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The Coulomb attraction by the charged surface groups pulls the counterions back
towards the surface, but the osmotic pressure forces the counterions away from
the interface. This results in a diffuse double layer.
The various parts of the electrostatic double layer have been shown in the figure.
The double layer very near to the interface is divided into two parts: the Stern
layer and the GouyChapman diffuse layer. The compact layer of adsorbed ions
is known as Stern layer in honor of Otto Stern (1924), who proposed the
existence of this layer. This layer has a very small thickness (say, 1 nm).
The counterions specifically adsorb on the interface in the inner part of the Stern
layer, which is known as inner Helmholtz plane (IHP). The potential drop in this
layer is quite sharp, and it depends on the occupancy of the ions.
The outer Helmholtz plane (OHP) is located on the plane of the centers of the
next layer of non-specifically adsorbed ions. These two parts of the Stern layer
are named so because the Helmholtz condenser model was used as a first
approximation of the double layer very close to the interface.
The diffuse layer begins at the OHP. The potential drop in each of the two layers
is assumed to be linear. The dielectric constant of water inside the Stern layer is
believed to be much lower (e.g., one-tenth) than its value in the bulk. The value is
lowest near the IHP.
The diffuse part of the electrostatic double layer is known as GouyChapman
layer. The thickness of the diffuse layer is termed Debye length (represented by
1 ). This length indicates the distance from the OHP into the solution up to the
point where the effect of the surface is felt by the ions. is known as
DebyeHckel parameter.
The Debye length is highly influenced by the concentration of electrolyte in the
solution. The extent of the double layer decreases with increase in electrolyte
concentration due to the shielding of charge at the solidsolution interface. The
ions of higher valence are more effective in screening the charge. We will discuss
the Debye length in detail later.
When a liquid moves past a solid surface, the relative velocity between the liquid
and the surface is zero at the surface. At some distance from the surface, the
relative motion sets in between the immobilized layer and the fluid. This
boundary is known as the surface of shear. The Stern layer is quite immobile. The
surface of shear may not coincide with the boundary of the Stern layer, but it may
be located somewhat farther.
The location of the surface of shear can be estimated from the knowledge about
the adsorption from solution and the Stern layer. Therefore, it can be concluded
that the surface of shear is located inside the double layer at a distance
approximately equal to the thickness of the Stern layer from the surface.
The potential at this surface is known as zeta potential , which is expected to
be close to d for systems having smooth surfaces and simple ions, but less than
Note that is constant in the diffuse layer but it varies significantly with position
inside the Stern layer.
Let us consider the one-dimensional problem in the direction perpendicular to the
solidsolution interface. Equation (3.3.1) in this case simplifies to,
d 2
(3.3.2)
dx 2 0
Outside the OHP, there will be an accumulation of the oppositely charged ions.
The work required to bring an ion from infinity to a position where the potential
is is zi e (where, zi is the valence of ith the ion). The ion concentration near
where ni is the number of ions of type i per unit volume near the interface, ni is
the number of ions of type i per unit volume in the bulk solution, and e is the
electronic charge.
The charge density can be related to the concentration of ions ni as,
zi e
zi eni zi eni exp (3.3.4)
i i kT
Combining Eqs. (3.3.2) and (3.3.4) we obtain,
d 2 e z e
zi ni exp i (3.3.5)
dx 2 0 i kT
Equation (3.3.5) is known as the PoissonBoltzmann equation. The solution of
this equation gives the potential, , at a distance x.
Let us retain the first two terms of the series represented by Eq. (3.3.6) (the other
terms will be smaller and hence neglected). Therefore,
z e zi e
exp i 1 kT (3.3.7)
kT
With this approximation, Eq. (3.3.4) becomes,
zi e
zi eni 1 (3.3.8)
i kT
d 2 1 2 2
z n e (3.3.11)
dx 2 0 kT i i i
Equation (3.3.11) is known as the linearized PoissonBoltzmann equation, which
was obtained by the DebyeHckel approximation.
Let us define the DebyeHckel parameter, , as,
e2 2
2 z n (3.3.12)
0 kT i i i
Therefore, Eq. (3.3.11) can be written in terms of as,
d 2
2 (3.3.13)
2
dx
The two boundary conditions for solving Eq. (3.3.13) are given below.
Condition 1: As x d , d (3.3.14)
where d is the thickness of the Stern layer.
Condition 2: As x , 0 (3.3.15)
The solution to Eq. (3.3.15) is,
d exp x d (3.3.16)
N Ae 2
In aqueous medium at 298 K, 5.404 1015 m. Therefore, Eq. (3.3.17)
0 kT
can be written as,
1 2
1
5.404 1015 zi2ci (3.3.18)
i
Example 3.3.1: Calculate the Debye lengths in 10 mol/m3 aqueous solutions of NaCl,
CaCl2 and AlCl3 at 298 K.
Example 3.3.2: Calculate the variation of surface potential with the distance from the
surface for 1:1, 2:1, 2:2 and 3:1 type of electrolytes at 10 mol/m3 concentration at 298 K
using the DebyeHckel equation.
as x , 0 and d dx 0 . Therefore,
2kT
I ni (3.3.21)
0 i
We can proceed to solve Eq. (3.3.22) further for the systems in which the
electrolyte is symmetric (i.e., z : z type, such as NaCl or MgSO4). In that case, we
have,
z e ze ze
ni exp i 1 n exp kT exp 2 (3.3.23)
i kT kT
Therefore, Eq. (3.3.22) can be written as,
2kTn
2
d ze ze
exp exp 2 (3.3.24)
dx 0 kT kT
Solution of Eq. (3.3.24) with the boundary condition: d at x d gives the
variation of with x . We can write the term inside the parenthesis on the right
side of Eq. (3.3.24) as,
2
ze ze ze ze
exp kT exp kT 2 exp 2kT exp 2kT (3.3.25)
Therefore, Eq. (3.3.24) becomes,
2
2kTn
2
d ze ze
exp exp (3.3.26)
dx 0 2kT 2kT
ze
Let us substitute, p . Therefore, we have,
kT
d kT dp
(3.3.27)
dx ze dx
2 2 2
d kT dp
(3.3.28)
dx ze dx
From Eqs. (3.3.26) and (3.3.28) we get,
2 2 2 2
dp 2z e n p p
exp exp
(3.3.29)
dx 0 kT 2 2
12
dp 2 z 2e2 n p p
exp 2 exp 2 (3.3.30)
dx 0 kT
dp p p
exp exp (3.3.31)
dx 2 2
Now, we know that,
p 1
sinh exp p 2 exp p 2 (3.3.32)
2 2
Therefore, Eq. (3.3.31) becomes,
dp p
2 sinh (3.3.33)
dx 2
Solving Eq. (3.3.33) and substituting for p we get,
ze
ln tanh x I1 , I1 constant (3.3.34)
4kT
Applying the boundary condition: at x d , d , the integration constant I1
is found to be,
ze d
I1 ln tanh d (3.3.35)
4kT
Therefore, we can write the solution as,
ze
tanh 4kT
x d
ln (3.3.36)
tanh ze d
4kT
ze ze d
tanh tanh exp x d (3.3.37)
4kT 4kT
Equation (3.3.37) can also be written as,
ze ze d
exp 2kT 1 exp 2kT 1
exp x d
(3.3.38)
exp ze ze d
1 exp 1
2kT 2kT
The derivation of Eq. (3.3.38) from Eq. (3.3.37) is left as an exercise for the
reader. This equation is known as the GouyChapman equation, which describes
the variation of potential in the diffuse part of the electrostatic double layer with
distance starting from the Stern layer.
ze ze
tanh . The potential in that case can be calculated from the
4kT 4kT
equation,
4kT ze d
tanh exp x d (3.3.39)
ze 4kT
d 2 d d d
d dx 0 dx 0 0 (3.3.40)
2
d d dx dx dx d dx d
d
where is the potential gradient at the interface. The potential gradient is
dx d
zero as x .
From Eq. (3.3.26) we get,
12
d 2kTn ze d ze d
exp 2kT exp 2kT (3.3.41)
dx d 0
ze d
12
d 8kT 0 n sinh (3.3.43)
2kT
Equation (3.3.43) is known as Grahame equation. In terms of the concentration,
ze d
12
d 8RT 0c sinh (3.3.44)
2kT
where R kN A is the gas constant.
Example 3.3.3: If the charge density of a surface is 0.1 C/m2, calculate the surface
potential at 298 K in 1 mol/m3 and 10 mol/m3 aqueous NaCl solutions using the Grahame
equation.
Solution: Rearranging Eq. (3.3.44), the surface potential can be calculated from the
equation,
2kT 1 d
d sinh , z 1 for NaCl
ze 1 2
8 RT 0c
For c 1 mol/m3:
d 0.1 0.1
26.94
8RT 0c 8 8.314 298 78.5 8.854 10 3.712 103
12 12
12
1
sinh 1 d sinh 1 26.94 3.987
12
8 RT 0c
Therefore, d 0.0514 3.987 0.2049 V = 204.9 mV
For c 10 mol/m3:
d 0.1 0.1
8.55
8RT 0c 8 8.314 298 78.5 8.854 1012 10
12 12 0.0117
1 d
sinh sinh 1 8.55 2.84
12
8RT 0c
The results from Example 3.3.3 illustrate how the potential of a charged surface
can be reduced by the increase in concentration of the electrolyte in the bulk
solution.
The effects of divalent and trivalent ions are stronger which is anticipated from
Eq. (3.3.44). The surface charge density is reduced very effectively by the
binding of counterions on the surface groups. This strongly reduces the surface
potential.
When a surface contains sites where both anions and cations can bind (i.e.,
amphoteric surfaces such as the protein surfaces), the charge density can be
negative or positive depending on the type of electrolytes in the solution and their
concentration. The condition where the mean surface charge density is zero is
termed the isoelectric point.
Sometimes counterion-binding leads to the reversal of charge of the surface.
Binding of counterions has important consequences in the adsorption of ionic
surfactants at airwater or waterhydrocarbon interfaces (Kalinin and Radke,
1996). Counterion-binding is also important in micellization.
Fig. 3.3.4 The profiles of the coions and the counterions near a charged surface.
The concentration of the counterions is high near the surface whereas the
concentration of the coions is less, as expected. These profiles show how the
concentrations of the ions reach their bulk values.
A comparison of the prediction by Grahame equation with experimental data has
been presented by Ghosh (2009) for the surface potential of egg lecithindicetyl
phosphate in aqueous NaCl solution at 295 K.
Exercise
Exercise 3.3.1: Generate the potential profile (i.e., variation of with distance from the
surface) in a 1 mol/m3 NaCl solution at 298 K. The surface potential is 150 mV. Explain
your results.
Exercise 3.3.2: Calculate the Debye lengths in 1 mol/m3 and 10 mol/m3 aqueous
solutions of MgSO4 at 298 K.
Exercise 3.3.3: The surface potential at airwater interface when sodium dodecyl sulfate
Suggested reading
Textbooks
P. C. Hiemenz and R. Rajagopalan, Principles of Colloid and Surface Chemistry,
Marcel Dekker, New York, 1997, Chapter 11.
P. Ghosh, Colloid and Interface Science, PHI Learning, New Delhi, 2009,
Chapter 5.
R. J. Hunter, Foundations of Colloid Science, Oxford University Press, New
York, 2005, Chapters 7 & 8.
Reference books
A. W. Adamson and A. P. Gast, Physical Chemistry of Surfaces, John Wiley,
New York, 1997, Chapter 5.
G. J. M. Koper, An Introduction to Interfacial Engineering, VSSD, Delft, 2009,
Chapter 4.
J. Lyklema, Fundamentals of Interface and Colloid Science, Vol. 2, Academic
Press, London, 1991, Chapter 3.
J. N. Israelachvili, Intermolecular and Surface Forces, Academic Press, London,
1997, Chapter 12.
Journal articles
D. C. Grahame, Chem. Rev., 41, 441 (1947).
O. Stern, Z. Elektrochemie und Angewandte Physikalische Chemie, 30, 508
(1924).
V. V. Kalinin and C. J. Radke, Colloids Surf., A, 114, 337 (1996).