Journal of Electroanalytical Chemistry 521 (2002) 183 189

www.elsevier.com/locate/jelechem

The thermodynamics of the insertion electrochemistry of solid

metal hexacyanometallates
Maximiliano Barcena Soto 1, Fritz Scholz *
Ernst-Moritz-Arndt-Uni6ersitat Greifswald, Institut fur Chemie und Biochemie, Soldmannstrae 23, D-17489 Greifswald, Germany
Received 17 October 2001; received in revised form 18 January 2002; accepted 18 January 2002

Abstract
A strict treatment of the thermodynamics of the electrochemical reactions of solid metal hexacyanometallates is given. For the
first time the relations between the formal potentials of the insertion electrochemical reactions and their solubility products are
reported as well as their relation with structure parameters such as ion potentials and lattice constants. All derived relationships
are proved by experimental data published earlier. 2002 Elsevier Science B.V. All rights reserved.
Keywords: Electrochemical thermodynamics; Insertion electrochemistry; Metal hexacyanoferrates; Metal hexacyanometallates

1. Introduction
Metal hexacyanometallates form a class of compounds that lends itself to a detailed study of the
insertion electrochemistry because most of these compounds possess reversible electrochemistry when studied at ambient temperature, in the presence of aqueous
electrolyte solutions, and with scan rates up to some
hundreds of millivolts per second. Prussian blue, i.e.
iron(III) hexacyanoferrate(II), is the best known and
most intensively studied member of this group of com-

pounds [1,2]. Other solid hexacyanometallates, e.g.

iron(III) hexacyanochromate(III) [3] and octacyanometallates, e.g. silver octacyanomolybdate and
tungstate [4] have been studied as well. In 1995 we
published experimental findings that the formal potentials of solid hexacyanoferrates depend linearly on the
ion potential of the metal ions that are N-coordinated
in the cyanide framework of the hexacyanometallates
[5]. In the present publication we derive theoretically
and exactly these dependences, which have been observed experimentally and published previously.

2. Results and discussion

2.1. The relations between the formal potentials of the

solid metal hexacyanometallates and their solubility
products

Scheme 1.
* Corresponding author. Tel.: + 49-3834-86-4450; fax: + 49-383486-4451.
E-mail address: fscholz@uni-greifswald.de (F. Scholz).
1
This work was part of a Ph.D. thesis submitted by M.B.S. to
Humboldt-Universitat zu Berlin.

The following scheme describes the electrochemistry

of solid metal hexacyanometallates and its relation to
solubility equilibria and the solution electrochemistry of
the hexacyanometallate moiety (Scheme 1).
M+ is the inserting cation; M%, the nitrogen coordinated metal ion; and M, the carbon coordinated metal
ion of the metal hexacyanometallate framework. The
structure of solid metal hexacyanometallates is depicted
in Fig. 1. The index s indicates solid and the index aq

0022-0728/02/$ - see front matter 2002 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 7 2 8 ( 0 2 ) 0 0 7 1 0 - 6

184

M. Ba rcena Soto, F. Scholz / Journal of Electroanalytical Chemistry 521 (2002) 183189

late; and (D) is the electrochemical equilibrium between

the dissolved oxidized and reduced hexacyanometallate
ions. The Gibbs energies of all these equilibrium reactions are connected with each other as follows:
DG qA = DG qD + DG qC DG qB

(1)

2.1.1. The ratio of the solubility products of the

reduced and oxidized forms
Using the solubility products Ksol(C) and Ksol(B) to
characterize the equilibria (C) and (B) the following
equation follows:
DG qA = DG qD + RT ln
Fig. 1. 1/8 of the unit cell of a solid metal hexacyanometallate.

Solid compound b

q
q%
E q%
A/V vs. SHE E DE A/V Ksol(C)/Ksol(B)

Cr3+[Fe(CN)6]
Cd2+[Fe(CN)6]
Cu2+[Fe(CN)6]
Ni2+[Fe(CN)6]
Pb2+[Fe(CN)6]
Fe3+[Fe(CN)6]
Co2+[Fe(CN)6]
In3+[Fe(CN)6]
Ag+[Fe(CN)6]
Ga3+[Fe(CN)6]
Al3+[Fe(CN)6]
Mn2+[Fe(CN)6]
Cr2+[Cr(CN)6]
Mn2+[Cr(CN)6]
Fe2+[Cr(CN)6]
Mn2+[Mn/2+(CN)6]
Mn2+[Mn2+/3+(CN)6]
Fe2+[Mn2+/3+(CN)6]
Cr3+[Mn2+/3+(CN)6]

1.005
0.858
0.982
0.857
0.976
1.168
0.966
1.006
0.880
1.173
1.151
0.811
0.562
0.804
0.860
0.172
0.052
0.075
0.352

0.65
0.503
0.627
0.502
0.621
0.813
0.611
0.651
0.525
0.818
0.796
0.456
0.578
0.336
0.28
0.338
0.292
0.315
0.592

7.941012
2.57109
1.961011
2.68109
2.481011
1.311014
3.681011
7.641012
1.08109
1.071014
2.551014
1.63108
1.351010
1.83106
1.65105
1.69106
1.03105
4.18106
7.771011

Potassium ions are in all cases the inserting ions.

a
The formal potentials have been determined as midpeak potentials in cyclic voltammetry and by extrapolation to unit activity of the
inserting ion K+.
b
The formulae are written as M%[M(CN)6] indicating the nitrogen
coordinated metal ion M% and the carbon coordinated metal ion M.

indicates species in the aqueous phases. (A) is the

electrochemical reaction of the solid metal hexacyanometallate that comprises an electron and ion
transfer; (B) is the solubility equilibrium of the oxidized
form of the metal hexacyanometallate; (C) is the solubility equilibrium of the reduced metal hexacyanometal-

(2)

In terms of standard potentials Eq. (2) can be written

as:
q
E q%
A=ED

Table 1
The ratios Ksol(C)/Ksol(B) of the solubility products of the reduced and
oxidized forms of metal hexacyanometallates calculated from the
electrochemical data a published in Ref. [5]

Ksol(C)
Ksol(B)

RT Ksol(C)
ln
zF
Ksol(B)

(3)

whereas E qD is the exactly defined standard potential of

the hexacyanometallate ion in aqueous solution, the
value E q%
A is not a standard potential, but a formal
potential. The standard state, as it is defined for solutions, i.e. a solution of 1 mol l 1 concentration with the
properties of an indefinitely diluted solution cannot be
realized for solids. Both the concentration of the redox
active ion and its activity are fixed for each metal
hexacyanometallate. Nevertheless one can try to compare the E q%
A values of different metal hexacyanometallates, because the concentrations of redox active ions in
different compounds defined as mol redox active ions
per volume of the compound are the same (the molar
volumes differ insignificantly because the cyanide ions
mainly determine the lattice constants, which indeed
vary by only 23%), and the activity coefficients can be
assumed not to differ significantly because of the chemical similarities. Eq. (3) shows that the formal potential
of reaction (A) is closely related to the ratio of solubility products of the oxidized and reduced form of the
metal hexacyanometallate. Table 1 gives the ratios
Ksol(C)/Ksol(B) of a number of metal hexacyanometallates
calculated on the basis of the formal potentials reported
in Ref. [5]. Obviously the reduced forms of the metal
hexacyanometallates are always less soluble than the
oxidized forms. This result is in line with calorimetric
measurements of the precipitation enthalpies of metal
hexcyanoferrates(II) and -(III), where it was found that
these values are less negative for the latter [6]. There are
literature data available for the two silver hexacyanoferrates Ag3[Fe(CN)6] (Ksol(B) = 9.8 10 26 mol4 l 4 at
25 C) and Ag4[Fe(CN)6] (Ksol(B) = 9.8 10 41 mol5
l 5 at 25 C), yielding Ksol(C)/Ksol(B) = 1.53 10 16 mol
l 1. This ratio cannot be the same as that listed in
Table 1 for silver hexacyanoferrate, as in the table it is

M. Ba rcena Soto, F. Scholz / Journal of Electroanalytical Chemistry 521 (2002) 183189

a potassium instead of a silver ion that is inserted,

however there is general agreement in the trend that the
reduced form is less soluble.

2.1.2. The ratio of the solubility products of the

reduced forms of one metal hexacyanometallate with
two different inserting metal ions
Now, it is interesting to see whether information on
the solubility products of metal hexacyanometallates
with different inserting metal ions, e.g. sodium and
potassium ions, can be derived from electrochemical
data. When one writes Eq. (3) for the inserting ion i in
the form
q
E q%
A,i =E D

RT
ln(Ksol(C)/Ksol(B))i
zF

(4)

and for the inserting ion j as

q
E q%
A,j =E D

RT
ln(Ksol(C)/Ksol(B))j
zF

(5)

and when Eq. (5) is subtracted from Eq. (4) one

obtains:
q%
E q%
A,i E A,j =

!    "

RT
ln
zF

Ksol(C)
Ksol(B)

Ksol(B)
Ksol(C)

(6)

Since Ksol(B) is independent of the ions i and j, it has

in both cases the same value and cancels in Eq. (6).
Thus it follows that:
q%
E q%
A,i E A,j =

RT
(Ksol(C))j
ln
zF
(Ksol(C))i

"

(7)

185

   
(E q%
A
(T

(E qD
RT Ksol(B) ( Ksol(C) R
Ksol(C)

ln
(T
zF Ksol(C) (T Ksol(B) zF Ksol(B)
(8)

For the calculation of the term (#/#T)(Ksol(C)/Ksol(B))

it is necessary to know the temperature coefficients of
the reactions (A) and (D) and also to obtain the ratio
Ksol(C)/Ksol(B). The standard temperature coefficient of
reaction (A) of copper hexacyanoferrate has been determined with the help of a thermostated electrochemical
cell [8] to be 0.40 mV K 1 (an isothermal reference
electrode (RE) was used). The standard temperature
coefficient of reaction (D) is 1.891 mV K 1 [9]. With
these data one obtains for copper hexacyanoferrate
(#/#T)(Ksol(C)/Ksol(B))= 4.83 10 13, i.e. the ratio increases with increasing temperature.
To derive the temperature dependence of the ratio of
the solubility products of the reduced metal hexacyanometallates for two different inserting metal ions,
one has to calculate the derivative of Eq. (7) with
respect to temperature:

   
(E q%
A,i
(T

(E q%
A,j
(T

RT (Ksol(C))i ( (Ksol(C))j R
(K
)
=
+ ln sol(C) j
zF (Ksol(C))j (T (Ksol(C))i zF (Ksol(C))i

(9)

As an example the temperature dependence of the ratio

(Ksol(C))j/(Ksol(C))i can be calculated for copper hexacyanoferrate and sodium and potassium as inserting
ions. With standard temperature coefficients of
0.00040 V K 1 for K+ and 0.00075 V K 1 for Na+
one obtains

Eq. (7) can be applied to the electrochemical data

published by Engel [7] to calculate the ratio (Ksol(C))j/
(Ksol(C))i for copper hexacyanoferrate and the alkali
metal ions. The results are given in Table 2. From
Table 2 the general trend is: (Ksol(C))Na+ \(Ksol(C))K+ \
(Ksol(C))Rb+ \ (Ksol(C))Cs. Obviously the solubility drops
when the inserting metal cation is less solvated.

2.2. The relations between crystallographic data and

the formal potentials of the solid metal
hexacyanometallates

2.1.3. The temperature dependences of the ratios of the

solubility products
It is also possible to derive the temperature dependence of the ratio Ksol(C)/Ksol(B). The derivation of Eq.
(3) with respect to temperature gives

2.2.1. The dependence of the formal potentials of solid

metal hexacyanometallates on the ion potentials of the
nitrogen coordinated metal ions M%
The enthalpy of the reaction (A) can be calculated as
follows:

( (Ksol(C))Na+
= 2.52
(T (Ksol(C))K+

DHA = DHD + DHC DHB

Table 2
Ratios (Ksol(C))j/(Ksol(C))K+ for copper hexacyanoferrate based on the
data published in Ref. [7] (25 C and 0.1 mol l1 of M+
j )
M+
j

E q%
E q%
A,j /V
A,K+

(Ksol(C))j/(Ksol(C))K+

Na+
K+
Rb+
Cs+

0.115
0
0.163
0.309

87.92
1
1.76103
5.97106

(10)

The enthalpies of the reactions (B) and (C) can be

calculated using a BornHaber cycle from the hydration enthalpies (DHhyd) and lattice energy Ulat. For the
reaction (C) it is possible to write the following Born
Haber cycle (Scheme 2). The subscript g denotes ions in
the gaseous state. For reaction (C) one can write:
DHC = Ulat,C DHhyd,C

(11)

Similarly reaction (B) can be described by the following equation:

M. Ba rcena Soto, F. Scholz / Journal of Electroanalytical Chemistry 521 (2002) 183189

186

Scheme 2.

DHB = Ulat,B DHhyd,B

(12)

The Gibbs energy of reaction (A) follows as:

The difference of enthalpies of reactions (C) and (B)

is as follows:

DGA = DHD + Ulat,C Ulat,B + DHHyd,[Ox] DHHyd,[Red]

DHC DHB =Ulat,C Ulat,B +DHhyd,B DHhyd,C

Eq. (18) allows us to derive an equation which relates

the shift in formal potentials between two metal hexacyanoferrates with different nitrogen coordinated metal
ions M% to the ionic properties of M%. For this purpose,
one can write Eq. (18) in the form

(13)

The hydration enthalpies of the reactions (C) and (B)

can be calculated as follows:
DHhyd,B DHhyd,C =DHhyd,[Ox] DHhyd,[Red] DHhyd,M+
(14)
DHhyd,[Ox] and DHhyd,[Red] are the hydration enthalpies
of the oxidized and reduced forms of the hexacyanometallate ion, respectively. The lattice energy can
be estimated with the help of the Born Lande equation
[10]:
2

 

(15)

A is the Madelung constant, a is the number of charges

of the nitrogen coordinated metal ion M%, bB is the
number of charges of the oxidized form of the hexacyanometallate ion, ra is the radius of the nitrogen
coordinated metal ion M%, rbB is the radius of the
oxidized form of the hexacyanometallate ion, m is a
repulsion constant and the other symbols have their
usage meaning. All charges are normalized versus the
elementary charge. In case of the lattice energy of the
reduced form one has to take into account the interaction with the inserted ion:

 
 

1 NAAe 2abC
1
1
4ym0 (ra + rbC)
m

1 NAAIe 2abI
1
1
4ym0 (ra + rI)
mI

(16)

The index C refers to the reduced form of the hexacyanometallate ion and the index I to the inserting
metal ion. The difference in lattice energies between the
reduced and oxidized forms is:

!
 

Ulat,C Ulat,B =

NAe 2a
bC
bB
A

4ym0
(ra +rbC) (ra +rbB)

DGA = s+ Ulat,C Ulat,B = sx

"

1
AIbI
1

1
m
(ra +rI)
mI

(17)

(18)

q
ra

(19)

with s= DHD + DHHyd,[Ox] DHHyd,[Red] DHHyd,M+

TDSA comprising all values that are independent of M%.
The meaning of x is:
x=

1 NAAe abB
1
Ulat,B =
1
4ym0 (ra + rbB)
m

Ulat,C =

DHHyd,M+ TDSA

!

n 

NAe 2
bB
bC
A

4ym0
(1+r*bC ) (1+r*bB )

"

AIbI
1
1
mI
(1+r*)
I

1
m

(20)

where r*bC = rbC/ra, r*bB =rbB/ra, and r*=

rI/ra. From
I
Eq. (19) the formal potential of the reaction (A) is as
follows:
E q%
A=

s
x a
+
zF zF ra

(21)

Eq. (21) is exactly what has been found experimentally in a study of the dependence of the formal potentials of solid metal hexacyanoferrates [5]. The formal
potentials are proportional to the ion potentials of the
nitrogen coordinated metal ions M% (cf. Fig. 2). As has
been pointed out in the previous communication of the
experimental data [5], it is very interesting that this
relation extends from the solid compounds up to the
hexacyanoferrate ion in aqueous solution. In Fig. 2 is
included the standard potential of the hexacyanoferrate
ion in water and the effective radius of the proton was
used to calculate the ion potential of the proton in
water. The straight line shown in Fig. 2 was calculated
as a linear fit of the data of the solid compounds,
without the value for the proton! This line crosses the
point for the proton ion and the standard potential of
the hexacyanoferrate ion in water, and it can be explained by the assumption that the protons of the water
are the nearest neighbors of the nitrogen end of the

M. Ba rcena Soto, F. Scholz / Journal of Electroanalytical Chemistry 521 (2002) 183189

cyanide ions of the hexacyanoferrate ions in water,

where obviously the protons play a similar role as the
metal ions M% in the solid hexacyanoferrates. Fig. 2 was
the first experimental proof that there is a smooth
relation between the formal potentials of an electroactive ion in water with its formal potential in solids.

187

solution. Using Eq. (24), Eq. (22) may be written as

follows:
DGA = const+ Ulat,C DGHyd,M+ T(SM,S Se)
(25)
Summarizing all terms that are independent of M+
as const1 one can write:

2.2.2. The dependence of the formal potentials of a

solid metal hexacyanometallate on the ion potentials of
the inserting metal ions M+
To address the title question, Eq. (18) can be used
after summarizing all values that are independent of the
inserting ion M+ as const:

DGA = const1 + Ulat,C DGHyd,M+ TSM,S

DGA = const + Ulat,C DHHyd,M+ T DSA

Here m is the dielectric constant of the solvent, rI and bI

are the radius and the charge number, respectively of
the inserting metal ion, andrWthe radius of a water
molecule. Therefore, it follows that the Gibbs energy of
reaction (A) depends on the ion potential of the inserting metal ion as follows:

(22)

The entropy of the reaction (A) can be calculated as

DSA =SRed SOx SHyd,M+ Se

(23)

with Red indicating the reduced and Ox indicating the

oxidized form of the solid metal hexacyanoferrate.
With the help of the Neuman Kopp rule (additivity of
molar heat capacities of elements in compounds, [12])
for the heat capacities of solid multiatomic compounds,
with the relation between entropy and heat capacity,
and with the help of the third law of thermodynamics,
Eq. (23) simplifies to:
DSA =SM,S SHyd,M+ Se

(24)

with SM,S being the molar entropy of the inserting

metal ion. It generally holds for the class of compounds
studied that SM,S B SHyd,M+ since the entropy of the
inserting metal ion is larger in the solution phase than
in the solid. This is a consequence of the hydration in

(26)

The Gibbs energy of hydration according to the Born

model is:
DGHyd,M+ =

 

NAb 2I e 2
1
1
m
4ym0(rI + 2rW)

DGA = const2 TSM,S + b

where

(27)

bI
rI

 

(28)

bI
1
A Ia
1
NAe 2
1 +
1
m
m
4ym0 2(1+ 2r*W )
4y(r*+
1)
a
I
(29)

b=

n

ra /rI. This means that the

here is r*W = rW/rI and r*=
a
relation between the formal potential of reaction (A)
and the ion potential of the inserting metal ion M+ is:
E q%
A:

const3 b bI

zF
zF rI

(30)

Fig. 2. Dependence of the formal potentials of solid metal hexacyanoferrates on the ion potential of the nitrogen coordinated metal ions. The
element symbols in the figure denote the nitrogen coordinated metal ion. The symbol H denotes the ion potential of the hydrogen ion in water
and the corresponding value on the vertical axis is the standard potential of the hexacyanoferrate ion in water. (Figure adopted from Ref. [5].)

M. Ba rcena Soto, F. Scholz / Journal of Electroanalytical Chemistry 521 (2002) 183189

188

Fig. 3. Dependence of the formal potentials of two solid metal hexacyanometallates (copper and iron hexacyanoferrate) on the ion potential of
the inserting metal ions. The data for copper hexacyanoferrate are taken from Ref. [7] and those for Prussian blue from Ref. [11].

This relation can also be proved with experimental data

from the literature. Fig. 3 gives a plot of the formal
potentials of reaction (A) for copper hexacyanoferrate
and Prussian blue as a function of the ion potentials of
potassium, rubidium and cesium ions as inserting ions.

where c =(NAe 2aA)/(4ym0)[1(1/m)]. Eq. (35) can be

written with the lattice constants in the form:

2.2.3. The dependence of the formal potentials of a

solid metal hexacyanometallate on the properties of the
hexacyanometallate ions
To see the influence of the properties of the hexacyanometallate ions on the formal potentials of the
solid compound, Eq. (18) can be used when all terms
that are independent of these ions are summarized as
:
DGA = DHD +Ulat,C Ulat,B +DHHyd,[Ox] DHHyd,[Red]
(31)

The enthalpy of reaction (D) is given by:

DHD = DHHyd,[Ox] DHHyd,[Red] DHe

(32)

where DHe is the molar enthalpy of the electrons in

the electrode. Substituting Eq. (32) into Eq. (31) yields:
DGA = Ulat,C Ulat,B DHe

(33)

From Eq. (17) it follows that:

DGA=

NAe 2aA
bC
bB

4ym0
(ra +rbC) (ra +rbB)

n 
1

1
1
m
(34)

with 1 summarizing all terms that are independent of

the hexacyanometallate ions. Eq. (34) can be rearranged to give:
DGA = c

bC(ra + rbB) bB(ra +rbC)

1
(ra + rbC)(ra +rbB)

(35)

Fig. 4. Dependence of the formal potential of metal hexacyanometallates on the reciprocal lattice constant multiplied by the charge
difference of the oxidized and reduced form of the hexacyanometallate ions. In the figure, the first metal denotes the nitrogen coordinated metal ion and the second one denotes the carbon coordinated
metal ion (thus FeMn stands for iron hexacyanomanganate). The
inserting ions were in all cases potassium ions. (Figure adopted from
Ref. [5].)

DGA = 2c

M. Ba rcena Soto, F. Scholz / Journal of Electroanalytical Chemistry 521 (2002) 183189

bCLB bBLC
1
LCLB

(36)

where LB and LC are the lattice constants and: LB =

2(ra +rbB) and LC = 2(ra +rbC). Assuming that the lattice
constants of the reduced and oxidized forms differ only
marginally, one can write DGA : 2c[(bC bB)/L]
1, and from that, the equation for the formal potential
follows as:
E q%
A:

2c bC bB
I

zF
L
zF

189

sound basis for research into new compounds with

tailored properties.

Acknowledgements
M.B.S. acknowledges provision of a Ph.D. scholarship by Deutscher Akademischer Austauschdienst. F.
Sch. thanks Fonds der Chemischen Industrie for constant support.

(37)

Fig. 4 proves with the help of experimental data that

this dependence holds true. I contains the entropy
contribution. An exact comparison of the slope and
intercept as described by Eq. (37) with the experimental
plot shown in Fig. 4 is not yet possible because neither
the Madelung constant nor the repulsion constant are
known exactly, however an order of magnitude assessment suggests a good fit.

3. Conclusions
A strict thermodynamic description of the insertion
electrochemistry of solid metal hexacyanometallate allowed, for the first time, the fundamental relations
between the formal potentials of these compounds and
their solubilities and structures to be rationalized. This
new insight into these dependences should provide a

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