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Diffusion in Liquids

Diffusion in liquids encounters greater resistance than in gases, with diffusion coefficients being 104 to 105 times lower. The Stokes-Einstein equation relates diffusion coefficient to particle size and liquid viscosity. Later equations improved on this, such as ones by Wilke and Chang incorporating association parameters, and by Reddy and Doraiswamy showing good agreement with experimental data. Diffusion coefficient depends on concentration, temperature, and other factors. In electrolyte solutions, salt dissociates into ions that diffuse depending on degree of dissociation.

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130 views3 pages

Diffusion in Liquids

Diffusion in liquids encounters greater resistance than in gases, with diffusion coefficients being 104 to 105 times lower. The Stokes-Einstein equation relates diffusion coefficient to particle size and liquid viscosity. Later equations improved on this, such as ones by Wilke and Chang incorporating association parameters, and by Reddy and Doraiswamy showing good agreement with experimental data. Diffusion coefficient depends on concentration, temperature, and other factors. In electrolyte solutions, salt dissociates into ions that diffuse depending on degree of dissociation.

Uploaded by

Ady Fath
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Diffusion in liquids.

As has been noted, diffusion in liquids


encounters greater resistance and the diffusion coefficients for
liquids lower than 104 to 105 times.
One of the earliest equations for determining the diffusion
coefficient in dilute solutions was the Stokes-Einstein equation,
based on the model of motion of a spherical particle of diffusing
substance A in a viscous liquid continuum B

where r0 is the particle (molecule) radius and ηB, the liquid viscosity.
The constant b depends on the size of diffusing molecules: b = 6 for
molecules larger than those of the base substance; b = 4 for
identical molecules; and b can be less than 4 for smaller molecules.
Assuming that the molecule diameter , where is the
molar volume of a diffusing substance and N0 is the Avogadro
number, then

Comparison of this formula with experimental data has shown that


in most cases, the discrepancy is moderate and reaches 40% only in
some cases.
In 1955, Wilke and Chang have suggested a more general formula
based on extensive experimental investigations, but involving many
empirical values as well

where DAB is the interdiffusion coefficient in an infinitely-dilute


solution, cm2/s; φ, the parameter of association of solvent B; ,
the molecular mass of substance B; , the molar volume of solute
A at a boiling point under normal conditions, cm3/mol; ηB, the
substance viscosity, Ns/m2; and T, the temperature, K.
Introduction of the association parameter into the formula is
brought about by the fact that associated molecules behave like
large-size molecules and diffuse at a lower rate; the degree of
association varying with mixture composition and with molecule
types. Therefore, Wilke and Chang presented the values for most
widespread solvents: for water φ = 2.6; methanol, 1.9; ethanol, 1.5;
benzene, ester, heptane and nonassociated solvents, 1.
A semiempirical formula suggested by Scheibel,

is worthy of attention. In some cases, it appears to be more exact


than the preceding one; but for vA/vB ≤ (1 - 2), the deviation from
experiment becomes important and the following relations are
recommended:

Reddy and Doraiswamy have suggested the equation

where KRS varies depending on the ratio of molar volumes: KRS = 8.5
10−8 for and KRS = 10−7 for . Comparison of
this equation with 96 experimental points has shown good
agreement, the spread of points being about +15%.
All formulas suggested above for calculating the diffusion
coefficient hold true for low-viscosity liquids. For a high-viscosity
solvent, they are in great error and therefore inapplicable.
The temperature effect on the diffusion coefficient has been poorly
studied so far. Within a narrow temperature range—from 10 to
20°C—the temperature dependence of the diffusion coefficient can
be assumed to be linear

where D298 is the diffusion coefficient at T = 298K, ;


η298, the solvent viscosity at T = 298K, Ns/m; ρ, the solvent density,
g/cm3.
Theoretically, this must be an exponential dependence of the type D
= AT exp (-E/RT).
The experimental data of Wilke and Chang give available evidence
that the activation energy varies from 12.6 to 28.1 kJ/mol.
The dependence of the diffusion coefficient on concentration of
diffusing substance, strictly speaking, is a consequence of the fact
that diffusion flow depends on the difference (gradient) of the
thermodynamic potential of the system rather than concentration,
i.e., the formula must allow for activity of the diffusing substance.
Hence, at VB = const,

where D0 and D are the diffusion coefficients, respectively, in an


infinitely-dilute solution and in a solution with finite concentration
c; a and c, the activity and the concentration of diffusing substance;
and n, the activity coefficient of this substance. The semiempirical
formulas presented above are more exact than the theoretical ones
because the latter were derived making assumptions. Nevertheless,
to avoid an appreciable error it is advisable to make calculations by
several formulas concurrently and to compare the results.
In electrolyte solutions, salts dissociate and diffuse as ions and
molecules depending on the degree of dissociation. The theory of
salt diffusion is elaborated mainly for dilute solutions in which the
degree of dissociation is close to one. Thus, the diffusion coefficient
for a simple salt that is infinitely diluted can be found using the
Nernst-Heckell equation

where DAB is the diffusion coefficient, defined as the proportionality


factor between the molecular flow of dissolved salt and the gradient
of its molecular concentration, cm2/s; T, the temperature, K; Fa, the
Faraday number, n+ and n-, the cation and anion valences; and
, the limit (under an infinite dilution) ionic conductions of cation
and anion, cm2/Ω mol.
In electrolyte solutions, the diffusion coefficient substantially
depends on the concentration of diffusing substance. If its
concentration is no more than 2N, the formula

is suggested by Gordon, where D0 and D are the diffusion


coefficients for an infinitely dilute solution and a molar solution,
respectively; V, the solution volume; V1, the partial volume of the
solvent; x1, the number of solvent moles in volume V; ν, the molarity
of the solution; η and η1, the viscosity of solution and solvent; v, the
molar activity coefficient.

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