Role Of Kinetic Theory Of Gases

in Vacuum Science And

Technology
A vacuum is a region where the pressure is less than
atmospheric i.e. where the number of molecules per unit
volume is less than what is normally expected.
The behavior and characteristics of gases are
fundamental to vacuum systems. Even at the extremely
low pressures typically encountered in vacuum
technology, gases essentially still behave as gases.
The necessity for creating a vacuum is usually related to
the need to reduce the number density of gaseous
molecules, or their surface collision rates. The purpose
of vacuum technology is to create regions of vacuum,
maintain them, measure them and use them .
Behavior of gases in vacuum systems can be generally
discussed in terms of the ideal gas laws.

 pressure-volume (constant
temperature)
What happens to the volume of a gas as the pressure on it
changes. Let's try the following experiment using
equipment that might be found in your kitchen.
Marshmallows in a kitchen vacuum pump. The
volume of a marshmallow increases as the
pressure on it decreases

Marshmallows are a mixture of sugar, air, and gelatin.

Sugar makes them sweet, air makes them fluffy, and
gelatin makes them elastic. Marshmallows are a frozen
foam and are mostly air by volume. When placed in a
vacuum pump, they expand as the pressure
decreases. Break the seal on their container and they
shrink during the return to normal atmospheric
pressure. Since the vacuum pump pulls on the
marshmallows hard enough to burst some of the air
bubbles, they are actually a bit smaller and more shriveled
at the end of this experiment. This illustrates a
fundamental, yet important, property of gases. The
pressure of a gas is inversely proportional to its volume
when temperature is constant. Symbolically…

1
P∝ (T constant)
V
or

P1V1 = P2V2 = constant

This correlation was discovered independently
by Robert Boyle (1627–1691) of Ireland in 1662
and Edme Mariotte (1620–1684) of France in 1676. In
Great Britain, America, Australia, the West Indies and
other remnants of the British Empire it is called Boyle's
law, while in Continental Europe and other places it is
called Mariotte's law.
Mariotte added the important provision that temperature
remain constant. Boyle neglected to mention it, but the
data he used to derive his law were most likely collected
during a period in which the temperature did not
experience any significant change. Since the gas needs to
be in thermal equilibrium with its environment (or some
other heat reservoir) to maintain an even temperature, the
pressure-volume relationship normally applies only to
"slow" processes. The marshmallow-vacuum
experiment shown above is an example of a "slow"
process. The pressure is reduced at a rate slow enough
that heat from the environment is able to keep the jar and
its contents at nearly room temperature. Such a
transformation that takes place without a change in
temperature is said to be isothermal.
Pumping a bicycle tire with a hand pump is an example of
a "fast" process. The work done pushing the piston
transforms into an increase in the internal energy (and
thus an increase in the temperature) of the air molecules
within the pump.
People familiar with hand bicycle pumps will attest to the
fact that they get hot after use. Likewise, when a gas is
allowed to expanded into a region of reduced pressure it
does work on its surroundings. The energy to do this work
comes from the internal energy of the gas and so the
temperature of the gas drops.
You can experience this yourself without the aid of any
apparatus other than your mouth. Purse your lips so that
your mouth has only a tiny opening to the outside and
blow hard. The air rushing from your mouth will be quite
cool despite coming from the core of your body, which is
normally quite hot (around 37 ℃). During a "fast" process
like the ones just described, pressure and volume are
changing so rapidly that heat doesn't have enough time to
get into or out of the gas to keep the temperature
constant. Such a transformation that takes place without
any flow of heat is said to be adiabatic.

 volume-temperature (constant
pressure)
What happens to the volume of a gas when its
temperature changes? Let's try another kitchen
experiment.
 Bread dough before and after baking. Increasing the
temperature of bread dough increases its volume.

Bread is made from wheat flour, water, yeast, and a bit of

sugar. Yeast are tiny microorganisms. They are quite
possibly the very first domesticated animals and, much
like dogs and horses, yeast have been bred for different
purposes. Just as we have guard dogs, lap dogs, and
hunting dog; draft horses, race horses, and war horses;
we also have brewer's yeast, champagne yeast, and
bread yeast. Bread yeast have been selectively bred to
eat sugar and burp carbon dioxide (CO2). When wheat
flour and water are mixed together and kneaded, the
protein molecules are mashed and stretched until they line
up neatly to form a substance called gluten that, like
chewing gum, is both elastic and plastic. Let this special
matrix sit and the CO2vented from the yeast get trapped in
thousands of tiny resilient, stretchy pockets. As this
process continues these tiny pockets expand, which
causes the volume of the dough to expand or rise in a
process called proofing. We now have a fluffy gummy blob
ready for the oven.
While there the dough expands again, but his time it's not
due to the action of microorganisms (they all die around
the boiling point of water). This time it's the heat, or rather
the temperature. The temperature inside a bread oven is
roughly 50% greater (in absolute terms) than the
temperature outside. And similarly, the baked bread that
comes out of a bread oven is also roughly 50% greater
than the room temperature dough that goes in. This
domestic example illustrates quite nicely a fundamental
property of gases. The volume of a gas is directly
proportional to its temperature when pressure is constant.
Symbolically…

V ∝ T (P constant)
While no doubt known and understood informally by
billions of bakers since the dawn of civilization, the precise
mathematical relationship was first discovered by the
French physicist Guillaume Amontons (1663–1705) in
1699. The experiment was repeated much later
by Jacques Charles (1746–1823) in 1787 and much, much
later by Joseph Gay-Lussac(1778–1850) in 1802. Charles
did not publish his findings, but Gay-Lussac did. It is most
frequently called Charles' law in the British sphere of
influence and Gay-Lussac's law in the French, but never
Amonton's law.
An isobaric process is one that takes place without any
change in pressure.

Let's recall what it means when two quantities are directly

proportional like volume and temperature. Heat up a gas
and it's volume will expand. Cool it down and it's volume
will contract. The two quantities change in the same
direction. More specifically, an increase in one results in a
proportional increase in the other and a decrease in one
results in a proportional decrease in the other. For
example…

 Doubling the absolute temperature of the air in an

engine cylinder will double its volume.
 Halving the absolute temperature of the air in a bag of
potato chips will cause it to shrink to one half its original
volume.
 The absolute temperature of a bread oven is one and a
half times that of room temperature. Therefore, the loaf
of baked bread that comes out of an oven has 50%
more volume than the ball of dough that went into it.

There's a symmetry at work here somewhere. A symmetry

is a change in one quantity that leaves another, more
fundamental quantity unchanged. It's something like
multiplying both the numerator and denominator of a
fraction by the same thing.

a ⎛x⎞ ax a
= =
b ⎝x⎠ bx b

No wait, it's exactly like that. The only way two quantities
can change in direct proportion is if their ratio remains
constant. Thus…
V1 V2
= = constant
T1 T2

 pressure-temperature (constant
volume)
Fix this, too.

The pressure of a gas is directly proportional to its

temperature when volume is constant. Symbolically…

P ∝ T (V constant)
An isochoric process is one that takes place without any
change in volume.

This relationship doesn't really have a name, but I have

heard it called the "pressure law" or (mistakenly) "Gay-
Lussac's law".

Temperatures drop 6 ℃ for every 1,000 m of altitude.

P1 P2
= = constant
T1 T2

 A complete ideal gas law

Combine the these eq.
P1 V1 P2V2
= = constant
T1 T2

There are two ways to write the complete statement of the

ideal gas law as an equation…

functional thermodynamics

PV = nRT

where…

P = absolute pressure
T = absolute temperature
V = volume

and…

n = number of moles
R = Gas
constant = 8.315 J/molK

statistical thermodynamics

PV = NkT

where…
P = absolute pressure
T = absolute temperature
V = volume

and…

N = number of particles
k = Boltzmann's constant = 1.382 × 10−23J/K

 Kinetic Theory of Gases

Consider a gas consisting of a large number ,N, of hard

molecules. These molecules will each have mass m and
speed v. They will also be allowed to have only kinetic
energy.
The molecules will be constrained to move along one of
the 3 axes - i.e. i , j, or k , and initially will collide only with
the walls of a container. The walls will be rigid so that in
any collision the molecules will collide elastically: they
simply reverse their direction, but continue at the same
speed.
Consider the box shown in Figure . What is the average
force exerted by the molecules on the wall? The number
of molecules moving toward the wall will be 1/6 N. The
molecules will be spread out uniformly in the box and will
strike the walls at different times. We can say that all of
the

Figure : Box containing an ideal gas. In a

simplified model, all molecules move at same
speed and along one of the axes.

1/6 N molecules will hit the wall in a time ∆t = d/v . As

each molecule bounces of, its momentum (a vector) will
change.
……..(1) Commented [1]:

This is equal to the impulse of the wall on the molecule.

In a time ∆t the total impulse on all 1/6 N molecules will
be
………(2)
where F is the force of the wall on the molecules. Thus
………..(3)
is the average force of the molecules on the wall, and
the average pressure, P , on the wall of area A is
…..…. (4)
But Ad=V , the volume, and

is the kinetic energy of a molecule (for real gas this will

be the average kinetic energy.)
So
……….(5)
The model chosen is over simplified. A real kinetic
model would allow molecules to have a range of
speeds, and allow motion in any direction. Then
integrals must be evaluated to obtain the final result for
the average pressure. Surprisingly, the detailed result is
exactly the same as the above, with KE being the
average kinetic energy of a molecule.
The equation above is known as the Ideal Gas Law,
with the average kinetic energy measured by absolute
temperature, T .
PV=NkT ….(6)
with
 ……..(7)
Here k, sometimes written K , is Boltzmann’s constant,
K=
In chemistry we usually write
PV= ….(8)
with R being the gas constant and being the number
of moles of gas. You can easily show that R = ,
where is Avogadro’s number. We will not use moles
in this text. Instead we will define n = N/V as the number
density of particles in such units as molecules per cm3.
Do not confuse the two meanings of n! The Ideal Gas
Law can thus be written as
P=nkT ……..(9)
A real kinetic model uses Maxwell Boltzmann
distribution functions to allow us to determine various
average speeds.
There are different ways to compute the average of the
speed. The rms (root mean square) speed is defined by
……(10)
The average speed is:
……(11)
where m is the mass of one molecule in kg and M is the
molecular mass (g/mol). For air (average M = 29 g/mol)
at room temperature, T =298 K, the molecules have
average speed of 466 m/s and an rms speed of 506m/s.
At the same temperature molecules with a smaller mass
will have larger average speeds. This was one of the
methods used to separate isotopes of uranium in the
Manhatten project.

we find about the Kinetic Theory that will

apply to our study of vacuums

First: Pressure is an average quantity close

measurements would reveal fluctuations around an
average.

Second: Pressure is dependent on temperature, but

not on the type of molecule. Two containers filled with
different gases, but at the same temperature, can have
the same pressure. However, some of the pressure
gauges will respond differently to different gases even if
they are at the same pressure.