Postulates of the Debye Hückel theory

Peter Debye and Erich Hückel in 1923 gave a theory for the determination of mean activity
coefficients ( 𝛾±). This theory is applicable to strong electrolytes. Debye and Hückel noticed
that solution that contains ionic solutes, do not behave ideally (even when the concentration is
low). In order to calculate the dynamics of a solution, concentration of the solute is the most
important parameter. Since in case of ionic solution there exists attraction between ionic species
therefore, Debye and Hückel have given an extra factor termed gamma (γ) which is defined as
activity coefficient. It takes into consideration the interaction energy of the ions in the solution.
In other words, mean activity coefficient ( 𝛾± ) is the measure of ion-ion interactions. Debye
and Hückel gave postulates in support of their theory which are as follows: -
1. Ions are treated as hard spheres and point charges.
2. The ion-ion interaction is assumed to be coulombic forces (varies with distance as 1/r2)
while short range non-coulombic forces (dispersion forces) play a negligible role.
3. The role of solvent is to provide a medium which is a continuum of dielectric constant
(ɛ) which is necessary for the operation of interionic forces.
4. The concept of charge density was introduced which measured charge density (ρ) as a
function of distance (r).
5. Bulk charge density (ρ ) is assumed to be zero i.e. the solution is overall electrically
neutral.

Ionic Cloud Theory

The Debye- Hückel theory applies to strong electrolytes. The electrolytic solution consists of
solute ions and water molecules. The first approach in Debye-Hückel theory is the arbitrary
selection of a reference ion or central ion from assembly of ions. Thus, in the electrolytic
solution, the central ion is considered to be standing alone in a continuum. The water molecules
provide a medium of continuum dielectric constant (ε). The remaining ions in the solution are
spread out into a continuous spatial distribution of charge.

Fig.1. A schematic comparison of (a) the assembly of ions and solvent molecules in a real electrolytic
solution (b) the Debye Hückel picture in which reference ion is surrounded by net charge density( 𝝆𝒓 )

If the concentration of ions of one sign exceeds that of the opposite sign then there is an excess
charge in the particular region which is in consideration. However, the total charge in the
atmosphere and the charge on the reference ions have opposite sign and are equal.
Excess Charge Density around central ion
Consider an infinitesimally small volume element dv situated at a distance r from the central
ion. Let the charge density inside the volume element be r and the electrostatic potential on
the volume element be  r. At this distance ‘r’, the ion-ion interactions are taking place between
the central ion and surrounding ions.

Fig. An infinitesimal volume element dv, at a distance r from the reference ion with the excess charge
density r and electrostatic potential  r

Excess Charge Density around central ion is considered to be given by two equations:
1. Poisson’s equation in spherical polar coordinates

(1)

On rearranging equation 1 we will get

(2)

2. Linearized Boltzmann distribution law

(3)

Where, zi is the valency of the ion

eo is the electronic charge

𝒏𝒐𝒊 is Bulk concentration of the ionic species ‘i’
refers to the summation over all the species of ions ‘i’
Equate equation (2) and equation (3)

(4)

Equation (4) is known as the linearized Poisson-Boltzmann (L-B) expression.

The terms on the right-hand side within parenthesis of equation (4) are constants, therefore
they can be clubbed together and called a new constant 2.

(5)

Therefore, in terms of , the linearized Poisson – Boltzmann expression (4) can be written as

(6)

Solution of the Linearized Poisson – Boltzmann equation

In order to solve the linearized Poisson – Boltzmann equation a new variable  is introduced.
The new variable  is defined by
(7)

Differentiating equation (7) with respect to r; we get the following equation

(8)
On rearranging equation (8) we get,

(9)
Differentiating equation (9) with respect to r, we get

(10)
Divide equation (10) by r 2

(11)
Using equation (11) in equation (6) we get,
(12)
Substitute the value of  r from eqn (7) to eqn. (12)

(13)

It is a second order differential equation and the general solution of the linearized Poisson
Boltzmann equation can be written as
(14)
where A and B are constants
From eqn. (7) and eqn. (14)

(15)

Evaluation of Constant B
The constant B is evaluated using the boundary condition, that is, the thermal forces completely
dominate the coulombic forces. When the ion is far enough from the central ion
(situated at r =∞) and their electro neutrality, i.e., the electrostatic potential  r vanishes at
distances sufficiently far from such an ion.

This will be satisfied only if B = 0. Hence equation (15) reduces to

(16)

Evaluation of Constant A
In order to evaluate the constant A (integration constant) a hypothetical condition is considered.
In this condition, the solution is considered to be so dilute, and on an average the ions are so
far apart that there is a negligible inter-ionic field. Also, the central ion is assumed to be a point
charge. Hence the potential near the central ion is simply due to an isolated point charge of
value zi eo
 (17)
At the same time:
As
Equation (16) reduces to

(from eqn 7)

(from eqn. 17)

Thus

Or, (18)

Using eqn. 18 in eqn 16 we get,

(19)

Eq (19) is the solution to the linearized Poisson – Boltzmann equation (6). It shows the variation
of electrostatic potential with distance r from an arbitrary chosen reference ionwhich is an
exponential decay (Fig.1)

Fig.1. Variation of electrostatic potentials  a function of distance from the central ion
expressed in units
The linear relation between excess charge density (r) and potential (r) can be derived using
Poisson’s equation (1) and linearized Poisson Boltzmann equation (6). Thus,

(20)
From eq. 19 in eq. 20
𝒁𝒊 𝒆 𝟎 𝝌𝒓
𝟐𝒆
𝒓 = − 𝝌 (21)
𝟒𝝅 𝒓

Physical Significance of equation (21):

Due to unequal distribution of positive and negative ions, there exists excess charge density.
Therefore equation (21) describes the distribution of ions around a reference or sample ion.
1. The arbitrary chosen central reference ion is surrounded by a cloud or atmosphere of excess
charge (Fig.2)

Fig.2. Distribution of excess charge density around a central ion can be visualized as a cloud or
atmosphere of net charge around the central Ion.

2. This ionic cloud extends into the solution (i.e., distance r increases). The variation of excess
charge density as a function of distance (r) from the central ions occurs in an exponential
way (Fig 3).

Fig 3: Variation of excess charge density  as a function of distance from the central ion.
3. The sign of the excess charge on the ionic cloud is opposite to that of the central ion.
Therefore, either a positively reference ion has negatively charged ion atmosphere or a
negatively charged reference ion will have a positively charged ion atmosphere (Fig. 4).

Fig 4: A negatively charged ion is surrounded by a positively charged ionic cloud and vice-versa

Thickness or radius of the ionic atmosphere – (Debye – Hückel length):

Consider a spherical shell of thickness dr at a distance r from the origin i.e. from the centre of
the reference ion

The charge of dq in this thin shell (dq) = charge density x volume of the shell
dq = (r ) x (4πr2dr) (22)
Put the value of r from the eq. 21 to eq. 22

(23)
Thus, the excess charge on a spherical shell varies with distance r and has a maximum value
for a given value of r which is given by
(24)

(from eq. 23)

Since the term (Zieo 2) is finite. Therefore, in order to satisfy the condition of equation (24),
we have

Or,

Or,

Or, (25)
Hence the maximum value of the charge contained in a spherical shell is attained only when
the spherical shells is at distance. r  1.
Therefore, 1 is known as the thickness or radius of the ionic cloud which surrounds are
reference ion (central ion) where, 1 is given by:

(26)

An elementary dimensional analysis of equation (26) reveals that has the dimension of
length.1.

Or

1 is also referred as Debye – Hückel length.

Effect of concentration on the thickness of Ionic Cloud

The thickness of Ionic cloud .1 is given by

(26)

For a given solution 1 is constant, since all the terms in this equation are constant.
Case I: Decrease in Concentration
On decreasing the concentration i.e. dilution of a solution decreases 𝒏𝒐𝒊 . That means the total
number of density of the bulk or number of ions for unit volume is decreases. Thus, from eq.
(26) implies an increase in 1. Therefore, on dilution the thickness of the cloud increases. In
other words, on dilution the cloud becomes more and more diffused.
Case II: Increase in Concentration
On increasing the concentration of a solution increases 𝒏𝒐𝒊 . That means the total number of ions
for unit volume is increases. As a result of this 1 is decreases. Therefore, on increasing the
concentration of the solution, the ionic cloud becomes concentrated on reference ion.

Computation of total Excess charge contained in ionic atmosphere around

central ion/ reference ion:
Consider a spherical shell of thickness dr at a distance r from the origin i.e. from the centre of
the reference ion

The charge of dq in this thin shell (dq) = charge density x volume of the shell
dq = (r ) x (4πr2dr) (22)
Put the value of r from the eq. 21 to eq. 22

(23)
 𝑞 =∫ 𝑑𝑞

𝑞 =∫  4π𝑟 𝑑𝑟
−𝝌𝒓
𝑞 =∫ − 𝒁𝟒𝝅
𝒊 𝒆 𝟎 𝝌𝟐 𝒆
𝒓
4π𝑟 𝑑𝑟
𝑟=∞
𝑞 =−𝒁𝒊 𝒆𝟎 ∫
𝑟=0
𝝌𝟐 𝒓 𝒆 𝝌𝒓
𝑑𝑟

Since, ∫ 𝝌𝟐 𝒓 𝒆−𝝌𝒓 𝑑𝑟 = 1
Therefore, 𝒒𝒄𝒍𝒐𝒖𝒅 =−𝒁𝒊 𝒆𝟎

Relationship between mean activity coefficient and Ionic strength

of strong electrolytes (Debye and Hückel Limiting Law)
In an electrolytic solution, ion-ion interactions are always present. Further the chemical
potential change ∆μi-I in going from a hypothetical state of non-interacting ions (discharge
state) to a state in which the ions of species ‘i’ interact with the ionic solution (charged state)
is considered as a quantitative measure of these interactions. We arbitrarily choose a reference
ion (i.e. central ion) from the assembly of ions. From the postulates of Debye–Hückel theory,
these ion-ion interactions are assumed to be purely columbic in origin. Hence, the chemical
potential change arising from the interaction of species ‘i’ with the electrolytic solution is
Avogadro number (NA) times the electrostatic work W, resulting from taking a discharged
reference ion and charging it up in the solution to its final charge.
Mathematically,
(1)
Now, we need to calculate the work of charging up the reference ion from zero charge
to its final charge 𝑧 𝑒 .
For this, we need to obtain the electrostatic potential at the surface of the reference ion. In
order to obtain the theoretical expression for the potential Ψref-ion, we need to understand
the distribution of ions around a given reference ion.
Debye–Hückel model treats only ion i.e., the central/reference ion as a discrete charge, while
the remaining ions in the solution are being smoothened out to give a continuous charge
density.
Excess Charge Density around central ion is considered to be given by two equations:
1. Poisson’s equation in spherical polar coordinates
 (2)

On rearranging equation 2 we will get

(3)

2. Linearized Boltzmann distribution law

(4)

Where, zi is the valency of the ion

eo is the electronic charge

𝒏𝒐𝒊 is Bulk concentration of the ionic species ‘i’
refers to the summation over all the species of ions ‘i’
We equate these two expressions (3) and (4) for the excess charge density, and we get the
fundamental partial differential equation of the Debye–Hückel model i.e. linearized Poisson
Boltzmann equation (P-B) equation i.e

(5)

where

We assume that ions can be treated as point charges. Therefore, based on this assumption, the
solution of the linearized P-B equation turns out to be

(6)

The potential at a distance r from the central ion (r) is the sum of potential due to the central
ion and that due to the ionic cloud. i.e
 (7)

The work required for charging the ions can be obtained by integrating the potential at ionic
cloud Ψionic cloud from initial state of zero to final state 𝑧 𝑒 . and can be obtained as

(8)

Substitute equation (8) in equation (1), we get

(9)

The activity coefficient is given by

∆
𝑙𝑛𝛾 = (10)

Substitute equation (9) in equation (10)

( )
𝑙𝑛𝛾 = (11)

This expression calculates theoretical activity coefficients for ion – ion interactions using
Debye – Hückel ionic cloud model.
Mathematically mean ionic activity coefficient is given as
(12)
Where, x is the number of cations with charge 𝑧 and y is the number of cations with charge
𝑧 . Now taking log of both sides in eq. (12) we get
 (13)

Use the Debye – Hückel expression equation (11) for 𝛾 and 𝛾

(14)

Substitute equation (14) in equation (13)

(15)
Since, the solution as a whole is electro-neutral so

therefore,

(16)
Using eq. (16) in eq. (15), we get

(17)

We know  is given by the relation:

(18)
 (19)

Therefore, using equation (19) in equation (18) we have

(20)

We know that, Ionic Strength, I is given by

Equation (20) can be written in terms of ionic strength

Or, (21)

Where,

On the basis of the expression (21) equation (17) becomes

(22)

For a greater compactness, we define a constant A given by

Thus, equation (22) can be written in the form

(23)

Achievements and limitations of Debye- Hückel theory:

The approximate theoretical equation derived from Debye – Hückel theory, i.e.,

This equation can be compared with the equation of straight-line y = – mx. Thus, it indicates
that the, logarithm of the activity coefficient must decrease linearly with square root of the
ionic strength.
The slope of 𝑙𝑛𝛾± versus I1/2 graph does not depend on the particular electrolyte but only on its
valence type, i.e., on the charges carried by the ions of the electrolyte (whether it is a uni – uni
valent electrolyte or bi – bi valent electrolyte).
Moreover, the slope of this graph will give value of A for the solvent.
At infinite dilution, concentration approaches to zero:

Thus from eq (23)

Thus, at infinite dilution, this theory yields the same value of activity coefficient as we would
expect from the experiment, i.e., unity. Thus, Debye – Hückel theory proves successful for the
infinite dilution case.
If we plot the experimental values of the activity coefficient at extremely low electrolyte
concentration with ionic strength i.e. plot of 𝑙𝑛𝛾± versus I1/2.
(i) The plots are linear and
(ii) They are grouped according to the valence type of the electrolyte
Thus, equation (23) has been found to be valid at liming low electrolyte concentrations and it
is referred to as the Debye – Hückel limiting law.
If we examine the experimental plot of 𝑙𝑛𝛾± versus I1/2 curves, at higher concentrations, the
Debye – Hückel limiting law fluctuates (falters). The plot of 𝑙𝑛𝛾± versus I1/2 no longer a straight
line but a curve as shown in figure;
Fig. The experimental l 𝒍𝒏𝜸± versus I1/2 curve is a straight line only at extremely low
concentrations.