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Deviation from the ideal gas law

The ideal gas law assumes gas particles are points that never attract each other. Real molecules have size and do attract — and under the right squeeze or chill, those two facts make a gas stop obeying PV = nRT.

§1

When the ideal picture breaks.

The ideal gas law rests on two assumptions: gas particles have negligible volume and no attractions. Real gases obey it well at ordinary conditions but deviate when those assumptions fail.

At high pressure, the particles are crowded, so their own volume becomes a significant fraction of the container — the gas takes up more room than ideal predicts. At low temperature, the particles move slowly enough that intermolecular attractions pull them together, lowering the pressure below ideal.

So deviations grow at high pressure and low temperature — the conditions where real particle volume and real attractions can no longer be ignored. Gases with stronger IMFs deviate more.

UNIT 3 TOPIC 3.6 • DEVIATION FROM IDEAL GAS LAW REAL VS. IDEAL Real gases deviate from the ideal gas law (PV = nRT) because of intermolecular attractions and finite particle volume. IDEAL GAS ASSUMPTIONS Particles have no volume No intermolecular attractions Compression factor PV nRT ≈ 1 Behaves ideally REAL GAS REALITIES Particles have finite volume Intermolecular attractions exist Compression factor PV nRT ≠ 1 Deviates from ideal ! WHAT INCREASES DEVIATION? LOW TEMPERATURE ↓ kinetic energy → attractions dominate HIGH PRESSURE particles crowd → finite volume dominates COMPRESSIBILITY (PV/nRT vs P) >1 1 <1 PV nRT T high T low Pressure (at constant T) THE TAKEAWAY Attractions pull particles together → PV/nRT < 1 (strongest at low temperature) Finite volume takes up space → PV/nRT > 1 (strongest at high pressure) CED ANCHOR Gases behave most ideally at high T and low P. (SAP-7.A) AP Chemistry · Unit 3 · Properties of Substances & Mixtures
Fig. 3.6.1 Real gases deviate from PV = nRT when the ideal assumptions fail: at high pressure the particles' own volume matters, and at low temperature intermolecular attractions pull particles together. Both push behavior away from ideal.
§2

Diagnosing a deviation.

Tie each deviation to the assumption that broke and the condition that broke it.

  1. Recall the two assumptions. No particle volume; no intermolecular attractions.
  2. High pressure → volume matters. Crowded particles occupy real space, so the gas resists compression more than ideal predicts.
  3. Low temperature → attractions matter. Slow particles feel their mutual attractions, pulling inward and lowering pressure.
  4. Stronger IMFs → bigger deviation. A gas with strong intermolecular forces (like water vapor) deviates more than a weakly attracting one (like helium).
§3

The pieces you'll meet.

Two assumptions, two failure conditions.

ideal
Ideal assumptions
Particles have no volume and no attractions.
high P
High pressure
Crowds particles so their real volume matters.
low T
Low temperature
Slows particles so attractions dominate.
volume
Particle volume
Real, nonzero size that ideal ignores; matters at high P.
attraction
Attractions
Real IMFs that ideal ignores; matter at low T.
IMF effect
IMF strength
Stronger intermolecular forces cause larger deviations.
§4

Worked example: which gas is more ideal, and when?

Question. Compare helium and water vapor. Which behaves more ideally, and under what conditions do both deviate most?

Which is more ideal. Helium is tiny and has only weak dispersion forces, so it barely attracts and takes little space — it behaves nearly ideally. Water vapor hydrogen-bonds strongly, so it deviates more.

When deviation is worst. Both deviate most at high pressure (particle volume matters) and low temperature (attractions matter).

Reasoning. The deviation is not random: it appears exactly where the ideal assumptions of no-volume and no-attraction stop being good approximations.

§5

Mistakes that cost real points.

Pitfall · 01

"Real gases deviate most at low pressure and high temperature."

It is the reverse. At low pressure and high temperature the particles are far apart and fast, so their volume and attractions are negligible — the gas is nearly ideal. Deviations grow at high pressure and low temperature.

Fix. Remember the failure conditions: high pressure (volume matters) and low temperature (attractions matter). Low P and high T are the ideal-friendly conditions.

Pitfall · 02

"Deviation happens because the gas particles get heavier."

Mass does not change; deviation comes from particle volume and intermolecular attractions becoming significant. Attributing it to changing mass misreads the cause. The molecules are the same — the conditions changed.

Fix. Attribute deviation to the correct cause: real particle volume (at high P) and real attractions (at low T), not a change in the particles.

Pitfall · 03

"All gases deviate from ideal behavior by the same amount."

Gases with stronger intermolecular forces deviate more. Water vapor, which hydrogen-bonds, departs from ideal much more than helium, which has only weak dispersion. The particle model, including IMF strength, predicts how much.

Fix. Rank deviation by intermolecular-force strength and particle size. Small, weakly attracting gases stay closer to ideal.

§6

Skill Check.

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