Law of Equipartition of Energy
The law of equipartition of energy states that in thermal equilibrium at absolute temperature , every independent quadratic term in a molecule's energy (every degree of freedom) gets the same average energy, . Counting degrees of freedom (3 for a monatomic gas, 5 for a rigid diatomic, 6 for a rigid non-linear molecule) then gives the internal energy of any ideal gas. The law of equipartition of energy is in the JEE Main and NEET syllabus and leads straight to specific heats.
- ★ Must learnEquipartition: each degree of freedom (quadratic energy term) has average energy per molecule, per mole
- ★ Must learnEnergy per molecule ; internal energy of moles
- ★ Must learnRigid molecules: monatomic , diatomic or linear , non-linear
- Each active vibrational mode adds 2 terms (): diatomic with vibration
- Rigid molecule of atoms with independent constraints:
- ★ Must learnAll motions: = 3 translations + 2 (linear) or 3 (non-linear) rotations + or vibrational modes
- Diatomic (rigid): rotational KE : translational KE ; per molecule each is and
1. Degrees of Freedom
The degrees of freedom of a molecule are the number of independent ways in which it can store energy: the independent coordinates (positions or angles) needed to describe its motion, counted by the quadratic energy terms they produce.
A molecule can store energy in three kinds of motion: translation of its centre of mass, rotation about its centre of mass, and vibration of its atoms along the bonds.
1.1 Translational degrees of freedom
Motion of the centre of mass is described by , , , and the translational kinetic energy has three independent terms:
Every molecule, whatever its shape, has 3 translational degrees of freedom. A monatomic gas (He, Ne, Ar) has only these: the atom is point-like, so it stores no rotational energy.
2. Rotational Degrees of Freedom
A diatomic molecule such as or is like a rigid dumbbell. Besides translating, it can rotate about the two axes perpendicular to its bond, each with rotational energy :
The moment of inertia about the bond axis itself is negligible (the atoms are almost points on that axis), so that rotation stores no energy and is not counted.
Polyatomic molecules follow the same rule. A linear molecule (, ) has 2 rotations, like a diatomic one. A non-linear molecule (, , ) has a moment of inertia about every axis and has 3.
2.1 Counting rule for rigid molecules
free atoms need coordinates. Each independent rigid condition (a fixed bond length, a fixed angle) removes one:
| Molecule (rigid) | Translational | Rotational | Examples | |
|---|---|---|---|---|
| Monatomic | 3 | 0 | 3 | He, Ne, Ar |
| Diatomic | 3 | 2 | 5 | , , , CO |
| Linear polyatomic | 3 | 2 | 5 | , |
| Non-linear polyatomic | 3 | 3 | 6 | , , |
Why is rotation of a diatomic molecule about its own axis not counted?
How many degrees of freedom does a rigid molecule have?
Is treated like or like ?
3. Vibrational Degrees of Freedom
Real bonds are not perfectly rigid. The atoms of a diatomic molecule can vibrate along the bond like two masses on a spring. The vibrational energy has a kinetic and a potential term, both quadratic:
Here is the reduced mass and the spring constant of the bond (written so it is not confused with Boltzmann's constant ).
One vibrational mode counts as two terms (one kinetic, one potential), so it stores . A diatomic molecule with its vibration active has and energy .
Vibrations need a comparatively large energy to start. For most diatomic gases (, , ) they are "frozen" at room temperature and become active only at high temperatures (several hundred to a few thousand kelvin). Unless a problem says so, treat molecules as rigid.
In general a molecule of atoms has independent motions: 3 translations, then 2 rotations and vibrational modes if linear, or 3 rotations and vibrational modes if non-linear. (, linear) has vibrational modes; has .
3 translational + 2 rotational terms. , energy per molecule. Good for , at room temperature.
Adds one vibrational mode = 2 terms (KE + PE). , energy per molecule. Needed at high temperature or when a question says the molecule vibrates.
4. The Law of Equipartition of Energy
Kinetic theory already showed that the average translational energy of a molecule is . Because the motion is random, no direction is special, so this energy is shared equally among the three components:
Collisions constantly transfer energy between translation, rotation and vibration. Maxwell and Boltzmann showed that in equilibrium every quadratic term receives the same average share. This is the law.
Law of equipartition of energy: in equilibrium at absolute temperature , the total energy of a molecule is equally distributed among all its degrees of freedom, each translational and rotational degree of freedom contributing and each vibrational mode (two quadratic terms).
Energy per degree of freedom is per molecule, per mole, for every gas. So rotational KE of a rigid diatomic gas is per mole (2 terms) and translational KE is (3 terms): ratio , whatever the gas or temperature. For a non-linear molecule the ratio is .
5. Internal Energy of an Ideal Gas
An ideal gas has no intermolecular forces, so it has no potential energy between molecules. Its internal energy is just the sum of the molecular energies:
depends only on temperature (for a given amount of gas), not on pressure or volume separately.
| Gas | Energy per molecule | for moles | |
|---|---|---|---|
| Monatomic | 3 | ||
| Diatomic (rigid) | 5 | ||
| Diatomic (vibrating) | 7 | ||
| Non-linear (rigid) | 6 |
Mixtures. Energy adds: for moles with and moles with at the same temperature,
Find from any energy statement: . If a gas has , then (non-linear). If the energy per molecule is , it is a rigid diatomic or linear gas. The same trick with is on the next page: .
What is the internal energy of of helium at ?
Does the internal energy of an ideal gas change in an isothermal expansion?
What is for 1 mol He and 1 mol ?
6. Limitations of the Law
Equipartition is a result of classical physics. It works well for translation at all ordinary temperatures and for rotation above a few tens of kelvin, but it fails when the energy step needed to start a motion is large compared with :
- Frozen vibrations: at room temperature is much smaller than the vibrational energy step of or (a few tenths of an eV), so vibrations take almost no share.
- Frozen rotation: light molecules like stop rotating below about and behave as monatomic.
- Temperature dependence: as a result the measured heat capacities of gases and solids increase with temperature instead of being constant (next concept).
- It applies only to energy terms that are quadratic in a coordinate or velocity.
Why ? In equilibrium the probability of a state with energy is proportional to (Boltzmann factor). For a term :
The answer does not depend on : mass, moment of inertia and spring constant all drop out. For a non-quadratic term the share differs, e.g. a potential gives . Vibrations of : modes, so with all of them active and .
7. Solving Problems and Revision Map
Use the flowchart to decide and the energy, then revise with the mind map.
8. Solved Examples
Rigid diatomic: . .
Answer: ().
Translational: 3 terms, .
Rotational: 2 terms, .
Answer: and ; rotational : translational .
.
Answer: . (Here .)
(A)
(B)
(C)
(D)
Answer: (B). Per molecule it is ; for molecules it is . Option (A) is per molecule, not per mole.
(A)
(B)
(C)
(D)
Answer: (C). 3 translational + 2 rotational terms give ; the vibrational mode adds two terms (KE and PE), . Total .
.
Answer: : a rigid non-linear molecule such as vapour or .
(a) Linear, rigid: , .
(b) Linear triatomic: vibrational modes, each . , .
Answer: (a) ; (b) . The real value at is only a little above (a), because most vibrations are frozen.
(A)
(B)
(C)
(D)
Answer: (B). Half the molecules have and half ; the average is ().
- Find the internal energy of of argon at .Answer:
- Find the total rotational kinetic energy of of oxygen at .Answer:
- How many degrees of freedom does a rigid molecule have?Answer: 6
- Find the ratio of the average energy of a helium atom to that of a rigid oxygen molecule at the same temperature.Answer:
- An ideal gas has internal energy . What is its ?Answer: 6
- How many vibrational modes does a linear triatomic molecule have, and what is if all are active?Answer: 4 modes;
- Find the average total energy of a rigid nitrogen molecule at .Answer:
Common Mistakes to Avoid
- Counting a vibrational mode as one degree of freedom. It has two quadratic terms (KE and PE) and stores , not .
- Counting rotation of a diatomic or linear molecule about its own axis. Its moment of inertia is negligible; only 2 rotations count.
- Treating as non-linear (). It is linear: when rigid.
- Including vibrations when the problem does not mention them. At ordinary temperatures take molecules as rigid.
- Mixing up per molecule and per mole: per degree of freedom per molecule, per mole.
- Thinking is the total energy of every molecule. It is only the translational part; diatomic molecules have in all.
- Averaging of a mixture without weighting by moles: .
- Applying equipartition at very low temperatures (for example below ), where rotations are frozen and the classical law fails.
Frequently Asked Questions
What is the law of equipartition of energy?
In thermal equilibrium at absolute temperature T, the energy of a molecule is shared equally among all its degrees of freedom. Each translational and rotational degree of freedom gets one half k T on average, and each vibrational mode gets k T because it has kinetic and potential energy.
What are degrees of freedom of a gas molecule?
They are the independent ways in which a molecule can store energy: translation along three axes, rotation about two or three axes, and vibration along bonds. A monatomic gas has 3, a rigid diatomic or linear molecule 5, and a rigid non-linear molecule 6.
Why does a diatomic molecule have only two rotational degrees of freedom?
Rotation about the bond axis has an almost zero moment of inertia, because the atoms lie on that axis, so it stores no appreciable energy. Only the two rotations about axes perpendicular to the bond are counted.
Why does a vibrational mode contribute k T instead of one half k T?
A vibration has two quadratic energy terms: the kinetic energy of the moving atoms and the potential energy of the stretched bond. Equipartition gives one half k T to each term, so a full vibrational mode holds k T.
What is the internal energy of an ideal gas according to equipartition?
It is f over 2 times n R T, where f is the number of degrees of freedom and n the number of moles. It depends only on temperature because an ideal gas has no intermolecular potential energy.
When does the law of equipartition fail?
It fails when the energy needed to excite a motion is large compared with k T. Vibrations are frozen at room temperature and rotations of hydrogen freeze below about 80 kelvin, so measured heat capacities are lower than predicted and rise with temperature.
How is equipartition of energy asked in NEET?
NEET asks for the number of degrees of freedom of a molecule, the energy per degree of freedom, the average energy of a diatomic molecule, or the ratio of rotational to translational energy. Remember 3, 5 and 6 for rigid molecules.
How does JEE Main test the law of equipartition?
JEE Main combines it with heat capacities: finding internal energy of gas mixtures, degrees of freedom from the ratio of specific heats, the effect of vibrational modes at high temperature, and energy ratios for diatomic and polyatomic gases.
Previous year questions on Law of Equipartition of Energy
10 questions from past papers, each with a step-by-step solution.
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