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Place equal numbers of radii $r_1,r_2$ on alternating sites of a square nearest-neighbour lattice of spacing $d$. Nonoverlap requires $d\ge \max (r_1+r_2,\sqrt{2}{r}_1,\sqrt{2}{r}_2)$. A two-circle cell has area $2d^2$, giving the displayed packing fraction. Its maximum within this geometry occurs at large-to-small radius ratio $1+\sqrt{2}$ and is $\pi (1-1/\sqrt{2})$; smaller interstitial circles leave unused space, while larger ones force the large-circle lattice apart.

A particle suspension contains two particle species with separate particle volume fractions. In an independent-settling model, each species obeys its own flux conservation equation, while a shared stationary deposit can couple the jump conditions through its maximum total packing fraction. Such independence is an imposed model; general hindered settling need not decouple species.

Arrangement of circles in a plane without interior overlap. The covered area fraction is its packing fraction. Equal-radius square packing has fraction $\pi /4$.

Crystallization favored by greater total accessible configurational entropy, despite increased spatial order. Ordered cages at sufficiently high packing fraction can allow more positional/free-volume configurations than a disordered crowded fluid.

Placement of geometric objects without interior overlap. A packing fraction measures how much area or volume they occupy. Circle packing and sphere packing are examples.

A hard-sphere gas is a classical model of identical impenetrable spheres, each of diameter $\sigma$ and radius $\sigma /2$. Its pair potential is $u(r)=+\infty$ for centre separation $r<\sigma$ and $u(r)=0$ for $r\ge \sigma$; the convention at exact contact has no effect on the integral. It isolates the effect of particle size without an attractive potential energy.

The upper-left panel is a cross-section of a three-dimensional forbidden region: the second centre cannot enter a sphere of radius $\sigma$ around the first centre. The particles themselves have radius $\sigma /2$. Consequently, with particle volume $v_{\mathrm{s}}$ and pair excluded volume $v_{\mathrm{ex}}$,The last equality follows directly from the Mayer f-function: $f=-1$ throughout the forbidden volume and zero outside it. Confusing particle radius with contact separation changes the answer by a factor of eight; omitting the unordered-pair factor changes it by a further factor of two.

Define the packing fraction $\eta =n{v}_{\mathrm{s}}$, where $n$ is number density. Then the virial expansion beginsFor example, at the toy value $\eta =0.01$, the leading correction predicts $Z\approx 1.04$; the omitted terms still matter if accuracy beyond this approximation is needed. The classical second virial coefficient is independent of temperature because the geometry of forbidden configurations does not change when the gas is warmed. The pressure itself still scales with temperature at fixed number density.

This model makes the positive correction particularly clear: eliminating overlapping configurations changes the dependence of the available configuration space on volume, even though the allowed configurations all have zero interaction energy. The figure's other panels add a toy attractive shell and show how its Boltzmann factor competes with that geometry. The hard-sphere gas is a useful reference model, while a low-order virial expansion remains a dilute-gas approximation rather than a dense sphere packing formula.

The stipulated conventional cell is a square of side $2a$. Although introduced as a centered rectangular lattice, this equal-side case is a square Bravais lattice viewed with a rotated primitive basis. A corner-to-center separation iswhich is shorter than the $2a$ separation between adjacent conventional corners. Consequently the first contact of equal circles occurs atThe conventional square represents two lattice points: one from its four shared corners and one from its center. Its packing fraction is thereforeEquivalently, one circle occupies each primitive area $2a^2$. This is square circle packing; the drawing does not define a triangular close-packed lattice.

At sufficiently low packing fraction, neglect overlaps of the excluded regions around different disc centres. Sequential insertion gives the configurational integralTaking logarithms and expanding to first order in density,For large $N$, replace $N-1$ by $N$. The expression $N\ln (a-Nb)$ has the same leading-density expansion when $b=2a_d$. Thus the hard-disc excluded-area approximation yieldsThe factor $N!$ accounts for indistinguishable particles and ${\Lambda }^{2N}$ for two-dimensional momentum integration. The factor one-half between pair-excluded area and $b$ avoids counting every pair twice. Equality of leading expansions does not make this free-volume resummation exact at high density.

The nearest-neighbor displacement is $a[111]/4$, of length $a\sqrt{3}/4$. Touching hard spheres therefore obeyThere are eight atoms per conventional cubic cell, givingFor monatomic FCC close packing, four atoms per cell touch along a face diagonal, so $r_{\mathrm{atom}}=a/(2\sqrt{2})$ andThus the diamond packing fraction is much smaller. The tetrahedral network leaves substantial open volume. Although its Bravais lattice is FCC, the two-atom motif and the shorter hard-sphere contact distance prevent it from inheriting the FCC close-packing fraction.

Using the contact model of (b), $r_a=a/4$ and $r_c=(\sqrt{3}-1)a/4$. Divide the volume of four cation spheres and eight anion spheres by $a^3$ to obtain the packing fraction:For one-radius cubic close-packed structure, face-diagonal contact gives $4r=\sqrt{2}a$, hence ${\eta }_{\mathrm{ccp}}=4(4\pi r^3/3)/a^3=\pi /(3\sqrt{2})\simeq 0.7405$. The limiting fluorite value is lower than the one-radius close-packed value. Its two sizes, stoichiometry and eight-to-four coordination impose a different geometry: the fluoride sites form a simple-cubic array, and the calcium sites are too far apart for calcium–calcium contact. A face-centred arrangement of one species is therefore not sufficient to infer a close-packed whole crystal.

The actual ionic radii need not equal the limiting ratio, and electronic charge distributions are not rigid sphere boundaries. In the same unlike-contact hard-sphere model, put $q=r_a/r_c$ and use $a=4(r_a+r_c)/\sqrt{3}$ to getA cation somewhat larger relative to the anion than the limiting size opens gaps between the anions. Starting from $q=1.366$ and reducing $q$ modestly reduces this packing fraction; thus a lower value is expected for that departure from the ideal contact construction. The formula is not monotonic for all imaginable ratios, so no universal inequality should be inferred without specifying radii. Coordination-dependent ionic radii, polarizability, nonionic contributions to bonding, thermal expansion and point defects also limit the model. No numerical real-crystal packing fraction is determined by the supplied data alone.

A square circle packing of equal radii has one circle per cell of side $2r_1$. Its packing fraction is thereforeFor the alternating-radius square circle packing shown in the source figure, let $d$ be the nearest unlike-centre separation. A two-circle repeat cell has area $2d^2$ and solid area $\pi (r_1^2+r_2^2)$. Unlike circles require $d\ge r_1+r_2$; like circles on the two sublattices require $\sqrt{2}d\ge 2r_1$ and $\sqrt{2}d\ge 2r_2$. ThusAll three nonoverlap constraints matter when varying the radius ratio.

Take $r_1\ge r_2$ as in the illustrated arrangement and set $s=r_2/r_1$. If $0\le s\le \sqrt{2}-1$, the large circles determine the spacing and $\eta =(\pi /4)(1+s^2)$ increases with $s$. If $\sqrt{2}-1\le s\le 1$, unlike contacts determine it and $\eta =(\pi /2)(1+s^2)/(1+s{)}^2$, whose derivative is proportional to $s-1$ and is nonpositive. The maximum is therefore at the joining point:The large circles then touch their large neighbours, while each small circle exactly fills a square interstice. Interchanging the species gives the reciprocal radius ratio. This is the highest packing fraction within the specified alternating square arrangement; it is not a claim about every possible unequal-circle packing.

Use downward distance $y=H-z$, with $z$ the height above the bottom, and write $W=W_s(a)>0$. This convention will also reproduce the printed negative deposit-front velocity in part (d). The ideal simple-cubic sphere packing has packing fraction $\pi /6$; leaving ${\varphi }_{\max }$ symbolic keeps the jump calculation independent of its value. In suspension, the kinematic sedimentation equation isIntegrate this conservation law across a moving discontinuity to obtain the Rankine-Hugoniot conditionThe brackets denote values on the increasing-$y$ side minus those on the other side. A sedimentation shock is a concentration jump moving at this secant slope of the particle flux. Deposited material is stationary and has zero flux.

For the upper clearing front, the states are $0$ and ${\varphi }_{\max }/8$, giving $U_1=7W/8$ downward. For the lower deposition front, the states are ${\varphi }_{\max }/8$ and ${\varphi }_{\max }$, giving $U_2=-W/8$, upward. ThusIn terms of height above the bottom, the shock paths areThey meet when $H=Wt$. Therefore complete settling occurs atThe final height also follows directly from particle volume fraction conservation, ${\varphi }_{\max }{h}_c=({\varphi }_{\max }/8)H$. The stationary deposit after the meeting carries no particle flux.

The diagram plots time vertically against height, as requested. Its shock slopes have the opposite spatial sign to $U_1,U_2$, because those velocities were defined in the downward coordinate.

For ideal hard spheres, potential energy is zero for nonoverlapping configurations and infinite for overlaps. At fixed temperature and volume, the accessible fluid and crystal configurations therefore have no energetic preference of the ordinary bonding kind: the phase with larger entropy has lower Helmholtz free energy.

Ordering particle centers costs some configurational freedom, but at a high packing fraction it can give each particle more usable cage/free volume than a disordered crowded arrangement. The total number of allowed vibrational and positional configurations can then be greater in a crystal despite its visible long-range order. This is entropy-driven hard-sphere crystallization.

The crystal need not be at close packing. At the stated volume fraction near $0.55$, substantial free space remains for thermal motion. Close packing near $0.74$ is the geometric upper bound for equal spheres, not the fraction at which the crystal first becomes thermodynamically favorable. Treating crystallization as an inevitable decrease in total entropy would confuse visible positional order with the full phase-space count.

Equal spheres of radius $r$ occupy the sites of a cubic lattice of spacing $2r$. A cell contains one sphere, so its packing fraction is $(4\pi r^3/3)/(2r{)}^3=\pi /6$. This is an ideal arranged deposit rather than a claim about all settling suspensions.

Arrangement of spheres without interior overlap. The occupied volume fraction is its packing fraction; it depends on the spatial arrangement and on the radii.