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Hirschfelder's Equation for Diffusion Coefficient

Hirschfelder's equation attempts to account for molecular forces of repulsion and attraction by using the Lennard-Jones potential to model their influence on diffusion coefficients. The Stefan tube method, developed by Josef Stefan in 1874, measures diffusion coefficients by observing the rate at which a volatile liquid evaporates through a stagnant gas within a narrow tube. Under the assumption of pseudo-steady state, the diffusion coefficient can be calculated using an equation that considers factors like liquid density, ambient pressure, distances of the liquid level over time, vapor pressures, and gas composition.

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572 views3 pages

Hirschfelder's Equation for Diffusion Coefficient

Hirschfelder's equation attempts to account for molecular forces of repulsion and attraction by using the Lennard-Jones potential to model their influence on diffusion coefficients. The Stefan tube method, developed by Josef Stefan in 1874, measures diffusion coefficients by observing the rate at which a volatile liquid evaporates through a stagnant gas within a narrow tube. Under the assumption of pseudo-steady state, the diffusion coefficient can be calculated using an equation that considers factors like liquid density, ambient pressure, distances of the liquid level over time, vapor pressures, and gas composition.

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Abdullah
Copyright
© © All Rights Reserved
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Hirschfelder’s Equation:

As an attempt to account for the Molecular Forces of repulsion and attraction,


Hirschfelder et al (1949), proposed an expression in which The Lennard-Jones Potential
was utilized to gauge the influence of Molecular Forces, the expression presented is
meant to calculate The Diffusion Coefficient for dilute gases consisting of nonpolar,
spherical monatomic molecules.:

Hirschfelder's Expression 2.1

Equation 2.2

Equation 2.3

Equation 2.4

Table 1 Hirschfelder's Parameters 1

Parameter Definition Unit


DAB Diffusion Coefficient Cm2/S
T Absolute Temperature K
MA and MB Molecular Weights of A, g/mol
and B
P The System Pressure atm
Collision Integral For Dimensionless
Molecular Diffusion
Collision Diameter
Equation 2.2 through 2.4 must be modified for polar, reacting molecules.

Stefan Tube Method:


In 1874, Josef Stefan came up with a method to measure The Diffusion
Coefficient of the vapor of a volatile liquid, as it vaporizes through a stagnant gas. A
Stefan Tube is a tube with a narrow diameter by convention, to suppress any convection
that might occur, within it, a volatile liquid is to fill the lower part of the tube. By
mechanism of diffusion, the liquid will evaporate through the tube until it gets swept by
the surrounding gas, say Air, at the top of the tube, in an attempt decrease the
concentration of the vapor, at that point to zero. The Experimental approach is to
basically measure the rate at which the liquid level drops, which can be remotely
observed through a Cathetometer. For the experiment to be conducted successfully and
with negligeable errors, the Air rate must be constant, and low.
Experimental setup:

Under the assumption of Pseudo-steady state, The Diffusion Coefficient of vapor A in


gas B (Air) can be obtained through this equation:
Equation 3.1

Parameters used in Equation 3.1


Density of Liquid A at T
P Ambient Atmospheric Pressure
zt Distance from the mouth of the tube to liquid level, at t=0
Z1 Distance from the mouth of the tube to liquid level, at t
t Time during which the liquid level dropped from z1 to zt
R Gas law constant
PA1 Vapor Pressure of liquid A at temperature T
PA2 Partial Pressure at the mouth of the tube
PB,lm

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