limiting step. If experimental electrochemical
jzj j FAuj Cj ΔE reaction rates are much lower than the Cottrell current, then material
im;j = ð4Þ can be supplied to the electrode fast enough so that another electrode
l
processes is rate-limiting. Typical values of time-dependent Cottrell
where im,j is the current due to the electromigration of j; |zj| is the currents for 2 M and 0.25 M FeCl2 solutions—such as the one we use in
absolute value of the charge on j; F is Faraday's number; A is the area our experiments—are plotted in Fig. 1, along with our estimated
of the electrode; Cj is the concentration of species j; Δɛ is the voltage experimental plating currents (cf. Section 3).
A. Kavner et al. / Chemical Geology 267 (2009) 131–138 133
sffiffiffiffiffiffiffiffiffi !
D0;2 Isotopic analysis of the plated material and remaining solution was
2
δ M = 1000 −1 ð10Þ performed following the procedures reported in Kavner et al. (2005).
D0;2
An effort was made to collect all of the deposited material from each
electrode. Each electrode was collected and gently washed with
where 2M is the isotope fractionation of the metal's heavy isotope distilled water to remove the excess plating bath solution. The elec-
(M,2) with respect to its light isotope. The diffusivities of the two trodes were then placed in clean Teflon beakers. Electroplated iron
isotopologues are D0,2 for the heavy isotope and D0,1 for the light. Eq. was removed from the electrodes with hot concentrated HNO3 acid for
(10) predicts a time-independent fractionation factor during mass- about 6 h followed by hot concentrated HCl acid for about 10 h.
transport limited electroplating. Subsequent scanning electron microscopy examination of cleaned
These equations for mass transport at an electrode suggest that electrodes showed no remaining iron and a small amount of increase
isotope fractionation will be a constant related only to the diffusivity in the roughness of the electrode surface. All solutions were dried
of the species in solution at the electrode. Although the concentrations down after acid baths, and were finally re-dissolved in 0.3 N nitric acid
of the species adjacent to the electrode varies as a function of time for analysis. In addition, for each set of experiments, a small amount of
according to these solutions to the diffusion equation, the ratio of the the starting solution was dissolved in hot concentrated HNO3 acid and
concentrations of the two isotopes themselves do not vary as a then diluted to 0.3 N for analysis. The samples were diluted to Fe
function of time. Therefore, fractionation by diffusive transport is concentrations ranging from 3 to 5 ppm. Dilutions were recorded to
predicted to be a constant, even if the kinetics of the reaction changes provide an estimate of the amount of material collected from the
due to application of overpotential. Rodushkin et al. (2004) measured electrode, in milligrams (Table 1). This is likely a lower bound to the
a fractionation factor (α) due to diffusion of iron isotopes in aqueous actual amount plated, and we estimate a factor of ~ 2 uncertainty in
systems equal to D56Fe/D54Fe−1 = − 9 × 10− 5, and observed isotope the estimate. This value was used to estimate the electroplating cur-
fractionations in their experimental system up to −0.3‰. rent, via the formula ideop (milliamps) = 1000 × zFgplated / (W t) where
z = 2 electrons transferred, F is Faraday's constant = 96,485 C/mol,
3. Experimental procedure gplated is the amount of material plated, W is the atomic mass of Fe,
equal to 55.56 g/mol, and t is the total amount of time for the
3.1. Electroplating experiments electrodeposition experiment. These values, which vary from 10 s of
µA to 10 s of mA, are shown in Table 1. The ratio of this value to the
The goal of the experiments is to perform a series of Fe elec- total amount of current passed in the experiment (=Q/t, where Q is
trodeposition experiments under a variety of controlled potential the total amount of Coulombs passed in each experiment, and is
conditions, and to examine how the isotope composition of the shown in Table 1) provides a lower-bound estimate to the efficiency of
electroplated iron metal varies as a function of the ratio of the the iron electroplating reaction with respect to hydrogen evolution at
electrodeposition rate to the calculated mass-transport limited the electrode. Estimated efficiencies were highly variable among
current. Eight sets of electrodeposition experiments were per- individual experiments, and between sets of experiments, with many
formed, as outlined in Table 1. In all cases, Fe metal was electroplated values in the 0.1% and 10% ranges. For each experiment, an estimated
from FeCl2 starting solutions, with concentrations varying from 2 M plating rate in mol/m2/s is calculated using the relation rate = (i/AzF)
down to 0.125 M. In all cases, plating solutions were acidified with where i is the estimated plating current in amps and A is the electrode
1 M HCl. area in m2. We consider these values in plating rate to be order-of-
The experimental procedure follows a similar approach to what magnitude estimates, given sources of uncertainty in the estimate of
was reported in Kavner et al. (2005). Iron electroplating experiments plating current and uncertainty in electrode area, which was not
were performed under potentiostatic (constant voltage) conditions monitored directly for these experiments, but in all cases was approx-
with an Autolab Potentiostat using a three-electrode electrochemical imately ~ 1 cm2.
134 A. Kavner et al. / Chemical Geology 267 (2009) 131–138
Table 1
Data summary from all plating experiments.
A. Kavner et al. / Chemical Geology 267 (2009) 131–138 135
Table 1 (continued)
a
calculated with respect to starting solution, referenced to standard reduction potential adjusted to Fe concentration using Nernst's law.
b
two-sigma errors are reported.
c
efficiency calculated by…
d
Ratio of the observed average current/Cottrell average current.
Fig. 2. All iron electrodeposition data on a three-isotope plot, with two-sigma error bars. Our best fit β value (See Young et al. (2002)) is equal to 0.671 (± 0.004), shown in red.
The inset shows the measured β value (purple square) in comparison with calculated β values for equilibrium fractionation (dotted line) and for kinetic processes involving hydrated
Fe+2 species as a function of solvation number (solid black line). (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this
article.)
The relationship between the experimental current and the When the estimated experimental current is above the Cottrell
calculated Cottrell current enables the data to be sorted into two current, the resultant observed isotope fractionation decreases weakly
regimes. Fig. 4 shows the measured isotope fractionation as a function with increasing rate (current), with measured δ56Fe clustered about
of the ratio of the estimated electroplating current to the calculated values varying from − 1.5‰ to −1‰. As shown in Fig. 4, fractionation
Cottrell current for each plating experiment. When this ratio is much factor measured for diffusion processes by Rodushkin et al. (2004) is
greater than 1, the plating kinetics are likely to be limited by mass much lower than our observations in the mass-transport limited
transport to the electrode. When the ratio is much less than 1, the regime, though diffusion processes may be helping to place a lower
overall plating kinetics are governed by electrode processes. Close to 1, bound on our observed fractionations.
mass transport and electrode processes likely compete to govern the To examine trends of fractionation in the non mass-transport-
overall kinetics. Fig. 4 shows that the fractionation—although limited regime, we plot isotope fractionation as a function of plating
scattered—shows different trends within each regime. In the next rate only for the data where the plating current is less than 50% of the
paragraphs, we consider each regime separately. Cottrell limiting current (Fig. 5). Given the order-of-magnitude level
of uncertainty in our estimated plating rate, with this data set we
cannot deconvolve possible effects of fractionation as a function of
time, voltage, current, or charge passed. However, the data suggest
that for the dilute starting solutions, fractionation is approximately
constant with plating rate, with values from − 1.5‰ to − 2.75‰.
Isotope fractionations from the more concentrated solutions are
significantly more varied, with the trend showing that the extent of
fractionation general increases as a function of plating rate. This result
is in agreement with the original study of Kavner et al. (2005). Indeed,
all of the data in that study were performed under conditions of low
current with respect to the Cottrell current (Table 1). The results in
Figs. 4 and 5 suggest that mass-transport limited kinetics is damping
down an isotope signature that would be much larger, in the extreme
of fast diffusion to an electrode. Although the data are consistent with
the hypothesis proposed in Kavner et al. (2005) and Kavner et al.
(2008) that rate-dependent isotope fractionation is expected in elec-
tron transfer conditions, this current data set is not able to explicitly
test this hypothesis.
Also plotted in Fig. 5 are the predicted equilibrium isotope
exchanges between different species in solution (e.g. Schauble et al.,
Fig. 3. Estimated deposition rate as a function of applied overpotential in the elec- 2001), which range from + 0.9 for equilibrium partitioning between
troplating experiments. Fe+2[H2O]6 and Femetal, to − 1.3 for Fe+2[Cl− 1]4–Femetal to − 2.2 for
A. Kavner et al. / Chemical Geology 267 (2009) 131–138 137
Fig. 4. Plot of fractionation as a function of the ratio of the estimated iron electroplating current to the average diffusion-limiting current. The vertical dashed line separates mass-
transport limited regime (to the right of the plot) and the electron transfer limited regime (to the left). Thin horizontal dashed gray line shows the measured isotope fractionation
factor due to diffusion measured by Rodushkin et al. (2004).
Fig. 5. Plot of iron isotope fractionation with respect to plating solution versus the plating rate in mol/m2/s for data where the plating current was less than half of the Cottrell current.
Black squares are from the 2 M stock solution and open circles are from the 0.25 M stock solution. 2σ error bars often fall within marker size. Thick horizontal dashed lines show
calculated equilibrium fractionation factors between iron species in solution and the metal phase [Schauble et al., 2001].
138 A. Kavner et al. / Chemical Geology 267 (2009) 131–138
varied, and often significantly larger. These observations strongly from the Transvaal Craton. Contributions to Mineralogy and Petrology 144 (5),
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Kavner, A., Bonet, F., Shahar, A., Simon, J., Young, E., 2005. The isotopic effects of electron
transfer: an explanation for Fe isotope fractionation in nature. Geochimica Et
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and Pam Hill. AK and AS acknowledge support from the NASA Kavner, A., John, S.G., Sass, S., Boyle, E.A., 2008. Redox-driven stable isotope
fractionation in transition metals: application to Zn electroplating. Geochimica Et
Exobiology under grant number NNG05GQ92G.
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Mandernack, K.W., Bazylinski, D.A., Shanks, W.C., Bullen, T.D., 1999. Oxygen and iron
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