Physics · Kinetic Theory of Gases

Law of Equipartition of Energy

Kinetic theory tells us the average translational energy of a molecule is $\tfrac{3}{2}k_BT$. The law of equipartition of energy is the principle that explains why the number is $\tfrac{3}{2}$ — and how it changes when a molecule can also rotate and vibrate. NCERT §12.5 states it cleanly: in thermal equilibrium, each quadratic degree of freedom carries an average energy of exactly $\tfrac{1}{2}k_BT$ per molecule. From that one rule the internal energy of any ideal gas, $U = \tfrac{f}{2}nRT$, and the specific heats of monatomic, diatomic and polyatomic gases all follow. This deep-dive builds degrees of freedom from scratch, applies equipartition gas-type by gas-type, and drills the counting traps NEET reuses every year.

Degrees of freedom

The degrees of freedom of a molecule are the number of independent ways in which it can store energy of motion. NCERT frames it geometrically: a molecule free to move in space needs three coordinates to specify its location, so it has three independent directions of motion. If it were constrained to a plane it would need two; constrained to a line, just one. Motion of the body as a whole from one point to another is called translation, so a molecule moving freely in space has three translational degrees of freedom.

The crucial refinement is that what equipartition counts is not "directions" but quadratic terms in the energy expression. Each translational degree of freedom contributes a term containing the square of a velocity component — $\tfrac{1}{2}mv_x^2$, $\tfrac{1}{2}mv_y^2$, $\tfrac{1}{2}mv_z^2$. Rotation about an axis contributes a term $\tfrac{1}{2}I\omega^2$. Vibration is special: it contributes two quadratic terms, a kinetic energy term $\tfrac{1}{2}m(\mathrm{d}y/\mathrm{d}t)^2$ and a potential energy term $\tfrac{1}{2}ky^2$. This distinction — quadratic terms, not axes — is the entire game.

Monatomic x y z 3 translational f = 3 Diatomic (rigid) translate 3 trans + 2 rot f = 5 Polyatomic 3 trans + 3 rot f = 6
Degrees of freedom by molecular geometry. A monatomic atom can only translate (3). A rigid diatomic adds rotation about the two axes perpendicular to the bond (3 + 2 = 5). A nonlinear polyatomic rotates about all three axes (3 + 3 = 6). Vibrational modes, when active, add further quadratic terms on top of these.

The law of equipartition

NCERT derives the seed of the law from the kinetic interpretation of temperature. The average translational energy of a molecule in thermal equilibrium is

$$\langle \varepsilon_t \rangle = \left\langle \tfrac{1}{2}mv_x^2 + \tfrac{1}{2}mv_y^2 + \tfrac{1}{2}mv_z^2 \right\rangle = \tfrac{3}{2}k_BT.$$

Because the gas is isotropic — no direction is preferred — the three terms must be equal, so each one averages to $\tfrac{1}{2}k_BT$:

$$\left\langle \tfrac{1}{2}mv_x^2 \right\rangle = \left\langle \tfrac{1}{2}mv_y^2 \right\rangle = \left\langle \tfrac{1}{2}mv_z^2 \right\rangle = \tfrac{1}{2}k_BT.$$

Maxwell proved that this equal sharing is not special to translation. The full statement, as NCERT gives it:

In equilibrium, the total energy is equally distributed in all possible energy modes, with each mode having an average energy equal to $\tfrac{1}{2}k_BT$. Each translational and rotational degree of freedom of a molecule contributes $\tfrac{1}{2}k_BT$ to the energy, while each vibrational frequency contributes $2 \times \tfrac{1}{2}k_BT = k_BT$, since a vibrational mode has both kinetic and potential energy modes.

Per mole, multiply by Avogadro's number $N_A$ and use $R = N_A k_B$: each quadratic degree of freedom contributes $\tfrac{1}{2}RT$ per mole. The proof itself is beyond the NEET syllabus; the application is the examinable part.

Monatomic gas — f = 3

A monatomic gas such as helium, neon or argon is, for kinetic purposes, a structureless point. It has no bond to rotate about and nothing to vibrate, so it has only the three translational degrees of freedom. Each contributes $\tfrac{1}{2}k_BT$, giving an average molecular energy of $\tfrac{3}{2}k_BT$ — exactly the translational result from kinetic theory, now seen as a special case of equipartition with $f = 3$.

Diatomic gas — f = 5 rising to 7

A diatomic molecule such as $\mathrm{O_2}$ or $\mathrm{N_2}$ still has its three translational degrees of freedom, but it can also rotate. NCERT (Fig. 12.6) identifies two independent axes of rotation, both perpendicular to the line joining the two atoms. Rotation about the bond axis itself has a negligible moment of inertia and is ignored for quantum mechanical reasons. So at moderate temperature the molecule is treated as a rigid rotator with

$$f = \underbrace{3}_{\text{translational}} + \underbrace{2}_{\text{rotational}} = 5, \qquad \langle \varepsilon \rangle = \tfrac{5}{2}k_BT.$$
Moderate T — rigid rotator 3 trans + 2 rot, no vibration f = 5   U = (5/2)RT High T — vibration activates + vibration (KE + PE = 2 terms) f = 7   U = (7/2)RT
A diatomic molecule at moderate temperature behaves as a rigid dumbbell with f = 5. At high temperature its atoms oscillate along the bond like a one-dimensional spring; the vibrational mode adds two quadratic terms (kinetic + potential), so f rises to 7.

The rigid-rotator assumption is not always valid. NCERT notes that molecules like CO, even at moderate temperatures, have a vibrational mode in which the atoms oscillate along the interatomic axis like a one-dimensional oscillator. When that mode is active, the molecule gains a vibrational energy term carrying two quadratic contributions, and

$$f = \underbrace{3}_{\text{trans}} + \underbrace{2}_{\text{rot}} + \underbrace{2}_{\text{vib}} = 7, \qquad \langle \varepsilon \rangle = \tfrac{7}{2}k_BT.$$

Vibration switches on only at high temperature, which is why the experimental specific heats of diatomic gases rise above the rigid-rotator prediction as temperature increases.

Polyatomic gas

A nonlinear polyatomic molecule — water vapour, ammonia, methane — has its centre of mass free to translate in three directions and can rotate about all three independent axes, because none of those axes carries a negligible moment of inertia. That gives $3 + 3 = 6$ degrees of freedom before vibration. In addition, NCERT writes the general polyatomic molecule as having a certain number $f$ of vibrational modes, each contributing $k_BT$. The internal energy per mole becomes

$$U = \left(\tfrac{3}{2}k_BT + \tfrac{3}{2}k_BT + f\,k_BT\right)N_A = (3 + f)RT,$$

so $C_v = (3 + f)R$ — recovering $C_v = 3R$ for the rigid (non-vibrating) nonlinear polyatomic case where $f = 0$.

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Where this goes next

The whole payoff of equipartition is computing molar heat capacities — see specific heat from kinetic theory for $C_v$, $C_p$ and $\gamma$ across all gas types.

Degrees of freedom across gas types

The one table to commit to memory. Every entry below follows from the single rule $\tfrac{1}{2}k_BT$ per quadratic term, with vibration counted twice.

Gas typeTranslationalRotationalVibrationalTotal fEnergy / molecule
Monatomic (He, Ne, Ar)3003$\tfrac{3}{2}k_BT$
Diatomic, rigid — moderate T (O2, N2)3205$\tfrac{5}{2}k_BT$
Diatomic, vibrating — high T (CO at high T)3227$\tfrac{7}{2}k_BT$
Polyatomic, nonlinear, rigid (H2O, NH3)3306$3k_BT$
Polyatomic with vibration33$2f_{\text{vib}}$$6 + 2f_{\text{vib}}$$(3 + f_{\text{vib}})k_BT$

Read the table as a single rule applied repeatedly: count one quadratic term for each translational direction, one for each genuine rotational axis, and two for each active vibrational mode. Multiply the total $f$ by $\tfrac{1}{2}k_BT$ for the energy per molecule, or by $\tfrac{1}{2}RT$ for the energy per mole.

Internal energy U = (f/2)nRT

Because an ideal gas has no intermolecular potential energy, its internal energy is purely the sum of these molecular energy modes. For $n$ moles of a gas whose molecules each have $f$ active quadratic degrees of freedom,

$$\boxed{\,U = \frac{f}{2}\,n R T\,}.$$

Two consequences NEET tests directly. First, $U$ depends only on temperature (and on $f$), never on pressure or volume — a fact that underlies the result that the internal energy of an ideal gas is a function of $T$ alone. Second, for a mixture of non-reacting ideal gases the total internal energy is simply the sum over the components, each evaluated with its own $f$. That additivity is exactly what the 2017 PYQ below exploits.

Worked example

A vessel holds 3 mol of a monatomic gas and 2 mol of a rigid diatomic gas at the same temperature $T$. Find the total internal energy of the mixture.

Monatomic part. $f = 3$, so $U_1 = \tfrac{3}{2}n_1 RT = \tfrac{3}{2}(3)RT = \tfrac{9}{2}RT$.

Diatomic part. $f = 5$, so $U_2 = \tfrac{5}{2}n_2 RT = \tfrac{5}{2}(2)RT = 5RT$.

Total. $U = U_1 + U_2 = \tfrac{9}{2}RT + 5RT = \tfrac{19}{2}RT = 9.5\,RT$. Each gas keeps its own $f$; never apply a single $f$ to the whole mixture.

Counting traps

Score every degree-of-freedom count against this checklist before you compute energy or specific heat.

  • Vibration counts twice. One vibrational mode = 2 quadratic terms = $k_BT$, never $\tfrac{1}{2}k_BT$.
  • Diatomic rotation has 2 axes, not 3. The bond-axis rotation is dropped, so rigid diatomic $f = 5$.
  • Vibration is temperature-gated. At room temperature most diatomics are rigid ($f = 5$); vibration only switches on at high $T$, raising $f$ toward 7.
  • Mixtures keep separate $f$ values. Sum $\tfrac{f_i}{2}n_i RT$ over each component; do not average the atomicities.
  • Translational KE is universal. $\tfrac{3}{2}k_BT$ per molecule for any ideal gas; only total $U$ depends on $f$.
  • Per molecule vs per mole. $\tfrac{1}{2}k_BT$ per molecule equals $\tfrac{1}{2}RT$ per mole — check which the question wants.
Quick recap

Equipartition in one breath

  • Each quadratic term in a molecule's energy carries $\tfrac{1}{2}k_BT$ per molecule, or $\tfrac{1}{2}RT$ per mole, in thermal equilibrium.
  • Translational and rotational modes give one quadratic term each; a vibrational mode gives two (kinetic + potential), so it counts as $k_BT$.
  • Monatomic $f = 3$; rigid diatomic $f = 5$; vibrating diatomic $f = 7$; nonlinear polyatomic $f = 6$ (plus $2f_\text{vib}$ if vibrating).
  • Internal energy of $n$ moles: $U = \tfrac{f}{2}nRT$, a function of temperature alone for fixed $f$.
  • Average translational KE is $\tfrac{3}{2}k_BT$ for every ideal gas; only the total energy grows with $f$.
  • In a mixture, add $\tfrac{f_i}{2}n_i RT$ over each component separately.

NEET PYQ Snapshot — Equipartition of Energy

Three genuine NEET questions that reduce to counting degrees of freedom and applying $\tfrac{1}{2}k_BT$ per mode.

NEET 2020

The average thermal energy for a mono-atomic gas is ($k_B$ is Boltzmann constant and $T$ absolute temperature):

  1. $\tfrac{3}{2}k_BT$
  2. $\tfrac{5}{2}k_BT$
  3. $\tfrac{7}{2}k_BT$
  4. $\tfrac{1}{2}k_BT$
Answer: (1) (3/2) k_B T

Equipartition. A monatomic gas has only translational motion, $f = 3$. Each degree of freedom contributes $\tfrac{1}{2}k_BT$, so the average thermal energy is $3 \times \tfrac{1}{2}k_BT = \tfrac{3}{2}k_BT$. Options (2) and (3) are the diatomic ($f=5$) and vibrating-diatomic ($f=7$) values, planted as distractors.

NEET 2021

Match Column-I with Column-II. (A) Average kinetic energy of a molecule, (B) Total internal energy of 1 mole of a diatomic gas — among the options are $\tfrac{3}{2}k_BT$ and $\tfrac{5}{2}RT$.

  1. (A) → $\tfrac{5}{2}RT$, (B) → $\tfrac{3}{2}k_BT$
  2. (A) → $\tfrac{3}{2}k_BT$, (B) → $\tfrac{5}{2}RT$
  3. (A) → $RT$, (B) → $\tfrac{7}{2}RT$
  4. (A) → $\tfrac{3}{2}RT$, (B) → $\tfrac{5}{2}k_BT$
Answer: (2)

Equipartition. Average KE of a molecule is $\tfrac{3}{2}k_BT$ (translational, $f=3$, per molecule). For 1 mole of a rigid diatomic gas $f = 5$, so $U = \tfrac{f}{2}nRT = \tfrac{5}{2}(1)RT = \tfrac{5}{2}RT$. Note the per-molecule ($k_BT$) versus per-mole ($RT$) bookkeeping in the two parts.

NEET 2017

A gas mixture consists of 2 moles of $\mathrm{O_2}$ and 4 moles of Ar at temperature $T$. Neglecting all vibrational modes, the total internal energy of the system is:

  1. $11\,RT$
  2. $4\,RT$
  3. $15\,RT$
  4. $9\,RT$
Answer: (1) 11 RT

Equipartition, mixture. $\mathrm{O_2}$ is diatomic, $f = 5$: $U_{\mathrm{O_2}} = \tfrac{5}{2}(2)RT = 5RT$. Ar is monatomic, $f = 3$: $U_{\mathrm{Ar}} = \tfrac{3}{2}(4)RT = 6RT$. Total $U = 5RT + 6RT = 11RT$. Each component keeps its own degrees of freedom.

FAQs — Law of Equipartition of Energy

Short answers to the equipartition questions NEET aspirants get wrong most often.

What does the law of equipartition of energy state?
In thermal equilibrium at absolute temperature T, the total energy of a molecule is distributed equally among all its possible energy modes, each quadratic term in the energy expression carrying an average energy of ½kBT per molecule, or equivalently ½RT per mole. This was first proved by Maxwell and applies to translational, rotational and vibrational modes alike.
Why does a vibrational mode contribute kBT and not ½kBT?
A vibrational mode has two quadratic terms in its energy — a kinetic energy term ½m(dy/dt)² and a potential energy term ½ky². Equipartition assigns ½kBT to each quadratic term, so one vibrational mode contributes 2 × ½kBT = kBT. This is why one vibrational mode counts as two degrees of freedom, not one.
Why is the degree of freedom of a diatomic gas 5 and not 6 at room temperature?
A diatomic molecule has 3 translational degrees of freedom and 2 rotational degrees of freedom about the two axes perpendicular to the bond. Rotation about the bond axis itself has a negligible moment of inertia and does not come into play for quantum mechanical reasons, so it is not counted. At moderate temperatures vibration is not yet active, so f = 3 + 2 = 5, not 6.
What is the total internal energy of an ideal gas in terms of degrees of freedom?
If each molecule has f active quadratic degrees of freedom, equipartition gives each molecule an average energy (f/2)kBT. For n moles, U = (f/2)nRT. The internal energy of an ideal gas depends only on temperature and on f — not on pressure, volume or the chemical identity of the gas at fixed f.
Does the average kinetic energy of a molecule depend on whether the gas is monatomic or diatomic?
The average translational kinetic energy is (3/2)kBT for every ideal gas, monatomic, diatomic or polyatomic, because translation always supplies exactly 3 quadratic degrees of freedom. What differs is the total internal energy, which includes rotational and vibrational modes and therefore grows with f. A diatomic molecule at room temperature carries (5/2)kBT total, but still only (3/2)kBT of it is translational.
How does the degree of freedom of a diatomic gas rise to 7 at high temperature?
At sufficiently high temperature the vibrational mode of a diatomic molecule activates. That mode contributes two quadratic terms — kinetic and potential — adding 2 degrees of freedom to the 5 already present. The total becomes f = 3 translational + 2 rotational + 2 vibrational = 7, and the internal energy per mole becomes (7/2)RT.