To use all functions of this page, please activate cookies in your browser.
With an accout for my.chemeurope.com you can always see everything at a glance – and you can configure your own website and individual newsletter.
- My watch list
- My saved searches
- My saved topics
- My newsletter
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 (Fig. 1), the Mason-Weaver equation may be written
where t is the time, c is the solute concentration (moles per unit length in the z-direction), and the parameters D, s, and g represent the solute diffusion constant, sedimentation coefficient and the (presumed constant) acceleration of gravity, respectively.
The Mason-Weaver equation is complemented by the boundary conditions
at the top and bottom of the cell, denoted as za and zb, respectively (Fig. 1). 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 (Fig. 1), 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., dNtot / dt = 0.
Additional recommended knowledge
Derivation of the Mason-Weaver equation
A typical particle of mass m moving with vertical velocity v is acted upon by three forces (Fig. 1): the drag force fv, the force of gravity mg and the buoyant force ρVg, where g is the acceleration of gravity, V is the solute particle volume and ρ is the solvent density. At equilibrium (typically reached in roughly 10 ns for molecular solutes), the particle attains a terminal velocity vterm 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 mb 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
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 vterm 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 z0
and a time scale t0
Defining the dimensionless variables and , the Mason-Weaver equation becomes
subject to the boundary conditions
at the top and bottom of the cell, ζa and ζb, respectively.
Solution of the Mason-Weaver equation
This equation may be solved by separation of variables. Defining , we obtain the two equations coupled by a constant β
where acceptable values of β are defined by the boundary conditions
at the upper and lower boundaries, ζa and ζb, respectively. Since the T equation has the solution T(τ) = T0e − βτ, where T0 is a constant, the Mason-Weaver equation is reduced to solving for the function P(ζ).
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 Pk(ζ) that satisfy the ordinary differential equation and boundary conditions. Second, the corresponding eigenvalues βk are real, bounded below by a lowest eigenvalue β0 and grow asymptotically like k2 where the nonnegative integer k is the rank of the eigenvalue. (In our case, the lowest eigenvalue is zero, corresponding to the equilibrium solution.) Third, the eigenfunctions form a complete set; any solution for c(ζ,τ) can be expressed as a weighted sum of the eigenfunctions
where ck are constant coefficients determined from the initial distribution c(ζ,τ = 0)
At equilibrium, β = 0 (by definition) and the equilibrium concentration distribution is
which agrees with the Boltzmann distribution. The P0(ζ) function satisfies the ordinary differential equation and boundary conditions at all values of ζ (as may be verified by substitution), and the constant B may be determined from the total amount of solute
To find the non-equilibrium values of the eigenvalues βk, we proceed as follows. The P equation has the form of a simple harmonic oscillator with solutions where
Depending on the value of βk, ωk 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 ω is real and strictly positive.
By introducing the oscillator amplitude ρ and phase φ 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 ρ and the endpoints ζa and ζb
Therefore, we obtain an equation
giving an exact solution for the frequencies ωk
The eigenfrequencies ωk are positive as required, since ζa > ζb, and comprise the set of harmonics of the fundamental frequency . Finally, the eigenvalues βk can be derived from ωk
Taken together, the non-equilibrium components of the solution correspond to a Fourier series decomposition of the initial concentration distribution c(ζ,τ = 0) multiplied by the weighting function eζ / 2. Each Fourier component decays independently as , where βk is given above in terms of the Fourier series frequencies ωk.
|This article is licensed under the GNU Free Documentation License. It uses material from the Wikipedia article "Mason-Weaver_equation". A list of authors is available in Wikipedia.|