Non-Ideal (Real) Gases: Virial Equations

Virial (force) Equations à Power series of V and P

,.- !"# ($) !&# ($) !'# ($)
*= = 1+ - + - " + - & + ⋯
/$ . . .
,.-
*= = 1+!") $ , + !&) $ ," + !') $ ,& + ⋯
/$

!"# $ , !&# $ , !'# $ , …

!") $ , !&) $ , !') $ , …
are the virial coefficients
They are functions of T
Values for the second virial coefficient B2V (cm3/mol)
CH3510 - PChem I Teaching Material by L. Valenzano-Slough 1
 Non-Ideal (Real) Gases: Virial Equations
Virial coefficients vary with T

At what T virial coefficients are zero?

Boyle’s Temperature = TB

0
Z = 1 + + ... » 1
V

At TB a real gas behaves as an ideal gas

CH3510 - PChem I Teaching Material by L. Valenzano-Slough 2
 Non-Ideal (Real) Gases

To summarize:
1) Our ideal gases are composed of tiny particles
(without volume!) that do not interact (low P!)
2) Our real gases are composed of sizable particles
that DO interact

Q: What if the volume of the particles affects

the volume V of the gas ?
A: The interaction between the particles of the gas
will affect the P of the gas !
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 Non-Ideal (Real) Gases: vdW EOS
1837-1923
æ an ö
2
çç P + 2 ÷÷(V - nb) = nRT
è V ø
van der Waals equation
a, b = vdW constants for the gas of interest
a, b à do not explicitly depend from T
a = pressure correction ß interaction between particles
b = volume correction ß size of the particles
a à atm dm6 mol-2
b à dm3 mol-1
CH3510 - PChem I Teaching Material by L. Valenzano-Slough 4
 Non-Ideal (Real) Gases: vdW EOS
æ an ö
2
van der Waals equation çç P + 2 ÷÷(V - nb) = nRT
è V ø

2
nRT an RT a
P= - 2 = - 2
V - nb V V -b V

You can try to compute the partial derivatives

Virial equations à fits gas behavior to model

vdW equation à predicts gas physical behavior
CH3510 - PChem I Teaching Material by L. Valenzano-Slough 5
 Non-Ideal (Real) Gases: vdW EOS
Mathematica Demonstration

http://demonstrations.wolfram.com/VanDerWaalsIsothermsForRealAndIdealGases/
CH3510 - PChem I Teaching Material by L. Valenzano-Slough 6
 Non-Ideal (Real) Gases
We now have two equations describing the
behavior of real gases
#%$ *+, (') */, (')
P=
RT a
- 2
!= = 1+ $ + $ + + ⋯
&' % % V -b V
The relationship between them is given by
(see notes for the math)
3
*+, ' =1−
&'
And we can also find TB (Boyle’s Temperature)
a a Good estimation of the T
0=b- Þ TB =
RTB bR where real gases act as ideal
CH3510 - PChem I Teaching Material by L. Valenzano-Slough 7
 Non-Ideal (Real) Gases
Mathematica Demonstration

http://demonstrations.wolfram.com/SecondVirialCoefficientsUsingTheLennardJonesPotential/
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