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P F A NMV V P NM V V V: Example: Calculate The Rms Speed of He Atoms at 298 K

The document discusses the Maxwell-Boltzmann distribution of molecular speeds. It introduces: 1) The Maxwell-Boltzmann distribution depends on molecular mass and temperature, and describes the distribution of molecular speeds. 2) Key speeds that can be determined from the distribution are the mean speed, which is proportional to the square root of the temperature, and the most probable speed, which also is proportional to the square root of temperature. 3) The distribution was derived to account for the fact that molecules travel at a variety of speeds, rather than a single average speed.

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Akib Imtihan
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33 views

P F A NMV V P NM V V V: Example: Calculate The Rms Speed of He Atoms at 298 K

The document discusses the Maxwell-Boltzmann distribution of molecular speeds. It introduces: 1) The Maxwell-Boltzmann distribution depends on molecular mass and temperature, and describes the distribution of molecular speeds. 2) Key speeds that can be determined from the distribution are the mean speed, which is proportional to the square root of the temperature, and the most probable speed, which also is proportional to the square root of temperature. 3) The distribution was derived to account for the fact that molecules travel at a variety of speeds, rather than a single average speed.

Uploaded by

Akib Imtihan
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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7

Last lecture, we had connected the pressure on the wall of a container with the molecular speed
F n Mvx2
of the particles within the container, i.e., p = =
A V
However, this expression is not quite right because molecules travel with different velocities.
Therefore, we need an average velocity and the pressure expression becomes,
n M⟨vx2⟩
p=
V
where the angular brackets denote an average. Secondly, molecules also move in all directions,
not just in x. To account for this, we introduce the root mean square (RMS) speed, where
2
vrms = ⟨v 2⟩ = ⟨vx2⟩ + ⟨vy2⟩ + ⟨vz2⟩
Since orientation is not important (random motion), the average speed in any direction x, y, or z,
should be equal, i.e.,
⟨vx2⟩ = ⟨vy2⟩ = ⟨vz2⟩
such that,
1 2 1
⟨vx2⟩ = vrms = ⟨v 2⟩
3 3
Substituting this back into our expression for the pressure, we have
1 n M⟨v 2⟩
p=
3 V
or
1 1
pV = n M⟨v 2⟩ = n Mvrms
2
3 3
Recall the ideal gas law (pV = nRT ) which upon equating with the equation above yields an
expression relating the RMS speed with the temperature and the molar mass of the particles, i.e.,

( M ) ( m )
1/2 1/2
3RT 3k T
vrms = =
Example: Calculate the RMS speed of He atoms at 298 K
1/2

( M )
1/2

( )
3RT 3 × 8.3144621JK −1m ol −1 × 298K
vrms = = = 1.36 × 103m s −1
4.0026 × 10−3kgm ol −1
NOTE: As mentioned previously, be careful about your choice of units for R. Here I have used R
= 8.3144621 J K-1 mol-1 as 1 J = 1 kg m2 s-2 such that the final speed is in m/s.

1.2.2 The Maxwell-Boltzmann Distribution of Speeds (Textbook Section 1.B.1(c))


We mentioned that there is an average speed, i.e., all atoms/molecules are not travelling with the
same speed, and, hence, there must be a distribution of molecular speeds. We will nor derive the
Maxwell-Boltzmann distribution (if you are interested, please see Justification 1B.2 in the
textbook) but rather we must understand some of the implications of the distribution. The
distribution is given as

( 2π RT )
3/2

( 2RT )
M −Mv 2
f (v) = 4π v 2 exp

Hence, the distribution of speeds depends on two important parameters: (1) the atomic/molecular
mass, M, and (2) the temperature, T. We can then consider how the distribution changes as we
change these two parameters:
8

Once we know the distribution of speeds, we can determine a number of speeds of interest from
the distribution:
1. The mean speed, vmean

( 2π RT ) ∫0 ( 2π RT ) 2 ( M )
∞ 3/2 ∞ 3/2 2

( 2RT )
M −Mv 2 M 1 2RT
∫0
3
vmean = v f (v)d v = 4π v exp d v = 4π

Therefore,

( πM ) ( πm )
1/2 1/2
8RT 8k T
vmean = =

ASIDE: How did we solve the integral above?


(1) Use mathematical software such as Maple or Mathematica or Octave. A link to the
‘Mathematica Online Integrator” has been posted on eClass.
(2) Look up the integral in a table of integrals (or if writing an exam on the data sheet). You
should know how to integrate simple functions, e.g, xn, eax, sin(x),….but for more
complicated ones, you are welcome to use software or tables of integrals. If you do an
assignment, please indicate how integrals were solved and, if a table of integrals was used,
what the expression was and how it was used, e.g., for the integral above used (this is how it
would appear on the data sheet)
∞
n!
∫0
2
x 2n+1e −a x d x =
2a n+1
with n = 1 and a = (M/2RT).
END OF ASIDE

2. The most probable speed, vmp


The speed where the distribution is a maximum, i.e., a stationary point (derivative = 0):
d f (v)
=0
dv
9

[ ( 2RT )]
d 4π ( 2πRT )
3/2
M −Mv 2
v 2 exp
=0
dv
To perform this derivative, we must use the Product Rule (you should know how to use the
Product Rule for performing derivatives).

( 2π RT ) ( 2π RT ) ( 2RT )
3/2 3/2

( 2RT ) ( 2RT )
M −Mv 2 M 2Mv −Mv 2
0 = 4π 2v exp − 4π v2 exp

( 2π RT ) ( 2RT ) [ 2RT ]
3/2
M −Mv 2 M
0 = 4π 2v exp 1 − v2
f (x)
de d f (x) f (x)
NOTE: We have used = e
dx dx
The above equation can only equal zero if

[ 2RT ]
M
1 − v2 =0
Therefore, solving for the most probable speed from this equation we obtain (we choose the
positive answers as speeds are always positive)

( M ) ( m )
1/2 1/2
2RT 2k T
vmp = =

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