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Viral Equation Updated

The virial equation of state is used to describe the behavior of diluted gases and relates the compressibility factor to density and pressure through virial coefficients. The second virial coefficient represents the initial departure from ideal gas behavior due to pair-wise molecular interactions, while higher order coefficients account for interactions of more molecules. The virial equation can be rearranged to relate pressure, volume, temperature, and virial coefficients. At the Boyle temperature, where the second virial coefficient is zero, the attractive and repulsive molecular forces balance and the gas most closely approximates ideal behavior over a wide pressure range.

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Manan IFtikhar
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227 views3 pages

Viral Equation Updated

The virial equation of state is used to describe the behavior of diluted gases and relates the compressibility factor to density and pressure through virial coefficients. The second virial coefficient represents the initial departure from ideal gas behavior due to pair-wise molecular interactions, while higher order coefficients account for interactions of more molecules. The virial equation can be rearranged to relate pressure, volume, temperature, and virial coefficients. At the Boyle temperature, where the second virial coefficient is zero, the attractive and repulsive molecular forces balance and the gas most closely approximates ideal behavior over a wide pressure range.

Uploaded by

Manan IFtikhar
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© © All Rights Reserved
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Viral Equation & Its Applications

The virial equation of state is used to describe the behavior of diluted gases. It is usually
written as an expansion of the compressibility factor, , in terms of either the density or the
pressure.

Here the quantity

 
Is the compressibility factor. And if we further simplify it, we have

 BB is the second virial coefficient,


 CC is called the third virial coefficient, etc.

The second virial coefficient represents the initial departure from ideal-gas behavior,
and describes the contribution of the pair-wise potential to the pressure of the gas. The third
virial coefficient depends on interactions between three molecules. The jth virial coefficient can
be calculated in terms of the interaction of j molecules in a volume V. The second and third
virial coefficients give most of the deviation from ideal P/ρRT up to 100 atm. It is important to
note that value of the virial coefficients are temperature dependent.

Because

ρ=n/V=1/V¯

And the virial Equation can be rearranged to

PV¯=RT (1+B/V¯+C/V¯2+⋯)..... (A)

Recall that

PV¯/ RT=Z

And it is easy to see that because

PV¯=ZRT
Then

Z=1+B/V¯+C/V¯2+⋯

The virial Equation of state is a model that attempts to describe the properties of a real gas. If it
were a perfect model, the virial Equation would give results identical to those of the perfect gas
law as the pressure of a gas sample approached zero. For the virial Equation to collapse to the
perfect gas law, all of the virial coefficients would need to have a value of zero at the same
temperature. This is an unlikely occurrence, but because the second term in the virial
Equation, B=B/V¯ is the largest term in the Equation (1/V¯≪1/V¯2≪1/V¯3≪⋯), we can focus
on the temperature at which BB is zero. This temperature is known as the Boyle temperature,
TB, and it is the temperature at which the repulsive forces between the gas molecules exactly
balance the attractive forces between the gas molecules.
The Eq. (A) can be Re-written as

P=RT (1+BP/RT+CP2/ (RT) 2 +⋯)

In which case

Z=1+BP/RT+CP2/ (RT) 2 +⋯

Then

dZ/dP→B/RT as P→0
At the Boyle temperature, B = 0, and the slope of the graph of the compression factor versus
the pressure is zero at P = 0. Compared to other temperatures, the slope of the plot of Z versus
P at the Boyle temperature begins to approach zero at relatively higher pressures, and so the
real gas closely approximates a perfect gas over a wider range of pressures. A second look at
Figure 1C.31C.3 for N2N2, shows us that the TB is near 298 K. (In fact it is roughly 327 K.)

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