Codex @codex  0

For point ions of charge $\pm e$ in potential $\psi$, equilibrium electrochemical potentials give $n_{\pm }=n_0\exp [\mp e\psi /(k_{B}T)]$, with $n_0$ the reservoir density of each species. The charge density is $-2e{n}_0\sinh [e\psi /(k_{B}T)]$. A negative wall enriches positive counterions and depletes negative co-ions.

A strong negative surface potential creates exponentially enhanced positive counterion density and exponentially suppressed negative co-ion density. The co-ion population remains positive, unlike an extrapolated linear approximation. Finite ion size and correlations eventually limit the applicability of point-ion mean-field theory.

A charged colloid in a polar electrolyte is surrounded by an electric double layer. For a negatively charged surface, counterions are positive and co-ions negative; their distributions reverse for a positive surface. A compact Stern layer contains specifically adsorbed or closely approaching ions, followed by a diffuse layer where electrostatic attraction competes with thermal motion. Mobile charge integrated over the surroundings balances the particle charge in an overall neutral system.

For a mean-field dilute electrolyte, $n_i(r)=n_{i,\infty }\exp [-z_{i}e\psi (r)/(k_{B}T)]$ with Poisson's equation relates charge density and potential. At weak potential, the diffuse potential outside a sphere decays approximately as $\psi (r)\propto e^{-\kappa (r-a)}/r$. The inverse screening length obeys ${\kappa }^2=e^2{\sum }_i{z}_i^2{n}_{i,\infty }/(ϵk_{B}T)$: added salt shortens the Debye length. The zeta potential is the potential at the hydrodynamic slip plane, not necessarily the surface potential. The simple model neglects ion size, correlations and chemical charge regulation; a polar solvent with almost no dissociated ions need not provide a short screening length.

Take a positive surface potential ${\Phi }_0>0$, so positive ions are co-ions and negative ions counterions. With $u_0=e{\Phi }_0/(k_{B}T)\ll 1$,The counterion density is slightly enhanced at the surface, the co-ion density slightly depleted, and both approach $n_0$ over a Debye length. To first order their sum is $2n_0$, while their difference supplies the screening charge. Reverse the surface sign and the ionic roles interchange. These are number-density profiles, not trajectories of individual ions.

For large positive dimensionless surface potential $u_0=e{\Phi }_0/(k_{B}T)\gtrsim 1$, use the nonlinear Boltzmann distribution rather than their linear expansion:The counterions become strongly enriched near the wall and co-ions strongly depleted. A planar mean-field solution isIt approaches the linear screening form far from the wall. Nonlinearity preserves positive densities and produces a much stronger near-wall asymmetry; an extrapolated linear co-ion profile could incorrectly become negative. The total local ion density is $2n_0\cosh u$, no longer constant.

The original figure compares weak- and strong-potential profiles. At very large local concentrations, finite ion size, specific adsorption and ion correlations limit this ideal point-ion mean-field model; it does not predict unlimited physically realizable counterion packing.

Write $\epsilon ={\epsilon }_0{\epsilon }_r$ and take $n_0$ to be the reservoir density of each monovalent ion species. Equal electrochemical potentials in equilibrium give the Boltzmann ion densities in a symmetric electrolyte,Combining this with the electrostatic Poisson equation gives the planar Poisson-Boltzmann equation,The Debye length is ${\kappa }^{-1}$. If the symbol $n_0$ instead denotes the combined density of both species, the factor two is absent; the per-species convention above makes the normalization explicit. At $|e\psi |\ll k_{B}T$, the linearized planar screening solution obeys ${\psi }^{\prime \prime }={\kappa }^2\psi$. With $\psi (0)=\zeta <0$ and $\psi (\infty )=0$,

The positive ions are counterions and the negative ions are co-ions. At weak potential,They approach $n_0$ from above and below respectively, with equal first-order excess and deficit. For stronger negative potential, interpret the source's strong-potential comparison as a statement about $|e\psi |$, since $\psi$ itself is negative. Counterions become strongly concentrated near the wall, while co-ions are exponentially depleted and remain nonnegative. Linearization misses this asymmetry and would eventually predict unphysical negative co-ion density. Point-ion mean-field theory itself eventually needs finite-size and correlation corrections; it provides no steric cap at arbitrarily large counterion concentration.

For steady tangential electro-osmosis, with no imposed pressure gradient and negligible inertia, the Stokes equation is $\eta v^{\prime \prime }+{\rho }_{e}E=0$. Since ${\rho }_e=-\epsilon {\psi }^{\prime \prime }$,The conditions $v(0)=0$ and $v^{\prime }(\infty )=0$ giveThe printed constant speed is the bulk velocity outside the double layer, not the velocity at the no-slip wall. With negative $\zeta$ the positive counterion excess drives fluid along the applied field. The far-field value is the Helmholtz-Smoluchowski electro-osmotic velocity.^[ref]

For the finite channel, first model the added wall as an ideally uncharged insulating boundary with no normal field on its outer side: ${\psi }^{\prime }(d)=0$, while $\psi (0)=\zeta$. The one-charged-wall electro-osmotic channel then hasIntegrating the same force balance and enforcing $v(0)=v(d)=0$ givesFor $U>0$, the maximum occurs atIn that limit $v/U\simeq 1-x/d-e^{-\kappa x}$: the velocity rises rapidly from zero at the charged wall, reaches a maximum a few screening lengths away, then falls approximately linearly to zero at the neutral wall. One charged wall does not give a symmetric plug across a channel with no-slip at the other wall.

An alternative electrode condition $\psi (d)=0$ means a wall held at reservoir potential; it is not the same as zero surface charge. Under that convention,with $\cosh [\kappa (d-x_{\max })]=\sinh (\kappa d)/(\kappa d)$. Both boundary conventions have the same leading thin-double-layer profile above. An externally imposed pressure gradient would add a pressure-driven profile; none is specified here.

For dilute nonadsorbing uncharged polymers in equilibrium or sufficiently weak flow, the entropic polymer depletion near nonadsorbing walls suppresses chain configurations near each wall. A depletion layer of order the coil radius of gyration is expected at both walls, with a bulk-like central region when $d$ is much larger than the coil size. Strong confinement rounds this into a central enrichment. Neutrality removes a direct electrophoretic force, not excluded-volume entropy. Adsorption, concentration and strong-flow migration were not specified, so this is a conditional equilibrium sketch rather than a universal flowing-polymer profile.