Non-Ideal (Real) Gases

PV = nRT PV = RT V =V
n
Molar Volume
often not good enough for
real gases

Real à Ideal Ideal ≠ Real

low P high P
high T low T

CH3510 - PChem I Teaching Material by L. Valenzano-Slough 1

 Non-Ideal (Real) Gases
What is the origin of the deviation ?
In real gases molecules interact !
Repulsion
Attraction à
Equilibrium
Separation/
Dissociation
r r

CH3510 - PChem I Teaching Material by L. Valenzano-Slough 2

 Non-Ideal (Real) Gases
Lennard-Jones Potential:
Intermolecular potential comprising
long-range (attractive) and short-range (repulsive) terms
éæ s ö12 æ s ö 6 ù
V ( R ) = 4e êç ÷ - ç ÷ ú
êëè R ø è R ø úû
σ
repulsion attraction

ε R = distance between atoms

ε = depth of the potential
σ = distance at which V(R)=0
http://clearscience.tumblr.com/
CH3510 - PChem I Teaching Material by L. Valenzano-Slough 3
 Non-Ideal (Real) Gases

http://phet.colorado.edu/en/simulation/atomic-interactions
CH3510 - PChem I Teaching Material by L. Valenzano-Slough 4
 Non-Ideal (Real) Gases
How can we treat more accurately real gases ?
If the gas is ideal
PV PV V =V
n
PV = nRT =
nRT RT
=1 Molar Volume

PV = RT
PV
If the gas is non-ideal ¹1
Compressibility factor RT
PV The farther Z is from 1,
Z= the least ideal the
RT behavior of the gas is
CH3510 - PChem I Teaching Material by L. Valenzano-Slough 5
 Non-Ideal (Real) Gases

N2

Ideal Gas à Z = 1, under all conditions

Low P (Pà 0, Và¥) à Z à 1 à Ideality condition
High P à Z > 1, molecules are closer à repulsion
Intermediate P à Z < 1, molecular attraction
CH3510 - PChem I Teaching Material by L. Valenzano-Slough 6
 Non-Ideal (Real) Gases
Deviation from ideality due to:
1) Intermolecular forces
2) Molecules do actually have a volume

Ideality Limit defined as:

1) At zero density: molecules are infinitely apart à
intermolecular forces are null
2) At infinite volume: molecular volume is
negligible w.r.t. the infinite volume of the gas
itself
CH3510 - PChem I Teaching Material by L. Valenzano-Slough 7