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Kinetic Molecular Theory Of Gases

ChemistryStates Of MatterFor JEE aspirants

The kinetic molecular theory of gases explains the gas laws by picturing a gas as a huge number of tiny molecules in constant, random motion. Their collisions with the walls create pressure, and their average kinetic energy is fixed by the absolute temperature alone: per mole. From this come the three molecular speeds (, , ) and the Maxwell-Boltzmann distribution. The kinetic molecular theory of gases, with the speeds and their temperature dependence, is examined in JEE Advanced.

On this page1Laws vs theory2Postulates3Pressure from collisions4KE and temperature5Three speeds6Maxwell curve7Gas laws explained8Examples
Key Formulas - Quick Reference
  1. ★ Must learn Kinetic gas equation: , and .
  2. ★ Must learn Average kinetic energy: per mole, per molecule; J K.
  3. ★ Must learn , with in kg mol.
  4. and .
  5. ★ Must learn (always ).
  6. ★ Must learn For any speed, : .
  7. Definitions: and .

1. From Laws to a Theory

Boyle's and Charles's laws are summaries of experiments: they say what happens. A theory is a mental model that says why. The kinetic molecular theory (KMT) builds a microscopic picture of a gas and then derives every gas law from it. Its success in matching experiment is the evidence that the picture is right.

2. Postulates of the Kinetic Molecular Theory

  1. A gas consists of a very large number of identical molecules. They are so small and so far apart that their own volume is negligible compared with the volume of the container: they are treated as point masses.
  2. There are no attractive forces between the molecules at ordinary temperature and pressure.
  3. The molecules are in constant, random motion in straight lines, in all directions.
  4. They collide with one another and with the walls. Pressure is the result of collisions with the walls.
  5. All collisions are perfectly elastic: individual molecules may gain or lose energy, but the total kinetic energy is unchanged.
  6. At any instant molecules have different speeds, which keep changing, but the distribution of speeds at a given temperature stays constant.
  7. The average kinetic energy of the molecules is directly proportional to the absolute temperature.
Kinetic molecular model of a gas: tiny molecules far apart in random motion A container holds identical molecules drawn as small circles, each with an arrow for its velocity in a random direction. A zoomed circle shows that for nitrogen at STP the molecules are about 0.37 nanometre across but about 3.3 nanometres apart on average. spacing ≈ 3.3 nm size ≈ 0.37 nm zoom: N2 at STP Molecules in random motion elastic collisions with each other and the walls
Figure 1: The kinetic model. For at STP the average spacing is about nine times the molecular size, so the molecules fill under of the volume.

Each postulate is chosen to match something we observe:

Postulates of the kinetic molecular theory and the observations they explain Six postulates of the kinetic molecular theory on the left, each joined by an arrow to the observation it explains on the right: point masses explain compressibility, no attraction explains expansion to fill the container, random motion explains uniform pressure, wall collisions explain pressure, elastic collisions explain why the gas never settles, and kinetic energy proportional to temperature explains the pressure rise on heating. The first two postulates are outlined in red because they fail for real gases. Postulate Observation it explains Tiny point masses, far apart gases are highly compressible No attraction between molecules gases expand to fill any container Constant, random, straight-line motion no fixed shape; pressure is the same on every wall Pressure = collisions with the walls more or faster hits give higher pressure Collisions are perfectly elastic gas never 'settles down' in a closed flask Average KE ∝ absolute temperature heating at fixed V raises the pressure Red boxes: the two postulates that fail for real gases (high p, low T)
Figure 2: Every postulate is there to explain an observation. The two outlined in red, negligible molecular volume and no attraction, are exactly the ones that break down at high pressure and low temperature.
Postulates 1 and 2 are only approximations. At high pressure the molecular volume is no longer negligible, and at low temperature the attractions matter. This is why real gases deviate from ideal behaviour (see Deviation From Ideal Gas Behaviour).

3. Pressure from Molecular Collisions

Take molecules, each of mass , in a cube of side (volume ). Follow one molecule moving towards wall A with velocity component .

Deriving gas pressure from molecular collisions with the wall of a cube A cube of side l with one molecule moving with velocity u, whose x component u x points towards the shaded wall A. An inset shows one elastic collision: momentum plus m u x before and minus m u x after, so the wall receives an impulse 2 m u x. The molecule returns after a time 2 l over u x, so the average force it exerts is m u x squared over l. x y z u ux l wall A (area l2) one hit on wall A before: +mux after: −mux impulse on wall = 2mux time between hits = 2l/ux force = 2mux × ux/2l = mux2/l
Figure 3: Each molecule hits wall A every seconds and gives it each time, so its average force is . Adding all molecules and using gives .
  1. On an elastic hit its -momentum changes from to , so the wall receives an impulse .
  2. It travels to the opposite wall and back, a distance , before hitting A again: time between hits .
  3. Average force of this molecule on A .
  4. For all molecules: force . Motion is random, so .
  5. Pressure = force/area .

This is the kinetic gas equation. Here is the total mass of gas, so : the rms speed can be found from pressure and density alone.

Key idea
Pressure is momentum delivered to the walls per second per unit area: .

4. Kinetic Energy and Temperature

The total translational kinetic energy is , so the kinetic gas equation becomes . For one mole, , so

At 300 K this is kJ mol, or J per molecule, for every gas. The average kinetic energy depends only on the absolute temperature, not on the nature, mass or pressure of the gas. Absolute temperature is simply a measure of this energy, and at 0 K the translational motion (in this classical model) would stop.

Average kinetic energy and rms speed of gas molecules against absolute temperature Left: average translational kinetic energy per mole against absolute temperature, a straight line through the origin, 3.74 kilojoule per mole at 300 kelvin, the same for every gas. Right: root mean square speed against temperature for nitrogen and carbon dioxide, curves that rise as the square root of temperature, nitrogen above carbon dioxide. 0 250 500 750 1000 0 3 6 9 12 T / K KE per mole / kJ 300 K: 3.74 kJ mol-1 same line for every gas 0 250 500 750 1000 0 250 500 750 1000 T / K urms / m s-1 N2 CO2 urms ∝ √T (not ∝ T) (a) KE ∝ T (b) speed ∝ √T
Figure 4: (a) per mole is a straight line through the origin, identical for , or . (b) Speed grows only as : at 300 K is for and for ; quadrupling only doubles the speed.
Exam Trick Energy follows , speed follows . At the same temperature and have equal average KE, but moves times faster. To double a speed you must quadruple the kelvin temperature.
Key idea
Average KE is per mole for every gas; temperature is a direct measure of molecular motion.
Quick Recall: tap to check
What is the average KE of one molecule of any gas at ?
J.
Why is ?
, and random motion makes the three averages equal.
Which postulates fail for real gases?
Negligible molecular volume and no intermolecular attraction.

5. Three Molecular Speeds

Collisions keep changing each molecule's speed, so a gas can only be described by averages. Three are used:

SpeedDefinitionFormula at 300 K
Most probable, speed of the largest number of molecules (peak of the curve)422 m s
Average, arithmetic mean of all speeds476 m s
Root mean square, square root of the mean of the squared speeds517 m s

The mean square speed is the direct measure of kinetic energy, which is why appears in the kinetic gas equation. The formulas differ only in the number under the root, so the three speeds are always in the same ratio:

Most probable, average and root mean square speeds of nitrogen at 300 K on one scale A speed scale for nitrogen at 300 kelvin with the most probable speed 422, the average speed 476 and the root mean square speed 517 metres per second marked, with their formulas root 2 R T over M, root 8 R T over pi M and root 3 R T over M, in the ratio 1 to 1.128 to 1.225. u / m s-1 400 420 440 460 480 500 520 540 ump = 422 √(2RT/M) ratio 1 uav = 476 √(8RT/πM) ratio 1.128 urms = 517 √(3RT/M) ratio 1.225 N2 at 300 K on one speed scale ump : uav : urms = √2 : √(8/π) : √3 = 1 : 1.128 : 1.225
Figure 5: The three speeds differ only in the number under the root: 2, and 3. So their ratio is fixed for every gas at every temperature, and the order is always .
Exam Trick Remember the numbers under the root as 2, 2.55, 3 for mp, av, rms (). Bigger number, bigger speed, so the order writes itself. And always put in kg mol: .

6. The Maxwell-Boltzmann Distribution

Maxwell and Boltzmann worked out how many molecules have each speed. The plot of the fraction of molecules against speed is the Maxwell-Boltzmann distribution:

Maxwell-Boltzmann distribution of molecular speeds for nitrogen at 300 K Maxwell-Boltzmann speed distribution for nitrogen at 300 kelvin. Very few molecules are very slow or very fast. The curve peaks at the most probable speed, 422 metres per second, and has a long tail to high speeds, so the average speed 476 and the root mean square speed 517 lie to the right of the peak. 0 200 400 600 800 1000 1200 1400 u / m s-1 fraction of molecules per unit speed ump = 422 m s-1 (peak) uav = 476 m s-1 urms = 517 m s-1 N2 at 300 K area under curve = 1 long tail of fast molecules
Figure 6: Computed Maxwell-Boltzmann curve for at 300 K. The long high-speed tail pulls the averages right of the peak: . The area under the whole curve is 1 (all the molecules).
  • Very few molecules are very slow or very fast.
  • The peak is at ; the curve is not symmetric but has a long tail on the high-speed side, which pulls and to the right of the peak.
  • The total area under the curve is 1 (all the molecules), whatever the temperature or gas.
  • Individual speeds keep changing, but at a fixed temperature the curve itself does not change.

6.1 Effect of temperature

Effect of temperature on the Maxwell-Boltzmann distribution of nitrogen Speed distributions of nitrogen at 300 kelvin in blue and 900 kelvin in red. At the higher temperature the peak moves to a higher speed and becomes lower and the curve spreads out, with the same total area. The shaded tails show that the fraction of molecules faster than 800 metres per second rises from 6.6 percent to 49 percent. 0 400 800 1200 1600 2000 u / m s-1 fraction per unit speed 300 K 900 K faster than 800 m s-1: 6.6% → 49% peak moves right and drops; curve spreads; area stays 1
Figure 7: Heating from 300 K to 900 K moves from 422 to (a factor ), lowers and broadens the peak, and raises the share of molecules faster than from to . This fast tail is why reaction rates climb steeply with temperature.

On heating, the peak shifts to a higher speed and becomes lower, and the curve broadens. More molecules move at high speed. Because the area stays 1, a taller peak and a wider spread cannot both happen.

6.2 Effect of molar mass

Maxwell-Boltzmann distributions of chlorine, nitrogen and helium at 300 K Speed distributions at 300 kelvin for chlorine, nitrogen and helium. Chlorine, the heaviest, has the tallest and narrowest curve with its peak at 265 metres per second. Nitrogen peaks at 422 and helium, the lightest, has a low, wide curve peaking at 1117 metres per second. 0 400 800 1200 1600 2000 2400 u / m s-1 fraction per unit speed Cl2 (M = 71): ump = 265 N2 (M = 28): ump = 422 He (M = 4): ump = 1117 all at 300 K lighter gas: faster peak, lower and wider curve
Figure 8: Same temperature, different molar mass. Because , the peaks sit at 265, 422 and for , and He. Molecules of every gas have the same average KE; lighter ones need higher speeds to carry it.
Higher temperature (same gas)

Peak moves right (), becomes lower, curve spreads. More fast molecules.

Lower molar mass (same T)

Peak moves right (), becomes lower, curve spreads. The average KE stays the same.

JEE Advanced The distribution function is , where is the fraction of molecules with speeds between and . Setting gives . Substituting back, the peak height , so heating a gas four-fold halves the peak height. The fraction of molecules with energy above grows roughly as , which is the origin of the Arrhenius factor in chemical kinetics.
Key idea
The Maxwell curve has fixed area: anything that raises speeds (higher , lower ) moves the peak right and makes it lower and wider.
Quick Recall: tap to check
At the same temperature, which has the taller Maxwell peak, or ?
: heavier molecules have a lower and a narrower, taller curve.
Ratio of of He at 1200 K to at 300 K?
.
Does heating raise the fraction of molecules at ?
No. The peak height falls as ; the molecules spread over more speeds.

7. The Gas Laws Follow from the Theory

Everything in the Gas Laws concept can be derived from and :

LawHow KMT explains it
BoyleAt fixed , is fixed, so is constant.
CharlesAt fixed , .
Gay-LussacAt fixed , : heated molecules hit harder and more often.
AvogadroEqual , and give equal total ; equal KE per molecule then means equal .
DaltonMolecules do not interact, so each gas delivers its own momentum to the walls independently.
GrahamMolecules escape through a hole at a rate .
How the kinetic molecular theory explains Boyle's and Gay-Lussac's laws Left: a box of gas is squeezed to half its volume at constant temperature; the molecules keep the same speeds but hit each unit of wall twice as often, so pressure doubles. Right: a box of gas at fixed volume is heated from T to 2T; the velocity arrows grow longer, the molecules hit harder and more often, and the pressure doubles. Boyle: halve V at fixed T p 2p same speeds, twice the hits per unit area per second Gay-Lussac: heat at fixed V T, p 2T, 2p faster molecules hit harder and more often
Figure 9: Both laws come from . Halving at fixed keeps fixed, so doubles. Doubling at fixed doubles , so doubles; the average speed rises only by , but each hit is harder and hits come more often.

Because the theory reproduces every gas law and the measured speeds, it is accepted as a correct model of an ideal gas.

8. Solving Speed Problems

Flowchart for molecular speed and kinetic energy problems Flowchart: if energy is asked, use three halves R T per mole or three halves k T per molecule. If a ratio between two gases or temperatures is asked, use u proportional to the square root of T over M. Otherwise choose the speed, using 2 for most probable, 8 over pi for average and 3 for root mean square under the root, put M in kilograms per mole and T in kelvin, or use root 3 p over d when pressure and density are given. yes no yes no Speed or KE question Energy asked? per mole: (3/2)RT per molecule: (3/2)kT Ratio between two gases / temps? u ∝ √(T/M): cancel constants Choose the speed: mp → 2, av → 8/π, rms → 3 under the root M in kg mol-1, R = 8.314, T in K → u in m s-1 Given p and d instead? urms = √(3p/d)
Figure 10: Most speed questions are ratios; the absolute formulas are needed only for a numerical speed. The single most common error is putting in g mol, which makes about 31.6 times too small.

8.1 The whole concept at a glance

Mind map of the kinetic molecular theory of gases Mind map with seven branches: postulates, origin of pressure, kinetic energy and temperature, the three molecular speeds, the Maxwell-Boltzmann curve, gas laws explained by the theory, and the limits of the theory. Kinetic molecular theory Postulates point masses, far apart no attraction random, elastic collisions Pressure wall collisions pV = (1/3)mN(urms)2 pV = (2/3)Ek Energy Ek = (3/2)RT per mole (3/2)kT per molecule same for all gases Three speeds mp: √(2RT/M) av: √(8RT/πM) rms: √(3RT/M) Maxwell curve peak = ump heat: peak right, lower heavier: peak left, taller Gas laws explained Boyle, Charles, Avogadro Dalton, Graham Limits fails at high p, low T see real gases
Figure 11: The whole concept on one page. The chain to remember: collisions give pressure, pressure gives , and gives the speeds.

9. Solved Examples

Solved Example 1
Calculate , and of at .
Solution:

K, kg mol, m s.

Check: .

Solved Example 2
At what temperature will the rms speed of equal that of at 300 K?
Solution:

Equal speeds need equal : , so K.

Solved Example 3
Find the total translational kinetic energy of 2 mol of helium at , and the average KE of one He atom.
Solution:

J kJ.

Per atom: J. The same value holds for any gas at 300 K.

Solved Example 4
The density of a gas is 1.25 g L at 1 atm (101325 Pa). Find its rms speed without knowing its identity or temperature.
Solution:

kg m. m s.

Solved Example 5
The rms speed of molecules at K is . If the absolute temperature is doubled and the molecules dissociate into O atoms, the rms speed becomes:
(A)
(B)
(C)
(D)
Solution:

Answer: (D). . doubles and halves (32 to 16), so becomes four times larger and doubles.

Solved Example 6
When a gas is heated from 300 K to 600 K at constant volume, which statement about its Maxwell-Boltzmann curve is WRONG?
(A) The most probable speed increases by a factor
(B) The height of the peak increases
(C) The area under the curve is unchanged
(D) The fraction of fast molecules increases
Solution:

Answer: (B). The peak height is proportional to , so it falls by when doubles. The curve gets lower and wider; its area stays 1.

Solved Example 7
A container holds a mixture of and at 300 K. Find the ratio of (a) their average kinetic energies per molecule and (b) their rms speeds.
Solution:

(a) : average KE depends only on .

(b) .

Practice Questions
  1. Calculate the total number of electrons present in 1.4 g of dinitrogen gas. (Ex. 5.13)Answer: mol electrons.
  2. How long would it take to distribute one Avogadro number of wheat grains at grains per second? (Ex. 5.14)Answer: s years: a sense of how many molecules a mole holds.
  3. In terms of Charles's law, explain why is the lowest possible temperature. (Ex. 5.21)Answer: gives at ; lower would give a negative volume, which is impossible. In KMT terms, the average KE would reach zero.
  4. rms speed of at ?Answer: m s.
  5. At what temperature is the average speed of equal to 500 m s?Answer: K.
  6. By what factor does change if the pressure of a gas is doubled at constant temperature?Answer: No change: depends only on and (doubling also doubles ).
  7. Average KE per molecule of at 400 K?Answer: J.

Common Mistakes to Avoid

Watch out
  • Putting in g mol in the speed formulas. It must be kg mol, or the speed comes out about 31.6 times too small.
  • Thinking speed is proportional to . Speed is proportional to ; kinetic energy is proportional to .
  • Saying heavier gases have more kinetic energy at the same temperature. Average KE is the same for all gases; heavier molecules just move more slowly.
  • Saying the Maxwell peak rises on heating. It moves right and gets lower; the area is fixed at 1.
  • Using for one molecule. Per molecule it is , with .
  • Taking as the square of the mean speed. It is the square root of the mean of the squares, which is larger than .
  • Swapping the order of the speeds. Always .
  • Forgetting that dissociation halves (for example to 2O), which raises the speed.

Frequently Asked Questions

What are the postulates of the kinetic molecular theory of gases?

A gas has a huge number of tiny, identical molecules whose own volume is negligible. They do not attract each other, move randomly in straight lines, and collide elastically with each other and the walls. Wall collisions cause pressure, speeds are distributed but the distribution is steady, and average kinetic energy is proportional to absolute temperature.

How is the kinetic gas equation derived?

A molecule hitting a wall reverses its x-momentum, giving an impulse 2mu_x, and returns after 2l/u_x seconds. Its average force is m u_x squared over l. Summing over N molecules, and using the fact that u_x squared averages to one-third of u squared for random motion, gives pV = one-third m N u squared, the kinetic gas equation.

What is the relation between kinetic energy and temperature of a gas?

Combining the kinetic gas equation with pV = RT gives the average translational kinetic energy as 3/2 RT per mole, or 3/2 kT per molecule. It depends only on absolute temperature, so all gases at the same temperature have the same average kinetic energy, 3.74 kJ per mole at 300 K.

What is the ratio of most probable, average and rms speed?

The most probable speed is root of 2RT/M, the average speed root of 8RT/(pi M) and the rms speed root of 3RT/M. They are in the ratio 1 : 1.128 : 1.225 for every gas at every temperature, so the most probable speed is always the smallest and the rms speed the largest.

How does temperature affect the Maxwell-Boltzmann distribution?

On heating, the peak of the Maxwell-Boltzmann curve moves to a higher speed and becomes lower, and the curve spreads out, while the area under it stays 1. A larger fraction of molecules moves at high speed, which is why reaction rates rise sharply with temperature.

Why do lighter gas molecules move faster at the same temperature?

At the same temperature all gas molecules have the same average kinetic energy, one-half m u squared. A lighter molecule must move faster to carry the same energy. Speed varies as one over the square root of molar mass, so hydrogen moves four times faster than oxygen.

Is kinetic theory of gases part of JEE Advanced chemistry?

Yes. The JEE Advanced syllabus lists kinetic theory of gases with average, root mean square and most probable velocities and their relation with temperature under States of Matter: Gases and Liquids. The chapter has been dropped from NCERT Class 11, JEE Main and NEET, so JEE Advanced is where it is examined.

What types of kinetic theory questions are asked in JEE Advanced?

Typical questions compare speeds of two gases or two temperatures, test the shape of Maxwell-Boltzmann curves when temperature or molar mass changes, use dissociation to change molar mass, compute average kinetic energy per molecule, and find rms speed from pressure and density. Most reduce to u proportional to root T over M.

Previous year questions on Kinetic Molecular Theory Of Gases

1 question from past papers, each with a step-by-step solution.

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