Kinetic Theory & the Gas Laws
A few hundred hard discs in a box, and the gas law falls out of them without ever having been assumed.
Introduction
Inside the box
A litre of air holds something like 2.5 × 10²² molecules. No single one of them is hot or has a pressure: those belong to the crowd.
All 160 nitrogen molecules start at 422 m/s. Collisions soon spread them over a wide range of speeds. Meanwhile, what does the 'Temperature (from ⟨v²⟩)' readout do?
The simulation assumes no gas law. It moves a few hundred hard discs in a box, adds up the impulse they deliver to the walls, and averages the squares of their speeds. The dashed curve over the histogram is the Maxwell–Boltzmann distribution, and each rose flash marks a real momentum transfer to a wall.
Pressure is a count of impacts
A wall in this box feels nothing continuous. It gets hit, then nothing, then hit again. Each hit is a molecule arriving with velocity component , leaving with , and handing the wall
Pressure is that impulse per unit time, per unit length of wall. The simulation simply counts it: every , divided by the elapsed time and the box's perimeter. That is the measured bar. The dashed line, , is the prediction, and nothing in the model consults it.
Switch 'Molecule–molecule collisions' off and run it again. The molecules now pass straight through one another. What happens to the measured pressure?
With pair collisions off, this gas sits at a well-defined 300 K, delivers essentially the right pressure, and every molecule in it moves at 422 m/s forever. So the Maxwell–Boltzmann distribution is something other than the definition of temperature: it is what molecular collisions do to a set of speeds, given a little time.
Temperature is a mean kinetic energy
The temperature readout has one input, , computed fresh every frame. In two dimensions each molecule has two independent directions of motion, and equipartition gives each :
Set the gas to xenon, 131 u, more than four times the mass of a nitrogen molecule. Leave the temperature at 300 K and run. Which readouts move?
What one temperature looks like
The dashed curve on the histogram is the two-dimensional Maxwell–Boltzmann distribution, a prediction rather than a fit:
Its long tail pulls the three "typical" speeds apart. For nitrogen at 300 K: , and m/s. Pressure comes from , so the gas law is built from the largest.
Halving the box at 300 K doubled the predicted pressure, and the measured bar followed. Which sentence describes what actually doubled?
What this leaves open
You watched a temperature hold while the speeds spread, doubled a pressure three ways, and crowded a gas until it stopped being ideal. Every collision here conserves kinetic energy, which made temperature easy to define. Real nitrogen is two atoms on a bond that can rotate and stretch, with places to store energy these discs lack, which is why a real gas's heat capacity differs from this box's and changes with temperature. And the piston has been a fixed wall. Let it move during the run and energy crosses the boundary as work: that is where thermodynamic cycles begin.
Ideas this lesson took on
Each of these is a common intuition the lesson put to the test. If one still feels right, the section that tests it is worth another look.
- “A gas at one temperature has all its molecules at one speed”
- “Pressure comes from molecules colliding with each other”
- “Heavier molecules are hotter, or at least hit the wall harder”
- “Halving the volume speeds the molecules up”
Finished with this lesson?
Progress is stored on this device only. There is no account and nothing is sent anywhere.
Research behind this lesson
- Jasien & Oberem 2002: A survey spanning non-majors, lower- and upper-division science majors, and both prospective and practising K-12 teachers found the same misconceptions about thermal equilibrium, specific heat, heat capacity and heat transfer at every level, traceable in part to everyday uses of the words 'heat' and 'temperature'.
- Kautz et al. 2005: Many undergraduate science and engineering majors hold seriously flawed microscopic models for the pressure and temperature of an ideal gas; the paper identifies common mistaken ideas about the microscopic processes and shows research-based instruction improving understanding of the gas law, especially its substance independence.
- Robertson & Shaffer 2013: University students and K-12 teachers often treat the volume of a gas as something different from the volume of its enclosing container, and frequently justify incorrect answers with faulty statements about how the particles move.
- Robertson & Shaffer 2016: An analysis of over a thousand written responses from university physics and chemistry students found that the justifications they give for changes in the pressure of an ideal gas vary widely in the extent to which they are mechanistic and consistent with kinetic-molecular theory.