1Ways to store energy
Warm 1 mol of helium and 1 mol of nitrogen by 1 K at fixed volume: helium needs 12.5 J, nitrogen 20.8 J. Helium atoms can only move about; nitrogen molecules can also spin, and the extra heat goes into spinning.
The degrees of freedom of a molecule are the number of independent ways it can store energy: translation (moving along x, y, z), rotation (spinning) and vibration (atoms shaking in and out).
2Moving and spinning
- Single atom (He, Ne, Ar): 3 ways to move; it is so small that spinning stores no energy. .
- Two atoms (H₂, N₂, O₂): 3 ways to move and 2 spins, about the two axes at right angles to the bond. .
- Bent, three or more atoms (H₂O, NH₃, CH₄): 3 ways to move and 3 spins. .
3Vibration
A bond behaves like a spring. The energy of a vibration swaps between kinetic energy (moving atoms) and potential energy (stretched bond), so one vibration gives 2 degrees of freedom. Vibrations only become active at high temperature (above about 1000 K for many gases).
| Molecule | Moving | Spinning | f |
|---|---|---|---|
| Single atom (He, Ar) | 3 | 0 | 3 |
| Two atoms, room temperature (N₂, O₂) | 3 | 2 | 5 |
| Two atoms, very hot (+1 vibration) | 3 | 2 | 7 |
| Bent, 3 atoms (H₂O) | 3 | 3 | 6 |
| Straight, 3 atoms (CO₂), as usually taken | 3 | 2 | 7 |
In general, atoms need numbers to place them: a straight molecule has 3 translations, 2 rotations and vibrations; a bent one has 3, 3 and . Each active vibration adds 2 to .
4The law of equipartition
Collisions keep passing energy between the ways of storing it, so each share jumps up and down; but on average every share gets the same amount.
A nitrogen molecule at 300 K holds J. For a two-atom gas, the spinning energy and the moving energy are in the ratio 2 : 3.
5Internal energy
| Gas | f | U per mole |
|---|---|---|
| Single atom | 3 | 3RT/2 |
| Two atoms (room T) | 5 | 5RT/2 |
| Two atoms (hot) | 7 | 7RT/2 |
| Bent, 3 atoms | 6 | 3RT |
With no forces between molecules there is no potential energy between them, so the internal energy of an ideal gas depends only on its temperature: squeezing or expanding it at constant temperature leaves unchanged.
6Heat capacities and γ
At fixed volume all the heat goes into ; at fixed pressure the gas also does work per mole per kelvin (Mayer's relation):
| Gas | f | Cᵥ | Cₚ | γ |
|---|---|---|---|---|
| Single atom | 3 | 3R/2 | 5R/2 | 1.67 |
| Two atoms (room T) | 5 | 5R/2 | 7R/2 | 1.40 |
| Two atoms (hot) | 7 | 7R/2 | 9R/2 | 1.29 |
| Bent, 3 atoms | 6 | 3R | 4R | 1.33 |
7Frozen modes
The molar heat capacity of hydrogen is below about 80 K (only moving), near room temperature (spinning has woken up) and climbs towards above a few thousand kelvin (vibration too).
Energy at the scale of molecules comes in small packets. A motion stays frozen until is large enough to supply its packet, so equipartition counts only the modes that are active. Single-atom gases have at every ordinary temperature.
Summary
Key ideas
- Degrees of freedom count the independent ways a molecule stores energy: moving, spinning and vibrating.
- A single atom has f = 3; a two-atom molecule 5 at room temperature; a bent molecule 6.
- Spinning about the axis of a straight molecule stores no energy, so it does not count.
- Each active vibration adds 2 degrees of freedom: kinetic and potential.
- Equipartition: in equilibrium each degree of freedom holds ½kT per molecule on average.
- One molecule holds (f/2)kT; n moles hold U = (f/2)nRT.
- The internal energy of an ideal gas depends only on its temperature.
- C_v = (f/2)R, C_p = C_v + R, and γ = 1 + 2/f.
- For a mixture, weight f (or C_v) by the number of moles.
- Modes whose energy packet is larger than kT are frozen; only active modes count.
Every equation
- Energy per degree of freedom
- Per molecule
- Internal energy
- Molar Cᵥ
- Molar Cₚ
- Mayer
- Ratio of heat capacities
- Cᵥ from γ
- Mixture
- Straight molecule
- Bent molecule
- Adiabatic work