11/1/2017 Darken's equations - Wikipedia

Darken's equations
In 1948, Lawrence Stamper Darken published an article entitled "Diffusion, Mobility and Their Interrelation through Free
Energy in Binary Metallic Systems", in which he derived two equations describing solid-state diffusion in binary solutions.
Specifically, the equations Darken created relate “binary chemical diffusion coefficient to the intrinsic and self diffusion
coefficients”.[1] The equations apply to cases when a solid solution's two interdiffusing components do not have the same
coefficient of diffusion. The result of this article had a large impact on the understanding of solid state diffusion and as a
result the equations have come to be known as “Darken’s equations”.

Darken's first equation is

Darken's first equation is used to calculate marker velocity, given here as , in respect to a binary system where the
different components have their own corresponding diffusion coefficients, D1 and D2, as was discussed in the Kirkendall
experiment.[2] The marker velocity is in terms of length per unit time and the diffusion coefficients are in terms of length
squared per unit time. The variables N1 and N2 represent the atom fraction of the corresponding component. In addition,
the variable x is the distance term. It is important to note that this equation only holds in situations where the total
concentration remains constant. For a binary system this is defined by C1 + C2 = C, where C is the overall concentration of
the system that remains constant, and C1 and C2 are the corresponding component's concentration. This is equivalent to
saying that the partial molar volumes of the two components are constant and equal.[3] In addition, the ends of the system
need to be fixed in position for the equation to hold. These constraints will be further analyzed in the derivation.

Darken's second equation is

Darken's second equation is used to calculate the chemical diffusion coefficient (also known as the inter-diffusion
coefficient), , for a binary solution.[2] The variables N and D are the same as previously stated for Darken's first equation.
In addition, the variable a1 is the activity coefficient for the component one. Similar to the first equation, this equation
only holds in situations when the total concentration remains constant.

To derive these equations Darken mainly references Kirkendall and Smigelskas’s experiment,[4] and W. A. Johnson’s
experiment, along with other findings within the metallurgical community.

Contents
1 Experimental methods
2 Darken's first equation
2.1 Background
2.2 Derivation
2.3 Accompanying derivation

https://en.wikipedia.org/wiki/Darken%27s_equations#Derivatio 1/8
n
11/1/2017 Darken's equations - Wikipedia

3 Darken's second equation

3.1 Background
3.2 Derivation

4 Applications
5 Biography
6 References

Experimental methods
In deriving the first equation, Darken referenced Simgelskas and Kirkendall's experiment, which tested the mechanisms
and rates of diffusion and gave rise to the concept now known as the Kirkendall effect. For the experiment, inert
molybdenum wires were placed at the interface between copper and brass components, and the motion of the markers was
monitored. The experiment supported the concept that a concentration gradient in a binary alloy would result in the
different components having different velocities in the solid solution. The experiment showed that in brass zinc had a
faster relative velocity than copper, since the molybdenum wires moved farther into the brass. In establishing the
coordinate axes to evaluate the derivation, Darken refers back to Smigelskas and Kirkendall’s experiment which the inert
wires were designated as the origin.[2]

In respect to the derivation of the second equation, Darken referenced W. A. Johnson’s experiment on a gold–silver
system, which was performed to determine the chemical diffusivity. In this experiment radioactive gold and silver isotopes
were used to measure the diffusivity of gold and silver, because it was assumed that the radioactive isotopes have relatively
the same mobility as the non-radioactive elements. If the gold–silver solution is assumed to behave ideally, it would be
expected the diffusivities would also be equivalent. Therefore, the overall diffusion coefficient of the system would be the
average each components diffusivity; however, this was found not to be true.[2] This finding led Darken to analyze
Johnson's experiment and derive the equation for chemical diffusivity of binarysolutions.

Darken's first equation

Background
As stated previously, Darken's first equation allows the calculation of the marker velocity in respect to a binary system
where the two components have different diffusion coefficients. For this equation to be applicable, the analyzed system
must have a constant concentration and can be modeled by the Boltzmann–Matano solution.

For the derivation, a hypothetical case is considered where two homogeneous binary alloy rods of two different
compositions are in contact. The sides are protected, so that all of the diffusion occurs parallel to the length of the rod. In
establishing the coordinate axes to evaluate the derivation, Darken sets the x-axis to be fixed at the far ends of the rods,
and the origin at the initial position of the interface between the two rods. In addition this choice of a coordinate system
allows the derivation to be simplified, whereas Smigelskas and Kirkendall's coordinate system was considered to be the
non-optimal choice for this particular calculation as can be seen in the following section. At the initial planar interface
between the rods, it is considered that there are infinitely small inert markers placed in a plane which is perpendicular to
the length of the rods. Here, inert markers are defined to be a group of particles that are of a different elemental make-up
from either of the diffusing components and move in the same fashion. For this derivation, the inert markers are assumed
to be following the motion of the crystal lattice. The motion relative to the marker is associated with diffusion, ,
while the motion of the markers is associated with advection, . Fick’s first law, the previous equation stated for

https://en.wikipedia.org/wiki/Darken%27s_equations#Derivatio 2/8
n
Thank you for using www.freepdfconvert.com service!

Only two pages are converted. Please Sign Up to convert all pages.

https://www.freepdfconvert.com/membership