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Differentiate the Grahame equation for a planar symmetric monovalent electrolyte with respect to surface potential at fixed reservoir concentration and temperature. The result is the displayed capacitance per unit area. It approaches $\epsilon {\kappa }_D$ in the Debye–Hückel approximation. A compact surface layer can contribute a separate series capacitance; point-ion packing assumptions also fail at sufficiently high near-surface concentration.^[ref]

For an ideal planar electric double layer at fixed surface charge density, let $v=e{\varphi }_0/(k_{B}T)$. Adding bulk divalent chloride concentration $\delta c$ adds two monovalent coions per counterion. Differentiating the squared Grahame equation gives the displayed expression, with all denominator concentrations evaluated at the surface. The numerator concentrations are bulk increments. Dropping depleted coions at strongly negative potential gives the leading counterion approximation. A large finite increment instead requires solving the fixed-charge equation at the new composition; exponentiating a first-order voltage estimate does not make that estimate exact.

Write $e=q>0$ for the elementary charge and $ϵ={ϵ}_0{ϵ}_r$ for the permittivity. Taking the bulk electric potential as zero, the Boltzmann distribution of point ions gives $c_i(x)=c_i^{\infty }\exp [-e{z}_i\varphi (x)/(k_{B}T)]$. Here $c_i$ is a number density, not a molar concentration. Combining this with Poisson's equation gives the planar Poisson-Boltzmann equationMultiplying by ${\varphi }^{\prime }$ and integrating from the neutral bulk, where $\varphi ={\varphi }^{\prime }=0$, yieldsFor the solution occupying $x>0$, with the field on the other side neglected, Gauss's law gives $\sigma =-ϵ{\varphi }^{\prime }(0)$. On the branch that decays to zero without crossing it,Source sign qualification: the unsigned square root printed in the paper gives $|\sigma |$. A negative wall electric potential, such as the next part's $-73\mathrm{mV}$, has ${\varphi }^{\prime }(0)>0$ and hence $\sigma <0$, providing a concrete counterexample to interpreting that printed expression as signed surface charge density. This is the planar Grahame equation, with an explicit sign convention.

Full dissociation gives bulk concentrations in $\mathrm{mM}$ of $155$ for sodium, $5$ for potassium, $2$ for calcium, $114$ for chloride, and $25$ for hydrogen phosphate. The positive and negative charge concentrations are both $164\mathrm{mM}$, so the bulk is electrically neutral. At $T=298.15\mathrm{K}$,The Boltzmann distribution then givesFor completeness the coion concentrations are $114e^{-\nu }=6.65196\mathrm{mM}$ and $25e^{-2\nu }=0.0851195\mathrm{mM}$. They are depleted, not zero. Using $1\mathrm{mM}=1\mathrm{mol}{\mathrm{m}}^{-3}$ and multiplying molar concentrations by the Avogadro constant in the Grahame equation givesThis calculation retains every species. Since $|{\varphi }_0|/V_T=2.84$, a linear Debye–Hückel approximation is not justified. The large accumulation, especially of divalent counterions, follows from the valence in the Boltzmann factor. However, multi-molar local concentrations also warn that point-ion mean-field theory neglects finite ion size, hydration, specific adsorption, correlations, and changes in local permittivity. These are predictions of the stated idealized model, not precise measured interfacial concentrations.

Assume the structural surface charge density stays fixed while a divalent chloride is added, without changing $T$ or $ϵ$. Let $v=e{\varphi }_0/(k_{B}T)$ and $\delta c$ be the increment of the bulk divalent concentration. Electroneutral addition also increases bulk chloride by $2\delta c$. Varying the squared Grahame equation at fixed $\sigma$ givesAt a strongly negative wall, coions are small. Dropping their contribution to the denominator and $2e^v$ in the numerator gives the requested leading approximationThe $-3$ includes the change in bulk osmotic concentration of one added divalent counterion and its two monovalent coions. The numerator's increment is a bulk concentration; the denominator contains surface concentrations.^[ref] Extra counterions screen the wall and make its negative electric potential less negative. At fixed bulk calcium, $c_{\mathrm{Ca}}(0)=c_{\mathrm{Ca}}^{\infty }{e}^{-2{\varphi }_0/V_T}$ therefore decreases. Under the stipulated proportionality, synaptic activity decreases as well; this argument isolates electrostatic accumulation rather than assuming a separate specific magnesium effect on the ion channels.

For $\delta c=5\mathrm{mM}$, the printed linear approximation gives $\delta {\varphi }_0=9.53434\mathrm{mV}$. Linearizing the activity too gives $\delta A/A=-2\delta {\varphi }_0/V_T=-0.7422$, or approximately a $74\%$ reduction. Exponentiating this approximate voltage instead gives $A^{\prime }/A=0.4761$. Neither is a controlled finite-increment prediction: the added divalent concentration is 2.5 times its initial value.

A consistent finite-change calculation is possible within the same Poisson-Boltzmann equation. Define, using $\mathrm{mM}$ throughout,Fixed $\sigma$ requires $S_5(u^{\prime })=S_0(2.84129)$. The physical positive root is $u^{\prime }=2.58241$, givingThus the self-consistent finite-change estimate is about a 40.4% reduction. Both estimates rely on fixed surface charge, ideal ionic activities, and unchanged bulk calcium; the limitations of the large local concentrations remain.

Stabilization and screening. Charge stabilization of colloids means suppressing aggregation through repulsion between similarly charged particles and their electric double layers. In DLVO theory, this repulsion competes with attractive Van der Waals forces. A substantial repulsive barrier compared with thermal energy $k_{B}T$ can make aggregation slow, even when the dispersed state is only metastable.

The Debye–Hückel screening length ${\lambda }_D={\kappa }^{-1}$ is the characteristic range over which a weak electric potential is attenuated by rearrangement of mobile ions. It measures the thickness of a diffuse screening cloud, not a molecular diameter. For a plane, a weak potential decays as $e^{-\kappa x}$ into the bulk.

Derivation and the source convention. Put a planar interface at $x=0$, with electrolyte in $x>0$, bulk potential zero, and absolute permittivity $\epsilon ={\epsilon }_0{\epsilon }_r$. For a symmetric $z:z$ electrolyte, let $n_{\infty }$ be the bulk number density of each ionic species. The Boltzmann distribution givesso the mobile charge density isSubstitution into the SI Poisson equation, ${\nabla }^2\psi =-{\rho }_e/\epsilon$, gives the Poisson-Boltzmann equationFor $|ze\psi |\ll k_{B}T$, linearize the hyperbolic sine. The Debye–Hückel approximation is thenHere $z$ is the ionic valence magnitude, $e$ the elementary electric charge, $k_B$ the Boltzmann constant, $T$ absolute temperature, ${\epsilon }_0$ the vacuum permittivity, and ${\epsilon }_r$ the solvent's relative permittivity. For several ionic species, the numerator $2z^2{e}^2{n}_{\infty }$ is replaced by $e^2{\sum }_i{z}_i^2{n}_{i,\infty }$.

The original PDF includes an additional $4\pi$ in the denominator. That factor does not follow from SI Poisson equation with number densities and the stated permittivities. The Bjerrum length provides a useful check: ${\ell }_B=e^2/(4\pi \epsilon k_{B}T)$ and the consistent result is ${\kappa }^2=8\pi {\ell }_B{z}^2{n}_{\infty }$. A Gaussian-unit convention moves factors of $4\pi$ together with the charge and permittivity conventions; it does not justify inserting this extra factor while retaining all the given SI quantities. Both numerical interpretations are reported below rather than silently changing the source.

Conditions favoring stability. Increasing the surface-potential or surface-charge magnitude usually strengthens the electrostatic barrier. Lower ionic strength increases ${\lambda }_D$ and generally makes repulsion longer ranged; added salt and especially multivalent counterions shorten it and can promote aggregation. Suitable pH can keep an ionizable surface charged, while conditions near an isoelectric state weaken charge repulsion. The solvent-dependent Van der Waals forces, charge regulation and particle geometry also affect the barrier, so a long screening length is not by itself sufficient. At fixed density and valence, the linear formula gives ${\lambda }_D\propto \sqrt{\epsilon T}$, but actual temperature changes can also alter the permittivity and surface chemistry.

Surface charge at small potential. Take the usual one-sided planar-interface model, with negligible electric displacement on the nonaqueous side. The solution decaying into the solution isThe electric field is $E_x=-{\psi }^{\prime }=\kappa {\psi }_0{e}^{-\kappa x}$. The electrostatic interface boundary conditions then give the surface charge densityOne can also derive it by integrating the diffuse charge density:Thus the diffuse layer neutralizes the surface charge. This is the planar Debye-Hückel double layer. If instead the object is an isolated sheet wetted by identical electrolyte on both sides, each side screens half its total charge and ${\sigma }_{\mathrm{sheet}}=2\epsilon \kappa {\psi }_0$. The one-sided assumption is the conventional local model for the exterior of a large charged colloid; it must be stated because the question does not specify the material on the other side.

Numerical ion density. For $T=298.15\mathrm{K}$, $z=1$, $\kappa =10^9{\mathrm{m}}^{-1}$ and $\epsilon =80{\epsilon }_0=7.0834\times 10^{-10}\mathrm{F}{\mathrm{m}}^{-1}$, the consistent SI result isThis is $\boxed{0.0943\mathrm{mol}{\mathrm{L}}^{-1}}$ for each ion species, and hence also the salt concentration for a monovalent $1:1$ salt. The combined number density of both signs is $2n_{\infty }$.

Literal substitution into the formula printed in the PDF instead givesThese values are distinct consequences of the source's extra factor; they cannot both describe the same physical screening length in SI with the same definition of $n_{\infty }$.

Surface potential and validity. The requested linear estimate in the one-sided model isHowever, the thermal voltage is $k_{B}T/e=25.7\mathrm{mV}$, so $e{\psi }_{0,\mathrm{linear}}/(k_{B}T)\simeq 13.7$. Thus the small-potential approximation is not self-consistent for the supplied surface charge. The boxed value is its formal extrapolation, not a reliable prediction of the actual surface potential.

For a valid nonlinear comparison within the ideal one-sided planar Poisson-Boltzmann equation, multiply the differential equation by ${\psi }^{\prime }$ and use zero potential and field in the bulk. This givesUsing the surface boundary condition yields the Grahame equation and its inverse:With the SI screening length, the latter gives $\boxed{{\psi }_{0,\mathrm{PB}}\simeq 0.135\mathrm{V}}$. This is a nonlinear mean-field estimate under explicit assumptions, not a unique experimentally determined potential: compact interfacial layers, finite ion size and surface chemistry were not supplied. The source's normalization problem and its use of a linear formula far outside the small-potential regime are separate issues.

Use SI units, uniform absolute permittivity $\epsilon$ and a neutral bulk reservoir. Local equilibrium of ideal mobile ions gives $n_i=n_{i,\infty }{e}^{-z_{i}e\psi /(k_{B}T)}$. Combining their charge with the Poisson equation yieldsThe reference is $\psi =0$ in the bulk. Boundary data specify fixed charge, fixed potential or a surface reaction/charge regulation law. These are physically different problems. The mean-field theory assumes point ions, thermal equilibrium and a continuum solvent; ion-size packing, dielectric structure and strong electrostatic correlations can invalidate it.

For a symmetric monovalent electrolyte let $n_{\infty }$ count each sign and define $u=e\psi /(k_{B}T)$, ${\kappa }_D^2=2e^2{n}_{\infty }/(\epsilon k_{B}T)$. Outside fixed sources,For $|u|\ll 1$, the Debye-Hückel approximation is ${\nabla }^{2}u={\kappa }_D^{2}u$. A planar wall bounding electrolyte in $z>0$ has $\psi ={\psi }_0{e}^{-{\kappa }_{D}z}$; assuming zero field on the other side, its charge is $\sigma =\epsilon {\kappa }_D{\psi }_0$. A sphere of radius $a$ and total charge $Q$ instead givesThe factors arise from geometry and boundary conditions; planar screening cannot be substituted unchanged for a small sphere. The weak-potential condition must hold where the potential is largest, particularly at the surface.

The nonlinear planar Poisson-Boltzmann profile is also exactly integrable. Multiply $u^{\prime \prime }={\kappa }_D^2\sinh u$ by $u^{\prime }$ and use $u,u^{\prime }\to 0$ at infinity:The sign selects a profile decaying to the bulk for either sign of surface potential. Integration givesFor weak $u_0$ this reduces to the linear solution. Strong surface potentials have a bounded far-field amplitude $4\gamma$, while the near-wall ion density still grows strongly. There is no need to permit the negative ion densities produced by an invalid extrapolation of a linearized density formula.

The same first integral yields the Grahame equation and its diffuse-layer differential capacitance per unit area:These describe the diffuse layer. A compact interfacial layer adds a voltage drop and can place its capacitance in series with $C_D$; a measured electrode capacitance need not equal the ideal diffuse contribution.^[ref]

For comparison, a planar counterion-only double layer next to a negative plane has positive counterions and no salt reservoir. Its profile is algebraic:Integrating $en(z)$ over $z>0$ gives $|\sigma |$, checking charge neutrality. This problem cannot be obtained by putting a finite reservoir density into the symmetric-electrolyte answer without changing its boundary conditions.

Applications include screening around synthetic colloids, diffuse-layer electrode capacitance and forces between charged plates. In planar geometry, the bulk-subtracted normal stress is constant:At the midpoint of identical plates, symmetry sets $E=0$, so the remaining excess ionic osmotic pressure determines their repulsion. A comparison with force or capacitance measurements should vary salt and surface potential independently, test charge regulation and adsorption, and distinguish compact-layer effects from failures of diffuse screening. Nonlinear Poisson-Boltzmann theory retains finite-potential Boltzmann populations, but still omits correlations and finite-ion-volume saturation.