Diffusion Coefficients of Ferri- and Ferrocyanide
Ions in Aqueous Media,
Using Twin-Electrode Thin-Layer Electrochemistry
S. J. Konopka and Bruce McDuffie
Department of Chemistry, State University of New York at Binghamton, Binghamton, N. Y. 13901
The diffusion coefficients, D0 and Dr, of the species
ferri- and ferrocyanide, respectively, in aqueous KCI
media were determined by twin-electrode thin-layer
electrochemistry using a micrometer-type thin-layer
cell. The values obtained for D0 and DR at 25° C in
LOOM KCI were 0.726 (±0.011) X IQ-5 and 0.667(±0.014) X
10-5 cmVsec, respectively, covering a concentration
range from 0.61 to 6.36mM in total electroactive species.
Identical values within experimental uncertainty were
found in 0.10M KCI medium. Criteria for the reliability
of this absolute method for measuring the D values of
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a soluble, stable redox pair are presented, and com-
parisons of D values with those obtained by other
workers are made.
Various methods have been devised for determining the
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diffusion coefficients (D values) of species in solution, such as
the use of the calibrated diaphragm cell (1-3), radiochemical
tracers (4, 5), electrical conductance (6), and optical methods
(7). For electroactive species in an excess of supporting
electrolyte, electrochemical methods often have been used.
Such methods, for the most part relative methods requiring
calibration with a substance of known D value, have in-
cluded Cottrell-type (8-13), chronopotentiometric (12,14,15),
and rotating disk (16) measurements at platinum electrodes,
and polarographic measurements at the dropping mercury
electrode (11, 17). Results by these electrochemical methods
may differ from one another by 10-20% (13, 77). Macero
and Rulfs (13) have attributed these differences largely to
uncertainties in the effective electrode area and to the necessity
for using a suitable reference ion.
Thin-layer steady-state methods are characterized by mathe-
matical simplicity and relative freedom from time-dependent
(1) J. H. Northrup and M. L. Anson, J. Physiol. Chem., 10, 523
(1929).
(2) R. H. Stokes, J. Amer. Chem. Soc., 72, 763 (1950).
(3) C. L. Rulfs, ibid., 76, 2071 (1954).
(4) J. H. Wang and F. M. Polestra, ibid., p 1584.
(5) T. A., Miller, B. Prater, J. K. Lee, and R. N. Adams, ibid., 87,
121 (1965).
(6) H. S. Harned and R. L. Nuttall, ibid., 69, 736 (1947).
(7) G. Kegeler and L. J. Cosling, ibid., p 2916.
(8) . A. Laitinen and I. M. Kolthoff, ibid., 61, 3344 (1939).
(9) . A. Laitinen and I. M. Kolthoff, /. Phys. Chem., 45, 1061
(1941).
(10) I. M. Kolthoff and J. J. Lingane, “Polarography,” 2nd ed.,
Interscience, New York, N. Y., 1952, pp 409-411.
(11) M. von Stackelberg, M. Pilgram, and V. Toome, Z. Elektro-
chem., 57, 342 (1953).
(12) P. J. Lingane, Anal. Chem., 36, 1723 (1964).
(13) D. J. Macero and C. L. Rulfs, J. Amer. Chem. Soc., 81, 2942
(1959).
(14) C. N. Reilley, G. W. Everett, and R. H. Johns, Anal. Chem.,
27,483 (1955).
(15) D. M. Oglesby, S. V. Omang, and C. N. Reilley, ibid., 37,1312
(1965).
(16) A. J. Arvia, J. C. Bazan, and J. S. W. Carrozza, Electrochim.
Acta, 13, 81 (1968).
(17) L. Meites, “Polarographic Techniques,” 2nd ed., Interscience,
New York, N.Y., 1965, pp 145-150.
ANALYTICAL CHEMISTRY, VOL. 42, NO. 14, DECEMBER 1970
experimental problems (18-21). The twin-electrode thin-
layer method proposed by Anderson and Reilley (19) for
measuring the D values of a redox couple is an absolute
method based on measurement of the limiting steady-state
current, iss, followed by coulometric analysis of the thin
layer. The iss between closely spaced twin working elec-
trodes is given by the equation:
~nFAC~ 2DqDr
l _Dq + Dr_
where n is the number of electrons transferred in the redox
reaction, F is the value of the Faraday, A is the projected
electrode area, C is the total concentration of electroactive
species in the thin layer, / is the thickness of solution between
the two working electrodes, and D0 and DI{ are the diffusion
coefficients of the oxidized and reduced species, respectively
(19, 22).
D values are calculated according to the following equations
(19):
iss(c)l2
Do (2)
IqT
iss{a)l2
Dr (3)
where /33(C) and iSS(a) are the limiting steady-state currents at
the cathode and anode, respectively, Qc is the charge
required to reduce all of the oxidized species between the thin-
layer electrodes once the condition of /33 has been reached, and
Qa is the charge required to oxidize all of the reduced species
in the thin layer at the iss condition. The values of iSS(c) and
iSS(a) will be equal if there is negligible electrolysis current along
with the steady-state current. From Equations 2 and 3, it is
evident that the D values can be determined independently
of n, A, and C.
From Equation 1 and Faraday’s law for the coulometry of
thin layers of solution (23, 24), straight lines should be ob-
tained if the experimental values of l/z'3S(c), 1 /iss(a), Qc and Qa
are each plotted against the /-setting of the micrometer, giving
the respective slopes, Si/i33<C), Si/usia), $q„ and SQa. Using
(18) R. C. Bowers and A. M. Wilson, J. Amer. Chem. Soc., 80, 2968
(1958).
(19) L. B. Anderson and C. N. Reilley, J. Electroanal. Chem., 10,
295(1965).
(20) H. Dahms, ibid., 11, 62 (1966).
(21) A. T. Hubbard and F. C. Anson, in “Electroanalytical Chem-
istry,” A. J. Bard, Ed., Vol. 4, Marcel Dekker, New York, N.Y.,
1970, pp 129-210.
(22) B. McDuffie, L. B. Anderson, and C. N. Reilley, Anal.
Chem., 38, 883 (1966).
(23) C. R. Christensen and F. C. Anson, ibid., 35, 205 (1963).
(24) L. B, Anderson, B. McDuffie, and C. N. Reilley, J. Electro-
anal. Chem., 12, All (1966).
· 1741
these slopes instead of absolute values, Equations 2 and
become:
Do = ---
(4)
2($ui„J(SJ
1
Dr -
(5)
2(Sm„J(SQa)
Thus the D values are determined independently of a knowl-
edge of the absolute layer thickness, although accurate
measurement of increments in / are required for accurate
determination of the various slopes.
In the present study, the thin-layer method is critically
evaluated using the ferri-ferrocyanide couple in aqueous
KC1 as a model redox system. Several modifications in
technique and procedure are introduced to develop the in-
herent potential of the method.
EXPERIMENTAL
A micrometer-type thin-layer electrochemical cell with twin
working electrodes, each of measured projected area 0.278
cm2, was used (15, 19). Before each set of measurements
with a fresh portion of solution, the platinum surfaces were
polished to a mirror-like consistency using gamma alumina
on a Gamal polishing cloth (Fisher Scientific Co., No. 12-282).
The Teflon (Du Pont) collar and cup were flush with the elec-
trode surfaces to minimize edge effects while still allowing the
attainment of /-values as small as 30 microns.
A microscope with a filar micrometer eyepiece (Gaertner
No. mllO-A), was positioned horizontally about 6 inches
from the micrometer scale of the cell and used to ensure
reproducibility of micrometer settings within ±0.05 micron
(µ). In each experiment, layer thicknesses were changed by
increments equivalent to the smallest division of the microm-
eter scale, i.e., 25.4 ± 0.1 µ, the accuracy of these increments
being limited more by the tolerance in placement of scale
lines on the micrometer barrel than by the reproducibility
of setting the micrometer at a given line.
Philbrick operational amplifiers were used (15, 19) to
achieve potential control of the two working electrodes, and
to measure and integrate current. All potentials were mea-
sured vs. an SCE reference electrode which was in contact
with the cell solution via a fiber-tip salt bridge containing
the supporting electrolyte. The auxiliary electrode was a
platinum wire ring. A dual pen recorder, Sargent model
DSRG, was used to record current and coulometric data.
Limiting potentials were obtained by the method of thin-
layer steady-state voltammetry (TLSSV) as follows: The
electrode for measurement of steady-state current was fixed
at an extreme anodic or cathodic potential, and the other
working electrode was scanned slowly (100 mV/min) from a
potential of zero steady-state current to a potential giving the
limiting steady-state current, iss, i.e., to a limiting cathodic
or anodic potential, respectively. A sensitive x-y recorder
was used to record steady-state current vs. E curves.
Reagent grade KC1 and distilled demineralized water were
used to prepare a large quantity of LOOM stock supporting
electrolyte solution, which was diluted to O.lOOMas necessary.
Weighed amounts of reagent grade KsFe(CN)e or K4Fe(CN)e·
3H20 were added to dry flasks and diluted to volume with
supporting electrolyte to obtain the desired concentration of
electroactive species. Solutions containing electroactive
species were used the same day as prepared. All solutions
were deaerated with presaturated nitrogen prior to use and
kept under a blanket of nitrogen during experiments (15).
Experiments were conducted at 25.0 ± 0.1 °C in a constant
temperature room, the temperature of the air and solutions
being monitored with a calibrated thermistor probe.
Resistance Method for Calibration of Micrometer. The
micrometer cell was calibrated for linearity and for /-zero
(i.e., the setting corresponding to zero solution thickness
1742 e ANALYTICAL CHEMISTRY, VOL. 42, NO. 14, DECEMBER 1970
3 between the electrodes) by measuring the resistance, R, of a
10~4M NaClG4 solution at various micrometer settings as
follows: a 5 kHz alternating current signal of 5 V rms
amplitude was passed to ground through a bridge circuit con-
taining in one arm, a 100-K resistor followed by a variable
resistor and variable capacitor in series, and in the other arm,
a 100-K resistor, and the twin electrode cell. The bridge
was balanced to within ±0.5 mV using a Tektronix Model
502-A oscilloscope with differential input channels as a null
detector. With this, arrangement, R values from 800 to
2400 ohms were measured with a precision of ±0.5%.
Assuming a direct proportionality between R and /, the least
squares best straight line corresponding to the R data at the
various settings was determined by a computer program.
The relative standard deviation of the slope constituted the
check for linearity of the micrometer scale, and the zero-
resistance intercept gave the setting corresponding to /-
zero, with its standard deviation. (See Figure 2 and dis-
cussion below.)
Determination of Electrode Configuration. Cottrell-type
chronoamperometric experiments were performed to estab-
lish the optimum electrode configuration, in view of solution
density considerations (8). With a deaerated ferricyanide-
KC1 solution in the cell, the top electrode was set at the limit-
ing anodic potential and adjusted so the solution layer thick-
ness was 0.2 inch. After the background current became
constant, the top electrode was stepped to the limiting re-
duction potential and its i-t curve recorded, the other twin
electrode being at ambient potential. The layer was flushed
out, by raising and lowering the upper electrode several times,
and the same procedure was followed at the bottom elec-
trode. Then a ferrocyanide solution was put in the cell and
analogous i-t curves for oxidation were recorded at the two
electrodes, with the same solution thickness. The results
(see Figure 1 ,a and b) are interpreted below.
Procedure for D Value Determinations. i„w and Qa were
measured first, as follows: the micrometer was carefully
adjusted to obtain the thickest desired layer, i.e., an /-value
in the range 80-100 µ. The upper electrode was set at the
limiting anodic potential to pre-oxidize the solution layer,
the other thin-layer electrode being at ambient potential.
After 15 seconds, the bottom electrode (for the ferri-ferro-
cyanide system) was adjusted to the limiting cathodic poten-
tial, which initiated the limiting steady-state current, measured
at the anode as iSS{a). The current was allowed to flow for 1
minute, enabling its constancy to be observed. The cathode
was then disconnected and simultaneously integration of the
electrolysis current at the anode was begun. The Qa curve
was recorded for 90 seconds, after which the cell was returned
to ambient potential. The solution between the electrodes
was flushed out by raising and lowering the upper electrode,
the micrometer was set to a layer precisely 0.001 inch thinner
than the first, and /„(«) and Qa were measured again. The
process was repeated at successively thinner / settings. This
first set of measurements at the various / values was dis-
carded as a preconditioning set, then at least four sets after the
first were run, at each of at least three l values. Immediately
after the i„w and Qa data were obtained, iSS(c) and Qc were
measured in an exactly analogous fashion by monitoring at
the cathode and disconnecting the anode for coulometry.
An identical sequence of /-values was used.
The procedure described above constitutes one experiment
or run. To allow for edge effects, the value of Q for each
Q-t curve was obtained by linear extrapolation of the coulo-
metric curve to zero time using the tangent to the curve in the
60-75 second region. All data were corrected for background
effects. The slopes of the 1 /iss-l and Q-l lines were deter-
mined by a least squares computer program, which also gave
the / intercepts and the relative standard deviations of the
slopes and intercepts. Then D0 and DR with their cumula-
tive standard deviations were calculated from Equations 4
and 5.
 Figure 1. Effect of electrode configuration
a. Reduction of 3.6 mM ferricyanide, at potential of —0.05
V vs. SCE
Curves A and B show response of top and bottom electrodes, respectively; layer thickness approximately 0.2 inch.
theoretical curve for diffusion to an unshielded circular, planar electrode (26), of area 0.278 cm2, at stated concentrations
RESULTS AND DISCUSSION
Using aImM ferricyanide solution in 1M KC1, the TLSSV
curve wasNernstian for a 1-electron transfer reaction, scan-
ning in either the anodic or cathodic direction, with a half-
current potential, Eim)S), of +0.23 V, in agreement with the
formal standard potential of this system (25). From the
TLSSV curves, +0.50 and —0.05 V vs. the SCE were limiting
anodic and cathodic potentials, respectively. The same
values were found in a 0.10M KC1 medium.
Laitinen and Kolthoff (8) pointed out that in electrolysis at
horizontal shielded planar electrodes, if the direction of diffu-
sion was such that the less dense material (i.e., ferricyanide)
formed above the material of greater density (i.e., ferrocy-
anide), agreement with theory for linear diffusion was ob-
tained. If the direction of diffusion was reversed, producing
an inverse density gradient, large and irregular currents were
obtained. Analogously, the experiment on determination of
optimum electrode configuration was run using the unshielded
electrodes of the thin-layer cell. For the reduction of ferri-
cyanide (Figure la), the smaller current (curve B) is obtained
at the bottom electrode, while for oxidation of ferrocyanide
(Figure 16), after about one minute, the smaller current
(curve A) is observed at the top electrode, in general agree-
ment with Laitinen and Kolthoff’s work. However, these
smaller currents are higher than the theoretical values (curve
C) for diffusion to an unshielded planar circular electrode at
short times (26), presumably because of some convective
(25) Ref. 10, p 480.
(26) Z. G. Soos and P. S. Lingane, J. Phys. Chem., 68, 3821 (1964).
ANALYTICAL CHEMISTRY, VOL. 42, NO. 14, DECEMBER 1970
on currents in chronoamperometric experiments
b. Oxidation of 4 mM ferrocyanide, at potential of +0.50
V vs. SCE
Curve C is a
stirring (8, 12). In the cases of electrode configurations giv-
ing rise to inverse density gradients (curve A, Figure la;
curve B, Figure 16) the larger currents are observed, with
a reproducible fluctuation in the ferrocyanide case such as the
irregularities noted previously (8). The optimum electrode
configuration is defined as that giving minimum current in the
chronoamperometric experiments (in the present case, top
electrode anode, bottom electrode cathode). Furthermore,
it is assumed that convective stirring will be even less when
the electrodes are very close together in the thin-layer experi-
ments. To test this assumption, z'8S for the optimum electrode
configuration was compared with the z'88 for the inverse con-
figuration: values only about 2% higher were found in the
latter case; the sum of the coulometric slopes was unchanged,
in accord with the concept of mass balance, but the slope ratio
was changed significantly, giving rise to different D values.
The closeness of the z88 values confirms the recent work of
Schmidt-Weinmar that convection is minimized in solution
layers less than 200 µ thick (27).
Table I presents a comparison of /-zero values from the
linear extrapolation of 1 /z'88<C) and 1 /iSs(a) data, illustrated in
Figure 2. The agreement of /-zeroes with each other and with
the /-zero from resistance measurements (Figure 2) indicates
the reproducibility of handling the cell, since it is taken apart
after each experiment in order to repolish the electrodes. It
has been observed that if nonlimiting potentials are used (e.g.,
the usual limiting potentials, but with electron transfer slowed
(27) H. G. Schmidt-Weinmar, Ber. Bunsenges. Phys. Chem., 71, 97
(1967).
· 1743
 0.0100 2500
Table I. Reproducibility of /-Zero Measurements
Data No. of
plot Medium expts" /-zero6
av ± std dev
l//»s(o) 1MKC1 10 0.136817 ± 0.000018
0.1MKC1 3 0.136798 ± 0.000003
l//ss(c) 1MKC1 10 0.136822 ± 0.000015
0.1MKC1 3 0.136822 ± 0.000032
“
For concentrations of ferri- and ferrocyanide, see
Table II.
6
Micrometer setting in inches corresponding to solution layer of
zero thickness.

Table II. Dependence of Steady-State Current

on Concentration
C, mM" Sl/Mo) Kh
1.00M KC1 Medium
0.30 17.89 5.37
0.61= 8.69 5.38
1.10 4.89 5.36
1.10 4.98 5.48
1.36 3.93 5.32
1.55 3.40 5.26
5.02= 1.06 5.33
5.09 1.05 5.32
5.23d 1.04 5.45
6.36 0.85 5.43
Figure 2. Comparison of methods for calibration of av 5.37
twin-electrode thin-layer cell std dev 0.07 (1.2%)
1/iOs) vs. I data; 5.23 mM ferrocyanide in l.OOM KC1. R 0.10M KC1 Medium
vs. I data: 10-4M Na004 solution 0.91 6.00 5.46
5.01d 1.06 5.32
5.09 1.07 5.45
by contamination of the electrode surfaces) the currents will av 5.41
be less than theoretical, and the /-intercept from the 1 //„ std dev 0.08
vs. I plots will be at a much smaller micrometer setting than “
100 % ferricyanide except as otherwise noted.
the /-zero obtained from the resistance measurements. Slight 6
K [Sin„(»)] [C], See text.
=

contamination will produce a shift in the /-intercept several =

orders of magnitude greater than the standard deviation for
the measurement. This effect can be tested easily by measur-
ing the steady-state current at various /-settings without clean-
ing the electrodes, then cleaning the electrodes and repeating
the measurements on another portion of the same solution.
The currents in the first case will be much lower than those in
the second case, resulting in widely varying /-zeroes.
According to Equation 1, /„ is proportional to C. Al-
ternatively using Sinss, one obtains:
1 lated from Equations 4 and 5, is based on the slopes of two
DSi/UtC]
nFA Du
where the right hand term, hereafter designated K, is a cali-
bration constant for a given redox system and twin-electrode
cell, Du being defined as a weighted diffusion coefficient
equal to 2D0D¡¡/(D0 + Dr). Table II lists the values of K
obtained for a range of concentrations in the two KC1 media.
The results indicate that the current is a true steady-state
current in agreement with Equations 1 and 6. Since K is
the same within experimental error in 1.00 as well as 0.1 OM
KC1, the value of Dw is the same for the ferri-ferrocyanide
system in both media.
From mass balance considerations, the coulometric data
should follow the relationship
nFA
[SQa + SgJ/C =
.
Thus, to establish the reliability of the coulometric measure-
ments, the quantity nFA was calculated from Equation 7
for each experiment. The average values so obtained, 2.71
Equimolar ferri-ferrocyanide mixture.
d
Ferrocyanide solution.
(±0.05) X 104 and 2.70 (±0.04) X 104 coulomb cm2 mole-1
for 1.00 and 0.10M KC1, respectively, were within 1 % of the
value calculated from the measured electrode area.
The individual diffusion coefficients found for the ferri-
and ferrocyanide species, with respective relative standard
deviations, are presented in Table III. Each D value, calcu-
(6) least squares data plots. The standard deviation, sd, of
each D value is the square root of the sum of the squares of
the relative standard deviations of the two slopes used. In
1M KC1 the value of sd0 ranged from 0.5 to 2.0% and sdr
from 0.9 to 3.2%, the averages being 1.4 and 1.6%, respec-
tively. The agreement of these individual sd values with the
standard deviations of the groups of D values, 1.5% and 2.1%,
respectively, indicates that there is no significant variance
between experiments. Similar comparisons of standard
deviations can be made using the 0.1M KC1 data. (The last
two results in 1MKC1 were obtained approximately 6 months
after the other results, indicating the stability and reproduci-
bility of the cell and the method over a period of time.)
From Table III it is evident that the diffusion coefficients are
independent of the total concentration of electroactive species,
(7) within the range of concentrations used, in accord with Pick’s
first law. Furthermore, the D values are independent of the
initial concentration ratio of oxidized to reduced species.
With this redox system, both D0 and Dr could be obtained

1744 · ANALYTICAL CHEMISTRY, VOL. 42, NO. 14, DECEMBER 1970

 Table III. Diffusion Coefficients of Ferri- and Table IV. Comparison with Selected Literature Values for
Ferrocyanide at 25 °C Ferri- and Ferrocyanide at 25 °C
Concn'1 Do X 10s Du X 10= Do X 10= Dr X 10=
mM :m2 sec-1
i ¡¡DO, % cm2 sec-1 SDR, % Method Medium cm2 sec-1 cm2 sec-1 Ref
1.00M KC1 medium Cottrell, absolute: 0.1MKC1 0.842 0.717 8
0.61= 0.731 2.0
0.1MKC1 0.836 0.687 13
1.9 0.671 1.9 0.1MKC1 0.763 0.650 11
1.10 0.731
0.718 1.4 0.697 2.1
0.1MKC1 0.670 12
1.10
1.36 0.719 1.7 0.673 3.2 Chronopotentio-
1.55 0.737 1.7 0.656 2.6 metric 0.1MKC1 0.697 12
0.718 0.7 0.667 0.9 Pt, relative to Pb 0.1MKC1 0.713 0.638 10
5.02=
0.705 1.6 0.666 1.0 Rot. Pt disk 1.0MKC1 0.677 0.588 16
5.09
5.23= 0.721 0.8 0.668 1.2 Thin layer 1.0MKC1 0.726 0.667 This work
6.36 0.741 1.9 0.641 1.1 Thin layer 0.1MKC1 0.72 0.67 This work
4.47= 0.730 0.5 0.668 1.0
5.00 0.738 0.9 0.664 1.2 difference between KC1 and KNCL as supporting electrolytes.
av 0.726 av 1.4 av 0.667 av 1.6 A comparison of results with those obtained by other meth-
std devd 0.011 (1.5%) std dev 0.014(2.1%) ods is given in Table IV. The first set of results (8) may be
0.10M KC1 medium high because of electromigration effects in the Cottrell ex-
0.91 0.739 1.7 0.681 2.1 periment, since a 5mM electroactive species concentration
5.01 =
0.717 0.7 0.656 1.6 was used with only a 0.1M supporting electrolyte concentra-
5.09 0.703 1.2 0.660 1.3 tion. [In our method, although these same concentrations
av 0.720 av 1.2 av 0.666 av 1.7 were used in two experiments, no appreciable electromigration
std devd 0.018 (2.5%) std dev 0.013(2.0%) effect was observed.] The high value of Do in the next set
“
100% ferricyanide except as otherwise noted. (13) may be traced to the neglect of solution density effects;
b
Equimolar ferri-ferrocyanide mixture.
=
Ferrocyanide solution. ferricyanide was reduced at an electrode where the direction
d
Standard deviation of the group of measurements, not standard of diffusion was upward, forming the heavier ferrocyanide
deviation of the mean. and thus increased current due to convection. The remaining
results show reasonable agreement except for the D values
obtained using a rotating platinum disk electrode (16),
at a total concentration of electroactive species of lmM or where nonlimiting potentials may have been used.
greater. At lower concentrations, the iss values were still Effect of Nonparallelism of Electrodes. Although the work-
reliable, but Q determinations became erratic. Electrode ing electrode faces are considered to be parallel to each other,
interferences may be responsible for erratic coulometric
nonparallelism could introduce errors in the steady-state
results at low concentrations. current. .This problem was treated by Anderson and Reilley
The D values obtained in 1M KC1 give Stoke’s law radii for square facing electrodes (19). For circular electrodes,
(IT) of 3.38 A and 3.68 Á for the diffusing ferri- and ferro- graphical integration yields the following results (same nota-
cyanide species, respectively. Both ions tend to ion pair with tion as in reference 19): 1 //8, will be 6.4% less than for per-
K+ (28, 29), and ferrocyanide appears to form an ion triplet
fectly parallel surfaces if / 2q, 2.7% less if /
=
3q, and 1.5%
=

to some extent (29). A small part of the observed difference less if l =

in Stoke’s law radii could be attributed to ion triplet formation
in the ferrocyanide case, but a larger part of the difference must
have some other explanation, such as a greater extent of hydra-
tion of the ferrocyanide species over that of the ferricyanide.
The calibration constant, K, can be used with n, F, and the
measured value of A to calculate the quantity, Dw. Since Dw
is defined as 2D0DrI(D0 + Dr), it can be calculated from the
experimentally determined values of D0 and DR which have
no dependence on C, A, or n. From the average values for
the 1.00M KC1 medium (Table II), Dw = 0.694 X 10"5
cm2 sec-1, whereas from the average D values (Table III),
Dw = 0.695 X 10-6 cm2 sec-1. In 0.10M KC1 the corre-
sponding values are 0.689 and 0.692 X 10-5 cm2 sec-1, re-
spectively. This agreement demonstrates that the twin-
electrode thin-layer method is an absolute method: i.e„
D values can be obtained for a soluble, stable redox pair with-
out a knowledge of n, A, and C and without the use of a
reference ion.
In one exploratory experiment, from steady-state current
data, a Dv; value of 0.709 X 10-5 cm2 sec-1 was obtained in
O.IMKNOj, [This datum was obtained five years earlier in
another laboratory using a 2mM ferri-ferrocyanide mixture
in the same type of thin layer cell] This result indicates little
(28) J. C. James and C. B. Monk, Trans. Faraday Soc., 46, 1041
(1950).
(29) S. R. Cohen and R. A. Plane, J. Phys. Chem., 61, 1096 (1957).
4q. [Corresponding decreases for the square
electrode case (19) are 9%, 3.8%, and 2.1%, respectively.
From the micrometer setting at which the cell “shorted" in
the present work, it appears that the thinnest layer used for
data collection was at / > 2q, thicker settings corresponding
roughly to / > 3>q and / > 4q. Thus nonparallelism could
have caused the slopes of the 1 ¡iss vs. /lines to be high, and the
D values low, by a maximum of 3 %, only slightly larger than
the standard deviation of the experimental results. For
increased accuracy, the degree of nonparallelism or tilt could
be reduced by a more careful polishing and assembling tech-
nique.
Coulometry with Elimination of Charging Current. For
thin-layer potential-step coulometry in a cell with only one
working electrode, Faraday’s law takes the form (24)
Q =
tlFAlC + Qads + Qd.l.
where Qaae and Qa.i. represent the contributions caused by
reaction of adsorbed species and by change in double layer
capacitance, respectively. A plot of Q vs. I gives an intercept
at /-zero equal to Qais + Qd.i., neither of which is usually
known. [The slope, Sq, equal to nFAC, provides the basis
for determining C.]
By contrast, in the coulometric method used here for D
value determinations, there should be no significant contribu-
tion from charging current. The electrode used for coulom-
etry after initiation of the steady-state current remains at

ANALYTICAL CHEMISTRY, VOL. 42, NO. 14, DECEMBER 1970 · 1745

 constant potential and has immediately adjacent to it in the
solution nearly the same concentration of electroactive species
(as 100% O or 100% R) before and after coulometry. Thus
one would expect no appreciable change in the double layer
capacitance of this working electrode. From a Q-l plot,
the number of coulombs at /-zero (obtained from /S5 or R data)
can be expected to give Qaas directly without any Qua. term:
the intercept from the Qa-l data should give the amount of
species R previously adsorbed at the cathode, and the Qc-l
intercept should give the amount of species O previously
adsorbed at the anode, assuming that the time required for
desorption of these species is short compared to the duration
of the individual Q-t curves. At the higher concentrations
used in the present studies, the amounts of adsorption of
Method and Apparatus for Determining
Helium Content of Gas Mixtures
David E. Emerson and Richard L. Kaplan1
Division of Helium, Bureau of Mines, V. S. Department of the Interior, Amarillo,
A method and apparatus are described for determining
the helium content of gaseous mixtures. The work was
done so that the Bureau of Mines could more accurately
and economically analyze helium-containing natural
gases, crude helium purchased from private indus-
tries, and helium in gases used in research. Activated
coconut charcoal Is utilized at liquid nitrogen tempera-
ture to adsorb components other than helium in the
mixture. A transducer is then used to determine the
helium pressure. Twenty or more analyses with a
standard deviation of ±0.04% can be made in an 8-hour
day.
Activated coconut charcoal at liquid nitrogen temperature
(77 °K) is used to adsorb all gases except helium and neon,
and the neon concentration is usually negligible. This ad-
sorptive property of activated charcoal was discovered by
Dewar (1) in 1875. Cady and McFarland (2) utilized acti-
vated coconut charcoal at liquid air temperatures to determine
the helium content of natural gas. The Bureau of Mines
adopted this method with minor modifications as reported
by Anderson (3). Frost in 1946 (4) also utilized activated
charcoal to analyze concentrations of helium below 10%.
Frost, Kirkland, and Emerson (J) described an apparatus
and procedure for determining the helium content of gases
containing 10% or more helium. However, these methods
require corrections for volumes, pressures, and temperatures,
and the apparatus must be calibrated with weighed primary
standard mixtures (6) to obtain accurate results.
The Bureau of Mines purchases crude helium from private
industry and must accurately determine the helium content to
1
Present address, Health and Safety, Bureau of Mines, U. S.
Department of the Interior, Denver, Colo. 80225
(1) J. Dewar, Nature (London), 12, 217-218 (1875).
(2) Hamilton P. Cady and David F. McFarland, J. Amer. Chem.
Soc., 29, 1523-1536(1907).
(3) C. C. Anderson, U. S. Bur. Mines, Inform. Cir., 6796 (1934).
(4) E. M. Frost, Jr., U. S. Bur. Mines Rep. Invest., 3899 (1946).
(5) E. M. Frost, C. G. Kirkland, and D. E. Emerson, ibid., 6545
(1964).
(6) J. E. Miller, A. J. Carroll, and D. E. Emerson, ibid., 6674(1965).
1746 · ANALYTICAL CHEMISTRY, VOL. 42, NO. 14, DECEMBER 1970
electroactive species at the anode and at the cathode appear
to be 2.0 X 10-9 and 2.6 X 10-9, respectively. These
results would indicate several monolayers of electroactive
material. Obviously further studies of this aspect of the
system are needed.
Received for review June 1, 1970. Accepted September 17,
1970. Presented in part at the Pittsburgh Conference on
Analytical Chemistry and Applied Spectroscopy, Cleveland,
Ohio, March 5, 1970. The authors acknowledge financial
support of the National Science Foundation under Grant
NSF-G9925 and the Research Foundation, State University of
New York, under Grants 40-223A, FRF-40-035, and 40-223B.
Texas 79106
assure proper payment. Approximately 2000 samples per
for the Helium Conservation Program must be analyzed.
year
Because the previous method (5) was time consuming and
required frequent calibrations, the present apparatus was
developed.
This paper describes the new apparatus and procedure for
determining the helium content of gaseous mixtures. This
method simplifies the calculations by eliminating the necessity
of correcting volume, temperature, and pressure. The pres-
sure of helium in the unknown sample is compared with the
pressure of high-purity helium at the same conditions. This
results in a primary standard method of determining the
helium content of samples that contain from 0.1 to 100% he-
lium.
APPARATUS
The gas flow and the essential elements of the analyzer are
shown schematically in Figure 1. Vacuum valve A is a pneu-
matic on-off valve. Sample inject valve B is an 8-port pneu-
matic valve and is shown in the sample flush and sample in-
ject positions in Figure 1. Valves C-F are 3-port pneumatic
valves, and the air-control valves G-K are 3-port solenoid valves.
Metering valves L-N control the gas flow to flowmeters
4 and 7. The pressure is measured by a 0-1 pound-pér-
square-inch-differential transducer, 1, with its electrical span
set to give 0 to 1.5 volts for the pressure of helium in the sam-
ple. The voltage is then converted by a voltage-to-frequency
converter and counter. The resulting reading for a 100%
helium sample is approximately 150,000 counts on the digital
readout, 3, for about 0.2 psid. Flowmeters 4 and 7 are dif-
ferential pressure gauges that have been calibrated by using a
predetermined length of Vie-inch capillary tubing to obtain
the pressure range required (7). Charcoal trap, 8, contains
3 grams of 50-60 mesh activated coconut charcoal. The in-
let line to the charcoal is as short as possible (6 inches) to
minimize the volume of Na pusher gas that must be extracted
by cryogenic pumping and diffusion. Volume tank, 10 (500
(7) G. W. Munns, Jr., and V. J. Frilette, J. Gas Chromatogr., 3,
145-146 (1965).