The Maxwell-Boltzmann

Distribution

A Chem 101A tutorial

So far, we’ve looked at properties of gases and how they
are related to one another.
We found that all gases obey the relationship PV = nRT,
where R is a constant that does not depend on the
chemical formula or molecular structure of the gas.

He O2 C4H10 SF6

All of these gases obey PV = nRT!

 However, we did not look at the behavior of the
individual molecules in gases. We would like to answer
questions such as:
Do all of the molecules in a sample of a gas move at the
same speed?
Do they all have the same kinetic energy?
Do speeds and energies depend on what gas we’re
looking at?
Do speeds and energies depend on the temperature of the
Teacher, I have
a question…
gas, or its pressure?
 Let’s start with some facts about molecular speeds.
A typical sample of a gas contains an enormous number of
particles (atoms or molecules), which have a very wide range
of speeds.
For example, one liter of gaseous nitrogen at 25ºC and 1 atm
contains roughly 24,600,000,000,000,000,000,000 N2
molecules.
The average molecular speed is 475 meters per second (about
1,060 miles per hour), but some molecules are going less than
1 m/sec (the speed of a slow walk)… and a few molecules are
going more than 3000 m/sec (over ten times as fast as a
commercial airliner).
In the mid-19th century, James Maxwell and Ludwig Boltzmann
derived an equation for the distribution of molecular speeds in a
gas. Graphing this equation gives us the Maxwell-Boltzmann
distribution.
Here is the Maxwell-Boltzmann distribution for nitrogen
molecules at 25ºC.
Nice graph - but
0.0025
what does it mean?

0.002
Fraction per m/sec

0.0015

0.001

0.0005

0
0 500 1000 1500 2000
Speed (m/sec)
 The horizontal scale shows the speeds of the molecules. The
overwhelming majority of nitrogen molecules have speeds
between 0 and 2000 m/sec at 25ºC.
The speeds are not limited to the range shown on this graph. The Maxwell-
Boltzmann curve approaches y = 0 as x becomes extremely large, but the curve never
reaches y = 0.
0.0025

0.002
Fraction per m/sec

0.0015

0.001

0.0005

0
0 500 1000 1500 2000
Speed (m/sec)
 The vertical scale (y axis) shows the fraction of
molecules whose speeds lie within ±0.5 m/sec of the
speed shown on the x axis.
Uh oh… I wonder
0.0025 what “fraction of
molecules”
means...
0.002
Fraction per m/sec

0.0015

0.001

0.0005

0
0 500 1000 1500 2000
Speed (m/sec)
 A fraction is a percentage before you multiply by 100.
For instance, if you have 20 molecules and 5 of them are
hydrogen, the fraction of hydrogen molecules is 5 ÷ 20, or
0.25.
The percentage of hydrogen molecules would be
(5 ÷ 20) × 100%, or 25%.
Another example: instead of saying “8% of doctors hate
coffee,” I could say “the fraction of doctors that hate coffee
is 0.08.”
Okay, I get it.
It’s a bit odd calling something a
fraction when it’s actually a decimal
number, but I’ve noticed that
scientists can be a bit odd at times…
 Going back to our graph…
When the speed is 500 m/sec, the y value is 0.00185. This tells us that
the fraction of molecules that have speeds between 499.5 and 500.5
m/sec is 0.00185.
You can always translate a fraction into a percentage by multiplying by 100.
For instance, the boldface words can be restated as “0.185% of the molecules
have speeds between 499.5 and 500.0 m/sec.”
0.0025

0.002
0.00185
Fraction per m/sec

0.0015

0.001

0.0005

0
0 500 1000 1500 2000
Speed (m/sec)
 The higher the curve at a given speed, the more molecules
travel at that speed.

For example, many molecules have speeds around 500 m/sec,

while far fewer molecules have speeds around 1000 m/sec.

0.0025

0.002 When x = 500 m/sec, the

fraction (the y value) is large.
Fraction per m/sec

0.0015

0.001

0.0005
When x = 1000 m/sec, the
fraction (the y value) is small.
0
0 500 1000 1500 2000
Speed (m/sec)
 The Maxwell-Boltzmann distribution can be thought of as a
smoothed-out bar graph.
To see how this works, let’s “zoom in” on the region between
700 and 730 m/sec.

0.0025

0.002
Fraction per m/sec

0.0015

0.001

0.0005

0
0 500 1000 1500 2000
700 730
Speed (m/sec)
 When we expand this part of the graph, we can see the
individual bars. Each bar covers a range of 1 m/sec.
For example, the fraction of molecules that have velocities
between 699.5 and 700.5 m/sec is 0.000932.
Actually, treating the Maxwell-Boltzmann distribution like this is a bit of an
oversimplification, but we needn’t worry about the reasons today.
0.001

0.0009

0.0008

0.0007

0.0006
Fraction

0.0005

0.0004

0.0003

0.0002

0.0001

0
Speed (m/sec)
699.5 - 700.5 729.5 - 730.5
 Note that all of the fractions are very small numbers.
This is because the range of speeds we are looking at is
very narrow, just 1 m/sec.
It is not surprising that a very small percentage of the
molecules have speeds in such a narrow range.
0.0025

Asking for the percentage of

0.002 molecules that have speeds
between 499.5 and 500.5 m/sec
is like asking for the percentage
Fraction per m/sec

0.0015 of people who have ages

between 30 years and 30 years
plus one month. The
percentage – and therefore the
0.001
fraction – will be very small.

(If you’re curious, about

0.0005
0.107% of Americans are
within this age range – a
fraction of 0.00107, or roughly
0 330,000 out of 308,000,000
0 500 1000 1500 2000
people.)
Speed (m/sec)
 The speed that corresponds to the peak of the curve is called
the most probable speed. More molecules travel at (or close
to) this speed than any other.
For N2 at 25ºC, the most probable speed is 421 m/sec.
0.0025

For any gas, the most

0.002 probable speed is given
by the formula
Fraction per m/sec

0.0015
2RT
v =
mp M
0.001

where T = the kelvin temperature

0.0005 R = 8.314 J/mol K
M = the molar mass in kg/mol
€
0
0 500 1000 1500 2000
Most probable speed: 421
Speed (m/sec)
The average speed is a little larger than the most probable
speed, and can be calculated by the formula
8RT
v =
ave πM
For N2 at 25ºC, the average speed is 475 m/sec.
0.0025
€
0.002
Fraction per m/sec

0.0015

0.001

0.0005

0
0 500 1000 1500 2000
Most probable speed:421
Speed (m/sec)
Average speed: 475
The root-mean-square speed is the speed that corresponds to
the average kinetic energy of the molecules. It is given by the
formula:
3RT
v =
rms M
For N2 at 25ºC, the root-mean-square speed is 515 m/sec.
0.0025

€
0.002
The root-mean-
Fraction per m/sec

square speed is
0.0015 always the largest
of these three
values. It is 22.5%
0.001
higher than the
most probable
0.0005
speed and 8.5%
higher than the
average speed.
0
0 500 1000 1500 2000
Most probable speed:421
Speed (m/sec)
Average speed: 475
Root-mean-square speed: 515
It’s hard to grasp speeds in meters per second, because we
usually don’t express speed this way. Here are the
equivalents in miles/hour and kilometers/hour.
Most probable speed: 421 m/sec = 942 miles/hr = 1516 km/hr
Average speed: 475 m/sec = 1063 miles/hr = 1710 km/hr
Root-mean-square speed: 515 m/sec = 1152 miles/hr = 1854 km/hr

For comparison, a typical commercial jet airplane flies around 550

miles/hr (880 km/hr), and the speed of sound at sea level is about
760 miles/hr (1220 km/hr).

Those molecules are

really moving!
Now, suppose we wanted to know the fraction of molecules
that have speeds in a wide range, say 500 to 1000 m/sec.
In principle, we could add up the fractions for each
individual speed in this range.
However, in practice this is not practical, because there are
too many fractions.
How many fractions would we need to add up?
So many numbers…
sob…
If we wanted to know the fraction of molecules that have speeds
between 500 and 1000 m/sec, we would need to measure and add
up five hundred individual fractions!
Recall that each fraction corresponds to a speed range of 1 m/sec.

We would need to consider…

Speed between 499.5 and 500.5 m/sec: fraction = 0.0018453
Speed between 500.5 and 501.5 m/sec: fraction = 0.0018422
Speed between 501.5 and 502.5 m/sec: fraction = 0.0018391
Speed between 502.5 and 503.5 m/sec: fraction = 0.0018360
Speed between 503.5 and 504.5 m/sec: fraction = 0.0018328
Speed between 504.5 and 505.5 m/sec: fraction = 0.0018297
Add them all up…
Speed between 505.5 and 506.5 m/sec: fraction = 0.0018264
etc….
Speed between 999.5 and 1000.5 m/sec: fraction = 0.0001066
YIKES!!!!
 A far better way to determine the fraction of molecules in a
wide range of speeds is to measure the area of the region under
the Maxwell-Boltzmann curve.
It can be proven that the fraction of molecules in any velocity
range equals the area under the corresponding part of the
curve. This is true because the area under the entire Maxwell-
Boltzmann curve is exactly 1.
0.0025

0.002
Fraction per m/sec

0.0015

0.001

0.0005
Area = 1

0
0 500 1000 1500 2000
Speed (m/sec)
 For example, if we want to determine the fraction of
molecules that have velocities between 500 and 1000 m/sec,
we need to measure the area of the shaded region below.

0.0025

0.002
Fraction per m/sec

0.0015

0.001

0.0005

0
0 500 1000 1500 2000
Speed (m/sec)
 There are several ways to estimate this area. The simplest,
which you will do in the lab, is to cut out and weigh the graph.
In principle, we could use calculus to determine the exact area
under the curve, since the equation that generates the Maxwell-
Boltzmann curve is known (and is shown below).
Unfortunately, this equation cannot be integrated analytically.
3
⎛ M ⎞ 2 2 −Mv 2 /2 RT
fraction = 4π ⎜ ⎟ ve
⎝ 2π RT ⎠

I’ve been working on this calculus problem

for 48 hours straight… I refuse to believe
that it can’t be done…
 If you’re curious, though, the area of the shaded region is
0.392, so the fraction of molecules that have speeds between
500 and 1000 m/sec is 0.392.
(As always, we can think of this as a percentage: 39.2%.)
0.0025

0.002
Fraction per m/sec

0.0015

0.001

0.0005

0
0 500 1000 1500 2000
Speed (m/sec)
 The shape of the Maxwell-Boltzmann curve depends on two
factors, the temperature and the molar mass of the gas.
Let’s explore how these factors influence the shape of the curve.
What if we heat
up our gas?

0.0025

0.002

???
Fraction per m/sec

0.0015

What if we have
0.001 really heavy molecules?

0.0005

0
0 500 1000 1500 2000
Speed (m/sec)
 The Maxwell-Boltzmann distribution for nitrogen at four
different temperatures is shown below.
Observe that when the temperature goes up, the particles in a gas
tend to move faster.
As a result, the entire distribution shifts to the right, toward
higher
Boltzmann velocity speeds.
distributions for N
at selected temperatures
2

0.0035

-150°C
0.003

0.0025
Fraction per m/sec

0.002 25°C

0.0015
300°C

0.001 1000°C

0.0005

0
0 200 400 600 800 1000 1200 1400 1600 1800 2000

Speed (m/sec)
 When we raise the temperature, the most probable speed
increases (the highest point on the curve shifts to the right). In
addition, the entire curve gets wider and lower: we have a
wider range of speeds, but we have fewer molecules at the
most probable speed.

0.0035
Most probable speed = 270 m/sec at -150ºC.
0.003

0.0025
Fraction per m/sec

0.002
-150°C
(Narrow
0.0015 curve)

Most probable speed = 870 m/sec at 1000ºC.

0.001

0.0005
1000°C
(Wide curve)
0
0 200 400 600 800 1000 1200 1400 1600 1800 2000

Speed (m/sec)
Also, when we raise the temperature, the fraction of molecules
moving at high speeds increases.
For example, when we raise the temperature from 25ºC to
300ºC, the fraction of molecules moving faster than 800 m/sec
becomes larger.
We could choose any velocity cutoff we want. In other words, if we raise the
temperature, the fraction of molecules moving faster than x m/sec increases, for all
possible values of x.

0.0035 0.0035

At 25ºC, the fraction of molecules At 300ºC, the fraction of molecules

0.003 0.003

moving faster than 800 m/sec is moving faster than 800 m/sec is
0.0025 small. 0.0025 larger.

Fraction per m/sec

Fraction per m/sec

0.002 0.002 25°C

25°C

0.0015 0.0015
300°C 300°C

0.001 0.001

0.0005 0.0005

0 0
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Speed (m/sec) Speed (m/sec)
 Likewise, when we raise the temperature, the fraction of
molecules moving at low speeds decreases.
For example, when we raise the temperature from 25ºC to
300ºC, the fraction of molecules moving slower than 800 m/sec
becomes smaller.
Again, we could choose any velocity cutoff we want. In other words, if we raise the
temperature, the fraction of molecules moving slower than x m/sec decreases, for all
possible values of x.

0.0035 0.0035

At 25ºC, the fraction of molecules At 300ºC, the fraction of molecules

0.003 0.003

moving slower than 800 m/sec is moving slower than 800 m/sec is
0.0025 large. 0.0025 smaller.

Fraction per m/sec

Fraction per m/sec

0.002 0.002 25°C

25°C

0.0015 0.0015
300°C 300°C

0.001 0.001

0.0005 0.0005

0 0
0 200 400 600 800 1000 1200 1400 1600 1800 2000 0 200 400 600 800 1000 1200 1400 1600 1800 2000
Speed (m/sec) Speed (m/sec)
 Summary
When you raise the temperature of a gas:
•  The Maxwell-Boltzmann curve shifts to the right
and flattens.
•  The most probable speed increases.
•  The fraction of fast-moving molecules increases.
•  The fraction of slow-moving molecules decreases.
Gas molecules are kind of like
lizards: the colder they get,
the slower they move!

Wow - this is one mighty big lizard…

That’s a dinosaur, silly!

Now let’s look at the effect of the molar mass of a gas on its
Maxwell-Boltzmann distribution.

How would the distribution of speeds change if we replaced

nitrogen by a different gas, such as helium or xenon?

Good question!
Maybe I can find the answer
on my friend’s Facebook page?
Here are the Maxwell-Boltzmann curves for three different
gases.
We see that the gas with the lowest molar mass (helium) has
the highest molecular speeds, while the gas with the highest
molar mass (xenon) has the lowest molecular speeds.
0.0045

Xenon (133.3 g/mol)

0.004

0.0035
fraction per m/sec

0.003

0.0025

0.002
Nitrogen (28.0 g/mol)
0.0015

0.001
Helium (4.0 g/mol)

0.0005

0
0 500 1000 1500 2000

speed (m/sec)
 When we increase the molar mass, the most probable speed
decreases (the highest point on the curve shifts to the left). In
addition, the entire curve gets narrower and taller: we have a
smaller range of speeds, but we have more molecules at the
most probable speed.

0.0045
Xenon (133.3 g/mol)
0.004 Most probable speed = 193 m/sec at 25ºC.

0.0035
fraction per m/sec

0.003

0.0025

0.002

0.0015

0.001 Most probable speed = 1113 m/sec at 25ºC.

Helium (4.0 g/mol)

0.0005

0
0 500 1000 1500 2000

speed (m/sec)
 Summary
When you increase the molar mass of a gas:

•  The Maxwell-Boltzmann curve shifts to the left

and gets taller and narrower.
•  The most probable speed decreases.
•  The fraction of fast-moving molecules decreases.
•  The fraction of slow-moving molecules increases.
This is exactly the opposite of the temperature effect.
Increasing the temperature speeds everything up, but
increasing the molar mass slows everything down!

By the way, we can’t really change

the molar mass of a gas,
but we can compare two gases
with different molar masses.
 We can also plot the distribution of kinetic energies for the
particles in a sample of a gas.
The Maxwell-Boltzmann kinetic energy graph for N2 at 25ºC is
shown below.
0.00025

0.0002
Fraction per J/mol

0.00015

0.0001

0.00005

0
0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000

Kinetic energy (J/mol)

 The x-axis shows molecular kinetic energies in units of joules
per mole.
Expressing particle energies in joules per mole is analogous to expressing atomic weights in
grams per mole. If we wish to calculate the energy of a single particle, we simply divide the
value in J/mol by Avogadro’s number. For instance, if a particle has an energy of 10,000 J/mol,
the energy of a single particle is 1.66 x 10-20 J.
10,000 J/mol
23
= 1.66 × 10-20 J/particle
6.022 × 10 particles/mol

0.00025
€

0.0002
Fraction per J/mol

0.00015

0.0001

0.00005

0
0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000

Kinetic energy (J/mol)

 The y-axis shows the fraction of particles whose energies are
within ± 0.5 J/mol from the value on the x-axis.
For instance, the fraction of molecules that have kinetic
energies lying in the range 4000 ± 0.5 J/mol is 0.000115.

0.00025

Another way to say the

0.0002 same thing is:
“0.0115% of the nitrogen
Fraction per J/mol

0.00015 molecules have kinetic

energies between 3999.5
0.000115 J/mol and 4000.5 J/mol.”
0.0001

0.00005

0
0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000

Kinetic energy (J/mol)

 The total area under this curve is exactly 1, just as it was with
the speed distribution curve. Therefore, we can measure the
fraction of molecules having a wide range of energies by
measuring the area under the curve.

0.00025
For instance, the area
0.0002
of the shaded region
is 0.467, so the
Fraction per J/mol

0.00015
fraction of nitrogen
molecules that have
0.0001
energies between
2000 and 6000 J/mol
0.00005
is 0.467.
AREA = 0.467
(that’s 46.7%)
0
0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000

Kinetic energy (J/mol)

The kinetic energy corresponding to the peak of the curve is called
the most probable kinetic energy, and is given by the formula
KE mp = 1 RT
2

For N2 at 25ºC, the most probable kinetic energy is 1240 J/mol.

0.00025
€

0.0002
Fraction per J/mol

0.00015

0.0001

0.00005

0
0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000
Most probable KE: 1240 J/mol Kinetic energy (J/mol)
 The average kinetic energy is given by the formula
KE ave = 3 RT
2

For N2 at 25ºC, the average kinetic energy is 3720 J/mol.

€
0.00025

Note that the average

kinetic energy is much
0.0002
larger than the most
probable kinetic energy.
Fraction per J/mol

0.00015 Compare this with the

speed distribution,
0.0001 where the most
probable speed was
fairly close to the
0.00005
average speed.

0
0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000
Most probable KE: 1240 J/mol Kinetic energy (J/mol)
Average KE: 3720 J/mol
The kinetic energy distribution depends on the temperature, just
as the molecular speed distribution did. Increasing the
temperature increases the most probable KE, and it shifts the
entire graph toward higher kinetic energies.
0.00025

0.0002 25ºC: KEmp = 1240 J/mol

Fraction per J/mol

0.00015

250ºC: KEmp = 2170 J/mol

0.0001

500ºC: KEmp = 3210 J/mol

0.00005

0
0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000

Kinetic energy (J/mol)

 At higher temperatures, the fraction of molecules with high
kinetic energies increases. This is analogous to what we saw
with molecular speeds.
For example, the fraction of molecules with kinetic energies
above 8000 J/mol is much larger at 250ºC than it is at 25ºC.

0.00025 0.00025

0.0002 0.0002
25ºC
Fraction per J/mol

Fraction per J/mol

0.00015 0.00015

0.0001 0.0001 250ºC

Small area = small fraction of Large area = large fraction of

molecules with KE > 8000 J/mol molecules with KE > 8000 J/mol
0.00005 0.00005

0 0
0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000 0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000

Kinetic energy (J/mol) Kinetic energy (J/mol)

 What about molar mass - what effect does that have on the
distribution of kinetic energies?
Here’s a hint: the formulas for the most probable KE and the
average KE did not contain the molar mass.

KE mp = 1 RT KE ave = 3 RT
2 2

Therefore, the KEmp and the KEave do not depend on the molar
mass; they are the same for any gas, as long as the temperature
€ is the same.
What does this tell us about the distribution?
In fact, the kinetic energy distribution is the same for any
gas, as long as the gases are at the same temperature.
The graph below represents the kinetic energy distribution of
H2, He, N2, O2, CO2, Ar, Xe, or any other substance that is a
gas at 25ºC.
0.00025

0.0002
Fraction per J/mol

0.00015

0.0001

0.00005

0
0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000

Kinetic energy (J/mol)

 Note the difference between kinetic energy and molecular
speed.
For molecular speed, the distribution depends on both
temperature and molar mass.
For kinetic energy, the distribution depends only on
temperature.
If the kinetic energy distribution depended on molar mass, we
would have a vast number of gas constants, one for each gas.
There would be no ideal gas law; each gas would behave
differently from all the others, just as solids and liquids do.
 How can the speed depend on the molar mass if the kinetic
energy does not?
The key is to recognize that the kinetic energy is the more
fundamental property for gases. Kinetic energy is a function of
temperature alone.
Now, consider two different particles that have the same kinetic
energy but different masses….

Same kinetic energy

Light particle Heavy particle

The kinetic energy of any particle is related to its mass and its
speed:
KE = 1 mv 2
2

If two particles have the same KE but different masses, they

€ speeds; in fact, the heavier particle must
must have different
have the lower speed.

Small mass, high speed

Equal kinetic
energies!
Large mass, low speed
The Boltzmann distribution helps understand many things about
gas behavior…
• Gases exert more pressure when they are heated - because their
speeds increase as the temperature goes up.
• The pressure exerted by a mole of a gas does not depend on the
chemical formula or molar mass of the gas - because all gases have
the same kinetic energy distribution at the same temperature.
• Helium escapes from balloons faster than air does - because helium
atoms are lighter than N2 or O2 molecules, so they travel at higher
speeds.
• There is no hydrogen or helium in the earth’s atmosphere - because
those gases have such high average speeds that they were able to
escape earth’s gravity long ago.
The Boltzmann distribution plays a critical role in determining the
speed of a reaction involving gases.
For any reaction, molecules must collide violently enough to
allow bonds to weaken enough so new bonds can form.
As a result, only molecules with a lot of kinetic energy can react.
For any reaction, there is a minimum kinetic energy required for a
reaction, called the activation energy.

Low kinetic energy - the High kinetic energy - the

molecules just bounce off molecules react!
each other.
 If the minimum energy required for a reaction is 8000 J/mol…
• 9% of the molecules will have enough energy at 25ºC.
• 30% of the molecules will have enough energy at 250ºC.
The reaction is more than three times faster at 250ºC than it is at
25ºC.

0.00025 0.00025

0.0002 0.0002
25ºC
Fraction per J/mol

Fraction per J/mol

0.00015 0.00015

0.0001 0.0001 250ºC

Fraction = 0.09 Fraction = 0.30

0.00005 0.00005

0 0
0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000 0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000

Kinetic energy (J/mol) Kinetic energy (J/mol)

The Boltzmann distribution plays
a central role in all aspects of the
behavior of gases!
Wow… Who knew that a
graph could tell us so
much….
THE END