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Librairie Félix Alcan, Paris, 1913. Original book by Jean Baptiste Perrin; Wikisource reproduces the inspected chapters.

Awarded to Jean Baptiste Perrin for the discontinuous structure of matter, especially sedimentation equilibrium. The Perrin sedimentation experiment describes the measurements.^[ref]

A colloidal grain in a liquid is large enough to see with a microscope, yet small enough for thermal motion to compete with its tendency to settle. In the Perrin sedimentation experiment, the equilibrium number density falls with height: a visible miniature atmosphere. Counting grains at different heights measures an energy scale; tracking their Brownian motion measures a transport rate. Connecting both to the same Avogadro constant makes the experiment a quantitative test of kinetic theory. The Wiener measure describes an idealized path law; these measurements instead test a physical model and its material parameters.

Jean Baptiste Perrin's 1909 memoir traces his sedimentation experiments to May 1908. It reports relative counts $100$, $47$, $22.6$, $12$ at heights $5$, $35$, $65$, $95\mu \mathrm{m}$, and compares radius estimates from Stokes settling velocity, counted grain mass, and rows of touching grains.^[ref]

The 1926 lecture describes resin precipitated from alcohol into water, washed and fractionated by centrifugation to obtain nearly monodisperse gamboge or mastic grains. Diameter and density were measured separately. A sealed slide-and-cover-glass chamber prevented evaporation; a vertical microscope resolved roughly $2\mu \mathrm{m}$ layers through a roughly $0.1\mathrm{mm}$ depth. Refocusing and photographing compared layer populations after equilibrium; changing temperature reversibly changed the distribution.^[ref]

In Les Atomes (1913), Jean Baptiste Perrin restricts the eyepiece view to fewer than five or six grains and alternates observations between heights. Focus displacement requires a refractive index correction to recover actual layer separation. Horizontal positions were marked with a camera lucida, usually every $30\mathrm{s}$, and distances calibrated with a micrometer; the polygon joins sampled positions rather than recording the intervening trajectory.^[ref][ref]

Take identical rigid spheres of radius $a$, particle density ${\rho }_p$ and displaced liquid density ${\rho }_f$, at uniform absolute temperature $T$. Let $z$ increase upwards from a reference layer and write $\Delta \rho ={\rho }_p-{\rho }_f>0$. The buoyancy correction gives the effective gravitational massThe actual grain mass is ${\rho }_{p}V$; the displaced liquid subtracts ${\rho }_{f}V$ from the effective gravitational mass. In a dilute, noninteracting particle suspension, the Boltzmann distribution therefore givesHere $n$ is number density and $k_B$ is the Boltzmann constant. Equivalently, the dilute osmotic pressure $\Pi =n{k}_{B}T$ supports the grains above it: $d\Pi /dz=-n{m}_{b}g$. Dividing by $n$ and integrating yields the same exponential function. No dynamic viscosity appears in this equilibrium argument. If ${\rho }_p<{\rho }_f$, the population instead increases upwards; at equal densities this gravitational model predicts uniform $n$.

A microscope counts a finite optical slab, not an infinitesimal plane. For equal viewed area $A$ and slab thickness $\delta$, an ideal uniform detection window centred at $z$ givesThus equal optical volumes preserve the exponential function count ratio exactly, even for finite $\delta$, provided the windows lie wholly inside the accessible chamber and have the same detection response. Unequal depth response or overlapping a boundary can corrupt this inference. Repeated observations estimate the mean count; closely spaced visits need not be independent because grains remain in view.

For an original chosen model, set $a=0.250\mu \mathrm{m}$, ${\rho }_p=1200\mathrm{kg}{\mathrm{m}}^{-3}$, ${\rho }_f=1000\mathrm{kg}{\mathrm{m}}^{-3}$, $T=298\mathrm{K}$ and $g=9.81\mathrm{m}{\mathrm{s}}^{-2}$. These are illustrative inputs, not Jean Baptiste Perrin's measurements. Using $k_B=1.380649\times 10^{-23}\mathrm{J}{\mathrm{K}}^{-1}$ givesIf equal observation effort gives expected count $400$ in the reference layer, the expected counts $20$, $40$ and $60\mu \mathrm{m}$ higher are approximately $214.3$, $114.8$ and $61.49$. Fractions describe expected values over observations, not fractional grains. Using the actual grain mass instead of its buoyancy-corrected value would make the inferred Avogadro constant six times too small for these chosen densities.

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.