When a liquid comes into contact with a dielectric surface, the interactions between the ions and the wall lead to a spontaneous charge distribution within both the fluid and the wall. The wall becomes charged, attracting counter-ions from the fluid while repelling co-ions. Consequently, an electrically charged layer forms in the fluid in close proximity to the wall, known as the electric double layer (EDL). For more details, see [
1]. The induced potential field within the EDL can be given by a Poisson equation:
$$\begin{aligned} \nabla ^2 \psi =-\frac{\rho _e}{\epsilon }, \end{aligned}$$
(7)
where
\(\psi \) denotes the EDL potential and
\(\epsilon \) is the dielectric constant of the solution. For fully developed flow, this simplifies to
$$\begin{aligned} \frac{\textrm{d}^2\psi }{\textrm{d}y^2}=-\frac{\rho _e}{\epsilon }. \end{aligned}$$
(8)
The net electric charge density in the fluid,
\(\rho _e\), can be given by the Boltzmann distribution:
$$\begin{aligned} \rho _e=-2n_{0}ez\sinh \left( \frac{ez}{k_{B}T}\psi \right) , \end{aligned}$$
(9)
where
\(n_0\) is the ion density,
e the elementary charge,
z the valence of the ions,
T the absolute temperature, and
\(k_B\) the Boltzmann constant. Combining this with Eq. (
8) for the induced potential equation leads to the Poisson-Boltzmann equation:
$$\begin{aligned} \frac{\textrm{d}^2\psi }{\textrm{d}y^2}=\frac{2n_{0}ez}{\epsilon }\sinh \left( \frac{ez}{k_{B}T}\psi \right) . \end{aligned}$$
(10)
Assuming the Debye–Hückel linearization principle, a valid approximation for small values of
\(\psi \) [
11,
14,
18,
20] and of the remaining ratio in the argument of
\(\textrm{sinh}\), then
\(\textrm{sinh}\; x \approx x\) in Eq. (
10). The assumption of small
\(ez\xi /k_{B}T\), where
\(\xi \) is the maximum value of
\(\psi \) at the wall, is equivalent to a small ratio of electrical to thermal energies, so the temperature effect on the potential distribution is negligible. For instance, for an electrolyte in water at ambient temperature, this implies a zeta potential of less than about 26 mV leading to
\(\frac{ez\xi }{k_{B}T} \sim 1\) [
14]. Under these conditions, the Poisson-Boltzmann equation (Eq. (
10)) for the 2D channel flow simplifies to
$$\begin{aligned} \frac{\textrm{d}^2\psi }{\textrm{d}y^2}=\kappa ^2\psi , \end{aligned}$$
(11)
where
\(\kappa ^2=2n_{0}e^2z^2/\epsilon k_B T\) is the Debye–Hückel parameter, which is related to the thickness of the Debye layer,
\(\lambda _D=1/\kappa \), also called the EDL thickness.
Integrating Eq. (
11) together with the boundary conditions for different zeta potential at the walls, specifically
\(\psi \left( y=-H\right) =\xi _1\) and
\(\psi \left( y=H\right) =\xi _2\), leads to the following induced electric field,
\(\psi \):
$$\begin{aligned} \psi \left( y\right) =\xi _1\left( \Psi _1\textrm{e}^{\kappa y} - \Psi _2\textrm{e}^{-\kappa y}\right) \end{aligned}$$
(12)
with
\(\Psi _1 = \frac{R_\xi \textrm{e}^{\kappa H}- \textrm{e}^{-\kappa H}}{2 \mathrm {\sinh }\left( 2\kappa H\right) }\) and
\(\Psi _2 = \frac{R_\xi \textrm{e}^{-\kappa H}- \textrm{e}^{\kappa H}}{2 \mathrm {\sinh }\left( 2\kappa H\right) }\), where
\(R_\xi =\frac{\xi _2}{\xi _1}\) denotes the ratio of zeta potentials of the two walls. This equation is valid for
\(-H \le y \le H\), and when
\(R_\xi =1\), the symmetric potential profile is recovered [
11,
18].
With the induced potential, the electric charge density,
\(\rho _e\) (Eq. (
9) with the Debye-Hückel linearization principle) becomes
$$\begin{aligned} \rho _e=-\epsilon \kappa ^2 \xi _1 \left( \Psi _1\textrm{e}^{\kappa y} - \Psi _2\textrm{e}^{-\kappa y}\right) = -\epsilon \kappa ^2 \xi _1 \Omega ^{-}\left( y\right) \end{aligned}$$
(13)
where the operator
\(\Omega ^{\pm }\left( y\right) = \Psi _{1} \textrm{e}^{\kappa y} \pm \Psi _{2} \textrm{e}^{-\kappa y}\) is a hyperbolic function of the transverse variable
y which depends on the ratio of zeta potentials and on the thickness of the Debye layer.