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The Debye–Hückel approximation linearizes mobile-ion Boltzmann densities about a neutral bulk electrolyte. It is valid for ionic potential energies small compared with $k_{B}T$. The inverse Debye–Hückel screening length satisfies ${\kappa }_D^2={\sum }_i{n}_i{z}_i^2{e}^2/(\epsilon k_{B}T)$. The quadratic screened charging free energy includes both electric field energy and the linearized ionic-response term $\epsilon {\kappa }_D^2{\varphi }^2/2$.

For a uniformly charged sphere of radius $a$, total electric charge $Q$, and an exterior dilute electrolyte of permittivity $\epsilon$, the Debye–Hückel approximation gives $(r^2{\varphi }^{\prime }{)}^{\prime }={\kappa }^2{r}^2\varphi$. Decay at infinity and Gauss's law, $-\epsilon {\varphi }^{\prime }(a)=Q/(4\pi a^2)$, select the displayed electric potential. Substituting $u=r\varphi$ reduces the proof to $u^{\prime \prime }={\kappa }^{2}u$. The screening parameter is ${\kappa }^2={\sum }_i{z}_i^2{e}^2{n}_{i,\infty }/(\epsilon k_{B}T)$, and the ion profiles are $n_i\simeq n_{i,\infty }(1-z_{i}e\varphi /(k_{B}T))$. The validity condition is $|z_{i}e\varphi (a)|\ll k_{B}T$ for every relevant species. Integrating the diffuse charge density using the radial equation gives total screening charge $-Q$.

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]

Mobile electric charges redistribute in response to an imposed electric potential, partly compensating its field. The induced density response and the Poisson equation must be solved self-consistently. Classical dilute mobile ions lead to the Debye–Hückel approximation; a degenerate electron system instead has a response set by its electronic compressibility and interactions. A high charge response can pin a partly occupied Landau level near the Fermi energy, whereas an incompressible gap suppresses that response. electrostatic screening is not a claim that every material perfectly excludes every static field.

Kenneth Pitzer modeled the thermodynamics of electrolyte solutions beyond the simplest dilute limit. His treatment modifies short-range binary-interaction terms to depend on ionic strength, combining physical guidance from the Debye–Hückel approximation with a compact representation of measured solution properties. The resulting equations accommodate both individual electrolytes and mixtures at substantially higher concentrations than a simple limiting law. This links molecular interactions with reusable predictions of nonideal solution behavior.^[ref]

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.

Adding $40000$ monovalent counterions makes the combined genome-plus-ion electric charge nominally zero. It does not make the local electric field or free energy vanish: opposite charges have spatial distributions, and confining mobile ions costs entropy.

A definite screened continuation of b replaces the bare Coulomb potential by $e^{-\kappa r}/(4\pi ϵr)$, with $\kappa =1/{\lambda }_D$ and ${\lambda }_D=1\mathrm{nm}$. In the Debye–Hückel approximation, a uniformly distributed fixed charge density $\rho =Q/V_c$ satisfies $({\nabla }^2-{\kappa }^2)\phi =-\rho /ϵ$ inside, with zero fixed charge outside and matching potential and radial field at $R$. Its interior solution isThe screened charging free energy $U_{\kappa }=\frac{1}{2}\int \rho \phi dV$ is thereforeFor $R\gg {\lambda }_D$, the bracket approaches one: only charges within roughly a screening length contribute appreciably, yielding the local estimate $U_{\kappa }\simeq Q^2{\lambda }_D^2/(2ϵV_c)$. With the same ${ϵ}_r=80$ as before, $x=20$ gives bracket $0.92519$ andabout $173$ times smaller than the unscreened packed-sphere self-energy. This is a specified continuum estimate of packed-state charging free energy; a full packaging free energy also subtracts the screened unpacked reference and includes ion redistribution. It should not be presented as a unique exact packaging work fixed by the problem's few inputs.

The supplied counterion count also permits an independent estimate of the entropic contribution. For $N$ ideal confined ions, $F_{\mathrm{ion}}=-N{k}_{B}T\ln V+\text{constant}$, so compression from an accessible reference volume $V_0$ to $V_f$ costsFor example, approximate the original screening atmosphere as an annulus of thickness ${\lambda }_D$ around a rod. With $a=0.5\mathrm{nm}$, $V_0=\pi [(a+{\lambda }_D{)}^2-a^2]L=4.27\times 10^4\mathrm{n}{\mathrm{m}}^3$. Taking $V_f=V_c-V_D=1.35\times 10^4\mathrm{n}{\mathrm{m}}^3$ gives $\Delta F_{\mathrm{ion}}\simeq 1.91\times 10^5\mathrm{pN}\mathrm{nm}$. This useful order-of-magnitude ion-entropy model is distinct from the screened charging model; the two estimates must not simply be added as independent terms without a consistent ionic free energy functional. The rod cutoff, fixed DNA volume and screening-atmosphere geometry are rough geometric assumptions, not a microscopic reconstruction of the source sketch.

There is a further consistency limit. The nominal ion number density is $n=N/V_c=1.19\mathrm{n}{\mathrm{m}}^{-3}$. For a uniform ideal monovalent screening gas, ${\lambda }_D^2=ϵk_{B}T/(n{e}^2)$ would give ${\lambda }_D\simeq 0.309\mathrm{nm}$ at $300\mathrm{K}$, rather than $1\mathrm{nm}$; added salt would shorten it further. Thus the stated ion inventory and screening length cannot both be interpreted as a self-consistent dilute uniform screening gas with this dielectric. Bound counterions, nonuniform distributions and an effective phenomenological screening length can change that interpretation. Linear screening is itself only an estimate near highly charged DNA.

An ionic atmosphere. A negatively charged molecule attracts positive counterions and repels negative co-ions; signs reverse for a positive molecule. The resulting electric double layer partially screens the bare electric field. Far from an isolated molecule, the electrolyte recovers its neutral bulk composition. At thermodynamic equilibrium, spatial uniformity of each species' electrochemical potential requiresThe logarithm implicitly uses a common reference density. This result for Boltzmann ion densities in a symmetric electrolyte neglects ion correlations, finite size and nonideal activities, but shows immediately why equal concentrations of the two signs do not persist close to a charged surface.

Self-consistent screening. Insert these densities into Poisson's equation, with solvent permittivity $ϵ$ and fixed charge density ${\rho }_f$:This is the Poisson-Boltzmann equation. For a symmetric monovalent salt with bulk density $n_s$ of each sign, outside the fixed charge it becomesFor $|z_{i}e\psi |\ll k_{B}T$, linearizing and using bulk neutrality gives the Debye–Hückel approximationThus added salt shortens the Debye length: electrostatic screening becomes stronger over a shorter distance. The factor of two in a $1:1$ salt comes from two ionic species, not from double-counting the density of salt pairs.

For example, a charged sphere of radius $a$ and total charge $Q$ has the exterior linearized solutionassuming fixed uniform surface charge and no ions inside. It follows from the decaying spherical solution and $-ϵ{\psi }^{\prime }(a)=Q/(4\pi a^2)$. At zero salt it reduces to the Coulomb potential; at finite salt it decays exponentially as well as geometrically. The excess mobile charge integrates to $-Q$ in an infinite neutralizing reservoir, although a finite sphere surrounding the molecule generally contains only part of that ionic atmosphere.

Biophysical scales and limitations. In water at room temperature, the monovalent formula is approximately ${\lambda }_D=0.304\mathrm{nm}/\sqrt{I/(\mathrm{mol}{\mathrm{L}}^{-1})}$, with $I$ the ionic strength. It gives about $0.79\mathrm{nm}$ at $0.15\mathrm{mol}{\mathrm{L}}^{-1}$ and $9.6\mathrm{nm}$ at $1\mathrm{mmol}{\mathrm{L}}^{-1}$. Consequently the same charged protein can exert very different long-range interactions mediated by electrostatics at different salt concentrations. Close to strongly charged DNA, the linear approximation fails; nonlinear screening, counterion condensation, ion-specific adsorption and changes of surface ionization through charge regulation may matter. Mean-field theory also misses strong multivalent-ion correlations and finite-size saturation: the exponential law cannot be extrapolated to arbitrarily large near-surface concentrations.

Let the electrolyte permittivity be $\epsilon$ and let ${\kappa }_D=1/{\ell }_D$ be the inverse Debye–Hückel screening length. We reserve $k$ for the imposed lateral wavevector. In the Debye–Hückel approximation, linearization about an electrically neutral bulk electrolyte givesaway from fixed charges. For ionic species of valence $z_i$ and bulk number density $n_i$, ${\kappa }_D^2={\sum }_i{n}_i{z}_i^2{e}^2/(\epsilon k_{B}T)$; the approximation requires $|z_{i}e\varphi |\ll k_{B}T$. Substitution of a lateral cosine into this screened Poisson equation leaves a vertical decay constantThe screened sinusoidal surface-charge mode thus decays faster than a laterally uniform charge mode. A nonzero $k$ retains a finite decay length even in the zero-salt limit.

The exterior media and their boundary conditions are not specified in the paper. Specifying the two surface charge densities alone does not fix the normal derivative on the inside unless the outside response is also fixed. We first take the confined-gap idealization, with the prescribed charge supplying all the displacement flux into the electrolyte between the sheets. The electrostatic interface boundary conditions are thenThis is, for example, the limit of negligible exterior displacement admittance. The electrostatic potential solving these conditions and the Debye–Hückel approximation equation isDifferentiation checks the two surface signs directly. This solution allows a sine as well as a cosine lateral component when the phase is nonzero.

In linear screened electrostatics, the quadratic charging free energy is $\frac{1}{2}\int \sigma \varphi dA$. It is equivalently $\frac{\epsilon }{2}\int [(\nabla \varphi {)}^2+{\kappa }_D^2{\varphi }^2]dV$ with the stated boundary conditions. The second term represents the linearized ionic response; integrating only the bare electric field energy would omit it. If $\mathcal{A}$ denotes membrane area, the wavelength-averaged energy density isUsing $⟨{\cos }^2(kx){⟩}_x=1/2$ and $⟨\cos (kx)\cos (kx+\theta ){⟩}_x=\cos \theta /2$ gives the phase registration of screened charged sheets energyThe positive cosine coefficient shows that, for nonzero charge amplitude and finite separation,At the minimum the electrostatic potential simplifies to $\varphi =\alpha \cos (kx)\sinh (pz)/[\epsilon p\cosh (pd/2)]$. Positive and negative charge patches face opposite signs across the gap. The two charge patterns therefore favor a half-wavelength lateral offset rather than like-charge alignment.

For comparison, if identical electrolyte fills all of space on both sides of infinitesimally thin charge sheets, the electrostatic interface boundary conditions are continuity of $\varphi$, decay at infinity, and the charge-induced derivative jumpsSuperposing the two screened sinusoidal surface-charge modes gives, in particular between the sheets,Its full-space continuation replaces each vertical distance by the corresponding absolute distance. Evaluating the electrostatic potential on both sheets now yieldsThe constant term is the two isolated-sheet self energies, and the cosine term is their screened interaction. The energy depends on the exterior convention, but both stated physical idealizations give the same phase registration of screened charged sheets: unlike charge patches oppose each other. In the full-space convention the optimum interaction energy is $-{\alpha }^2{e}^{-pd}/(4\epsilon p)$, giving an attractive normal force density $-{\alpha }^2{e}^{-pd}/(4\epsilon )$. Phase sensitivity becomes exponentially weak for $pd\gg 1$; if $\alpha =0$ or the separation tends to infinity there is no selected phase.

One can also display how an exterior dielectric response interpolates between these cases. Let $Y_o\ge 0$ be its normal displacement admittance for this lateral Fourier mode: $Y_o=0$ for the confined-gap idealization, $Y_o=\epsilon p$ for identical exterior electrolyte, and $Y_o={\epsilon }_o|k|$ for an ion-free exterior dielectric. DefineThe symmetric and antisymmetric surface-charge combinations giveSince $D_s<D_a$, its cosine coefficient is positive. This makes the phase-minimizing conclusion robust while exposing the boundary information needed for an absolute electrostatic energy.

The change from a positive surface potential to a negative potential outside the compact layer is consistent with specific phosphate adsorption that overcompensates the positive oxide charge. The negative compact-layer charge then has a diffuse excess of positive counterions. This charge reversal is an interfacial-chemistry interpretation, not something a single monotone double-layer profile with an unchanged positive boundary charge could generate by screening alone. Surface potential and zeta potential at a slip plane are distinct observables.

The Stern model separates the specifically adsorbed compact layer from a diffuse layer. In a spherical diffuse layer, a Poisson-Boltzmann equation description isAt sufficiently small $|z_{i}e\psi |/k_{B}T$, the Debye–Hückel approximation gives ${\nabla }^2\psi ={\kappa }^2\psi$. If $a_s$ is the outer compact-layer radius, its decaying solution isFor a locally flat surface, the geometric factor tends to unity. Thus the far-field negative potential approaches zero from below over the Debye–Hückel screening length. Neither $+120$ nor $-70\mathrm{mV}$ is safely in the low-potential linear regime at room temperature, so the simple exponential is a far-field approximation, not a globally valid fit. The phosphate layer requires adsorption chemistry or an equivalent specified boundary model.

Choose a positively charged plate to match the question's labels $n_{+}$ for co-ions and $n_{-}$ for counterions. Let $x=0$ denote the outer edge of its compact Stern layer, and set the bulk potential to zero.

In the weak-potential Debye–Hückel approximation, the diffuse-layer potential isThe key length is the Debye–Hückel screening length. For a symmetric monovalent electrolyte, the Boltzmann distribution givesPositive co-ions are depleted near the positive plate, while negative counterions accumulate. Both approach the same bulk density as the potential decays. Attraction and repulsion by the surface compete with mixing entropy, so diffuse ions do not simply collapse into one plane. The compact Stern layer represents finite closest approach and specifically associated charge; the diffuse continuum begins outside it. For large potentials the linear exponential potential needs the nonlinear Poisson-Boltzmann equation, though the far-field screening scale remains the same in this simple electrolyte.

The Debye–Hückel approximation linearizes the hyperbolic sine, giving $({\nabla }^2-{\kappa }^2)\psi =0$ withThe planar Debye-Hückel double layer has $\psi (s)={\psi }_0{e}^{-\kappa s}$. For an isolated sphere of radius $a$, the Debye-Hückel potential of a charged sphere is $\psi (r)={\psi }_0(a/r)e^{-\kappa (r-a)}$ outside the sphere; the factor $a/r$ accounts for spherical spreading as well as screening.

The Debye–Hückel screening length is the characteristic distance over which the ion cloud suppresses a weak surface potential. Adding salt increases ionic strength and therefore increases $\kappa$, shortening the interaction range. Linearization requires $|q\psi |\ll k_{B}T$, particularly near the surface where the potential is largest. It means the ionic electrostatic energy is small compared with thermal energy; for monovalent ions near room temperature, $k_{B}T/e\simeq 26\mathrm{mV}$. This condition alone does not remove other limitations of point-ion mean-field theory at high concentration or strong correlations.

In the planar Debye–Hückel approximation, a surface potential decays as $\psi (x)={\psi }_s{e}^{-\kappa x}$, with $\kappa \propto \sqrt{I}$ at fixed temperature and solvent permittivity; $I$ is the ionic strength. For a monovalent salt, reducing its concentration by ten reduces $\kappa$ by $\sqrt{10}$. Calibrating the first decay from the supplied potential ratio, and assuming unchanged ${\psi }_s$, givesHere the printed meV unit is interpreted as the electrostatic potential energy of a singly charged probe; the same ratio calculation applies to potentials in mV.

This numerical answer uses an effective exponential decay calibrated from the data. The inferred initial Debye length is $5/\log (35/6.6)=3.00\mathrm{nm}$, whereas the standard dilute aqueous-electrolyte expression at room temperature gives about $0.96\mathrm{nm}$ for $0.1\mathrm{M}$ monovalent salt. The numbers therefore are not consistent with that absolute ideal-electrolyte model. Moreover a spherical colloid has an additional radius-dependent geometric factor, and its surface potential need not remain constant when salt is changed. Without a surface boundary condition and geometry, the new potential is not uniquely specified beyond the stated planar, fixed-potential approximation.

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.

Let $\epsilon ={\epsilon }_0{\epsilon }_r$ be the permittivity, $\beta =(k_{B}T{)}^{-1}$, $e>0$ the elementary charge, and $c$ the bulk salt formula-unit number density. The Boltzmann distribution givesConsequently the exterior Poisson-Boltzmann equation isFor small $Q$, meaning $2\beta e|\varphi (a)|\ll 1$, linearize the exponentials. The Debye–Hückel approximation givesThis is also ${\kappa }^2=\beta e^2{\sum }_i{z}_i^2{n}_{i,\infty }/\epsilon$: the divalent cation contributes $4c$ and the two monovalent anions contribute $2c$. In terms of molar salt concentration $C$ in $\mathrm{mol}{\mathrm{m}}^{-3}$, replace $c$ by $N_{A}C$; if $C$ is in $\mathrm{mol}{\mathrm{L}}^{-1}$, use $c=10^3{N}_{A}C$. The molar ionic strength is $3C$ in the same concentration units.

The boundary conditions are $\varphi (\infty )=0$ and, by Gauss's law,Here the surface charge is uniform and the spherically symmetric interior field is zero. Set $u=r\varphi$; the radial equation reduces to $u^{\prime \prime }={\kappa }^{2}u$. Decay excludes the growing exponential, so write $\varphi =B{e}^{-\kappa (r-a)}/r$. Then ${\varphi }^{\prime }(a)=-B(1+\kappa a)/a^2$, givingIt solves the linearized Poisson-Boltzmann equation, not the full nonlinear equation at finite $Q$. The radial ion profiles, consistently to first order, areThe exponential Boltzmann distribution formulas above express the full mean-field relation, but substituting a linearized potential into them is accurate only to the retained order. A useful electroneutrality check isThe result is the Debye-Hückel potential of a charged sphere.

First hold the surface electric charge fixed and increase the bulk salt concentration. Since ${\kappa }^2\propto c$, the Debye–Hückel screening length decreases as $c^{-1/2}$. For surface gap $h=R-2a\ge 0$,Thus both the range and the strength of repulsion decrease. In the repulsive phase diagram, the sample moves downwards at fixed volume fraction and can melt from a crystal into a fluid. Because screening length is already a diagram axis, changing salt moves the state through that diagram rather than independently changing its fixed-charge coexistence curves. If Van der Waals forces become dominant, however, adding salt may instead destabilize the dispersion and cause aggregation. These are distinct physical regimes.

Second increase $\sigma$ at fixed salt concentration and particle size. The electric charge is $Q=4\pi a^2\sigma$, so the pair repulsion increases approximately as ${\sigma }^2$ within the Debye–Hückel approximation, while the reservoir screening length remains unchanged. Freezing then becomes possible at lower volume fraction or shorter screening length. At fixed ${\lambda }_D$, the coexistence curves shift towards lower $\eta$; a previously fluid sample may crystallize.

These statements assume fixed, uniform charge and a salt reservoir dominating the screening. Strong charging requires nonlinear screening and possibly charge regulation. At very low added salt or appreciable particle concentration, particle-released counterions also contribute to ionic strength, so the screening length is no longer independently fixed by the added salt alone.

For a plane bounding a symmetric electrolyte in $x>0$, assume no displacement field on the other side, bulk potential zero, and $|ze\psi |\ll k_{B}T$. The Debye–Hückel approximation gives ${\psi }^{\prime \prime }={\kappa }^2\psi$, whose decaying solution is ${\psi }_0{e}^{-\kappa x}$. The electrostatic interface boundary conditions give $\sigma =-\epsilon {\psi }^{\prime }(0^{+})=\epsilon \kappa {\psi }_0$. Equivalently, its diffuse charge density is ${\rho }_e=-\epsilon {\kappa }^2\psi$ and its integral is $-\sigma$. Here $\epsilon ={\epsilon }_0{\epsilon }_r$ in SI units and ${\kappa }^2=2z^2{e}^2{n}_{\infty }/(\epsilon k_{B}T)$ when $n_{\infty }$ counts each ionic species. An isolated sheet with identical electrolyte on both sides has two diffuse layers, so the total sheet charge is $2\epsilon \kappa {\psi }_0$ instead. A surface geometry and the field on its other side must therefore be specified.

A lateral sinusoidal surface charge density with wave number $k$ in the Debye–Hückel approximation generates vertical exponential or hyperbolic functions with inverse length $p=\sqrt{k^2+{\kappa }_D^2}$. In a homogeneous electrolyte filling all space, an isolated sheet at $z_s$ produces $\varphi ={\sigma }_k(x)e^{-p|z-z_s|}/(2\epsilon p)$. Boundary conditions determine the normalization when the electrolyte occupies only a gap.