Derivation of the Poisson-Boltzmann Equation by Minimization

of the Helmholtz Free Energy Using a Variational Principle

W. B. KLEIJN AND L. J. B R U N E R
Department of Physics, University of California, Riverside, California 92521
Received August 9, 1982; accepted April 6, 1983
From the classical derivation of the Poisson-Boltzmann (P.B.) equation one does not obtain a clear
insight into the approximations involved. As an alternative to sophisticated statistical theories we
present a straightforward (mainly thermodynamic) derivation o f the P.B. equation which does provide
insight into the approximations made. In this derivation a free energy density is defined within the
diffuse double layer. The free energy o f the entire diffuse double layer can then be minimized, using
a variational principle. The introduction of certain approximations results in the P.B. equation. The
present method allows some corrections to the P.B. equation to be included.

the interface at high surface charge densities

(~0.05 C/m2). Thus, while uncertainty about
the immediate vicinity of the interface remains, the P.B. equation gives good predictions at lower electrolyte concentrations.
Using certain approximations the P.B.
equation can be derived from statistical mechanical theories. Thus, the P.B. equation
has been shown to be the result of a zero-th
order closure of a hierarchy of electrostatic
equations (10). Similarly the P.B. equation
can be obtained from the Boguliubov-BornGreen-Yvon integral equations (7, 11, 12)
and also from the Ornstein-Zernike integral
equations in the hypernetted chain approximation (13). The assumptions implicit in
these statistical mechanical theories and the
approximations made in its derivation from
these theories provide insight into the assumptions implicit in the P.B. equation.
The assumptions implicit in the P.B. equation are not obvious from the equation itself.
Our goal is to provide a straightforward derivation of the P.B. equation from well-known
principles which demonstrates clearly the
assumptions made. We derive the P.B. equation by minimizing the free energy within the
diffuse double layer. Using a variational prin-

I. I N T R O D U C T I O N

The Poisson-Boltzmann (P.B.) equation

was developed independently by G o u y (1)
and Chapman (2) to describe the ion distribution functions and the mean electrostatic
potential near a charged interface. The P.B.
equation has been found to give good predictions for observable parameters over a
wide range of experimental conditions (3-5).
Many authors have tried to evaluate the
accuracy of the P.B. equation by comparing
it to revised theories and computer experiments. Almost all of these studies make use
of the "primitive model" (finite size ions in
a continuous solvent). Recently, it has been
shown that structural properties of the solvent become important close to the interface
(6). Therefore results accurate for the primitive model may not be realistic close to the
interface.
Monte Carlo simulations of the diffuse
double layer using the primitive model have
shown that the P.B. equation predicts the ion
distribution functions for a 1:1 electrolyte
accurately up to about 0.1 M (7-9). The
mean potential function was found to be
overestimated by the P.B. equation close to
20
0021-9797/83 $3.00
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All rightsof reproductionin any form reserved.

Journal of Colloidand InterfaceScience,Vol. 96, No, 1, November1983

21

DERIVATION OF THE POISSON-BOLTZMANN EQUATION

ciple we optimize the independent functionals (potential and concentrations) under fixed
boundary conditions.
II. THEORY

The free energy of an electrostatic system

at constant temperature is (14)

field components directed perpendicular to

the plane of the wall. Parallel feld components will vanish on time averaging and by
symmetry. The time average of E2~ can be
calculated if one assumes that there is no
correlation in the locations of the ions:
=

E E

Fe = <1 ~EoE2>

[1]

= Z

<Ei)(E,)

2 - Z <Ei>2

where E is the dielectric constant, 4o is the

permittivity of free space, E is the electric
field, and the angular brackets indicate time
averaging. Incorporated into Eq. [1] is the
configurational entropy of the dipolar mop
ecules of the dielectric medium. The diffuse
double layer can be considered as a solvent
medium of dielectric constant ~s containing
hydrated ions of dielectric constant Ek. If C~
is the concentration (ions/unit volume) of
ions of species k, Eq. [1] becomes
1

/We ----~ Es~0((E~) -- E

k

fk(E~)ck)

E~ = Z Z EiEj
j

= Z E~ + E Z EiEj j i .
i

j ~ i

[4]

where the last term on the right is negligible

and will be omitted in our derivation. This
is justified in Part A of the Appendix. Let us
consider a 1:1 electrolyte for which the anions and cations differ only in the sign of
their charge. Then Eq. [4] becomes
:

f (c+ + c )dr +

[51

[21 where Ej is the field at some fixed location

where fk is a coefficient which depends on

the geometry of the hydrated ion and on the
dielectric constants es and ~k- In Eq. [2] E~
is the electric field that would exist if the dielectric constant of the hydrated ions, ek,
were equal to that of the solvent, es. The second term on the right-hand side is of course
just the polarization energy of the hydrated
ions.
The electric field Eo~ can be attributed to
all of the individual charges (both mobile
ions and adsorbed surface charges) present
in the system

[3]

In the preceding equation each subscript

ranges over all the ions and adsorbed charges
present. Since we will be concerned with the
boundary layer adjacent to an infinite plane
wall, we need be concerned only with scalar

due to a single (mobile) ion. Note that

(E 2) is a function of position while the integral is a fixed normalization factor. The
contribution of the surface charge to the
mean square field is not considered In Eq.
[5] since this term does not influence our
final results. This is so because the surface
charge contribution to ( E ~ ) and to (E~o) 2
is constant throughout the half-space extending from the plane wall into the electrolyte
solution. Spatial variation of these quantities
comes about only by reason of screening due
to the asymmetric distribution of mobile ions
in the diffuse layer. The variational method
to be used below in deriving the P.B. equation is sensitive only to the spatially varying
part of the actual mean field, (E), related to
(Eoo) by Eq. [9], below.
If it is desired to include a correction for
the hard sphere character of the ions, we
must return to Eq. [3], and recognize that the
sources of the fields E~ and Ej, namely ions
i and j, cannot overlap in space. In a certain
volume element of the diffuse double layer
a volume fraction c+veis "occupied" by the

Journal of Colloid and Interface Science,

Vol. 96, No. 1, November1983

22

KLEIJN AND BRUNER

cations and a fraction c-l)e is "occupied" by

the anions, where ve is the exclusion volume
of an ion. The contribution of this volume
element to Eq. [3] (sums replaced by integrals) must therefore be diminished by -E~
(c+)2v,dr (cation-cation exclusion) and
-E~(c-)2v,dz (anion-anion exclusion), and
increased by 2E~c+c-vedr (anion-cation exclusion) where dr is the volume of the volume element. The total contribution due to
the hard-sphere character is thus -E~(c
- c - ) 2 d r . Incorporating the hard-sphere
character of the ions into Eq. [5] results now
in

(EL) =

f (e+ + c-)d

+ ( E , ) 2 - (E~) f~ (c + - c-)2v,dr.

Here it is assumed that & is a constant, i.e.,

that variations in the dielectric constant (and
in particular its discontinuity at the interface)
can be neglected. & is the hydration energy
of the hydrated ions.
As mentioned before, the electric field E~o
is a hypothetical field which would appear
if the dielectric constant of the hydrated ions,
~h, reduces to that of the solvent. The matter
of the dielectric constant of hydrated ions is
considered further in Part B of the Appendix.
From knowledge of the relation between the
dielectric constant of the pure solvent and
the actual mixture of solvent and ions, the
Maxwell-Lewin formula (16), a coefficient
relating the actual mean electric field, (E),
and (E~) is obtained:

[61
\2es + eh/)

The added term in Eq. [6] gives rise to the

so-called cavity potential, which has been
shown to be an important correction to the
P.B. equation (15). Note that the cavity-potential contribution vanishes in the bulk solution where c+ = c-.
Combination of Eqs. [2] and [6] followed
by integration over space formally gives the
free energy of the diffuse double layer. However, the double integrals arising in the evaluation of the polarization energy of the ions
do not allow use of the variational method.
To prevent this, we will omit the first and
last term of the right-hand side of Eq. [4] in
the evaluation of the polarization energy of
the ions. Thus we obtain

f Fo&= IgAc+ + c )
+ -~0~s
y {(Eoo) 2 - &(c + - c-)2ve
-

fj(c + +

c-)(e~)2}ld~

[7]

where Ve is the volume of an ion and

gj =

~-

[8]

Journal of Colloid and Interface Science, Vol. 96, No. 1, November 1983

x (E~) =- h(E~) [91

where vt is the total volume fraction of all
ions present.
Thus the calculation of the electrostatic
part of the free energy has been completed.
The major assumptions in this calculation
are (i) no spatial correlation between the ions
exists, except for hard-sphere exclusion, (ii)
the solvent medium in which the hydrated
ions are submersed is a continuum with a
well-defined dielectric constant (which may
vary in space).
To complete the computation of the free
energy of the diffuse double layer, another
contribution must be introduced which can
be obtained from either of two physical interpretations of the diffuse double layer system. One can consider the diffuse double
layer system as a gas of ions in a background
"ether" (the solvent) which screens the electrostatic interactions, or alternatively, as a
mixture of ions and water molecules. In the
first case (which we will not discuss in detail),
the expression for the Helmholtz free energy
of an ideal gas (again we neglect spatial correlations of the ions) must be added to
the electrostatic contribution to obtain an

DERIVATION

OF THE POISSON-BOLTZMANN

expression for the free energy of the diffuse

double layer. Using similar methods, such as
those described below for the mixture interpretation, the P.B. equation can also be obtained.
Before we begin our discussion of the derivation of the P.B. equation from the mixture
interpretation, we digress briefly to consider
an important approximation made in the
derivation of the P.B. equation (using either
interpretation). In both cases, expressions
developed for bulk phases are applied to an
inhomogeneous region. This makes it possible to define local free energy densities in
the diffuse double layer. It has been shown
(17) that the implicit assumption of such an
approach is that the spatial correlation of the
ions is short as compared to the inhomogeneity of the system. For the diffuse double
layer, this means that the (long-range) Coulombic correlations are neglected, which is
consistent with our earlier assumptions. The
finite size of the ions will invalidate the usage
of expressions developed for bulk phases only
at very high concentrations.
The free energy of mixing of the ions and
water molecules can be separated into energy
and entropy contributions. The energy of
mixing (dissolution) has already been included in the electrostatic contribution to the
free energy (Eq. [8]). As will be shown later,
the energy of mixing does not contribute to
the free energy of the diffuse double layer
when one considers the reference state, and
therefore, any nonelectrostatic parts of the
mixing energy are not considered. Therefore
only the entropy contribution due to mixing
has to be included. If we assume that mixture
to be ideal (18) we get

TSm = kT{-(1 - x + - x-) In (1 - x + - x-)

-x +lnx +-x-lnx-}

[10]

where x + and x- are the mole fractions of

cations and anions in the mixture.
In our present discussion of the diffuse
double layer, we have not yet considered the
fact that the ions and water molecules are in

23

EQUATION

equilibrium with the bulk solution (the reference level of the free energy). When removing ions and water molecules from the
bulk solution to create a diffuse double layer,
the free energy of the bulk solution diminishes by

Fb = g~(c + + C-) + kT{(1 - x + - x-)

In (1 - x~ - xS) + x + In x~+ x- In x8

[11]

where x~ and Xo are the mole fractions of

cations and anions in the bulk solution. In
Eq. [ 11 ] the first term describes the hydration
energy and the second term describes the
entropy. If the dielectric constant does not
vary within the diffuse double layer the hydration term will cancel out in calculation
of the free energy of the diffuse double layer
(wall effects are neglected).
From combination of Eqs. [7], [9], [10],
and [ 11] an expression for the free energy of
the diffuse layer can be obtained:

f Fdr=f[2eOes{h2(E)2-gj(c+-c

)2/.)e

- h2f~(c + + c-)(E) 2) - k T l ( 1 - x - - x +)
l n ( } - x - - X ~ ) x o + x - I n (x~)
+ x + In

dr

[12]

where it has been assumed that the dielectric

constant of the solvent does not vary within
the diffuse double layer.
The complete character of the Coulombic
interactions has not yet been incorporated
into our discussion. This is most conveniently accomplished by use of the Poisson
equation for the mean electrostatic potential,
denoted here as g,:
dx

= -q(c

+ -

c-)/~O~s

[131

where a fiat diffuse double layer has been

assumed. With Eq. [13] and from the relaJournal of Colloid and Interface Science, Vol. 96, No. 1, November 1983

24

KLEIJN AND BRUNER

tions x + = v~c+ and x - = v~c- the free energy

density of the diffuse double layer can be
written as a function of c+, d~k/dx = (E>, and

d/dx(h(d~/dx):

Combination of Eqs. [13], [16], and [18]

gives a modified P.B. equation:
~d2d/
x z = Co exp I ( _ q d / g j V- e ( C + C - -

o~ Fdx

de, d ( h~x/!
d~]]dx
= fo F ( C+,dx,dx

[14]

(for a flat diffuse double layer).

With the variational principle (19) the
functionals c+ and ~ of Eq. [ 14] can be optimized so that the free energy of the diffuse
double layer is at a minimum. At this point
we will assume that the coefficient h (Eq, [9])
can be set equal to unity. Including the coefficient h in our derivation is straightforward
but makes the computations tedious. The
variational derivative o f F ( c +, ~', ~") in c+ is

exp[(q~k+g, ve

(C+--C -)-leOeOf,~/2)/kT

].

[19]

This modified P.B. equation includes a cavity

potential correction and a correction for the
polarization energy of the ions. Using the
variational method, the effect of the electrolyte concentration and saturation (depending
on the analytical expression used) can also
be included in the modified P.B. equation.
Omission of the correction terms in Eq. [ 19]
gives the classical P.B. equation.
III. C O N C L U S I O N S

6c+ -- e0e~{-f?p '2} - kTln

= 0 [151

where the equalities x+-/x~ = c+-/c~ are assumed to hold. Equation [ 15] can also be written as
C+ C-

/--,oesf,~b'2~

4 C o = exp[

kT

]"

[16]

In the present derivation the P.B. equation

is obtained by minimizing the free energy of
the diffuse double layer. Such a derivation
provides useful insight into the approximations involved without employing sophisticated statistical theories. In summary the approximations leading to the P.B. equation
are;

The variational derivative in 1/' is

-~

= ,o,s -~x +

g~ve ~ x 2 (c + - c - )

1 E0~s
2 2 d2ff,2
d
+ ~ ~ f, ~
+ G,,of, dx ((c+ - c-)~b')

eseokT~--;~ In

c-

= 0.

[171

In the concentration range for which the P.B.

equation is used, (c+ + c-)fj ~ 1 and therefore the fourth term can be neglected compared to the first. Then Eq. [17] can be integrated with ~ = ~' = 0 in the bulk:

c-= Co exp[(q~+gjve(c+-c -)
l eoe.sfj~'2)/kT ]

[18]

Journalof Colloidand InterfaceScience,Vol. 96, No. 1, November 1983

(1) The solvent medium is assumed to

have a dielectric constant which is well defined on the molecular scale used; i.e., the
molecular structure of the solvent is ignored.
Saturation of the dielectric constant is assumed not to occur. Corrections due to saturation can be included by modifying Eq.
[ 13] appropriately, but the use of such (macroscopic) corrections is doubtful on the molecular scale considered.
(2) No spatial correlations between the
ions in the diffuse double layer are assumed
to exist. Strictly speaking, this is not true for
the derivation of the entropy contribution
(Eq. [10]) from the equations for an ideal
mixture. In this derivation ions and molecules are assumed to be of similar (finite) size

DERIVATION

OF THE

POISSON-BOLTZMANN

(18). The hard-sphere character of the ions

can be included in the electrostatic contribution to the free energy by introducing a
cavity potential term (Eq. [6]). If the P.B.
equation is derived from a gas model for the
ions the hard-sphere character could be included by a van der Waals type correction.
These corrections are inaccurate if the parameters of the diffuse double layer change
significantly within a length equal to the radius of the ion (17). Since correlations arising
from Coulombic interaction are long range
they cannot be included in a method using
local free energy densities.
(3) The polarization energy of the ions is
neglected. If one assumes a fixed dielectric
constant for the hydrated ion a correction for
this effect is rather straightforward (Eq. [2]).
(4) Changes in the hydration energy of the
ions are neglected. The hydration energy of
the ions is dependent upon the dielectric constant of its environment (Eq. [8]). Changes
in the hydration energy due to the discontinuity of the dielectric constant at the interface are called "image effects" and are often
significant. Dielectric saturation also leads to
sharp modifications of the P.B. equation
(20), but the use of macroscopic theories
gives information of little quantitative value.
(5) The compressibility of the solvent
medium is ignored. This leads to a small error (15).
Bell and Levine (21) have also considered
the approximations cited above in the context of a "local thermodynamic balance" derivation of the P.B. equation. These authors
also calculated the free energy of the diffuse
layer, using the result to determine the electrochemical potentials of the ion species in
the diffuse layer. Imposition of the requirement of constancy of the electrochemical
potentials, with summation over species, led
them to a first integral for the P.B. equation
with correction terms. The novelty of our
approach resides in the use of the variational
method, rather than in the discovery of any
hitherto unsuspected correction terms.

EQUATION

25

From the Monte Carlo studies it has been

shown that recent statistical-mechanical theories give a reasonable description of the
primitive model of the diffuse double layer
(9). The accuracy of the P.B. equation for the
primitive model can be assessed from these
theories, or directly from the Monte Carlo
studies. As mentioned in the introduction the
P.B. equation was found to give a satisfactory
description of the primitive model in a large
range of the parameters involved. Estimates
for the polarization energy correction are
probably fairly accurate (approximation 4).
However the magnitude of approximations (1) and (4) are most difficult to evaluate
because of the molecular structure of the solvent. Only recently a first approximate theory which treats the solvent molecules and
the ions on equal footing has been presented.
No Monte Carlo studies of such systems are
presently available. The approximate theory
predicts that effects due to solvent structure
are important close to the interface. Thus,
conclusions reached for the primitive model
are probably not accurate for a real system.
In conclusion it can be said that the structure of the diffuse double layer away from
the interface is well understood. The P.B.
equation gives a good description of this region in most cases. Properties of the diffuse
double layer close to the interface are presently not well understood and, therefore, the
accuracy of the P.B. equation in this region
is not certain. However it appears justified
to say that the P.B. equation is a good approximation also for this region at low electrolyte concentrations, and surface charge
densities.
APPENDIX

A. Macroscopic and Microscopic

Electric Fields
It is useful to rewrite Eq. [4] in the form

((E~ - (E~))2) -- ~ ( ( E i - (El))2). [AI]

i

This result states that, in the absence of spaJournal of Colloid and Interface Science, Vol. 96, No. 1, November 1983

26

KLEIJN AND BRUNER

tial correlation of charges, the mean squared

fluctuation of the macroscopic field about its
mean value at any point in space, (Eo~), is
obtained by summation over all charges
(both mobile and adsorbed) of the corresponding quantity for each charge. Restricting the summation to a 1:1 electrolyte of
mobile anions and cations identical except
for the sign of their charge, Eq. [A1] becomes
((E~ - (E~}) 2} = N((E~ - (E~}) 2}

[A2]

where N is the total number of such charges

in the system. Removal of adsorbed charges
from the summation at this point is justified
by the argument presented following Eq. [5]
above. If at this point we set (El} = 0, and
N = fv (c+ + c-)dr, Eq. [A2] reduces to Eq.
[5] of the text. We can, on the other hand,
permit (Ei} 4: 0, and estimate an upper limit
for (E~} 2 as follows, setting
( E ~ ) ~ N(Ei).

[A3I

Combining Eqs. [A2] and [A3] yields

((E~ - (E~}) 2}

(Eo~}2

I ((gi - (Ei})2
N

(Ei} 2

[A41

which states that the fractional mean squared

fluctuation in the macroscopic field varies in
inverse proportion to the total number of
particles contributing to that field. In this
form the result clearly resembles familiar results of the calculation of energy and density
fluctuations in many-particle systems (Ref.
(18), pp. 34-38). If we expand Eq. [A2] and
substitute from Eq. [A3], we get
(E2} - (1-1)(E,~}2

~ N(E~}.

[A5]

Since expansion of Eq. [A2] with (Ei} = 0

yields
(E2} - (Eo~}2 = N<E~}
[ASI
we see immediately that setting (Ei} = 0
leads to a maximum fractional error in
(E~o}2 of the order of 1/N, which is negligible.
In conclusion we point out that the derivation of the P.B. equation, including the
Journal of Colloid and Interface Science, Vol.96, No. 1, November1983

correction for the polarization energy of the

ions, can be carded out using the variational
method with the right-hand side of Eq.
[A 1] set equal to zero. Retaining the term,
N(E2i), introduces the ion hydration energy,
which does not enter the P.B. equation, in
our approximation, and the cavity potential
correction which has been included in our
derivation.
B. The Dielectric Constant
of Hydrated Ions
In introducing the dielectric constant of
hydrated ions, eh, it is our intent to establish
that the time average macroscopic field,
(E}, in a dielectric medium containing hydrated ions of finite radius would in general
be different from the corresponding field,
(Eo~}, at the same point in a homogeneous
dielectric medium of relative permittivity,
E~, containing point ions. This difference is
described by Eq. [9], above. Any relationship
between these fields will necessarily involve
both the size and the polarizability of hydrated ions. In an experimental approach to
this problem one could measure the high frequency complex dielectric permittivity of
aqueous ionic solutions and obtain the static
dielectric constant of the solutions by extrapolation of Cole-Cole plots to zero frequency. This has been done by Giese et al.
(22). To interpret their results on a microscopic scale these authors had to assume that
hydrated water could not contribute to orientational polarizability, assuming in effect
that ~h ~ 2. Then using a relation comparable to our Eq. [9], they were able to calculate the molar ratio of bound water to dissolved ions.
ACKNOWLEDGMENTS
This work was supported by Grant GM 27626 from
the National Institutes of Health, and by Grant PCM
79-26672 from the National Science Foundation.
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DERIVATION OF THE POISSON-BOLTZMANN EQUATION

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Journal of Colloid and Interface Science, Vol. 96, No. 1, November 1983