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S1.5.2 Deviations from ideal gas behavior

Limitations of the Ideal Gas Model and Deviations of Real Gases

  1. You're inflating a balloon on a chilly winter day.
  2. You notice that the balloon doesn’t expand as much as it would on a warm day, even though you’ve filled it with the same amount of air. Why is this?
The answer lies in the behavior of gases under different conditions.

Why Do Real Gases Deviate from Ideal Gas Behavior?

The ideal gas model is based on several simplifying assumptions, as explored in the previous section:

  1. Gas particles have negligible volume compared to the volume of their container.
  2. There are no intermolecular forces between gas particles.
  3. Collisions between gas particles are perfectly elastic.
  4. The kinetic energy of gas particles is directly proportional to their temperature in kelvin.
While these assumptions work well for many gases under standard conditions, they break down under specific circumstances.

Real gases deviate from ideal behavior primarily due to:

  • Intermolecular Forces: At low temperatures, attractive forces between particles become significant.
  • Finite Particle Volume: At high pressures, the volume occupied by gas particles themselves is no longer negligible.

1. Low Temperatures: The Role of Intermolecular Forces

At low temperatures, gas particles move more slowly because their kinetic energy decreases.

This reduced motion allows intermolecular forces—such as van der Waals forces—to become more pronounced.

These forces cause gas particles to attract each other, reducing the pressure exerted by the gas compared to what the ideal gas law predicts.

Example

Consider a gas like ammonia NH3, which has strong hydrogen bonding. At low temperatures, these intermolecular attractions can pull the particles closer together, causing the gas to deviate significantly from ideal behavior.

Analogy

  1. Imagine a group of people walking quickly in a crowded room.
  2. If they’re moving fast, they’re less likely to stop and interact with each other.
  3. This is similar to gas particles at high temperatures—they move too quickly for intermolecular forces to take effect.
  4. Now imagine the same group walking slowly.
  5. They’re more likely to stop and interact, just as gas particles are more likely to experience intermolecular attractions at low temperatures.

Tip

To minimize deviations from ideal behavior, gases should be studied athigh temperatures, where the kinetic energy of particles overcomes intermolecular forces.

Self review

Can you think of other examples where slowing down movement increases interactions? How does this relate to gas behavior?

2. High Pressures: The Significance of Particle Volume

At high pressures, gas particles are compressed into a smaller space.

Under these conditions, the volume of the gas particles themselves becomes significant compared to the total volume of the gas.
  • This means that the space available for the particles to move is less than the container’s volume, violating the ideal gas assumption that particle volume is negligible.
  • As a result, the gas occupies more volume than predicted by the ideal gas law.
  • This effect is particularly noticeable in gases with larger molecules, such as butane C4H10.

Analogy

  1. Think of a jar filled with marbles.
  2. If the jar is large, the marbles take up only a small fraction of the total volume, leaving plenty of empty space.
  3. Now imagine squeezing the marbles into a much smaller jar.
  4. The volume occupied by the marbles themselves becomes a significant fraction of the total volume, just as the particle volume becomes significant for gases at high pressures.

Tip

To minimize deviations from ideal behavior, gases should be studied atlow pressures, where particles are far apart and their individual volumes are negligible.

Self review

How does the size of gas particles influence their behavior at high pressures?

Graph showing deviations of different gases.
Graph showing deviations of different gases.

Factors Affecting Deviations: The Nature of the Gas

Not all gases deviate from ideal behavior to the same extent. The degree of deviation depends on the nature of the gas, particularly:

  1. Intermolecular Forces: Polar gases with strong intermolecular forces (e.g., hydrogen fluoride, HF) deviate more than nonpolar gases (e.g., helium, He).
  2. Molecular Size: Larger gas molecules occupy more volume and deviate more than smaller molecules.

Common Mistake

Many students assume that all gases deviate from ideal behavior equally. Remember that factors like polarity and molecular size play a crucial role in determining the extent of deviation.

Real vs. Ideal Gases: A Summary of Conditions

ConditionIdeal Gas BehaviorReal Gas Behavior
Low TemperatureNegligible intermolecular forcesSignificant intermolecular attractions
High PressureNegligible particle volumeParticle volume becomes significant
High TemperatureParticles move too fast for interactionsDeviations are minimal
Low PressureParticles are far apartDeviations are minimal

Self review

Under what conditions do real gases behave most like ideal gases? Why?

Van der Waals Equation: A More Realistic Model (HL Only)

To account for the deviations of real gases, the van der Waals equation modifies the ideal gas law:

(p+aV2)(Vb)=nRT

Here:

  • a corrects for intermolecular forces. Gases with stronger intermolecular forces have larger (a) values.
  • b corrects for particle volume. Larger gas molecules have larger (b) values.

Note

The van der Waals equation provides a more accurate representation of real gas behavior but is more complex to use than the ideal gas law.

Reflection and Practice

Self review

  1. Why do gases deviate from ideal behavior at low temperatures and high pressures?
  2. Compare the behavior of helium He and ammonia NH3 under the same conditions. Which gas is more likely to deviate from ideal behavior, and why?
  3. How does the van der Waals equation improve upon the ideal gas law?

Theory of Knowledge

How do the assumptions of the ideal gas model influence our understanding of real-world phenomena? What are the risks of relying too heavily on simplified models?

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Questions

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Question 1

What happens to the volume occupied by gas particles at high pressures, and how does this lead to deviations from the ideal gas law?

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How do intermolecular forces affect gas pressure at low temperatures?

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Note

Introduction to Ideal vs Real Gases

  • The ideal gas model is a simplified representation of gas behavior that assumes gas particles have no volume and do not interact with each other.
  • Real gases deviate from this ideal behavior under certain conditions, such as low temperatures and high pressures.

Analogy

Think of the ideal gas model like a perfect frictionless slide - it works in theory, but real slides always have some friction. Similarly, real gases have interactions and volume that can't be ignored.

Example

When you compress air into a bicycle pump, you're experiencing real gas behavior - the pump gets harder to press because the gas particles' volume and interactions become significant.

Note

Ideal gas behavior is most closely approximated under conditions of high temperature and low pressure.

Tip

Remember that the ideal gas law (PV=nRT) assumes ideal behavior - deviations occur when these assumptions are violated.