Wall hindrance in Brownian diffusion

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.