ISSN 10683755, Surface Engineering and Applied Electrochemistry, 2015, Vol. 51, No. 6, pp. 540551.

Allerton Press, Inc., 2015.

Original Russian Text A.I. Zhakin, 2015, published in Elektronnaya Obrabotka Materialov, 2015, No. 6, pp. 3242.

Solvation Effects in Liquid Dielectrics

A. I. Zhakin
Southwestern State University, ul. 50 let Oktyabrya 94, Kursk, 305040 Russia
email: zhakin@mail.ru
Received June 18, 2014

AbstractThe solvation effects that arise on dissolving an ionizing impurity or with charge injection into a
nonpolar liquid dielectric are considered. The polarization energy of solvation is calculated for the contin
uum approximation in a boundless fluid and near the metal surface.
Keywords: ion, dipole, polarization, dielectric permittivity, solvation, solvation radius, image force
DOI: 10.3103/S1068375515060125

INTRODUCTION

can be outlined in the following chain of reactions

[24, 7]:

The application of redox systems to ensure a suffi

ciently large service life for electrohydrodynamics
(EHD) devices is a promising direction in EHD. For
example, liquid crystals are stabilized by a quinone
hydroquinone additive [1]. As a rule, nonpolar liquids
that are nontoxic and have acceptable thermal charac
teristics are used in EHD. Because of this, a set of
physicochemical problems have arisen related to dis
solution of salts and polar impurities in a nonpolar sol
vent. Thus, crystalline iodine as a strong electron
acceptor molecularly dissolves in nonpolar hydrocar
bons [24], forming monomolecules I2 and molecular
complexes I2 I2, I2 I2 I2, etc. In this case, it is
thought that the nonpolar solvent is indifferent; i.e., it
does not enter into any chemical bonding with iodine
and ions [2]. As for alcohols, they slightly dissolve in
them [5] and even at low concentrations form molec
ular complexes that cause layering or sedimentation of
the solution. The dissolution process for any substance
in a solvent is in fact a chemical reaction when inter
molecular bond open in the solvent and the new bonds
with impurity molecules form. Impurity molecules X
enter into chemical bonding with solvent molecules M
and form molecular complexes X M [24, 6]. If mol
ecule X is an electron acceptor, like, say, molecular
iodine I2, or it contains an electron withdrawing group
(Cl, Br, I in aromatic hydrocarbons, an OH hydroxyl
group in alcohols, etc.), then the molecular complex
gains a dipole moment (as the acceptor attracts elec
trons) and is denoted as X M +, where is the effec
tive charge. This case corresponds to the homopolar
bond in the molecular complex. When an electron is
captured by an accepter, a heteropolar bond is formed.
In this case, the molecular complex turns into a con
tact ion pair [X , M+], which can pass into a socalled
loose or diffusion ion pair X M +, which is capable of
dissociating into free ions X , M +. These processes

X+M

X M

X M

k2
11

[X , M ]

(1)

X +M .

Thus, it is necessary to specify the conditions for

ionization of a liquid dielectric with some electron
accepting additive. In this work, we consider solvation
effects as applied to low polarizable solvents, such as
liquid dielectrics. We calculate the solvation potential
of an ion in an infinite medium and of an ion near a
metal in the continuum approximation of the average
polarization in the solvation shell.
1. CHEMICAL SOLVATION
Chemical solvation is investigated using the calori
metric method with measurement of the solution
enthalpy H, cal/mol [8], which is assumed to be pos
itive if dissolution proceeds with heat absorption
(endothermic process) and negative with heat evolu
tion (exothermic process). At H < 0, the energy of the
impurity and attraction of solvent molecules is higher
than the binding energy between the solvent mole
cules; for H > 0 it is correspondingly lower.
The binding energy for molecule X and solvent
molecules M can be estimated as follows. At a constant
pressure and solution volume, the change in enthalpy
is equal to the change in energy H = U. Now, with
dissolution of the impurity in the liquid or crystalline
phase, there takes place the breaking of the bonds XX
bonds with the energy EXX occurs, as well as of MM
bonds with energy EMM. Then, new bonds form with
the energy EXM and reorganization of molecules M
around X with the consumption of energy Ur (solva
tion energy).

540

SOLVATION EFFECTS IN LIQUID DIELECTRICS

541

(b)

(a)
H, cal/mol

H, cal/mol

0C

20C

4
3

300

30C
200

200

100

100

(CH2)2OH

50

C6H14, mol

C6H6

(c)

H, cal/mol

50

100

(d)
50C

140

35C

H, cal/mol
100
35C

20C

80

60
0C

40

20
0

0
40
CCl4

50

CH3OH, mol %

40
C3H7OH

50

CCl4, mol %

Fig. 1. Heats of mixing of (a) hexane with acetone; (b) benzene with alcohols at 35C: (1) methyl, (2) ethyl, (3) propyl, (4) butyl
alcohols; (c) CCl4 with methyl alcohol; (d) CCl4 with propyl alcohol.

In the case of nonpolar solvents, the quantity U

can be neglected [4]; thus, the energy balance gives
H = N A E,

E = E XM E XX E MM ,

(2)

where H is the change in enthalpy during dissolution

of 1 g/mol of the impurity and NA is the Avogadro
number.
Solutions with and without hydrogen bonds are
distinguished according to the type of chemical bind
ing between the solvent and impurity molecules. The
mixtures of CCl4 with acetone and aromatic hydrocar
bons, benzene with acetone and diethyl ether, and

hexane with acetone are examples of solutions without

hydrogen bonds. In these solutions, H > 0, and it is
on the order of 400500 cal/mol (Fig. 1a). If the sol
vent molecules contain a chemically active compo
nent (chlorine in CCl2, oxygen in dioxane), polar
impurities, say, alcohols, are dissolved, a chemical
bond forms as evidenced by the complex dependence
of H on the impurity concentration (Figs. 1c, 1d).
Solutions of nonpolar hydrocarbons (benzene, hex
ane, etc.) with alcohols are examples of mixtures with
hydrogen bonds (Fig. 1b).
In physicochemical [24] and EHD [9, 10] inves
tigations, often solutions of dielectric liquids with

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Table 1. Heat and solution constant of molecular iodine in different solvents [11]
Liquid (electron donor)

H, kcal/mol

Equilibrium constant, L/mol

Benzene, C6H6
Toluene, C7H8
Dioxane, C4H8O2
Pyridine, C5H5N

0.15 (25C)
0.16 (25C)
1.14 (17C)
270 (20C)

molecular iodine are used, since the ionization pro

cess in them is determined by reactions (1). The
enthalpy of the iodide solution is always negative
(Table 1); i.e., in these solutions molecular complexes
and ion pairs always form [11].
Using the data of Table 1, we find that the energy of
binding I2 with benzene molecules is higher than the
benzene intermolecular binding energy by a value
E = 0.06 eV and, correspondingly, E = 0.15 eV for
dioxane. The existence of I2donor ion pairs is con
firmed by the absorption spectra due to contact ion
pairmolecular complex electron transitions [11], as
well as by spectrophotometric and conductometric
measurements.
Thus, the solvation interactions take place both
with the evolution and absorption of heat. An effective
modern method for studying the solvation of ions is
temperature field analysis using digital thermovisors.
Figure 2 shows the heat patterns of a transformer oil
(TO)iodine saturated solution with the injection of
negative ions from a cathode (a 0.5mmthick copper
plate) according to the following reaction [9, 10]:
MX+e

MX .

(3)

Figure 2 shows sections whose temperature is by

~0.10.9C higher than of the ambient liquid. Here,
at the cathode tip, two heated eddies are formed, sep
arated by a cold negatively charged jet. It is seen that in
the region of the jet stream, negative ions are frozen in
()

1.4
1.8
3.5
7.8

the liquid with only polarization interaction with the

TO (polarization solvation with heat absorption). At
the eddy boundaries, heating due to the viscous and
Joule heat evolution takes place.
Modern theories (molecular dynamics, for exam
ple, [12]; the statistical Monte Carlo method [13]; and
lastly, quantum chemistry methods [13, 14]) are based
on the concepts of solution microstructures. There
fore, these theories help to calculate the energies of
both chemical and polarization solvation, as well as to
determine the structures of the solvation shells. Thus,
calculation using molecular dynamics [12] shows that
the orientation of methanol MeOH molecules in the

first solvation shell of the negative ClO 4 ion takes

place in such a way that the hydroxyl group OH is radi
ally directed (into the center of the ion, Fig. 3). The
dipole moment of the methanol molecule is directed
at an angle to the radial direction.
2. POLARIZATION SOLVATION
Polarization solvation theory is rather complicated,
and it must be developed for a particular solvent. This
section formulates the problem of calculating the ion
solvation energy in a boundless solvent and near a
metal surface and derives the formula for estimating
the energy of interaction between the ion and the
medium dipoles in the continuum model of average
polarization in the solvation shell.
(b)

3 cm

Fig. 2. Infrared photos of the temperature distribution during the injection of negative charges from the cathode into the saturated
solution of iodine in TO; (a) U = 10 kV, (b) U = 20 kV.
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2.1. Formulation of the Problem

543

The solvent polarization model is based on experi

mental data on the distribution of the electric field
intensity around the ion, typical ion dimensions and
chemical bond lengths (i.e., bond radius), presented in
Table 2. This table shows that the typical atomic
dimensions r0 and interatomic bond lengths have the
same order of magnitude: 0.1 nm. For this reason, the
ion field has the highest effect at a distance of Rs = 5
10 nm from the center of the ion. This radius deter
mines the socalled coordination sphere of the ion.
Note that in solution electrochemistry, it is assumed
that the ion usually has two coordination shells
(FrankVenn model [2, 12, 17], Fig. 2a). Thus, the
molecules and atoms in volume Vs (solvation volume),
where r Rs, are actually polarized by a nonlinear law,
while for r > Rs, they are polarized by a linear law with
constant relative permittivity :

H
Cl
O
p

Me

O
Fig. 3. Model of the orientation of the methanol MeOH

molecules in the first solvation shell of the ClO 4 ion [12].

el

The computation of W s for the ion complex, consist

ing of N ions, gives the following expression:
el
Ws

1
= 
2

n=0

(n + 1) 

n + ( n + 1 )

ee

j k

j = 1k = 1

(5)

P = 0 ( 1 )E ( r > R s ).

( rj rk )

 P ( cos jk ),
2n + 1 n
r0

(4)

The ion polarization solvation energy is defined as the

energy of interaction between the ion and the dipoles
W p = e p ( 0 ), where p ( 0 ) is the total potential of
the dipoles at the ion location point. In the physical
chemistry of solutions, the polarization solvation
el

energy is defined as W s = 0.5e p ( 0 ); i.e., half the

value of Wp. The multiplier 0.5 appears since the sol
vation energy is defined as the work for the polariza
tion of the solvent during ion implantation. Here, ele

where r0 is the ion radius, e j, e k are the effective

charges of the jth and kth ions in the ion complex,
Pn are Legendres polynomials, jk are the angles
formed by the vectors r j and r k which determine the
locations of the jth and kth ions. In the case of a single
ion with the charge e from (5) there follows Borns
equation:
2

el
1
1e
W s =   1  .

2 r0

(6)

el

mentary work is defined as dW s = p ( 0 )dq, and

integration over the charge from q = 0 to q = e leads to
the appearance of the multiplier 0.5.
el

Let us present the calculation data for W s at the

continuum approximation when no solvation shell is
present and the medium polarization is determined
by (4) with the constant relative permittivity [13, 14].

In the case of polar media when the solvent consists

of dipole molecules with dipole moments p,
Onsager derived the following expression (reactive
field model [16]):
2
el
1 2 ( 1 )p
W s =  2 ,
2 ( 2 + 1 )r 0

p = p.

(7)

Table 2. Field intensity distribution E = e/(40r2), r = r around ion, typical dimensions of atoms, and interatomic bond
lengths [5, 15]
r, nm

10

15

E, mV/cm

14

0.56

0.14

0.06

Typical dimensions of atoms r0, nm Carbon C 0.077

Oxygen O 0.066

Iodine I 0.133

Typical bond lengths, nm

OH 0.096
CO 0.14
OO 0.12

CI 0.2
HI 0.16
II 0.266

CC 0.15
C=C 0.13

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Many works, e.g., [24], point out that formulas (5)(7)

are not always in agreement with experimental data. It
is supposed that one of the reasons for such a discrep
ancy is the nonlinear polarization of the solvent mole
cules in the solvation shell. The data in Table 2 clearly
demonstrate this. Thus, it is necessary to develop a
nonlinear theory of polarization solvation of ions,
which is considered below using a simplified average
polarization model.
2.2. Ion Solvation in a Boundless Medium
Using the Average Polarization Model
The simplified theory of polarization solvation as an
average polarization continuum model is based on the
combined continuum and microscopic approaches. It is
developed as follows. A single ion with charge e is consid
ered, which is assumed to be positive for convenience of
calculations. The electric field potential at an arbitrary
point M determined by radius vector r (see geometry and
notation in Fig. 2b) can be written as [18]
( r ) = 0 ( r ) + p ( r ),
e ,
0 ( r ) = 
r

p ( r ) =

pi Ri

,

R

where P ( E ) is the averaged polarization vector which

must in general be calculated on the basis of micro
scopic theories [1116]; R = r r 1 , R = R , inte
gration is performed with respect to the current point
M1, whose location is determined by the radiusvector
r 1 = ( x 1, y 1, z 1 ), so that dV 1 = dx 1 dy 1 dz 1 . Using the
relation (the subscript 1 denotes differentiation with
respect to the coordinates r 1 )
P
R
P div 1 P

= div 1  

3

R
R
R
and the GaussOstrogradskii formula, expression (9)
is brought to the following form:
P ( Ei )
div 1 P
p ( r ) = 
 dS + 
 dV 1 ,
R
S R

(11)

where Si is the effective ion surface, and Ei is the value

of the electric field intensity on Si.
(8)

Expression (11) has a simple physical meaning: the

electric field potential induced by the solvent dipoles is
determined by the total of the potentials of the bound
surface charges q s, b = P ( E i ) on Si and spatial charges

Here 0 ( r ), p ( r ) are the potentials of the ion and

solution dipoles, summation is done over all dipoles

q b = div 1 P in the solvation shell. If the dependence

with dipole moment p i around the ion, R i = r r i is

the radiusvector connecting the ith dipole at the point
Mi and the point M (Fig. 2b).

tial p ( r ) at any point M. Please note that relation

(11) also makes it possible to take into account, apart
from the nonlinearity of the solvation shell polariza
tion, the finite size and form of the ion.

3
i

1
= .
4 0

We calculate p ( r ) with the continuum approxi

mation assuming that polarization in the solvation
shell r R s is isotropic, i.e.,

P ( E ) is known, then (11) allows calculation of poten

Let us consider two limiting cases when point M far

from the ion r  Rs and at the center of the ion r = 0.

p ( r ) = c ( r ) + s ( r ),

In the first case (r  Rs), we have p ( r ) =

R dV ,
c ( r ) = ( 1 ) 0 E

1
3
V R

4R s P ( E s )/r, where Es is the field intensity at

r = R s . The parameter Rs can be chosen in such a way
that at r = R s polarization law (4) is satisfied, where

(9)

R dV .
s ( r ) = P

1
3
Vs R

Here c ( r ) is the potential induced by the dipoles in

the continuum region V of the linear polarization
according to law (4), s ( r ) is the potential of dipoles
in the solvation shell Vs with the polarization law
(average polarization law)
E
P = P ( E )  ,
E

(10)

E = Ee r , E = e'/(40r 2). Here, e r = r/r, e' is the

resulting charge determined by the sum of the ion
charge and the bound charges in the solvation shell

e' = e + eb, where e b = s P ( E i ) dS

2

Vs

div 1 P dV 1 =

4R s P ( E s ). It follows from these relations that e' =

e/; thus, at a far distance from the ion r  Rs, we have
1 e
p ( r ) =  ,
4 0 r

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(a)

545

(b)
V
Mi

Vs

Rs

Ri
rj
M
r

Rs
S0

Fig. 4. Medium polarization by a positive ion: (a) FrankVenn model of solvation shells [12, 17], (b) calculation model: V is the
region of the linear continuum polarization and Vs is the solvation volume Rs in radius where the nonlinear polarization takes
place.

and for the total potential we obtain the classical

expression,
e
( r ) = 0 ( r ) + p ( r ) =  .
4 0 r

(13)

It is noteworthy that expressions (12), (13) are true for

any law of nonlinear polarity in the solvation shell: (10).
To calculate the energy Wp, we must consider the
second limiting case of computing the potential p(0)
in the ion center r = 0. In this case in formula (11) in
the first integral there will be ( R = r 0 ), and in the sec
ond integral R = r. On integrating in the case of a
spherical ion r0 in radius, we obtain:
Rs

p ( 0 ) = 1 R s P ( E s ) + P ( E ( r ) ) dr .
0

where P is the mean value of the polarization vector in

the solvation shell.
This relation can be used for the evaluation calcu
lations. Thus, in the case of dense gases saturated with
impurity molecules with a constant dipole moment p0
and concentration n, the polarization vector is deter
mined as [18] P ( E ) = p 0 nL ( ), where
L ( ) = coth 1/ is the Langevin function,
= p 0 E/ ( k B T ); kB, T are the Boltzmann constant
and absolute temperature. For typical p0 1D = 3.34
1030 C/m, r0 2 even at distances about 10 molec
ular diameters (see Table 2, E = 5.6 107 V/m at r
50 ), saturation with the dipole polarization L() 1
occurs. Thus, in view of

(14)

P p 0 n  P ( E s ),

r0

This is a general expression in the sense that the aver

aged polarization vector P ( E ) is arbitrary, and it must
be estimated for each particular solvent. For example,
with no solvation shell when polarization law (4) is
true, that is,
1 
e ,
P ( E ) = ( 1 ) 0 E = 
4r 2
1 
e  , that in
from (13) we obtain p ( 0 ) = 
4 0 r 0
el

view of W s = 0.5e p ( 0 ) leads to Borns formula (6).

Using the meanvalue theorem, formula (11) can
be written as
1
p ( 0 ) =  ( R s P ( E s ) + P ( R s r 0 ) ),
0

(15)

Rs  r0

it is possible to estimate p ( 0 ) as
p ( 0 ) = p 0 nR s / 0 ,

(16)

where Rs should be read as the radius of the iondipole

interaction correlation. Formula (15) can also be the
evaluation formula for iondipole solvation in liquids
containing polar molecules that can rotate.
2.3. Ion Solvation Near the Metal Surface:
Formulation of Problem
If an ion is near a metal surface, its solvation is
influenced by the metal surface charge, whose electric
field is equivalent to the image charge field (Fig. 5).
For simplicity, we neglect the adsorption layer on the
metal surface S and assume that there is only polariza
tion solvation. It is apparent that this condition is sat
isfied only when the distance from the ion to S is

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M

M2

V2

V1

R2

R1

r2
V2s

R10

V1s

R20

M1
rj

Rs

Rs

S '0

S0
z0

z0

Fig. 5. Pattern of ion solvation near the metal surface: V1, V2 are the regions of linear continuum polarization; V1s, V2s are the ion
solvation volumes and images; S is the metal surface.

longer than the solvation shell radius z 0 > R s , unless

the solvation shell structure will be determined not
only by the interaction with the ion, but with the metal
atoms as well. To find the electric field potential ( r )
at point M of the solvent, we use the image method;
i.e., we find ( r ) in the form
( r ) = 0 ( r ) + p ( r ),

p ( r ) = 1p ( r ) + 2p ( r ),

(17)

1 R1
P2 R2
p ( r ) = P

 dV 1 + 
 dV 2 ,
3
3
V R1

R
2
V
1
2

1
= ,
4 0
where Vj are the regions occupied by the solvent (j = 1)
and the metal (j = 2) (including the solvation shells),
and P j are the polarization vectors in Vj. The other
keys are shown in Fig. 5.
The polarization vectors are related by the follow
ing rule: for every dipole charge, an image of it is con
structed, resulting in the dipole image in the metal
(Fig. 5). It follows that on the metal surface S,
P 1 = P 2, ( r ) = 0 is fulfilled. The zero potential fol
lows from the fact that on S there is R1 = R2, and the
sum of the integrals in p ( r ) is divided into two equal
terms of different sign, which results in zero.

(18)

jp ( r ) = I jp ( r ),
I jp ( r ) =

1
1
0 ( r ) = e   ,
R 10 R 20

The above method is used to transform integrals with

respect to volumes in p ( r ) to a form similar to (11):

Pj nj

div j P j

 dS +  dV ,

R
R

S ji

V js

(19)

( j = 1, 2 ).
Here n j are the external normals to the ion surfaces Sji
of the ion (j = 1) and its images (j = 2) (see Fig. 6). The
other keys are presented in Fig. 5. Recall that Rj is the
distance from current integration points Mj to point
M ( r ) , where the potentials are calculated; thus, dV j =
dx j dy j dz j (j = 1, 2).
2.3.1. Linear polarization model. Approximate solu
tion. To calculate potential (17), it is necessary to set a
polarization law in the ion solvation shell. Let us consider
the calculation procedure for linear polarization (4). In
this case, the polarization vector in the solvent is written
as P 1 = 0 ( E 1 + E 2 ), where = 1, E 1 ( E 2 ) is the
ion (image) field intensity, and the second integral with
respect to the solvation shell volume in (19) becomes
zero. To determine the field intensities, we obtain the fol
lowing system of integral equations:
' + E 2r'
e R + E
1r
E 1 ( r ) = 

 dS 1 ,
10
3
R1
R 10
S 1i

= 0 ,(20)

E 1r' + E 2r'
e
E 2 ( r ) = 
 R 20 + 
 dS 2 ,
3
R2
R 20
S 2i

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P2

P1

R2

R1

Fig. 6. Relationship between the dipoles in the solvent P 1 and their images P 2 in the metal.

(b)

(a)
x'

x '2

x1

'

M'
'

r'
M 1'

x2

M
r

''

'

M1

z'

z '2

''

z = z1

'
z2

y'

y '2

y1 = y2

Fig. 7. Choice of the coordinate system in the vicinity of image (a) and ion (b).

where the prime at the normal components of electric

field E 1r' , E 2r' on surfaces S1i, S2i means that they orig
inate at current points M1, M2 for integration; gradient
is taken at point M, whose coordinates are defined by
the radiusvector r.
Note that the integral in (20) is singular; thus, it is
incorrect to differentiate under the integral sign. Then
it is necessary to choose angles of the spherical system
that allow simplified calculation of the integral in (21),
i.e., to substitute the integration with respect to S2i by

the integration with respect to S1i using symmetry con

ditions.
Let the original coordinates K ( x, y, z ) has their
origin at the center of the sphere S1i (Fig. 7b). We
introduce system K 1 ( x 1, y 1, z 1 ) obtained by turning
the system K about the z axis through angle , and then
system K 2 ( x 2, y 2, z 2 ) about the y1 axis through angle .
Angles , are chosen in such a way that point M is on
the x2 axis (Fig. 7b). Thus, the radiusvector of fixed
point M in system K2 is defined as r = re x2 , of current

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point M1 in the form of r 1 = x 2 e x2 + y 2 e y2 + z 2 e z2 ,

M 1' . On these constructions the condition of the sym

with basis vectors e x2, e y2, e z2 of system K2 expressed

metric position of the points M1 and M 1' will be written

in the form of equality of their coordinates in the sys
tems K2 and K 2' or in the terms of the turn angles and
the basis vectors in the following form:
' = , ' = , '' = ',
(23)
'' = ', e x' = e x , e y' = e y, e z' = e z .
The symmetry conditions for the normal components
of the field intensities on S1i, S2i at the symmetric
points will be written as:
E 1r ( S 2i ) = E 2r ( S 1i ), E 2r ( S 2i ) = E 1r ( S 1i ). (24)

through basis vectors e x, e y, e z of system K as

e x2 = cos cos e x + cos sin e y + sin e z ,
e y2 = sin e x + cos e y ,

(22)

e z2 = sin cos e x sin sin e y + cos e z .

Similarly, we introduce the systems of coordinates
K ' ( x', y', z' ), K 1' ( x '1, y '1, z '1 ), K 2' ( x '2, y '2, z '2 ), of the
image with the origin in the image ion center with the
turn angles ', ' with the distinction that the axis z' is
directed oppositely to the axis z (Fig. 7). Then we intro
duce the spherical systems of coordinates (r, ', ') in the
system K2 and r, '', '' in the system K 2' reckoning the
polar angle ' from the axis x2, thus in the system K2:
x 2 = r cos ', y 2 = r sin ' cos ', z 2 = r sin ' sin '
and similarly in the system K 2' for the current point

The calculation of E 1r' , E 2r' on S1i is performed as follows.

Via scalar multiplication of (20), (21) by n 1, n 2 respec
tively, in terms of (22) and symmetry conditions (23),
(24), when calculating the integrals and the limiting tran
sition the point M to surface E 1r' , where n 1 is taken, we
obtain the following system of integral equations:

E 1r' + E 2r'
2
E 1r ( r ) = e
2 + r 0  d' d' 
 sin ',
r
R1
r0
0
0
R1 =

(25)

r + r 0 2rr 0 cos ' ,

2

' + E 2r'
e ( R cos + r ) r 2  d' d' E
1r
E 2r ( r ) = 

 sin ',
0
0
0
3
r
R1
R 20
0
0
R2 =

(26)

R 0 + r + r 0 + 2R 0 ( r cos r 0 cos 2 ) 2rr 0 cos ' ,

where r0 is the radius of the sphere S1i, R 0 = 2z 0 is the

distance between the ion and its image (Fig. 5), , 2
are the angles between the vectors r, r' and the axis z,
respectively (Fig. 7b). In Eqs. (25), (26), angle is
constant and cos2 is expressed through angles of sys
tem K2 as
cos 2 = sin cos ' + cos sin ' sin '.

E 2r ( r ) = B 0 + B 1 + B 2 +

(28)

Substituting (28) into (25) and maintaining terms

about 2 in (25) and terms about 1 in (26), we obtain
A 2

(27)

Relations (25) and (26) are a system of two integro

differential equations with the former being singular;
r 0 the denominator in integration
thus, at r
expression (25) for ' = 0 tends to zero. It is rather dif
ficult to solve these equations. An approximate ana
lytic solution in the case of a sufficient distance
between the ion and the metal surface = r 0 /R 0  1
can be obtained by an asymptotic method that repre
sents the solution in the form of the following asymp
totic series:

E 1r ( r ) = A 2 + A 1 + A 0 + A 1 + A 2 + ,

A ' 2
2 2
e
= 2 + R 0  d' d' 
 sin ',
r
R1
R0
0
0
2

e
B 0 = 2 cos + d' d'A ' 2 sin ' cos .
R0
0
0


r

The solution to these equations in terms of r = r0:

sin '
4
2
d' d'  = 2 has the form
0
0
R1
r0

e
A 2 = 2 ,
R 0

e
B 0 = 2 cos ,
R 0

(29)

= 1 + .

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SOLVATION EFFECTS IN LIQUID DIELECTRICS

Note that dielectric permittivity is calculated in

the first solvation shell of the ion; thus, the value of
can differ from its value within the bulk of the liquid far
from the ion. When calculating the other expansion
terms, it should be remembered that cos at the prime
functions under the integral is a variable and it is
defined by the righthand side of formula (27). The
calculations give
A 1 = 0,

e 2
A 0 =  2  cos ,
R 0 3

e 3 ( 1 3cos 2 ),
A1 =
 
R 20 5

e ( 3cos 2 1 ),
B 1 = 
2
R 0
(30)
3
e 3
B 2 = 2  ( 5cos 3 cos ),
R 0 2

e ( a cos b cos ),
A 2 = 
1
1
2
R 0
3

where a1, b1 are constants expressed through .

Finally, from (28)(30) with an accuracy up to
terms on the order of 2, it follows that at r = r0,
E 1r + E 2r = E 10 E 20 1 cos
2

Relation (32) shows that the total potential is

e, the image
made up of the ion potential 1 = 
r
e
potential 2 =  , and the solvation potential
R 20
p, which in turn consists of two parts. The first term
proportional to cos is on the order of and is struc
turally similar to the potential of the dipoles that
form near the ion and the image. The second term is
on the order of 2 and is structurally similar to a qua
drupole. It is also evident from (32) that as the ion
approaches the metal surface (R0 decreases), the
potential p increases. This indicates the increased
role of solvation by image forces as the ion
approaches the metal surface.
It is interesting to calculate the potential (0), i.e.,
at the ion location point, because its value determines
the solvation energy. In this case, in relations (17) R1 =
r0, and we can use a spherical system of coordinates in
system K with polar angle . Using (31) with an accu
racy up to terms on the order of 3, we obtain
e
( 0 ) =  + p ( 0 ),
R0

+ E 20 2 ( 3cos 1 ) E 20 ( acos + b cos ),

+2
1 = ,
3

+ 3 ,
2 = 2

5

e
E 20 = 
2 ,
R 0

e
E 10 = 
,
2
r 0

(31)

1 ,
= 
4 0

where a, b are constants determined only by , which

we will not describe, since they are absent in subse
quent formulas.
2.3.2. Calculation of potentials. Using (31) from
(17), we obtain the distribution of the electric field
potential in the vicinity of the ion r r0, r  R0 with an
accuracy up to the members on the order of 2:
e 
e + ,
= 
p
r R 20
3

2 2 r 0
e 1 r 0 P 
P
p =   
1
3 2 2
r 3R 30 r
5R 0 r
2

r 2r 0
+
 e
 rP 1 + 
 ,
2
R0 R0
2R 0
+ 2,
1 = 
3
P 1 = cos ,

+ 3 ,
2 = 2

5

2
1
P 2 =  ( 3cos 1 ),
2

where P1, P2 are the Legendre polynomials.

(32)

549

e + 
e 
e 1 r0.
p ( 0 ) = 

r 0
R 0
R 0 3 R 30

(33)

This expression shows that the ion interaction near

the metal surface is governed by the electrostatic
potential of the bare image charge e
 and the
R0
potential of interaction between the ion and dielectric
dipoles and image dipoles p(0). In turn, the potential
p(0) consists of the Born potentials of the ion
e and its image = 
e , as well as the
B = 
Bi
r 0
R 0
potential of the interaction between the ion and the
e 1 3 .
effective image dipole ip =  
The fact of
R 0 3
3

proportionality of potential ip to r 0 is due to the pro

portionality of the dipole moment of a single image
dipole to r0 and of the total dipole moment of the
image to the area of S2i. Summing up the dipole fields
3

over the area of S2i results in the proportionality of r 0 .

Note that formula (33) refines the Born theory on ion
polarization solvation near a metal surface using linear
continuum polarization.

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550

ZHAKIN

3. POTENTIAL AND IMAGE FORCE

Interpreting (33) as the ionits image interaction
potential, we find the following expression for the
force of attraction of the ion to the surface:
2

( 0) = 
e
F z = eE z = e d

2
dR 0
R 0
2 3

(34)

4 1 e r 0

 
 .
3 R 50
This expression for point ions (r0 = 0) coincides with
the universally accepted one [18]. However, when cal
culating the image force potential i, we need to
define it. The expression F z = d i /dz 0 is usually
used [19, p. 153]. Such a definition is due to the fact
that i is determined as some work to remove to infin
ity a point ion at a distance z0 from the metal surface,
which gives

e
i = F z dz = .
4z 0

(35)

z0

This expression is usually used in all calculations con

cerning image forces, e.g., [10, 19, 20]. However, if
proceeding from (33), the chargeimage interaction
energy is twice as large as i in the modulus:
e
W = e ( 0 ) = .
2z 0

(36)

The question now arises of which expression, (35) or

(36), is to be taken as the ionmetal surface interac
tion potential. In our opinion, expression (36) is cor
rect. In fact, because the ionsurface interaction is
equivalent to the interaction with the image, when cal
culating work (35), we should keep in mind the follow
ing. If the ion travels a distance z, the image also trav
els the same distance, but backwards; therefore, the
total distance between the ion and the image will be
2z. That is why integral (35) should be doubled,
which results in (36). Thus, in our opinion, the poten
tial of the image forces in view of finiteness of the ion
size should be defined as

i = 1
 2
 e
,
z 0 z 40 r 0
2

2
e 1 r 0
e
1 = 
 , 2 = 
,
2
72
+2
1
1 = , = ,
3
4 0

(37)

= 1.
It should be particularly emphasized that the value
of the dielectric permittivity must be taken inside the

ion solvation shell, which can considerably differ from

the corresponding value of far from the ion.
CONCLUSIONS
(1) In liquid dielectrics, the effective size of ions is
determined by the solvation radius, which is several
times larger than the crystallographic size of ions. The
size is defined by the iondipole interaction intensity
due to the solution to the problem of interaction
between the ion and solvent molecules in the neigh
borhood of the ion (in fact, it is a quantummechani
cal problem).
(2) In the ion solvation shell, the liquid polariza
tion is nonlinear. However, the electric field far from
the ion does not depend on the law of solvation shell
polarization. It is defined by the classical formula in
which the dielectric permittivity is determined by the
law of linear polarization beyond the solvation shell.
(3) The ion solvation shell substantially changes
near the electrode, because the image forces appear
there. This effect must be taken into account when
considering the electrochemical processes on the elec
trode surface.
(4) The concept of the infinity image force poten
tial should be revised.
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SURFACE ENGINEERING AND APPLIED ELECTROCHEMISTRY

Translated by M. Myshkina

Vol. 51

No. 6

2015