THE OXIDATION POTENTI AL OF THE SYSTEM POTASSIUM

VARIOUS I ONI C STRENGTHS

I. M. KOLTHOFF AND WILLIAM J . TOMSICEK
School of Chemistry, University of Minnesota, Minneapolis, Minnesota
Received January 85, 1936
FERROCYANIDE-POTASSIUM FER~I CY ANI DE AT
The oxidation potential of the ferrocyanide-ferricyanide system has
been determined by a number of investigators (1, 3, 8, 9, 10, 11, 12, 13).
After the introduction of the Debye-Huckel theory of strong electrolytes,
this system becomes of special interest, since we are dealing here with
highly unsymmetrical salts of high valence type. If potassium ferro-
cyanide and potassium ferricyanide behave like strong electrolytes, the
oxidation potential should be greatly affected by a change of the ionic
strength of the solution. In the first place, the purpose of this study was
to determine the potential of the potassium ferrocyanide-potassium
ferricyanide system at varying ionic strengths and to extrapolate the value
to an ionic strength of aero; in other words, to determine the normal po-
tential of the system. I n addition, the potential of a very dilute ferro-
ferricyanide solution was determined in the presence of different neutral
salts at varying ionic strengths, in order to test the applicability of the
Debye-Huckel equations.
At extremely small ionic strengths, the relation between the activity
coefficient of an ion and the ionic strength of the solution is given by the
expression : .
-log f = 0. 5~~ di
(1)
at 25C. in water, in which z is the valence of the ion, and 1.1 the ionic
strength. The oxidation potential E of the system ferrocyanide-ferri-
cyanide at 25C. then is given by:
CFeT;- fa
= 0 + 0.0591 log - * -
CFeOC- f 4
(2)
1 From the experimental part of a thesis submitted by William J . Tomsicek to
the Graduate School of the University of Minnesota in partial fulfillment of the
requirements for the degree of Doctor of Philosophy, 1934.
945
946 I. XI. KOLTHOFF AND WILLIAM J. TOMSICEK
The normal potential eo denotes the potential referred to the normal
hydrogen electrode in a system in which the activity of the ferricy-
anide aF&;- is equal to that of ferrocyanide aFi;--. CF;;- and CF~;;--
represent the corresponding concentrations, whereas fs and f 4 represent
the activity coefficients of the ferricyanide and the ferrocyanide ions.
If the limiting Debye-Hudkel expression (equation 1) holds at extremely
small ionic strengths and the system contains equimolecular amounts
of potassium ferricyanide and potassium ferrocyanide, it is found from
equations 1 and 2 that:
54
Therefore if the limiting Debye-Huckel expression holds, the measured
potential E should change by 0.2068 volt for one unit change in the square
root of the ionic strength.
The practical work in this study involves the use of a cell with liquid
junction, the ferro-ferricyanide half-cell being measured against the
quinhydrone electrode in a mixture containing 0.01 of an equivalent of
hydrochloric acid and 0.09 of an equivalent of potassium chloride per liter,
the saturated potassium chloride-agar salt bridge being used for making
electrolytic contact between the two half-cells. No correction has been
applied for the liquid junction potential, which is very small in dilute
solutions containing potassium ferrocyanide and potassium ferricyanide,
but may be greater in the presence of larger amounts of neutral salts.
The introduction of the liquid junction potential, however, does not invali-
date the conclusions arrived at in this paper.
EXPERIMENTAL PART
Materials used
IGFe(CN)a. 3Hz0. A C.P. product of potassium ferrocyanide was
recrystallized twice from conductivity water and kept over deliquescent
sodium bromide hydrate. An analysis of the salt showed that it had the
theoretical composition. .
K3Fe(CN)s : A C.P. product of potassium ferricyanide was recrystallized
twice from conductivity water and dried over anhydrous calcium chloride.
The various salts used in this work had been analyzed by W. Bosch
and had been used in a previous study (4). Conductivity water was used
throughout this work.
Apparat us and method for the measurement of the potential
The potential of the ferro-ferricyanide system was measured in a Pyrex
cell as shown in figure 1, a piece of bright platinum gauze serving as elec-
OXIDATION POTENTI AL OF FERROCYANIDE-FERRICYANIDE 947
trode. One terminal of the potassium chloride-agar salt bridge was
placed in the side well b, thus preventing diffusion of potassium chloride
from the bridge into the main body of the solution. Nitrogen gas from a
tank was introduced through e. Oxygen gas was removed from the nitro-
gen by passing the gas through electrically heated copper gauze at 500C.
The solution in the standard reference half-cell (0.01 N hydrochloric acid,
0.09 N potassium chloride saturated with quinhydrone) was prepared fresh
every day. The normal potential of the quinhydrone electrode is 0.6990
volt at 25C. Assuming that the paH of the acid mixture in the quin-
FIG. 1 FIG. 2
FIG. 1. THE CELL
FIG. 2.
Ratio of KsFe(CN)e to KI Fe(CN)s:o, ratio 1 : l ; A, ratio 1O:l; 0, ratio 1:lO.
D. H., calculated from simple Debye-Huckel expression.
hydrone half-cell is equal to 2.0755, we find that the potential of the latter
against the normal hydrogen electrode is equal to 0.5764 volt at 25C.2
All the measurements were made in a thermostat at 25"C.f 0.05'.
Various salt bridges were used, all yielding the same values. The measure-
ments were made with a Leeds and Northrup student potentiometer. For
the dilution experiments a stock solution containing 0.1 M potassium
ferrocyanide and 0.1 M potassium ferricyanide was carefully prepared by
weight from the pure salts. This stock solution was kept in the dark and
a Recently Guggenheim and Schindler (J . Phys. Chem. 38,533 (1934)) gave evidence
that the paH of the standard acid mixture used in the quinhydrone electrode is
equal to 2.10.
948 I. M. KOLTHOFF AND WILLIAM J. TOMSICEK
prepared fresh each day. The solutions from 0.1 to 0.004 molar were
found to give the same potential in air as in a nitrogen atmosphere. The
potential of the 0.004 molar solution in air referred to the normal hydrogen
electrode was 0.4009 volt after 5 minutes and 0.4011 volt after 60 minutes.
The same solution in a nitrogen atmosphere gave readings of 0.4011 and
0.4012 volts after 5 and 60 minutes respectively. More dilute solutions
gave higher readings in air than in nitrogen. The potential of the 0.0004
molar solution was measured at least ten times during the course of the
investigation. I n a nitrogen atmosphere, the values found after 5 minutes
TABLE 1
Oxidation potential of equimolecular mixtures of potassium ferrocyanide and potassium
ferricyanide
M
0.1*
0.04
0.02
0.01
0.007
0.004
0.002
0.001
0.0008
0.0004
0.0002
0.0001
0.00008
0.00006
0.00004
P
1.6
0.64
0.32
0.16
0.112
0.064
0.032
0.016
0.0128
0.0064
0.0032
0.0016
0.00128
0.00096
0.00064
1.265
0.8
0.5657
0.4
0.334
0.253
0.173
0.1265
0.1131
0.08
0.0566
0.04
0.0358
0.031
0.0253
E
(AGAINST STANDARD
QUINHYDRONE)
0.1178
0.1362
0.1490
0.1610
0.1670
0.1753
0.1856
0.1930
0.1950
0.2010
0.2O50
0.2100
0,2112
0.2122
0.2145
E
(AGAINST NORMAL
ELECTRODI)
HYDROQEN
0.4586
0.4402
0.4276
0.4154
0.4094
0.4011
0.3908
0.3834
0.3814
0,3754
0,3714
0.3664
0.3652
0.3642 .
0.3619
* M = 0.1 designates that the concentrations of both potassium ferrocyanide and
potassium ferricyanide are equal to 0.1 mole per liter.
remained unchanged for periods of twelve hours and more. The various
readings agreed within ~t 0. 0003 volt, the average being 0.3754 volt. The
reproducibility of measurements with solutions from 0.0004 to 0.00006
molar was within 0.0005 volt. Each of the solutions was prepared fresh
and measured at least four times.
Light was found to have a distinct effect on solutions whose concentra-
tions were 0.0004 M or less, the E.M.F. tending to increase in light. All
measurements were therefore made in a darkened room. Under these
conditions, the potentials of even the most dilute mixtures remained
constant for at least one hour.
OXIDATION POTENTIAL OF FERROCYANIDE-FERRICYANIDE 949
0.4450
0.4275
0.4153
0,4043
0.3915
0,3836
I 0.3775
I 0.3711
Experimental results
Table 1 gives the average of the results of measurements with equi-
molecular mixtures of potassium ferrocyanide and potassium ferricyanide,
p representing the ionic strength. The value of E O was found by plotting
the measured values of E against on large cross section paper and
TABLE 2
Osidation potentials measured in a mixture containing K8Fe(CN)6 and K,Fe(CN)s
in the ratio 1O:i
KaFe(CN)o
M
0. 1
0.04
0.02
0.01
0.004
0.002
0.001
0.004
KdFe(CN)o
M
0.01
0.004
0.002
0.001
0.0004
0.0002
0.001
0.00004
TOTAL p
0.7
0.28
0.14
0.07
0.028
0.014
0.007
0.0028
0.8366
0.529
0.3742
0.2646
0.1673
0.1183
0.0837
0.0530
E
(AGAINST
DRONE)
STANDARD
QUI NAY-
0.0723
0.0898
0.1020
0.1130
0.1258
0.1337
0.1398
0.1462
E
(AGAINST
ELECTRODE)
NORMAL
HYDROGEN
0.5041
0.4866
0.4744
0,4634
0,4506
0.4427
0.4366
0.4302
CALCULATED
TABLE 3
Oxidation potentials measured in a mixture containing K3Fe(CN)8 and KIFe(CN)8
KaFe(CN)e
M
0..01
0.004
0.002
0.001
0.0004
0.0002
0.0001
0.00004
KpFe(CN)s
M
0.1
0.04
0.02
0.01
0.004
0.002
0.001
0.0004
in the ratio 1 : l O
TOTAL p
1.06
0.424
0.212
0.106
0.0424
0.0212
0,0106
0.00424
1.0295
0.6511
0.4604
0.3256
0.2083
0.1456
0.1029
0.0651
E
(AOAINST
DRONI)
STANDARD
QUINHY-
0.1895
0,2068
0.2188
0.2295
0.2420
0.2495
0.2555
0.2615
E
(AGAINST
ELECTRODE)
NORMAL
HYDROQEN
0.3869
0.3696
0,3576
0.3469
0.3344
0.3269
0.3209
0.3149
60
CALCULATED
0.4460
0.4287
0,4167
0.4060
0'. 3935
0.3860
0.3800
0.3740
extrapolating to an ionic strength of zero. It was found to be equal to
0.3560 volt. The straight line repre-
sents the change of E, assuming that the limiting Debye-Huckel expression
holds (equation 3).
I n addition, the @oxidation potentials were measured in mixtures con-
taining ratios of potassium ferrocyanide and potassium ferricyanide of
10 : 1 and 1 : 10. They were recalcu-
The data are plotted in figure 2.
The data are given in tables 2 and 3.
950 I. M. KOLTHOFF AND WILLIAM J. TOMSICEK
0 0 0 0 0 0
0 0 0 0 0 0
0 0 0 0 0 0
0 0 0 0 0 0
0 0 0 0 0 0
000000
000000
0 0 0 0 0 0
0 0 0 0
0 0 0 0 0 0
0 0 0 0 0 0
0 0 0 0 0 0
, . . . . .
0 0 0 0 0 0
0 0 0 0 0 0
0 0 0 0 0 0
0 0 0 0 0 0
z
0 0 0 0 0 0
0 0 0 0 0 0
000000
OXIDATION POTENTIAL OF FERROCYANIDE-FERRICYANIDE 951
I
(AGAINST
ELECTBODE)
NORMAL
HYDROGEN
0.4187
0.4097
0.3987
0.3918
0.3864
0.3809
lated on the basis of a ratio of the concentrations of 1 : 1 and correspond to
the e; values plotted in figure 2. These E: values are identical with the
values of the potential E measured in the equimolecular mixtures of ferro-
cyanide and ferricyanide. The reproducibility of the measurements in
the very dilute solutions containing unequal molecular ratios of ferro-
cyanide and ferricyanide i s not as good as of those reported in table 1;
therefore, the extrapolated value of e: at an ionic strength of zero is less
reliable in the former cases.
Th e ef ect of neutral salts upon the potential
I n all of the following determinations a solution containing 0.0004 molar
potassium ferrocyanide and 0.0004 molar potassium ferricyanide, freshly
prepared by dilution of a 0.01 molar mixture, was used. Ten ml. of the
CONCENTRA-
TION OF
Nan CITRATE
hi
0.0833
0.0416
0.0166
0.0083
0.00416
0.00166
TOTAL p
0.5064
0.2564
0.1064
0.0564
0.0314
0.0164
In
CONCENTRA-
TION OF
NarPzOi
M
0. 05
0.025
0.01 .
0.005
0.025
0.001
TABLE 6
hence of salts on the oxidation potential
~~
E
(AGAINST
NORMAL
HYDROGEN
ELECTRODE)
0.4262
0.4154
0.4034
0.3953
0.3889
0.3826
CONCENTRA-
TION OF
MgSOi
.ti
0.125
0,0625
0.025
0.0125
0.00625
0.0025
E
(AGAINST
ELECTRODE)
NORMAL
HYDROOEN
i 0.4584
0.4474
0.4344
0.4246
0.4152
0.4028
latter was diluted with conductivity water in a 2 5 0 4 . volumetric flask, a
weighed amount of pure salt added, and the flask filled up to the mark.
The results are given in tables 4, 5, and 6. Total p refers to the sum
of the ionic strengths of the added salt and of the 0.0004 molar ferro-
cyanide-ferricyanide mixture ( p = 0.0064). From equation 3 i t is found
that
f 3 E - 0
log - = -
f4 0.0591
The values of log f3/f4 thus derived in various salt solutions are plotted in
figure 3 against di. The straight line again gives the values calculated
with the assumption that the limiting Debye and Huckel expression holds
at extreme dilutions.
DISCUSSION OF RESULTS
1. The generally accepted value of the normal potential of the ferro-
At an ionic strength
ferricyanide electrode of 0.44 volt is much too high.
952 I. M. KOLTHOFF AND WILLIAM J . TOMSICEK
of zero, a value of 0.356 volt was derived in this paper. From a practical
viewpoint i t is of interest to mention that the oxidation potential increases
very rapidly with the increasing ionic strength and that it even can exceed
the value of 0.44 in equimolecular mixtures of ferricyanide and ferrocyanide.
2. Even at infinite dilutions, the behavior of the system is not in har-
mony with the postulates of the simple Debye-Huckel expression. The
slope of the curve giving the change of the oxidation potential or of log
f3/f4 plotted against the square root of the ionic strength isgreater than
o ai
FIG. 3
FIG. 3.
a, CsCl; b, RbCl; c, KCl and NHcC1; d, LiCl. D. H., calculated from simple
Debye-Htickel expression.
FIG. 4.
a, Mg(NOs)z; b, BaCl2; c, Ca(NOa)n; d, SrC12; e, NazSOa; f, Nas citrate; g,
NarPzO,.
D. H., calculated from simple Debye-Huckel expression.
that calculated on the basis of the Debye-Huckel limiting equation. It is
impossible to account for this anomaly on the basis of ionic size, using the
present form of the Debye-Huckd theory, for, as V. K. La Mer (6) states,
absurd negative values of u would be demanded at very high dilutions
followed by positive values in more concentrated solutions. Deviations
of experimental data from the theoretically predicted curves have been
described by various authors, a discussion of which is given in a paper by
La Mer, Gronwall, and Greiff (7). Gronwall, La Mer, and Sandved (2)
have shown that these discrepancies disappear if the influence of higher
OXIDATION POTENTIAL OF FERROCYANIDE-FERRICYANIDE 953
terms of the Debye-Huckel theory in the case of unsymmetrical valence
type electrolytes is taken into account. On the basis of the extended
Debye-Huckel equation, values are found which fit the experimental data
without assuming ion association or incomplete dissociation of the strong
electrolytes. Undoubtedly, in a quantitative interpretation of the data
found in this study, the extended equation of Gronwall, La Mer, and
Sandved should be applied, since we are dealing with highly unsymmetric
valence type electrolytes. Still, we have evidence to believe that even the
extended equation does not account quantitatively for the results obtained,
and that potassium ferrocyanide has to be considered as an incompletely
dissociated electrolyte. I n a subsequent paper, it will be shown that the
curve obtained in a study of the potential of the potassium molybdo-
molybdicyanide electrode, a system very similar to that of ferro-ferri-
cyanide, does not intersect with the straight line calculated from the
simple Debye-Huckel expression, but is found below this line even at
extreme dilutions. I n addition i t was found that the fourth dissociation
of molybdocyanic acid
HMo(CN)s--- + H+ + Mo(CN)s----
is complete whereas that of ferrocyanic acid
HFe(CN)a--- H+ + Fe(CN)a----
is incomplete. This means that the proton combines with the ferrocyanide
ion tof~rmHFe(CN)~---, anditis quite plausible that other cations behave
similarly. I n the study of the influence of salts upon the potential of a
very dilute potassium ferrocyanide-potassium ferricyanide mixture
described in this paper it was found that the effect is virtually independent
of the type of the anions. Potassium bromide, chloride, and nitrate have
an identical effect at the same ionic strength; the same is true for sodium
chloride, nitrate, and perchlorate on the one hand and sodium sulfate,
oxalate, carbonate, and phosphate on the other.
With the
alkali cations i t decreased in the order Cs, Rb, K = NH,, Na = Li, and we
conclude that the degree of dissociation of the corresponding ferrocyanides
decreased in the same order. The dissociation becomes more incomplete
with the increasing valence of the cations, the effect of the various alkaline
earths being of about the same order. This larger effect of the divalent
ions is especially pronounced at the smaller ionic strengths.
Since the concentration of the cation is of primary importance, it is
easily understood why the oxidation potentials found in potassium ferro-
cyanide-potassium ferricyanide mixtures of various ratios and recalculated
on the basis of a ratio of 1: 1 are not the same at the same ionic strength
The type of cation, however, has a very pronounced effect.
954 I. M. KOLTHOFF AND WILLIAM J . TOMSICEK
(figure 2). The potentials found increase from the mixture with a ratio of
10 ferrocyanide to 1 ferricyanide to that with a ratio of 1 to 10. I n the
former, the potassium-ion concentration is much smaller than in the latter
at the same ionic strength. I n a similar way, it is explained why the 1-2
valence types of electrolytes (sodium sulfate, carbonate, etc.) have a
smaller effect than the 1-1 valence type of salts (sodium chloride, etc.).
SUMMARY
1. The normal potential of the ferrocyanide-ferricyanide electrode is
equal to 0.3560 volt at 25C.
2. The change of the potential of a very dilute ferrocyanide-ferricyanide
solution with increasing ionic strength is greater than calculated on the
basis of the simple Debye-Huckel expression. This is partly explained
by incomplete dissociation of alkali and alkaline earth ferrocyanides.
3. For the same valence type of salts the anion effect upon the potential
is the same for different anions at the same ionic strength. A pronounced
cation effect was observed, the effect decreasing in the order Cs, Rb, K =
NHI, Na =Li for the alkali ions and being of about the same order for the
alkaline earth ions. The latter, especially at the smaller ionic strengths,
have a much greater effect than the univalent cations.
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(3) KOLTHOFF, I. M.: Z. anorg. allgem. Chem. 110, 143 (1920).
(4) KOLTHOFF, I. M., AND BOSCH, W. : J . Phys. Chem. 36, 1685 (1932).
(5) KOLTHOFF, I. M. : The Determination of pH, Electrometric Titrations.
(6) LA MER, V. K.: Trans. Am. Electrochem SOC. 61, 543 (1927).
(7) LA MER, V. K., GRONWALL, T. H., AND GREIFF, L. J .: J . Phys. Chem. 36, 2245
(8) LEWIS, G. N., AND SAROENT, L. W.: J . Am. Chem. SOC. 31, 355 (1909).
(9) LINHART, G. A,: J . Am. Chem. SOC. 39, 615 (1917).
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