Name: Gillian Wyn E.

Amba Date: May 19, 2017

Course and Yr Level: BSChE-3 Subject: ChE 152

Correlation of Diffusion Coefficients in Dilute Solutions

C.R. Wilke and Pin Chang

I. Statement of the Problem

In the previous study of Wilke in 1949 about estimation of liquid diffusion coefficients, a
general correlation could not be achieved because of lack of data available for diffusion in liquids.
Also, more extensive studies of diffusion of various solutes in a given solvent were done than the
diffusion of a single solute in various solvents. This journal of Wilke and Chang gives an
improvement on the previous correlation of diffusion in liquids to provide a generalized correlation of
diffusion coefficients and a generalized diffusion factor chart.

II. Brief Background

Diffusion coefficient is the proportionality constant for the equation of unidirectional mass
transfer:

dCA
N A =D (Eq. 1)
dz

This constant depends on solute size and shape, interaction of solute and solvent, viscosity of
solvent, and as well as temperature and pressure. One of the earliest equations that connected a
relationship on these properties and was used as basis for this journal for determining the diffusion
coefficient in liquids was the Stokes-Einstein equation, with the assumption that molecules are
spherical with a radius equal to (3V/4N)1/3,

T
=1.004 107 V 1/3 (Eq. 2)
D

However, in the previous correlation of Wilke and also in the study of Wilke and Chang on
"Some Measurement of Diffusion in Liquids" in 1954, it was shown that the group T/D, designated
as the diffusion factor F, was essentially independent of temperature for the systems experimented, a
deviation from the Eyring theory and Stokes-Einstein equation, which shows an approximate
dependence of diffusion coefficients on temperature. F had also shown to be a function of molal
volume for diffusion of various solutes in a given solvent.

With the assumption that the function of Stokes-Einstein equation was extrapolated at large
solute molal volumes, the new correlation of Wilke and Chang focused on the effect of solute molal
volumes and the effect of solvent properties, rather than temperature, on the diffusion coefficients of
dilute solutions.

III. Materials and Methods

The study was involved in accomplishing a general correlation of diffusion coefficients of

liquids by getting the relationship of D with the available properties of dilute solutions, particularly
solute molal volumes and solvent molecular weights.
 Along with this journal, Wilke and Chang conducted a companion experimental study entitled
"Some Measurement of Diffusion in Liquids" to supply data about the diffusion of liquids and also to
help improve the correlations of liquid diffusions. The experiment was involved in the diffusion of
iodine and toluene in a wide variety of hydrocarbon solvents from hexane to tetradecane and also in
the diffusion of organic acids such as acetic acid, benzoic acid, cinnamic acid and formicacid in
solvents such as toluene and carbontetrachloride.

For a change, Wilke and Chang worked on understanding the diffusion of single solutes in a variety of
solvents, instead of various solutes in a given solvent, to observe the effect of solvent properties on
the diffusion coefficient.

To come up with a general correlation, first, using the obtained experimental data in the previous
study, the solute molal volumes were plotted against T/D x 10-7 values based on the values of the
diffusion of water. The plot is then compared to the function of Stokes-Einstein equation.

Figure 2.1 Diffusion of water as shown in different correlations

As seen on the graph, the function of the plot of solute molal volumes vs. F intersects with the
Stokes-Einstein equations line, which have a slope of 1/3 at high molal volumes. The line has a slope
of 0.6 and it is safe to assume that diffusion factor will be generally proportional to V 0.6 since even in
nonaqueous systems, the slope of 0.6 can still be obtained, as shown on the graphs below.
 Figure 2.2 Diffusion of
various solutes in
Hexane

Figure 2.3 Diffusion of organic acids in Toluene

The next property investigated was solvent properties, where a wide variety of variables were
considered but the solvent molecular weight only correlated the data most successfully. The effect of
solvent molecular weight on the diffusion of solutes in certain solvents can be seen in the plotted
graphs in their corresponding solvents, as shown in Figure 2.4 below:
 Figure 2.4 Relationship of molecular weight of solvents and diffusion factor

As a summary of the graphs in Figure 2.4, it is shown that the scatter of points form a line of
slope 0.5. It is therefore applied in making the correlation since such slope is evident in the graphs
above.

Thus, the general correlation can now be achieved from the empirical findings of the effects of solute
and solvent by the equation:

T M 1 /2
D=const . 0.6 (Eq. 3)
V
Next, Equation 3 is plotted as DT vs. V0.6/M1/2 using the data of unassociated solvents (non polar
liquids such as liquids with hydrocarbons) to achieve a general correlation for such solvents:

T M 1 /2
8
D=7.4 10 (Eq. 4)
V 0.6

As for the general correlation of associated liquids, such as water and other polar solvents, association
parameters were added since the plot of DT vs. V 0.6/M1/2 for diffusion in water has a deviation
depending on the association of the solvent. Thus, a more generalized correlation was concluded:

M
x

1/2T (Eq. 5)

D=7.4 108
where x is the association parameter used to define the effective molecular weight of the solvent with
respect to diffusion process. Equation 5 can also be used for nonassociated solvents, where x=1.00
and water=2.6. Jacobsens associated numbers can also be used as alternative for the association
parameters that Wilke and Chang had derived, but only for values which lie between 2.6 (for water)
and 1.0 (for nonassociated solvents).

IV. Results and Discussions

-discuss major findings and results of article

V. Conclusions

-summarize author's conclusions

VI. Critique