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A hard sphere has an impenetrable core and otherwise no pair interaction. Two identical spheres of diameter $d$ cannot have centre separation below $d$. Even without attractive potential energy, crowding can produce fluid–crystal coexistence because available configuration space and entropy differ between the phases.

For identical touching atoms represented by hard spheres of radius $r$, a face-centered cubic lattice has conventional side $a_F=2\sqrt{2}r$ and four atoms per conventional cell. A body-centered cubic lattice has side $a_B=4r/\sqrt{3}$ and two atoms per conventional cell. Their primitive unit cell volumes are respectivelyEach primitive cell contains one atom in the monatomic model, so its mass density is atomic mass divided by $\Omega$. These are contact-geometry estimates; a fixed hard-sphere radius does not encode thermal expansion or phase-dependent electronic bonding.

In a conventional face-centered cubic lattice cell of side $a_F$, touching nearest-neighbour hard spheres lie along a face diagonal. Four radii span that diagonal, so $\sqrt{2}{a}_F=4r$ and $a_F=2\sqrt{2}r$. In a conventional body-centered cubic lattice cell, the contact lies on the body diagonal: $\sqrt{3}{a}_B=4r$, giving $a_B=4r/\sqrt{3}$. ThereforeThese are the nonprimitive cubic unit cells requested. They contain four and two atoms respectively, so their volume ratio should not be confused with the volume-per-atom ratio, which is half as large, $3\sqrt{6}/8\simeq 0.9186$. The common sphere radius cancels.

Model air as a dilute ideal gas of molecules described by the hard sphere model. The number density and mean free path areThe factor $\sqrt{2}$ accounts for the relative motion of the colliding molecules. A molecular collision diameter has to be estimated because none is supplied. Taking $d\simeq 0.37\mathrm{nm}$, appropriate as an order-of-magnitude size for the main constituents of air, givesThus the mean free path is about $7\times 10^{-8}\mathrm{m}$, or $70\mathrm{nm}$. A slightly smaller assumed diameter $0.35\mathrm{nm}$ gives about $76\mathrm{nm}$, illustrating the intended precision of the estimate.

Colloidal particles experience attractive Van der Waals forces, arising from correlated molecular charge fluctuations and other dipolar interactions. Integrating many weak molecular attractions over two particles can give a deep near-contact well. For identical spheres of radius $a$ and surface gap $h\ll a$, a positive Hamaker constant gives approximatelyBrownian motion brings particles into encounters. Without a repulsive barrier, they can reach the attractive primary minimum; if the binding energy is much larger than $k_{B}T$, thermal motion rarely separates them again. Repeated sticking produces aggregates. This is a kinetic stability statement: thermal agitation causes encounters but does not itself supply a stabilizing interparticle repulsion. The molecular cutoff and hard sphere exclusion prevent the unphysical $h\to 0$ divergence of the continuum attraction.

In a magnesium chloride chemical solution, the principal pair interactions are hard sphere exclusion, repulsion of overlapping electric double layers, and attractive Van der Waals forces. The positive surface attracts chloride counterions and repels magnesium coions; mobile ions screen the bare Coulomb's law interaction. The competition between screened electrostatic repulsion and Van der Waals force attraction is described by DLVO theory.

For well-separated identical weakly charged spheres, the approximate repulsive pair potential energy, at centre separation $R\ge 2a$, isIt is a screened Coulomb pair potential. An attractive Hamaker constant adds a negative short-range contribution, while overlap is forbidden. Very near contact, solvation and molecular surface structure can also matter. No polymer-induced interaction should be assumed before polymer is added in part (f).

Write the particle volume fraction as $\eta =(4\pi a^3/3)n_p$. In a stable, repulsion-dominated colloid, low $\eta$ gives a disordered fluid. Increasing $\eta$ makes the interaction between neighboring particles important and can produce an ordered crystal, separated from the fluid by a phase coexistence curve. Increasing the Debye–Hückel screening length at fixed charge strengthens the repulsion at a given separation and allows freezing at smaller geometrical volume fraction.

The geometric intuition is that particles behave as though they occupy more than their bare diameter: roughly, an effective exclusion diameter $d_{\mathrm{eff}}$ extends out to the separation where $U_{\mathrm{el}}$ is of order $k_{B}T$. A hard sphere comparison then uses ${\eta }_{\mathrm{eff}}\sim \eta [d_{\mathrm{eff}}/(2a){]}^3$. This explains the trend; it is not an exact freezing criterion.

At short Debye–Hückel screening length and negligible attraction, the diagram approaches hard sphere fluid–crystal coexistence. For longer-ranged soft repulsion, body-centered cubic lattice and face-centered cubic lattice crystals can both be stable, with the former often appearing towards the softer, lower-density freezing boundary. Screened-Coulomb simulations exhibit both these crystal structures.^[ref]

No universal quantitative diagram follows from $(\eta ,{\lambda }_D)$ alone: the charge, Hamaker constant and surface conditions must also be fixed. If salt suppresses the stabilizing barrier enough for Van der Waals force attraction to dominate, a colloid-poor/colloid-rich separation or aggregation can replace part of this repulsive reference diagram. Dense colloidal glasses or colloidal gels may also be observed after kinetic arrest; they should not be mistaken for additional thermodynamic equilibrium thermodynamic phases.