University of Nebraska - Lincoln

DigitalCommons@University of Nebraska - Lincoln

Robert Katz Publications Research Papers in Physics and Astronomy

1-1958

Physics, Chapter 16: Kinetic Theory of Gases

Henry Semat
City College of New York

Robert Katz
University of Nebraska-Lincoln, rkatz2@unl.edu

Follow this and additional works at: http://digitalcommons.unl.edu/physicskatz

Part of the Physics Commons

Semat, Henry and Katz, Robert, "Physics, Chapter 16: Kinetic Theory of Gases" (1958). Robert Katz Publications. 166.
http://digitalcommons.unl.edu/physicskatz/166

This Article is brought to you for free and open access by the Research Papers in Physics and Astronomy at DigitalCommons@University of Nebraska -
Lincoln. It has been accepted for inclusion in Robert Katz Publications by an authorized administrator of DigitalCommons@University of Nebraska -
Lincoln.
 16
Kinetic Theory of Gases

16-1 General Gas Law

The behavior of a gas under various condition8 of temperature and pressure

has already been studied in 80me detail. When the pressure of a constant
mass of gas is not too great, say less than about 2 atm, we find that a gas
obeys the following relationships:
at constant temperature PV = constant; (16-1)

at constant volume P = KT; (16-2)

at constant pressure V = K'T. (16-3)

These three equations are special cases of a single experimental equation

which gives the relationship between the pressure P, the volume V, and the

Fig. 16-1 Two steps in the derivation of the general gas law; an isothermal process
followed by a constant-pressure process.

absolute temperature T of a constant mass of gas. We may derive the

general form of the gas law from the above equations.
Let us consider a gas contained in a cylinder with a closely fitting
piston, as shown in Figure 16-1. The initial condition of the gas may be
299
300 KINETIC THEORY OF GASES § 16-1

described in terms of its initial pressure Pi, its initial volume Vi, and its
initial temperature T i . The gas is allowed to expand at constant tempera-
ture, say by keeping the cylinder immersed in a bath of melting ice, until
its new pressure is P f and its new volume is V 2 • Since the expansion was at
constant temperature, we find from Equation (16-1) that
PiV i = Pf V2 •

Now suppose that the gas is heated to a higher temperature T f , the volume
being allowed to expand to a new value Vj, but the pressure on the piston
being maintained at the same value P f throughout this process. Then,
from Equation (16-3) we may write

V 2 = V f = /('
Ti Tf '

Ti
or V 2 =Vf -·
Tf

Substituting for V 2 into the first of the above equations, we find

PiVi = PfVf .
(16.4)
Ti Tf

Equation (16-4) is one form of the general gas law. Since the initial state,
described by the subscript i, and the final state, described by the subscript
!, are entirely arbitrary, the only way in which the quantities on the right-
and left-hand sides of the equation can be equal is for each quantity to be
separately equal to the same constant. Thus we may rewrite the gas law as

~ (16-5)

~
where c is a constant whose value depends upon the mass of the enclosed
gas. Any convenient units may be used for the pressure and volume, but
the temperature T must always be the absolute temperature.
Illustrative Example. A given mass of air occupies a volume of 2,000 cm 3
at 27°C when its pressure corresponds to the pressure at the base of a column of
mercury 75 cm high. The air is compressed until its volume is 1,200 cm 3, and
its pressure corresponds to 225 cm of mercury. Determine the temperature of
the gas after it has been compressed.
From Equation (16-4) we have

PiV i = PfVf.
Ti Tf
§16-3 KINl''l'lC THl'ORY OF GASl'S 301

The pressure at the base of a column of mercury h em high is given by P = hpg,

where p is the density of the mercury. Substituting numerical values, we have
75 em X pg X 2,000 cm 3 225 em X pg X 1,200 cm 3 ,
300.2° abs Tf
from which 1j = 540.4° abs.

16-2 The Universal Gas Constant R

The constant c appearing in Equation (16-5) can be evaluated for any

given mass of a gas. Let us designate the value of this constant for a gram
molecular weight, or mole, of a gas by the symbol R. A gram molecular
weight of any substance is an amount of that substance whose mass, expressed
in grams, is numerically equal to the molecular weight of the substance. In the
limit of low pressures, the value of R is independent of the chemical nature
of the gas, so that R is known as the universal gas constant. In the event
that n moles of gas are present in a container, Equation (16-5) may be
rewritten as
PV = nRT. (16-6)

The numerical value of the gas constant R can be determined by noting

that 1 mole of any gas occupies a volume of 22.4 liters at a pressure of 76
cm of mercury at ooe; putting these values into Equation (16-6), we get
7 erg cal -2 liter atm
R = 8.31 X 10 mole °K = 1.99 mo1e oK = 8.21 X 10 mo e
1 oK

16-3 Kinetic Theory of Gases

From the preceding discussion we have seen that all gases exhibit similar
thermal and mechanical properties, regardless of their chemical composi-
tion, as long as their pressure is sufficiently small. This behavior is quite
unlike that of the same substances in liquid or solid form, where these
substances exhibit widely different thermal and elastic properties. We are
led to infer that the molecules of a gas are sufficiently far apart so that they
rarely interact with each other. The pressure of a gas then results from the
collisions of the molecules of the gas with the walls of the container. The
moving molecules of the gas completely fill every container in which the
gas is placed.
We may construct a theory of an ideal gas which is in good agreement
with the experimental results described in the preceding sections on the
basis of a few simple assumptions. We shall assume that a gas is composed
of molecules that are so small that, to a first approximation, they may be con-
sidered as point masses. We assume further that the molecules do not
302 KINETIC THEORY OF GASES §16-3

exert forces on each other except during collisions. We shall further assume
that the molecules of the gas are perfectly elastic, and that the container is
made of perfectly elastic, rigid walls. This implies that mechanical energy
is conserved in collisions between molecules. If this were not the case,
we would expect to observe that the pressure of a tank of gas would di-
minish with time, as the molecules lost mechanical energy in inelastic col-
lisions. For the sake of simplicity we shall assume that the gas is in a
cubical container of edge d and of volume V = d 3•

Fig. 16-2 Moleeules with equal

velocity components v 1 near face
BeDE of the cube.
.-J--:l----+---..",)D

The pressure exerted by the gas on the walls of the container is due to
the impact of the molecules on the walls, and, when in equilibrium, is
equal to the pressure throughout the gas. To calculate this pressure let
us assume that the impact of a molecule with a wall is an elastic impact;
that is, if a molecule is approaching the wall with a velocity v and mo-
mentum mv, then it will leave the wall with a velocity -v and a momentum
-mv. The change in momentum of the molecule produced by this impact
will thus be - 2mv. To determine the pressure on the walls of the container,
let us first calculate the force exerted by the molecules on one of the six
faces of the cube, say the face BCDE of Figure 16-2, and then divide by
its area.
Let us consider those molecules which at some instant are very close to
this face. Only those molecules whose velocities have components perpen-
dicular to this face, and directed toward it, will strike it and rebound. Sup-
pose we consider a small number of molecules which have the same value
VI for this velocity component. The number of these molecules which will
strike this face during a small time interval t:.t will be one half of the num-
ber contained in a small volume A t:.l, where A is equal to the area of the
face of the cube and t:.l = VI t:.t; the other half having a velocity component
of magnitude VI are moving away from the wall. If ni represents the num-
ber of molecules per unit volume which have a velocity component of
magnitude Vb then the number striking this face of the cube in time t:.t
will be
§16-3 KINETIC THEORY OF GASES 303

Since each such molecule wiII have its momentum changed by - 2mvi
as a result of this impact, the impulse imparted to the wall will be equal and
opposite to it, or +2mvl' The impulse F 1 t:.t on the wall produced by these
collisions in time t:.t will then be

from which
The pressure on the wall produced by the impact of these molecules is
F1 2
PI = A = nlmvl·

We can now consider another group of molecules, n2 per unit volume, which
have a slightly different velocity component V2 in this direction; they will
produce an additional pressure P2 given by
P2 = n2mv~.
In this way, we can break up the gas into different groups of molecules,
each group contributing a similar term to the pressure on this face of the
cube. The total pressure P due to all the different groups of molecules
will therefore be of the form
P = nl mvi + n2mv~ + n3mv~ + ....
This equation can be simplified by introducing a new term called the
average of the squares of the components of the velocities of all the molecules
moving perpendicular to face A and defined by the equation

nlvi + n2v~ + n3v~ +

n

in which n represents the total number of molecules per unit volume. Sub-
stituting this value of v~ in the equation for the pressure, we get
P = nmv~. (16-7)

There will be a similar expression for the pressure on each of the six
faces of the cube, except that the factor v~ will be replaced by the appro-
priate average of the squares of the components of the velocities of the
molecules for that particular face.
The velocity v of anyone molecule may be in any direction; it can be
resolved into three mutually perpendicular components Vx , V y , V z • The
magnitude of v in terms of the magnitudes of these components is given by
v = v; + v~ + v;.
2
304 KINETIC THEORY OF GASES §16-3

There will be a similar equation for the square of the velocity of each mole-
cule of the gas in terms of the squares of its three mutually perpendicular
components. If we add the squares of the component velocities in the x
direction and divide this sum by the total number of molecules, we will get
the average value of the square of this velocity component; it will be
represented by~. Similarly, ~ and ~ will represent the average squares
of the velocities in the y and z directions, respectively. By adding these
average squares of the three velocity components, we get
2v = v2
x
+2
vy + 2
v.,
where v2 is the average of the squares of the velocities of all the molecules.
Since the velocities of the molecules have all possible directions, the average
value of the squares of the velocity in anyone direction should be the same
as in any other direction, or

so that
If we take the x direction as perpendicular to the face A, we can write
v2 = 3v~,
so that Equation (16-7) becomes

(16-8)

Recalling that the kinetic energy of a moving molecule is equal to !mv 2 ,

Equation (16-8) may be written as
P = in(!mv 2 ).
Since n is the number of molecules per unit volume, we see that the pressure
is numerically equal to two thirds the kinetic energy of the molecules in a
unit volume of gas.
Let us suppose that No is the total number of molecules in a mole of
gas, called Avogadro's number, which is contained in a volume V. Then
the number of molecules per unit volume n is given by the expression
No
n=V'
Substituting for n into Equation (16-8), we find
PV = iN o X !mv 2 • (16-9)

Equation (16-9) is a theoretical result obtained from our hypotheses about

an ideal gas, relating the pressure and volume of 1 mole of an ideal gas.
§16-3 KINETIC THEORY OF GASES 305

If we compare this result to the experimental equation given in Equation

(16-6), which for 1 mole of gas becomes
PV = RT,
we find the theoretical and experimental results to be in agreement if
RT iNa !mv 2 ,
=

or if
1:2
-mv = -3 -R 7.,
2 2 Na

It is customary to define a new constant k, called Boltzmann's constant,

such that
R
k=-· (16-10)
Na
Since R is the gas constant per mole, and N a is the number of molecules in
a mole of gas, the constant k may be described as the gas constant per
molecule. In terms of k the preceding equation becomes
(16-11)

that is, the mean kinetic energy of translation of a molecule of gas is given
by ! the product of Boltzmann's constant by the absolute temperature.
This equation gives us some physical meaning of temperature for an ideal
gas. For such a gas the temperature is associated with the kinetic energy
of the random translational motion of the molecules of the gas. According
to Equation (16-11) the average energy of each molecule, and therefore the
total internal energy of an ideal gas, is associated with its temperature.
Thus the internal energy oj an ideal gas is a junction oj its temperature only,
and not of its pressure or volume.
In our derivation of the gas law in the form of Equation (16-9), we
used the word "molecules" to describe the particles with which we were
dealing. These molecules were described by the condition that they were
small, relatively far apart, and perfectly elastic. Thus this equation might
be used to describe the behavior of any aggregate of particles whose physical
dimensions were small compared to their average separation, provided that
these particles were elastic and rarely interacted with each other. The
neutrons in a nuclear reactor satisfy these conditions. If the neutrons are
in equilibrium with the material of the reactor at a temperature T, we
speak of them as thermal neutrons. The mean velocity v of these thermal
neutrons may be obtained from Equation (16-11). The particles of a
colloidal suspension may also be thought of as though they were molecules
of an ideal gas, and it is found that these also obey the gas laws.
Equation (16-9) incorporates another result called Avogadro's hy-
pothesis, first stated by Avogadro in 1811, that all gases occnpying equal
306 KINETIC THEORY OF GASES §16-4

volumes at the same temperature and pressure contain equal numbers of mole-
cules. The accepted value for the number of molecules in a mole of gas
No is
No = 6.023 X 1023 molecules/gm molecular wt.
As we have already seen, 1 mole of gas occupies a volume of 22.4 liters at
ooe and at a pressure of 76 em of mercury. If we perform the calculation
indicated in Equation (16-10) to find the numerical value of Boltzmann's
constant, we obtain
k = 1.38 X 10-16 erg;oK.

16-4 Work Done by a Gas

Whenever a gas expands against some external force, it does work on the
external agency; conversely, whenever a gas is compressed by the action
of some outside force, work is done on the gas. To calculate the work done

n
,I F=PA
(a) p ll
AII
,I
U

(b)
p

v
Fig. 16-3 (a) Expansion of a gas at constant pressure. (b) Graphical representation of
the work done !1Jr as an area on the PV diagram.

by a gas, consider a gas enclosed in a cylinder with a tight fitting piston.

The piston may be connected to a mechanical device on which it exerts
some force. The force F acting on the piston owing to the pressure P of
the gas is given by
F = PA,
in which A is the cross-sectional area of the piston, as shown in Figure 16-3.
Suppose that the piston is pushed out a small distance /lS, while the pressure
of the gas remains essentially constant. The work MY done by the gas in
§16-4 WORK DONE BY A GAS 307'

moving the piston is given by

tiJY = F tis = PA tis,
or (16-12)

Thus the work done by an expanding gas at constant pressure is equal to

the product of the pressure by the change in volume. No mechanical work
is done by a gas unless there is a change in the volume of the gas. The
first law of thermodynamics,
tiQ = tiU + tiJY, (15.6)

may be rewritten for processes involving gases as

tiQ = tiU + P tiV. (16-13)

Thus, in any process in which the volume of the gas remains constant,
called an isovolumic process, any heat delivered to the gas must appear as
internal energy and is therefore exhibited as a change in the temperature
of the gas.
Let us calculate the work done by an ideal gas which expands iso-
thermally, that is, at constant temperature, from an initial volume VI to a
final volume V 2 • From the gas law the relationship between the variables
of pressure, volume, and temperature for one mole of gas may be stated as
PV = RT.
The work done may be represented as an integral, from Equation (16-12), as

JY = fdJY = .£V2 P dV,

and, substituting for P its value from the gas law,
RT
P=-,
V
V2 dV
we find JY = RT
Ivv,
-
V
at constant temperature. Recalling that
dX
f --; = In x + C,
where C is a constant of integration, we find that
V2
JY = RTln- (16-14)
VI
for the work done by one mole of an ideal gas in an isothermal expansion
308 KINETIC THEORY OF GASES §16-5

at temperature T from an initial volume VI to a final volume V 2 • From

Equation (16-14) we see that when the gas expands, that is, when V 2 is
greater than Vb the work done is
P positive, as is consistent with the sign
convention developed in Section 15-6.
The work done is shown as the area
under the isotherm in Figure 16-4.

16-5 Molar Heat Capacity of a Gas

When a quantity of heat t:.Q is delivered

to a gas, it may change the internal
energy of the gas by an amount t:.U
V and may also result in the performance
of an amount of external work t:.Jr by
Fig. 16-4 Work done by a mole of a
the gas upon the outside world, in ac-
gas in an isothermal expansion at
temperature T from volume V 1 to cordance with the first law of ther-
volume V 2 • modynamics. If the volume of the
gas is kept constant, all the heat is
converted into internal energy. Since the internal energy U of a mole of
gas is a function of temperature only, we may define the molar heat capac-
ity at constant volume of a mole of gas C v as
C _ t:.Q _ t:.U
v - t:.T - t:.T (at constant volume), (16-15)

so that the change in internal energy t:.U may be expressed as

t:.U = C v t:.T. (16-16)

From Equation (16-13) the first law of thermodynamics as applied to an

ideal gas may be rewritten as
t:.Q = C v t:.T +p t:.V. (16-17)

Let us consider the change in temperature of a mole of gas when a

quantity of heat t:.Q is delivered to the gas while the pressure is held con-
stant but the volume is permitted to change. The thermal energy delivered
to the gas must now be used to do external work as well as to change the
internal energy of the gas. The rise in temperature of the gas will therefore
be less than in the case where the volume of the gas is kept constant. The
molar heat capacity at constant pressure Cp might be expressed in such
units as calories per mole per degree, and may be defined through the
equation
t:.Q
Cp = - (at constant pressure), (16.18)
t:.T
§16-5 MOLAR REA'!' CAPACITY OF A GAS 309

and from Equation (16-17) we find

Cv~T+P~V
Cp =
~T

From the gas law for a mole of gas we have

PV = RT,
R
or V = pl'.
At constant pressure both Rand P are constant, so that a change of volume
~ V is related to a change in temperature ~T through the equation

R
~V = p~T.

Substituting this result into the preceding equation for C p, we find that
Cp = C v + R. (16-19)

The molar heat capacity of a gas at constant pressure is always greater

than the molar heat capacity at constant volume by the gas constant R.
The internal energy of a monatomic gas, such as helium, is entirely in
the form of kinetic energy of translation of the random motions of the
atoms of the gas. From Section 16-3 this internal energy may be stated as
U = No X !mv 2 = !RT. (16-20)

Since R is a constant, we find that the change in internal energy ~U asso-

ciated with a change in temperature ~T is given by
~U =!R ~T.
Thus the molar heat capacity of a monatomic gas at constant volume may
be found by substituting the preceding result into Equation (16-15), to find
C v =!R (monatomic gas). (16-21a)

Substituting this result into Equation (16-19), we obtain

Cp = iR (monatomic gas). (16-21b)

It is customary to designate the ratio of the specific heat at constant pres-

sure to the specific heat at constant volume by the letter 'Y (gamma). Thus
Cp
'Y = - . (16.22)
Cv
Substituting from Equations (16-21) into (16-22), we find the value of 'Y
for a monatomic gas to be
'Y = 1 (monatomic gas).
310 KINETIC '.rHEORY OF GASES §16-5

In our development of the kinetic theory of an ideal gas we assumed

that a molecule could be considered as a point mass and showed that the
average kinetic energy of translation per molecule is ikT (Equation 16-11).
There are three independent directions of motion of translation, say the
x, y, and z directions. We say that the molecule has three degrees of freedom;
that is, three coordinates are necessary to specify the position of the mole-
cule at any instant, one for each degree of freedom. Since there is no reason
for preferring one direction rather than another, we postulate the principle
of equipartition of energy, that each degree of freedom should have the
same amount of energy. Referring to Equation 16-11, the amount of
energy to be associated with each degree of freedom per molecule is !kT.
The internal energy of a mole of a monatomic gas will then be iRT, as
given by Equation 16-20.
The idea of degrees of freedom can be extended to diatomic and poly-
tomic gases. It can be shown that the value of 'Y can be expressed as

7=--'
f+2
f
where f is the number of degrees of freedom per molecule. For a monatomic
3+2 5
gas we find that 'Y = - - = - = 1.67, in agreement with measured
3 3
values as shown in Table 16-1.
We may extend these ideas to a diatomic molecule which we may
imagine to be two point masses a fixed distance apart; the line joining the
two atoms is the axis of the molecule. If the diatomic molecule is con-
sidered as a rigid body, then it will have three degrees of freedom owing to
the translational motion of the entire molecule, plus a certain number of
degrees of freedom owing to the rotational motion of the molecule. A
glance at Table 16-1 shows that 'Y = 1.4 for diatomic gas, indicating that
f = 5; thus there must be two additional degrees of freedom of rotation.
These would correspond to rotations about two mutually perpendicular
axes in a plane at right angles to the line joining the two atoms.
Thus if at ordinary temperatures the molecules of a diatomic gas may
be thought of as rigid, and possessing no vibrational energy, the mean
energy of each molecule must be ~kT. The total internal energy of a mole
of such a gas is given by

U = No X ~kT = ~RT (diatomic gas). (16-23)

From this expression we find the molal' heat capacities of a diatomic gas
to be
C v = ~R, Cp = iR (diatomic gas), (16-24)
§16-6 ADIABATIC PROCESSES 311

and the ratio of the specific heats l' is

l' = i- (diatomic gas). (16-25)

These results are in rather remarkable agreement with experiment, as

shown in Table 16-1.
TABLE 16-1 THE MOLAR HEAT CAPACITY AT CONSTANT VOLUME,
AND THE RATIO OF SPECIFIC HEATS FOR SEVERAL GASES

Atoms per Cv* l'

Gas
Molecule Theory Experiment Theory Experiment
Argon 1 2.98 2.98 1.67 1.67
Helium 1 2.98 2.98 1.67 1.66
Oxygen 2 4.97 5.04 1.40 1.40
Nitrogen 2 4.97 4.93 1.40 1.40
Carbon monoxide 2 4.97 4.94 1.40 1.40

* The units of Cv are given as calories per mole per degree centigrade.

At high temperatures the classical theory of the specific heats of gases

is no longer adequate to describe the experimental determinations. Addi-
tional rotational and vibrational modes are excited at high temperatures
in a manner which is best described by the quantum theory of specific
heats; this is beyond the scope of this book.

16-6 Adiabatic Processes

An adiabatic process is one in which no heat enters or leaves the system.
In the form of an equation
flQ = O.
If we apply the first law of thermodynamics, m the form of Equation
(16-17), to adiabatic processes, we find
flQ = 0 = C v flT + P flV.
flV
Thus flT = -p--.
Cv
The general gas law describes the behavior of a gas under all circumstances.
Thus for a mole of gas we have
PV = RT.
If P, V, and T are permitted small variations, we find, on taking differ-
entials, that
P fl V + V flP = R flT.
312 KINETIC THEORY OF GASES §16-6

If we replace the gas constant R by

R = Cp - Cy

from Equation (16-19), and substitute the value of t:,.T into the above
equation, we find
Pt:,.V
P t:,.V + V t:,.P = -(C p - C y ) - - = -("I - 1) P t:,.V,
Cy
for, from Equation (16-22), "I = CpjC y . On transposing, and dividing
the above equation by the product PV, we find
t:,.P t:,.V
p+'Y y = O.

In the limit of small increments we may replace t:,. by d, and integrate to

find
In P + "I In V = constant,
or PV'Y = constant. (16-26)

The value of the constant is determined by the quantity of gas present, so

that Equation (16-26) may be used to describe the relationship between
the pressure and the volume of any quantity of gas undergoing an adiabatic
change. If a gas originally at pressure PI, volume VI, and temperature T I
is compressed adiabatically, as in an insulated cylinder, to a new pressure
P z , the new volume of the gas V z may be found from Equation (16-26) by
writing
(16-27)

The final temperature of the gas T z may then be obtained from the gas law
PI VI PzV z
--=--,
TI Tz
in which all quantities except T z are now known.
Illustrative Example. A mass of gas occupies a volume of 8 liters at a pres-
0
sure of 1 atm and a temperature of 300 abs. It is compressed adiabatically to
a volume of 2 liters. Determine (a) the final pressure and (b) the final temperature,
assuming it to be an ideal gas whose value of "I = 1.5.
(a) The final pressure of the gas can be determined with the aid of Equation
(10-27) thus,

so that

from which
§16-7 'l'HE MAXWELL DISTRIBUTION FUNCTION 313

(b) The final temperature can be found with the aid of the general gas law
thus,
T2 = Tl P 2V2 ,
PlV l
0 b 8 atm X 21
so that T2 = 300 a s ,
1 atm X 81
or T2 = 600 0 abs.

16-7 The Maxwell Distribution Function

In Section 16-3 we showed how the properties of a gas could be accounted

for on the basis of a very simple set of hypotheses about the nature of a
gas. We assumed that the gas was made up of many molecules in rapid
motion, and that the molecules were sufficiently far apart so that the forces

3
Speed
Fig. 16-5 The Maxwellian distribution of molecular speeds. Relative numbers of
molecules having speeds in a unit speed interval at various speeds are shown as ordinate,
while speeds in units of the most probable speed are shown as abscissa.

that one molecule exerted on another were of minor importance and could
be neglected. We assumed that the molecules were perfectly elastic so
that there was no loss in mechanical energy in collisions between molecules
of the gas and the walls of the container. On the basis of such arguments,
we could account for the gas law, and we were able to show that the tem-
perature of a gas was directly related to the average value of the kinetic
energy of its molecules.
When a gas is in equilibrium at an absolute temperature T, the dis-
tribution of velocities of the molecules of the gas is given by Figure 16-5,
called the Maxwellian distribution, according to the theory first developed
by Maxwell (1831-1879). This theory has now been well verified by experi-
ment as actually describing the behavior of gas molecules. In fact, the
Maxwellian distribution may be taken as the meaning of the temperature
314 KINETIC THEORY OF GASES §16-7

of a gas, for, if a collection of gas molecules has a velocity distribution

which differs from Figure 16-5, then we may say that the gas has not yet
reached thermal equilibrium and therefore does not have a well-defined
temperature.
The average of the velocity components of the molecules of a gas in
a particular direction must be zero. If this were not so, the gas and its
container would be in translational motion. However, the average value
of the squares of the molecular velocities is not zero, and is given by Equa-
tion (16-11). From Figure 16-5 we see that molecules whose speeds are
more than three times the most probable speed are extremely rare. Never-
theless, there are some molecules in the gas which have very large speeds,
for the distribution curve approaches the horizontal axis asymptotically.
We must also note that, at a given temperature, the molecules of a gas of
low molecular weight are in more rapid motion than the molecules of a gas
of high molecular weight. This has the interesting consequence that
hydrogen and helium are steadily diffusing out of the earth's atmosphere,
for, at the temperature of the outer air, some of these lighter molecules are
moving sufficiently rapidly to attain the escape velocity of 11 km/sec
necessary for a projectile to escape the gravitational pull of the earth.
If we call the energy required to disrupt a chemical molecule its binding
energy, we see that, as the temperature of a gas is raised, a greater propor-
tion of gas molecules may have kinetic energies greater than the binding
energy, so that a molecule may be decomposed as a result of energy transfer
during a collision. Thus molecules which are stable at ordinary tempera-
tures must have binding energies which are large compared to the mean
kinetic energy of a molecule at room temperature, as given by Equation
(16-11).
It is interesting that modern theories of the structure of atoms and
molecules have provided a justification of a basic assumption of the kinetic
theory of gases. According to the quantum theory, molecules exist only in
certain quantum states, each having a fixed amount of energy. These are
sometimes called energy levels. The molecule normally exists in its state
of lowest energy, called its ground state, and can only absorb energy in a
collision with another molecule in exactly the right amount to raise it to a
state of higher energy, called an excited state, or to disrupt it completely.
In general, it is very unlikely that the colliding molecules will have just the
right amount of energy for excitation, so that the collisions between the
molecules of a gas result in no absorption of energy by the molecules. The
kinetic energy is conserved in the collision rather than being transferred
to internal excitation energy of one molecule. The collisions are therefore
perfectly elastic.
 PROBLEMS 315

Problems
16-1. A closed vessel contains dry air at 25°C and 76 cm of mercury pressure.
Its temperature is raised to 100°C. Determine the pressure of the air, neglecting
the change in volume of the container.
16-2. A mass of oxygen occupies a volume of 1 liter at a pressure of 76 cm
of mercury when its temperature is 40°C. The gas is allowed to expand until its
volume is 1.5 liters and its pressure is 80 cm of mercury. (a) Determine its final
temperature. (b) Determine the number of moles of oxygen in the system.
16-3. Derive the general gas law from Equations (16-1) to (16-3) by con-
sidering that the gas is taken from TiP i Vi by a constant-volume process to
T 2Pf Vi, and thence by a constant-pressure process to TfPf Vf'
16-4. A certain gas has a density of 0.001 gm/cm 3 when its temperature is
50°C and its pressure is 4 atm. What pressure will be needed to change the
density of the gas to 0.002 gm/cm 3 when its temperature is 100°C?
16-5. An automobile tire has a volume of 1,000 in. 3 and contains air at a
gauge pressure of 24 Ib/in. 2 when the temperature is ODC. ,"Vhat will be the
gauge pressure of the air in the tires when its temperature rises to 27 DC and its
volume increases to 1,020 in. 3 ?
16-6. Determine the pressure of 4.032 gm of hydrogen which occupies a
volume of 16.8 liters at a temperature of O°C. The molecular weight of-hydrogen
is 2.016.
16-7. Determine the average value of the kinetic energy of the molecules
of a gas (a) at ODC and (b) at 100°C.
16-8. (a) What is the mass of a hydrogen molecule? (b) Determine the
average velocity of a molecule of hydrogen at 27 DC.
16-9. The molecules of a certain gas have a mass of 5 X 10-24 gm. What
is the number of molecules per cubic centimeter of this gas when its pressure is
10 6 dynes/cm 2 and its temperature is 27 DC?
16-10. Calculate the work done in compressing one mole of oxygen from a
volume of 22.4 liters at ODC and 1 atm pressure to 16.8 liters at the same tem-
perature.
16-11. A cylinder contains a mole of hydrogen at ODC and 76 cm of mercury
pressure. Calculate the amount of heat required to raise the temperature of this
hydrogen to 50 DC (a) keeping the pressure constant, and (b) keeping the volume
constant. (c) What is the volume of the hydrogen when at ODC?
16-12. A cylinder contains 32 gm of oxygen at ODC and 76 cm of mercury
pressure. Calculate the amount of heat required to raise the temperature of this
mass of oxygen to 80DC (a) keeping the pressure constant and (b) keeping the
volume constant. (c) How much mechanical work is done by the oxygen in
each case?
16-13. A mass of a monatomic gas occupies a volume of 400 cm 3 at a tem-
perature of l7°C and a pressure of 76 cm of mercury. The gas is compressed
adiabatically until its pressure is 90 cm of mercury. Determine (a) the final
volume of the gas and (b) the final temperature of the gas.
16-14. A mass of a diatomic gas occupies a volume of 6 liters at a temperature
316 KINETIC THEORY OF GASES

of 27°C and 75 cm of mercury pressure. The gas expands adiabatically until its
volume is 8 liters. What is the final temperature of the gas?
16-15. A mole of gas at atmospheric pressure and O°C is compressed iso-
thermally until its pressure is 2 atm. How much mechanical work is done on
the gas during this operation?
16-16. Ten grams of oxygen are heated at constant atmospheric pressure
from 27°C to 127°C. (a) How much heat is delivered to the oxygen? (b) What
fraction of the heat is used to raise the internal energy of the oxygen?
16-17. An air bubble of volume 20 cm 3 is at the bottom of a lake 40 m deep
where the temperature is 4°C. The bubble rises to the surface where the temper-
ature is 20°C. Assuming that the temperature of the bubble is the same as
that of the surrounding water, what is its volume just as it reaches the surface?
16-18. An ideal gas for which l' = 1.5 is enclosed in a cylinder of volume
1 m 3 under a pressure of 3 atm. The gas is expanded adiabatically to a pressure
of 1 atm. Find (a) the final volume and (b) the final temperature of the gas if
its initial temperature was 20°C.
16-19. A mass of 1.3 kg of oxygen of molecular weight 32 is enclosed in a
cylinder of volume 1 m 3 at a pressure of 10 5 nt/m 2 and a temperature of 20°C.
From these data find the universal gas constant R assuming oxygen to be an
ideal gas.
16-20. A gas of mass m and molecular weight M undergoes an isothermal
expansion from an initial pressure PI and volume V I to a final pressure P 2 and
volume V 2 while at temperature T. Find (a) the work done by the gas in this
expansion, (b) the heat flow to the gas, and (c) the change in internal energy of
the gas in terms of these symbols.
16-21. A piece of putty is placed in a vise with insulating jaws. A constant
force of 100 nt is applied through a distance of 2 cm. The putty is found not to
have its volume changed in this process. What is the change in the internal
energy of the putty?
16-22. Prove that TV'Y- I = constant for an adiabatic process.
16-23. Show that the work done by a gas in an adiabatic expansion from
initial conditions Pi, Vi to final conditions P 1> V f is given by

}f' = Pi Vi (V}-'Y _ V~-'Y).

1 - l'