Kinetic Gas Theory Part II

Kinetic definition of temperature:

With an ideal gas, the individual gas particles only perform translational movements as
“mass points”. There are no vibrations or rotations of the molecule, so no internal degrees
of freedom.

By simply rearranging the Bernoulli equation you get:

1 ̅̅̅2̅
̅̅̅2 = 2 𝑁 𝑚⋅𝑣
𝑝 ⋅ 𝑉 = 3 𝑁𝑚𝑣 (kin. energy:
1
𝐸 = 2 ∙ 𝑚 ∙ 𝑣2)
3 2

Conclusion:
2
̅̅̅̅̅
𝑝 ⋅ 𝑉 = 3 𝑁𝐸 𝑘𝑖𝑛

Together with the equation of state of ideal gases:

𝑝 ⋅ 𝑉 = 𝑛𝑅𝑇

you can see that

̅̅̅̅̅
𝐸𝑘𝑖𝑛 ∝ 𝑇

This means that the average kinetic energy of the gas particles is proportional to the
temperature of the gas. Both sides of the equation can now be equated using a constant.
This is implemented in the following approach:
3
̅̅̅̅̅
𝐸𝑘𝑖𝑛 = 2 𝑘𝑇 (𝑛 ∙ 𝑅 = 𝑘 ∙ 𝑛 ∙ 𝑁𝐴 = 𝑘 ∙ 𝑁)

Inserting results in:

𝑝 ⋅ 𝑉 = 𝑁𝑘𝑇 where k is the Bolzmannkonstante

Since this is very important for understanding, once again we summarize the important
constants obtained and their meaning:

n: Number of moles or more precisely the number of moles in the gas

N: number of molecules in the gas
𝑒𝑛𝑒𝑟𝑔𝑦
R: general gas constant, a proportionality constant with the unit ~ 8.31 J/(mol∙°K)
𝑚𝑜𝑙∙°𝐾

NA: Avogadro constant, number of molecules in 1 mol ~ 6.022 ∙ 10-23/mol

𝑒𝑛𝑒𝑟𝑔𝑦
k: Bolzmann–constant, a proportionality constant with the unit ~1.38 10-23 J/°K
°𝐾

1
First generalization:
So far 3 degrees of freedom, therefore according to the approach, the average energy per
degree of freedom is:
1
𝑘𝑇
2

So more general for molecules that have other degrees of freedom, such as rotation and
vibrations:
𝑓
̅̅̅̅̅
𝐸𝑘𝑖𝑛 = 2 𝑘𝑇

Second generalization:

Kinetic definition on arbitrarily bodies. This is dealt with in thermodynamics.

Short insertion classic barometric formula

The barometric altitude formula describes the dependence of the air pressure on the
altitude p (h) or better p (z).

Definition: The atmosphere is isothermal what means the temperature is const.

Because of gravitation pressure (pressure is inverse to the altitude)

Δ𝑝 = −𝜌𝑔Δ𝑧 (𝜌 = 𝑔𝑎𝑠 𝑑𝑒𝑛𝑠𝑖𝑡𝑦)

or in differential form
𝑑𝑝
= −𝜌𝑔
𝑑𝑧

according to the law of Boyle-Mariotte:

1 𝜌 𝜌
𝑝∝𝑉∝𝜌 ⇒ = 𝑐𝑜𝑛𝑠𝑡 = 𝑝0
𝑝 0
𝑑𝑝 = −𝜌𝑔𝑑𝑧

The density depends on the height and thus also on the pressure
𝑑𝑝 𝜌
= −𝑔 𝑝0 𝑝(𝑧) Initial condition: 𝑝(0) = 𝑝0
𝑑𝑧 0

The solution to this differential equation is the exponential function

𝜌0 𝑔𝑧
𝑝(𝑧) = 𝑝0 exp(− ) The classical barometric formula
𝑝0

2
In the previous kinetic examination of the temperature, only the average velocity of the
particles was considered. But it is also important to consider the velocity distribution of the
gas particles. This leads to the

Maxwellian velocity distribution

We consider an ideal gas with the temperature T, which is in a classical gravitational field
and whose pressure and density are described with the classic barometric formula.

Transformation of this equation using the known gas equation and the equation previously
worked out:
𝑁
𝑝 ⋅ 𝑉 = 𝑁𝑘𝑇 to 𝑝 = 𝑛𝑑 𝑘𝑇 ⇔ ( 𝑉 = 𝑛𝑑 )

𝑝
𝑛𝑑 = 𝑘𝑇
with
𝑝⋅𝑚
𝜌 = 𝑛𝑑 𝑚 = 𝑘⋅𝑇
follows
𝜌 𝑚
= 𝑘𝑇
𝑝
with that is
𝜌0 𝑚
= 𝑘𝑇
𝑝0

Conclusion from the barometric formula

𝑚𝑔𝑧
𝑛𝑑 (𝑧) = 𝑛0 exp(−( )) where 𝑚𝑔𝑧 is a potential Energy
𝑘𝑇

Model: The gas molecules that are at z = 0 have different kinetic energy, on the basis of
which they can rise up to corresponding z and thus have the potential energy:
𝑚 ∙ 𝑔 ∙ 𝑧.

This means:
𝑚𝑣𝑧2
= 𝑚𝑔𝑧
2

With this one can rewrite the barometric formula whereby the expression representing the
potential energy is now replaced by kinetic energy.

This results in a speed distribution:

(𝑚𝑣𝑧2 )
𝑓(𝑣𝑧 ) ∝ exp(−( )⁄𝑘 𝑇)
2

The probability that the z- component of velocity ranges in the interval [vz,vz+dvz],

is: 𝑓(𝑣𝑧 )𝑑𝑣𝑧 Therefor f(vz) is a probability density.

3
In the case of a probability function, the integral is by definition one over all possibilities,
i.e. the entire range of variation.
The integration of the exponential function is not trivial and should therefore not be
considered here. Due to the integration and standardization, the pre-factor of the equation
can be determined and the result is:

𝑚𝑣2𝑧
𝑚 2
𝑓(𝑣𝑧 ) = √2𝜋𝑘𝑇 ⋅ exp(− )
𝑘𝑇

Assumption of isotropy, i.e. all coordinates are evaluated equally:

𝑚 ⃗⃗⃗⃗⃗
−(𝑚𝑣 2)
𝑓(𝑣⃗) = (2𝜋𝑘𝑇)3⁄2 ⋅ exp( )
2𝑘𝑇

𝑓(𝑣⃗)𝑑𝑣𝑥 ⋅ 𝑑𝑣𝑦 ⋅ 𝑑𝑣𝑧 is the propability that the

x-component is in the intervall [vx,vx+dvx],

y-component is in the intervall [vy,vy+dvy],
z-component is in the intervall [vz,vz+dvz].

In many cases, only the magnitude v = |v| is of interest, and the direction of v can be
arbitrary. The peaks of all velocity vectors v with length between v and v + dv fill a spherical
shell with volume 4 π v 2 dv. Therefore,

∫ 𝑓(𝑣𝑥 ∙ 𝑣𝑦 ∙ 𝑣𝑧 )𝑑𝑣𝑥 𝑑𝑣𝑦 𝑑𝑣𝑧

integration over all values of v = {vx , vy, vz } within this spherical shell, i.e., with the
constraint v2+ v2 + v2 = v2 = const. gives the factor 4 π v 2 dv, and the number n(v) dv of all
molecules per unit volume with velocity magnitudes between v and v + dv

𝑚 3⁄2 −𝑚𝑣 2⁄
𝑛(𝑣) ∙ 𝑑𝑣 = 𝑛 ∙ ( ) ∙ 4𝜋𝑣 2 ∙ 𝑒 2𝑘𝑇 𝑑𝑣
2𝜋𝑘𝑇

This is the Maxwell-Boltzmann velocity distribution.

In contrast to the distribution for the velocity component, this distribution for the amounts
extends only over the positive range. Therefore, it is not symmetric about v = 0. Because of
the factor v 2, n(v) dv is also not symmetrically distributed about a mean value.

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 Material dependence of velocity distribution at Temperature dependence of the velocity distribution
0 °C for hydrogen (H2), helium (He) and for nitrogene.
nitrogen (N2).

gastype chemical Molar waight average thermal

symol speed
M [g/mol] < 𝑣 >(20°C) [m/s]
Hydrogen H2 2 1762
Helium He 4 1246
Nitrogen N2 28 471
Air 29 463
Oxigen O2 32 440
Argon Ar 40 394
Carbondioxid CO2 44 376