Mason–Weaver equation


The Mason–Weaver equation describes the sedimentation and diffusion of solutes under a uniform force, usually a gravitational field. Assuming that the gravitational field is aligned in the z direction, the Mason–Weaver equation may be written
where t is the time, c is the solute concentration, and the parameters D, s, and g represent the solute diffusion constant, sedimentation coefficient and the acceleration of gravity, respectively.
The Mason–Weaver equation is complemented by the boundary conditions
at the top and bottom of the cell, denoted as and, respectively. These boundary conditions correspond to the physical requirement that no solute pass through the top and bottom of the cell, i.e., that the flux there be zero. The cell is assumed to be rectangular and aligned with
the Cartesian axes, so that the net flux through the side walls is likewise
zero. Hence, the total amount of solute in the cell
is conserved, i.e.,.

Derivation of the Mason–Weaver equation

A typical particle of mass m moving with vertical velocity v is acted upon by three forces : the
drag force, the force of gravity and the buoyant force, where g is the acceleration of gravity, V is the solute particle volume and is the solvent density. At equilibrium, the
particle attains a terminal velocity where the three forces are balanced. Since V equals the particle mass m times its partial specific volume, the equilibrium condition may be written as
where is the buoyant mass.
We define the Mason–Weaver sedimentation coefficient. Since the drag coefficient f is related to the diffusion constant D by the Einstein relation
the ratio of s and D equals
where is the Boltzmann constant and T is the temperature in kelvins.
The flux J at any point is given by
The first term describes the flux due to diffusion down a concentration gradient, whereas the second term
describes the convective flux due to the average velocity of the particles. A positive net flux out of a small volume produces a negative change in the local concentration within that volume
Substituting the equation for the flux J produces the Mason–Weaver equation

The dimensionless Mason–Weaver equation

The parameters D, s and g determine a length scale
and a time scale
Defining the dimensionless variables and, the Mason–Weaver equation becomes
subject to the boundary conditions
at the top and bottom of the cell, and
, respectively.

Solution of the Mason–Weaver equation

This partial differential equation may be solved by separation of variables. Defining, we obtain two ordinary differential equations coupled by a constant
where acceptable values of are defined by the boundary conditions
at the upper and lower boundaries, and, respectively. Since the T equation has the solution, where is a constant, the Mason–Weaver equation is reduced to solving for the function.
The ordinary differential equation for P and its boundary conditions satisfy the criteria
for a Sturm–Liouville problem, from which several conclusions follow. First, there is a discrete set of orthonormal eigenfunctions
that satisfy the ordinary differential equation and boundary conditions. Second, the corresponding eigenvalues are real, bounded below by a lowest
eigenvalue and grow asymptotically like where the nonnegative integer k is the rank of the eigenvalue. Third, the eigenfunctions form a complete set; any solution for can be expressed as a weighted sum of the eigenfunctions
where are constant coefficients determined from the initial distribution
At equilibrium, and the equilibrium concentration distribution is
which agrees with the Boltzmann distribution. The function satisfies the ordinary differential equation and boundary conditions at all values of , and the constant B may be determined from the total amount of solute
To find the non-equilibrium values of the eigenvalues, we proceed as follows. The P equation has the form of a simple harmonic oscillator with solutions where
Depending on the value of, is either purely real or purely imaginary. Only one purely imaginary solution can satisfy the boundary conditions, namely, the equilibrium solution. Hence, the non-equilibrium eigenfunctions can be written as
where A and B are constants and is real and strictly positive.
By introducing the oscillator amplitude and phase as new variables,
the second-order equation for P is factored into two simple first-order equations
Remarkably, the transformed boundary conditions are independent of and the endpoints and
Therefore, we obtain an equation
giving an exact solution for the frequencies
The eigenfrequencies are positive as required, since, and comprise the set of harmonics of the fundamental frequency. Finally, the eigenvalues can be derived from
Taken together, the non-equilibrium components of the solution correspond to a Fourier series decomposition of the initial concentration distribution
multiplied by the weighting function. Each Fourier component decays independently as, where is given above in terms of the Fourier series frequencies.