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For two observed layers $z_2>z_1$, define the positive logarithmic count slopeSince $k_B=R/N_A$, where $R$ is the molar gas constant, the sedimentation scale height givesSeveral heights check whether one slope fits the whole profile. A mixture of grain radii generally gives a sum of exponential functions, with the larger grains depleted faster aloft; one apparent radius need not describe every height.

An independent readout uses horizontal displacements at lag $\tau$, avoiding the vertical gravitational drift. Define the one-coordinate mean squared displacement $M_x(\tau )=⟨[x(t+\tau )-x(t){]}^2⟩$. In a stationary liquid without horizontal advection, translational diffusion predictsA camera sees two horizontal coordinates, so its squared radial displacement has twice the one-coordinate mean. Neither observable is path length or instantaneous velocity. The bulk Stokes–Einstein relation, with dynamic viscosity $\eta$, then gives

The 1926 lecture compares displacement-based and equilibrium determinations of the Avogadro constant.^[ref]

Rotational diffusion supplies a further observable when an identifiable grain orientation can be followed; centre positions alone cannot measure it.

For the chosen model above and $\eta =1.00\times 10^{-3}\mathrm{Pa}\mathrm{s}$, the bulk prediction is $D\simeq 0.8731\mu {\mathrm{m}}^2{\mathrm{s}}^{-1}$. At $\tau =10\mathrm{s}$, $M_x\simeq 17.46\mu {\mathrm{m}}^2$ and the planar value is $34.92\mu {\mathrm{m}}^2$. Reconstructing $N_A$ from these stipulated model outputs returns $6.02214076\times 10^{23}\mathrm{mo}{\mathrm{l}}^{-1}$ by construction; this arithmetic consistency check is not experimental confirmation. Historical force comes from comparing separately measured profiles and displacements using independently checked material parameters.

The diffusive flux and gravitational particle flux provide another useful connection. With constant drag coefficient $\zeta$, zero vertical net flux readswhere $v_s$ is the downward settling velocity magnitude. With $\zeta =6\pi \eta a$, the chosen model gives $v_s\simeq 0.02725\mu \mathrm{m}{\mathrm{s}}^{-1}$. The equilibrium profile forgets how rapidly it was established, while displacement measurements retain that rate information.

The sedimentation scale height simplifies because the same drag coefficient controls both drift and diffusion:Applying the given criterion $a\le z_0$ givesEquivalently, the gravitational Péclet number on the particle-radius scale is $a/z_0=m_{b}ga/(k_{B}T)$ and must be at most one.

At $300\mathrm{K}$ the limiting radius is $a_{\max }\simeq 8.42\times 10^{-7}\mathrm{m}=0.84\mu \mathrm{m}$, corresponding to diameter approximately $1.68\mu \mathrm{m}$. Viscosity cancels from this equilibrium criterion, although it affects the time to approach equilibrium.

For the $100\mathrm{nm}$ radius particle in part (i), $D\simeq 2.20\times 10^{-12}{\mathrm{m}}^2{\mathrm{s}}^{-1}$ and $z_0\simeq 0.50\mathrm{mm}$, about $5.0\times 10^3$ particle radii. It is therefore firmly diffusion-dominated on its own size scale. This does not mean uniform concentration over an arbitrarily tall vessel: the equilibrium density still decays on the finite scale $z_0$. The supplied size criterion is an approximate gravity-versus-diffusion criterion, not a universal definition of every stable colloid.

Balancing buoyant weight with Stokes drag givesThis needs isolated spherical particles, low Reynolds number and negligible wall corrections. The supplied settling measurement gives $\Delta \rho \simeq 99.1\mathrm{kg}{\mathrm{m}}^{-3}$, hence ${\rho }_p\simeq 1.10\times 10^3\mathrm{kg}{\mathrm{m}}^{-3}$. Its Reynolds number is about $7\times 10^{-5}$, consistent with the approximation.

Compare gravitational work over one radius with thermal energy, or use ${\mathrm{Pe}}_g=U_{s}r/D$ with $D=k_{B}T/(6\pi \eta r)$. The gravitational Peclet number givesBelow this sedimentation-Brownian crossover radius Brownian motion dominates settling on the particle-size scale. It does not eliminate gravity: the sedimentation scale height is ${\ell }_g=k_{B}T/[(4\pi r^3/3)\Delta \rho g]$. For negligible concentration gradients across a sample height $H$, the stronger condition is ${\ell }_g\gg H$. No universal permanently nonsedimenting size follows without a length/time criterion.

Brownian encounters bring small particles into contact; van der Waals attraction can then bind them. Surface charge can create a repulsive barrier through Debye screening of colloid repulsion. For a monovalent salt reservoir with number density $n$ of each ionic species, Poisson–Boltzmann theory hasFor $|e\psi |\ll k_{B}T$, linearization gives ${\nabla }^2\psi ={\kappa }^2\psi$, with ${\kappa }^{-1}=\sqrt{ϵk_{B}T/(2n{e}^2)}$. If $n$ instead means total ion density, the factor two is absent. The planar potential decays as $e^{-\kappa h}$; a sphere has an additional $1/r$ factor. This mean-field approximation neglects specific adsorption, ion correlations and finite ion size.

DLVO theory adds screened repulsion to dispersion attraction. At small surface separation $h$ for equal spheres of radius $r$, a useful schematic form iswith a short-range repulsive core needed outside the continuum model. Low salt can leave a barrier many times $k_{B}T$, giving kinetic stability. Higher salt shortens the repulsion and can lower or remove the barrier, allowing coagulation into a deep primary minimum. The primary and secondary DLVO minima have different consequences: a shallow secondary minimum permits looser, sometimes reversible aggregation. The surface boundary condition affects $C$; screening length alone is not a complete measured interaction law. Non-DLVO hydration or steric forces can matter at contact.

Setting the gravitational Péclet number to one gives the displayed particle-scale estimate. A macroscopic sample instead requires its height to be small compared with the sedimentation scale height. These different observational criteria give different size thresholds; “no sedimentation” is not an exact universal cutoff.

Buoyancy changes the effective gravitational mass; a nearby no-slip wall changes the hydrodynamic resistance matrix and therefore the diffusion coefficient. These are distinct corrections. Write the horizontal resistance as ${\zeta }_{\parallel }=6\pi \eta a/f$, with $0<f<1$ representing wall hindrance at a specified height. Applying the Stokes–Einstein relation with that resistance givesif one mistakenly uses the bulk resistance in the inversion. A chosen $f=0.8$ would overestimate $N_A$ by $25\%$; this is a sensitivity example, not a correction measured in Jean Baptiste Perrin's apparatus. Normal and parallel coefficients of the hydrodynamic resistance matrix need not coincide. Stokes settling velocity near a wall can likewise bias a radius inferred using an unbounded-fluid formula.

For a passive dilute particle suspension at uniform temperature, a change of mobility alone does not change the Boltzmann distribution. In the absence of additional wall forces the correct local vertical flux is $j_z=-D_z(z)[dn/dz+m_{b}gn/(k_{B}T)]$, so zero flux still gives the same sedimentation scale height. Walls can nevertheless invalidate that simple inference through adsorption, additional interaction energies, or sampling of inaccessible grain-centre positions. Optical position errors and exposure averaging also affect displacement readout; varying distance from the wall, observation lag and optical depth tests different possible errors.