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CHEM 1301 | KINETIC THEORY OF GASES

 A gas refers to a fluid state of matter which will fill a container

Properties

 Static properties: pressure, volume, temperature

 Transport properties: diffusion / effusion1 (Graham’s law of effusion), viscosity

(resistance to flow)

 Heat capacity

 Chemical properties: reactions between gases

Boyle’s Law

constant
 At constant T, pV = constant or p=
V

 When the pressure of gas is doubled, the volume halves

 Reason: pressure results from molecular collisions with the wall

 Pressure = Force / Area (As F increases, and A decreases, p increases)

Charles’ Law

 At constant p, V = constant x (T/oC + 273.15)

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Effusion refers to the escape of gas from a container
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 Charles’ Law implies a natural minimum temperature of –273.15oC / 0 K

T/K = T/oC + 273.15

 Another form of Charles’ Law: At constant V, p = constant x (T/K)

 Hence, p  0 as T  0, which is an example of a limiting law

pV
 Overall, =constant
T

 Avogadro’s Law states that all molar volumes of gases should be the same

V
V m= or V = constant x n
n

 Standard temperature and pressure refers to 1 atm (101325 Pa) and 273.16 K

 Volume of 1 mole of ideal gas = 22.414 dm3

pV 101325× 22.414 ×10−3

 Constant = = = 8.31441 J K mol-1
nT 1× 273.16

 Per molecule: k (Boltzmann constant) = R / NA

 Ideal gas equation pV = nRT

 For a fixed amount of ideal gas, the surface shows the only states that can exist in
equilibrium

 Real gases behave more like ideal gases at low p, and obey pV = nRT as p  0

3 Central Assumptions

1. The gas consists of molecules of mass m and diameter d in ceaseless random

motion
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2. The volume occupied by the molecules is negligible compared to the volume of the
gas

3. The molecules do not interact when they collide, making perfectly elastic collisions

 Elastic collision occurs when total KE is conserved (no energy goes into the internal
energy of the molecule)

Using the model to predict pressure

 The pressure results from molecules hitting the vessel walls, p = force / area

d dv
Force = rate of change of momentum = ( mv ) = m = ma
dt dt

 Calculate the change in momentum for one molecule hitting the wall and scale up to
the total change in momentum in a given time per unit area

Momentum change on hitting the wall

Before collision,

Momentum vector quantity = mv

Component momentum towards wall = mvx

After collision,

Component momentum towards wall = –mvx

Change in momentum = (–mvx) – (mvx) = –2mvx

Note: 2mvx transferred to wall in 1 collision

 In a given time, t, a molecule travels a distance of vx.t along the x axis

 All molecules closer than vx.t from the wall and travelling towards it will reach the
wall in t
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Defines a distance
from the wall

 Molecules have to be within vxDt of the wall and going in the right direction

 For a unit area A of wall, molecules have to be in a ‘collision volume’ of vx.Dt.A

n.NA
No of molecules per unit vol =
V

n.N A
No in collision vol = A . V x .t .
V

A .V x . t . n . N A
No colliding with wall in time Dt =
2V

Reason: Gases occupy volumes homogenously, so half

 Total change in momentum = no of collisions x momentum change per collision

A .V x . t . n . N A
= x 2mvx
2V

 Note: m.NA = M (molar mass)

nMA V 2x
 Rate of change of momentum = total change / Dt = = Force
V

nM V 2x
 Hence, pressure = force / area =
V

 However, molecules have a range of vx and an average of vx2 should be considered

(<vx2>)

 Molecules move randomly and there is no net flow in one direction,

<vx2> = <vy2> = <vz2>

 Mean square speed of molecules (c2) = <vx2> + <vy2> + <vz2> = 3<vx2>

c2
 <vx2> =
3
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nM c 2 nM c 2
p= or pV =
3V 3

Comparing Experimentally

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 Experimentally, pV = nRT while the model result predicts pV = nMc2
3

 If c2 depends only on T, then at constant T, model predicts pV = constant

(Boyle’s Law)

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 Also, it implies RT = M c2
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2 3 RT
 Mean square speed: c =
M

3 RT 3 kT
 Root mean square (rms) speed: c=
√ M
=
√ m
(after dividing by Avogadro’s no)

 Note: T increases as c increases and M increases as c decreases

 Example: rms speed of Ar atoms at 298 K

3 × 8.31× 298
c=
√ 39.95 ×10−3
= 431 ms-1

 Note: change relative atomic mass of atom from g mol-1 to kg mol-1

 Speeds of individual molecules are wide ranging

Kinetic Energy

 For 1 molecule, KE = ½ mv2

 Total KE = N. ½ mc2 (where c2 = mean square speed of molecules)

1 1
 pV = nM c 2 = Nm c 2
3 3

 Note: N.m = n.M where n = no of moles, N = no of molecules, M = mass of a mole, m

= mass of a molecule

2 3
 Hence, pV = KE or KE = pV
3 2
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 For an ideal gas, pV = nRT hence total KE = nRT
2

 Translational (kinetic) energy [energy resulting from motion] is the only energy for the
ideal model gas

 Considering c2= <vx2> + <vy2> + <vz2>,

Total KE = N. ½ mc2
= N. ½ m<vx2> + N. ½ m<vy2> + N. ½ m<vz2>

Since <vx2> = <vy2> = <vz2>,

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 Total KE = nRT
2

 KE = ½ nRT for each translational degree of freedom (each axis motion contributes
½ nRT)