*Real Gases and
the van der Waals
Equation
By Shawn P. Shields, Ph. D.
This work is licensed by Shawn P. Shields-Maxwell under a Creative Commons Attribution-
NonCommercial-ShareAlike 4.0 International License.
*Real Gases…What are they?
*Most gases behave ideally when they
are held at low pressures and “high”
temperatures.
(Room temperature is considered high T.)
*Remember that “ideal behavior” means that
the gas molecules do not interact with each
other. Only kinetic energy is present.
*Real Gases…What are they?
*However, sometimes gas molecules DO
interact with each other.
*Interactions between gas molecules is more
likely at
*low temperatures
*high gas pressures (i.e., high gas densities).
This introduces potential energy into
the picture!
*Real Gases…What are they?
* Molecules that have significant
intermolecular attractions (aka “polar”
molecules) may also interact with each other.



+


“partial charges” on the
molecules are attracted
to each other
Water is a
polar molecule.
*The Compressibility Factor, Z
*We can use the “compressibility factor”
(Z) to detect deviations of a gas from
ideal behavior in experiments.
𝐙 =
𝐏𝐕
𝐧𝐑𝐓
*When Z < 1, intermolecular attractions
exist, and gas molecules can “feel” each
other’s presence. 
*Real Gas Behavior
Compare 3 scenarios for gases in a piston…
The first piston shows a gas at low pressure.
Vactual = Videal
Ideal Gas Law and KTG are obeyed. 
Low P
*Real Gas Behavior
The second piston shows a gas at med-high pressure.
As the volume decreases, some molecules stick
together, effectively reducing the moles of gas.
Now, Vactual < Videal
The gas is more compressible, and attractions
dominate!
Med to high P
*Real Gas Behavior
Compare 3 scenarios for gases in a piston…
The third piston shows a gas at REALLY high pressure.
The gas cannot move and we see that it actually DOES
take up space…as our common sense might tell us.
Now, Vactual > Videal Repulsions dominate!
Ridiculously high P
*The Compressibility Factor, Z
*More about the compressibility factor Z
Z = 1
𝒁 =
𝑷𝑽
𝒏𝑹𝑻
P (atm)
Perfectly ideal
gas behavior
Real gases
Behaves as an ideal gas
under reasonable conditions
Attractions dominate
Repulsions dominate
*The van der Waals Equation
*Corrects the Ideal Gas Law for real gas
behavior.
𝑃 =
𝑛𝑅𝑇
𝑉 − 𝑛𝑏
−
𝑎𝑛2
𝑉2
*The van der Waals constants a and b are
experimentally-determined for each individual
gas.
*The vdw constant a describes the strength of
attractions with units L2 atm mole–2
*The vdw constant b increases with increasing
molecular size with units L mol–1
*The van der Waals Equation
*Corrects the Ideal Gas Law for real gas
behavior.
𝑃 =
𝑛𝑅𝑇
𝑉 − 𝑛𝑏
−
𝑎𝑛2
𝑉2
Correction for the
volume taken up by
the gas molecules
Correction for the
attractions between gas
molecules. The actual
pressure P is reduced by
this amount compared to
the Ideal Gas law.
*The van der Waals Equation
*Predict the relative size of the van der
Waals constants for the following gases:
H2 gas (very small and not polar)
SO2 gas (larger atoms and polar)
𝑃 =
𝑛𝑅𝑇
𝑉 − 𝑛𝑏
−
𝑎𝑛2
𝑉2
*The van der Waals Equation
*Predict the relative size of the van der
waals constants for the following gases:
H2 gas (very small and not polar)
SO2 gas (larger atoms and polar)
The vdw constant a and b would both be
larger for SO2 gas.
*The van der Waals Equation
*Which gas would produce the lowest
pressure, with moles, T and V constant?
CH4 (methane) gas
(small molecule and not polar)
H2O gas
(small molecules and polar)
𝑃 =
𝑛𝑅𝑇
𝑉 − 𝑛𝑏
−
𝑎𝑛2
𝑉2
*The van der Waals Equation
*Which gas would produce the lowest pressure, with
moles, T and V constant?
𝑃 =
𝑛𝑅𝑇
𝑉 − 𝑛𝑏
−
𝑎𝑛2
𝑉2
If CH4 is a small molecule, and not polar, this means that a
and b are both relatively small. (a = 2.25, b = 0.0428)
The gas should behave close to ideally.
If H2O gas is also a small molecule, then the vdw constant
b will be of a similar size. However, since water is polar,
the vdw constant a will be quite a bit larger.
(a = 5.46, b = 0.0305)
The pressure exerted by water will be lower than the
ideal pressure.
*Summary
*Real gases interact with each other and take
up volume in the container.
*The van der Waals equation corrects the Ideal
Gas Law for real gas behavior.
𝑃 =
𝑛𝑅𝑇
𝑉 − 𝑛𝑏
−
𝑎𝑛2
𝑉2
If the gas is under ideal gas conditions, the van
der Waals equation reduces to the Ideal Gas
Law PV=nRT
(Try this by making a and b = 0) 

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Unit 10 real gases vdw fl14 final

  • 1. *Real Gases and the van der Waals Equation By Shawn P. Shields, Ph. D. This work is licensed by Shawn P. Shields-Maxwell under a Creative Commons Attribution- NonCommercial-ShareAlike 4.0 International License.
  • 2. *Real Gases…What are they? *Most gases behave ideally when they are held at low pressures and “high” temperatures. (Room temperature is considered high T.) *Remember that “ideal behavior” means that the gas molecules do not interact with each other. Only kinetic energy is present.
  • 3. *Real Gases…What are they? *However, sometimes gas molecules DO interact with each other. *Interactions between gas molecules is more likely at *low temperatures *high gas pressures (i.e., high gas densities). This introduces potential energy into the picture!
  • 4. *Real Gases…What are they? * Molecules that have significant intermolecular attractions (aka “polar” molecules) may also interact with each other.    +   “partial charges” on the molecules are attracted to each other Water is a polar molecule.
  • 5. *The Compressibility Factor, Z *We can use the “compressibility factor” (Z) to detect deviations of a gas from ideal behavior in experiments. 𝐙 = 𝐏𝐕 𝐧𝐑𝐓 *When Z < 1, intermolecular attractions exist, and gas molecules can “feel” each other’s presence. 
  • 6. *Real Gas Behavior Compare 3 scenarios for gases in a piston… The first piston shows a gas at low pressure. Vactual = Videal Ideal Gas Law and KTG are obeyed.  Low P
  • 7. *Real Gas Behavior The second piston shows a gas at med-high pressure. As the volume decreases, some molecules stick together, effectively reducing the moles of gas. Now, Vactual < Videal The gas is more compressible, and attractions dominate! Med to high P
  • 8. *Real Gas Behavior Compare 3 scenarios for gases in a piston… The third piston shows a gas at REALLY high pressure. The gas cannot move and we see that it actually DOES take up space…as our common sense might tell us. Now, Vactual > Videal Repulsions dominate! Ridiculously high P
  • 9. *The Compressibility Factor, Z *More about the compressibility factor Z Z = 1 𝒁 = 𝑷𝑽 𝒏𝑹𝑻 P (atm) Perfectly ideal gas behavior Real gases Behaves as an ideal gas under reasonable conditions Attractions dominate Repulsions dominate
  • 10. *The van der Waals Equation *Corrects the Ideal Gas Law for real gas behavior. 𝑃 = 𝑛𝑅𝑇 𝑉 − 𝑛𝑏 − 𝑎𝑛2 𝑉2 *The van der Waals constants a and b are experimentally-determined for each individual gas. *The vdw constant a describes the strength of attractions with units L2 atm mole–2 *The vdw constant b increases with increasing molecular size with units L mol–1
  • 11. *The van der Waals Equation *Corrects the Ideal Gas Law for real gas behavior. 𝑃 = 𝑛𝑅𝑇 𝑉 − 𝑛𝑏 − 𝑎𝑛2 𝑉2 Correction for the volume taken up by the gas molecules Correction for the attractions between gas molecules. The actual pressure P is reduced by this amount compared to the Ideal Gas law.
  • 12. *The van der Waals Equation *Predict the relative size of the van der Waals constants for the following gases: H2 gas (very small and not polar) SO2 gas (larger atoms and polar) 𝑃 = 𝑛𝑅𝑇 𝑉 − 𝑛𝑏 − 𝑎𝑛2 𝑉2
  • 13. *The van der Waals Equation *Predict the relative size of the van der waals constants for the following gases: H2 gas (very small and not polar) SO2 gas (larger atoms and polar) The vdw constant a and b would both be larger for SO2 gas.
  • 14. *The van der Waals Equation *Which gas would produce the lowest pressure, with moles, T and V constant? CH4 (methane) gas (small molecule and not polar) H2O gas (small molecules and polar) 𝑃 = 𝑛𝑅𝑇 𝑉 − 𝑛𝑏 − 𝑎𝑛2 𝑉2
  • 15. *The van der Waals Equation *Which gas would produce the lowest pressure, with moles, T and V constant? 𝑃 = 𝑛𝑅𝑇 𝑉 − 𝑛𝑏 − 𝑎𝑛2 𝑉2 If CH4 is a small molecule, and not polar, this means that a and b are both relatively small. (a = 2.25, b = 0.0428) The gas should behave close to ideally. If H2O gas is also a small molecule, then the vdw constant b will be of a similar size. However, since water is polar, the vdw constant a will be quite a bit larger. (a = 5.46, b = 0.0305) The pressure exerted by water will be lower than the ideal pressure.
  • 16. *Summary *Real gases interact with each other and take up volume in the container. *The van der Waals equation corrects the Ideal Gas Law for real gas behavior. 𝑃 = 𝑛𝑅𝑇 𝑉 − 𝑛𝑏 − 𝑎𝑛2 𝑉2 If the gas is under ideal gas conditions, the van der Waals equation reduces to the Ideal Gas Law PV=nRT (Try this by making a and b = 0) 