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$3 An introduction to
the kinetic theory
or gases
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AN INTRODUCTION TO
THE KINETIC THEORY
OF G-ASES
CAMBRIDGE
UNIVERSITY PRESS
LONDON: BE1TTLEY HOUSE
NEW YORK, TORONTO, BOMBAY
CALCTJTTA, MADRAS: MACMILLAN
TOKYO: MABTJZB1T COMPANY LTD
A.II rights
reserved
AN INTKODUCTIQN
THE KINETIC THE;QBY
OF GASES
"
:
v :v
'
BY
SIR
JAMES JEANS
O.M., F.R.S.
>- j
PREFACE
I have intended that the present book shall provide such know
ledge of the Kinetic Theory as is required by the average serious
rigorous general proofs. This does not mean that many subjects
will not be found treated in the same way
and often in the
same words in the two books I have tried to retain all that
was of physical interest in the old book, while discarding much
of which the interest was mainly mathematical.
It is a pleasure to thank Professor E. N. da C. Andrade for
reading my proofs, and suggesting many improvements which
;
indebted to
my
all
old book,
ments.
J.
DORKING
June 1940
H.
JEANS
CONTENTS
Chap.
II.
Introduction
page
A Preliminary Survey
17
*'
III.
Pressure in a Gas
51
Law
103
131
VI. Viscosity
VII.
156
Conduction of Heat
185
VIII. Diffusion
198
X. General
Statistical
dynamics
XI. Calorimetry and Molecular Structure
App.
I.
Law
275
of Distribution
of Velocities
II.
225
The ^-theorem
III.
296
297
299
301
305
306
Index of Subjects
307
Index of Names
309
Chapter I
INTRODUCTION
The Origins
As soon
of
the,
Theory
man began to
as
and philosophies.
water,
fire.
air, fire and water were not transformable one into the
but constituted four distinct unalterable " elements ", and
that all material substances were composed of these four elements
mixed in 'varying proportions a sort of dim anticipation of
modern chemical theory. At a somewhat later date, Leucippus
and Democritus maintained that matter consisted of minute hard
that earth,
other,
particles
moving
there were as
substances.
as separate units in
many
INTRODUCTION
each other, so that they roll over and over like small globes;
on the other hand, the atoms of iron, being rough, jagged and
uneven, cling together to form a solid body. The "atoms" of
the Greeks corresponded of course to the molecules of modern
chemistry.
Similar views were advocated
rejected
by
Aristotle.
In a later age
when
large,
we have
INTRODUCTION
Twenty years
after Gassendi,
He
basis.
Newton accepted
1 856) ,
(
50, below.
t Opticks, Query 31 (this did not appear until the second edition of
the Opticks, 1718).
J Daniel Bernoulli, Hydrodynamica, Argentoria, 1738: Sectio decima,
"De afifectionibus atque motibus nuidorura elasticorum, praecipue
autem
aeris."
Annals
**
Poggendorff's Annalen.
INTRODUCTION
The Three
States of Matter
states,
It
is
may
how
arise.
particles.
and the
the forces of
pieces, another set of forces comes into play
cohesion. These also indicate the existence of forces between
individual particles, but the force between two particles is no
longer one of repulsion; it is now one of attraction. The fact that
INTRODUCTION
and
papers.
INTRODUCTION
is
The Liquid
sufficient length of time, can cause the mass to change its shape;
does this by taking advantage time after time, as opportunity
it
still
more heat
is
liquid.
INTRODUCTION
'
moved
very small solid particles as, for instance, of gamboge pr lycopodium are placed in suspension in a liquid, these particles are
set into motion as the moving molecules of the liquid collide with
them and
hit
direction
Robert Brown.
For, in 1 828 Brown had suspended grains of pollen in water, and
examined the mixture through a microscope. He found that the
to all
pollen grains were engaged in an agitated dance, which was
first thought was
His
interminable.
and
continuous
appearances
that he had found evidence of some vital property in the pollen,
* See in
particular,
INTRODUCTION
but he soon found that any small particles, no matter how nonvital, executed similar dances. The true explanation, that the
particles were acting merely as indicators of the molecular motion
of the liquid in which they were immersed, was given by Delsaux
in 1877 and again by Gouy in 1888. A full mathematical
theory of the movements was developed by Einstein and von
Smoluchowski about 1905.*
In 1909 Perrin suspended particles of gamboge in a liquid
of slightly lower density, and found that the heavy particles
did not sink to the bottom of the lighter liquid; they were pre
vented from doing so by their own Brownian movements. If the
liquid had been infinitely fine-grained, with molecules of in
finitesimal size
as
solid particle
its
180, below.
INTRODUCTION
If the liquid is contained in a closed vessel, each escaping mole
cule must in time strike the side or top of the vessel; its path is
diverted, and it may fall back again into the liquid after a
certain number of impacts. In time a state may be reached such
now
picture of a gas
may be
the gas.
*
10
INTRODUCTION
Recently E. Kappler* constructed a highly sensitive torsionbalance, in which the swinging arm was free to oscillate in an
almost perfect vacuum. The swinging arm had a moment of
momentum of 0-235 millionth of a gm. cm. 2 and when it swung
in a gas at pressure of only a few hundreds of a millimetre of
mercury, its period of oscillation was about 15 seconds. When the
oscillations were recorded on a moving photographic film, it was
seen that they did not proceed with perfect regularity. The speed
of motion of the arm experienced abrupt changes, and, as we
shall see later (p. 129), there can be no doubt
that these were caused by the impacts of
,
is
to be found
performed by
Dunoyer.f He divided a cylindrical tube into
three compartments by means of two parti
tions perpendicular to the axis of the tube,
these partitions being pierced in their centres
and form a deposit there, but a few escape through the hole in the
first partition, and travel through the second compartment of the
tube. These molecules do not collide with one another, since their
paths all radiate from a point the small hole through which they
and Le Badium, 8
INTBODTJCTIOK
11
is
elaborate
technique
known
as
"molecular
which a
solid
substance can
be partly
illustrations.
At
collisions
momentum and
They
a measure of the
IKTBODTJCTION
12
cule as a spherical
make
billiard ball.
its success;
is
'
dimensions.
are to be represented
by
billiard balls, let us represent the vessel in which the gas is con
tained by a large billiard -t^ble. The walls of the vessel will of
r
forces
condition of matter in
its
supposed
gaseous state. Each ball will be con-
fe
INTRODUCTION
13
tinually colliding with the other balls, as well as with the cushions
of the table. The velocities of the balls will be of the most varying
kinds; a ball may be brought absolutely to rest at one instant,
lisions, it
shall, in
initially against
infiTritftginifl.il
how
size; if
way
is
later
14
we
INTRODUCTION
to discuss how far the
shall have
theoretical law con
the
necting
pressure and density in a gas constituted of molecules
of finite size is in agreement with that found by experiment for an
actual gas.
Let us imagine the speed of each ball suddenly to be doubled.
stage,
is
INTRODUCTION
15
equally distributed over the whole of the table, and the average
velocities of the balls of the two colours will be the same. Here we
slow -moving
balls.
Let the space between the sloping barrier and the opposite
cushion of the table be filled with balls moving at all
possible
speeds to represent the molecules of a liquid. A ball which runs
against the sloping face of the barrier with sufficient speed to get
over the top will represent a molecule which is lost to the liquid
by evaporation. The total mass of the liquid is continually
diminishing in this way; at the same time, since only the quickescape, the average kinetic energy of the
molecules which remain in the liquid is continually being lowered.
moving molecules
ating machinery.
7. One further question must be considered. No matter how
elastic the billiard balls and table may be, the motion cannot
its
and
The
INTRODUCTION
16
The
most
and
by
this
many
Chapter II
A PRELIMINARY SURVEY
The Pressure in a Gas
8. The present chapter will contain a preliminary discussion
of some of the principal problems of the kinetic theory. We shall
not go into great detail, or strive after great mathematical
accuracy or rigour this is reserved for the more intensive dis
cussions of later chapters. Our immediate object is merely to make
the reader familiar with the main concepts of the theory, and to
give him a rapid bird's-eye view of the subject, so as to ensure
his not losing his bearings in
the more complete discussions
which come
later.
The main
drama of the
actors in the
kinetic theory
To begin with
the
very
Fig. 3
We
in
fig. 3.
JKT
A PRELIMINARY SURVEY
18
We
first cell,
extend the
Then it
of unit time,
Fig.
perpendicular to
Ox must be
,
cA
2mcA x -=I
A PRELIMINARY SURVEY
19
faces, of total
amounts
22
and
r-
Thus the
all
masses
m m 2 mz
l9
. . .
is
c i> C 2 , ca
- - *
2
...... (1)
.).
P =
("&!
- --
2 x kinetic energy
1
x volume
...... (2)
'
v
and see that the pressure is equal to two-thirds of the kinetic energy
per unit volume.
Since kinetic energies are additive, pressures must also be
additive. Thus the pressure exerted by a mixture of gases is the
sum of the pressures exerted by the constituents of the mixture,
separately. This is Dalton's law.
If the volume of the vessel is allowed to change, while the
molecules and their energy of motion are kept the same, we see
that the pressure varies inversely as the volume. This is Boyle's law.
A PRELIMINARY SURVEY
20
2
average value of c throughout the gas,
the average being taken by mass, we have
If we write
(7
for the
m a + m 2 -h
while
. . .
= pv,
where v is the volume and p the density of the gas. From equation
(2)
the pressure
is
now given by
...... (3)
so that
<7
...... (4)
With
this formula
in
we can
any
room temperature and
it affect
(2),
since energy
is
conserved at a
collision.
The answer is, of course, that after a short time either the molecule
boundary or else, through the medium of
communicate its high energy to other molecules
A PRELIMINARY STJBVEY
which
boundary
in
21
that formula
same angle, and with the same speed, at which they met
The assumption was introduced solely for the sake of
simplicity, and is probably not true (see 34, below). But it is in
no way essential to the proof. All that is necessary is that the
at the
this wall.
molecules should, on the average, leave the walls with energy equal
to that with which they arrive. The aggregate of the impacts
which the molecules exert on the walls before they are brought
to rest is then given by half of expression (1); the other half
represents the impacts which the walls exert on the molecules
to restore their motion. Then the total pressure is as before.
Even the supposition that the average energy of a molecule is
lision.
But
it
points the
way
Equipartition of Energy
of the walls.
A PRELIMINARY SURVEY
22
f
,
f
.
Since the impact occurs along the axis Ox, the components of
so that we may
velocity parallel to Oy and Oz are unaltered,
Wall
Gas
Fig. 5
The equations
of energy
forms
or,
by a
slight transposition,
m(u* -u*)
m(u
From
these equations
sponding
sides,
u)
we
= - m'(u' 2 - u' 2
= m'(u' u').
u'
...... (5)
...... (6)
u+u =
or
),
u=
u'
+ u'
...... (7)
(u
u),
by
(m
m')u + %m'u',
...... (8)
......
(9)
23
A PRELIMINARY SURVEY
that of
the molecule of the gas, this collision results in the wall gaining
energy of amount
m(u-u)
2mm'
(u + u)
,
,
f
(m'u
2mm
-,
4-
mu)
t
f
(u
- u)
\
'
i[(mV-M) + (- !')']
When
collision
zero,
2mm/--
(mV 2 - mu2
(m + m
2
where muz denotes the mean value of mu
-
775;
z,
),
and so on.
in temperature if
rises
so
and
Thus
2
the
than
is
average value of
the average value of
greater
2
the
and
vessel
gas have the same
mu and conversely. If the
loses
nor
energy on the
the vessel neither gains
,
mV
temperature,
average, so that
we have
_ =_
mV
......
(10)
11 Suppose next that two kinds of gas are mixed in the vessel,
second
the mass and velocity-components of the molecules of the
that
farther
and
suppose
kind being denoted by m", u", v", ?",
itself.
vessel
the
as
both kinds of gas are at the same temperature
Then there is no loss or gain of energy to the vessel through col
of equation
lisions with either kind of molecule, so that, in place
.
(10),
we must have
_
___
mV
'
we
also
and
have
m V' 2 - mu* = m V
mV
moving
= m'w' 2 =
2.
.....
(U)
A PRELIMINARY
24
Equation
(11) gives at
SURVEY
(13)
Thus when two gases are mixed at the same temperature, the
average kinetic energy of their molecules is the same. The less
massive molecules must move, on the average, faster than the
more massive, the difference of speed being such as to make the
average kinetic energy the same in the two cases. This is a special
case of a much wider theorem known as the equipartition of
energy. The general theorem is of very wide application, de
pending as it does only on the general laws of dynamics. (See
211 below.)
An
illustration, of
Brownian movements.
particles of freshly-burned
size
makes
Yet even
motion resulting from a succession of free paths, each of which
is performed with this velocity on the average.
Another illustration of the same dynamical principle can be
found in astronomy, being provided by the motion of the stars in
space. The stars move with very different speeds, but there is
found to be a correlation between their speeds and masses, the
lighter stars moving the faster, and this correlation is such that
the average kinetic energy of stars of any specified mass is
(with certain limitations) equal to that of the stars of any other
mass. Here, as so often in astronomy, the stars may be treated as
molecules of a gas, and the facts just stated seem to shew that the
stars
* Proc.
all
PRELIMINARY SURVEY
25
We
must
define temperature.
may
so far be
merely defines
by successive alge
and so as
Macmillan
26
A PRELIMINARY SURVEY
return to
its original
value.
Thus
we
must have
make
we
T=f(6).
The
scale.
is
way
is
known
as the
"
absolute"
and
particular substance.
On
is equal to 100
degrees. To
"absolute" scale is related to a
entropy
is
defined
by
W. Thomson,
Edinburgh (1854).
average
Soc.
A PRELIMINARY
SURVEY
27
Now
face increases
added to
dQ = NdE+pdv.
On
becomes
found for
""
2 AT 72
(14)
in equation
(2),
this
-dv.
.(15)
'6V
given by
a^dQ = **
is
rp
Since
S depends
only on
as
We
%NE
JTI
E and v, we have
N dS 2NE
=
dEdv
either
by
differentiating dS/dv
v.
A PRELIMINARY SURVEY
28
This shews that E/T must be a constant, and gives us our first
insight into the physical meaning of absolute temperature we
see that it is simply proportional to the average kinetic energy
of motion of a molecule. We may in fact write
;
where
is
a constant which
is
constant.
for
We
(17)
rm
mu 2 = mv 2 = mw 2 = RT.
......
(18)
The Gas-laws
13.
With
these relations
we can
- --
(2),
2NE
the total
NRT
If the
molecules consist of N-l molecules of one kind,
a second kind, and so on, so that
= Ni + 2 + .,., we have
of
A PRELIMINARY SURVEY
29
further that
when p
-273-2C.
At
(20)
E=
this temperature,
from
is
this zero-point.
we warm up
NRT
N correspondingly
it;
as
more energy
to each.
A PRELIMINARY SURVEY
30
14.
Formula
(19),
namely
pv
shews that
the
= NRT,
This
is
posed by
specified volume,
all gases,
and so
is
inde
commonly known
that gases
portions which are measured
by the
numbers.
Without tib.e kinetic theory to help us, it would have been rather
if a gas had specially massive molecules, the
of
one atmosphere would be produced by a
standard pressure
smaller number of molecules than in a gas with light molecules.
The kinetic theory shews that at any specified temperature
massive molecules move more slowly than light ones, so that in
actual fact the pressure exerted per molecule is the same for all,
namely RTjv. Thus the number of molecules per c.c. needed to
natural to think that,
commonly known
as Avogadro's
number and
will
be denoted
A PBELIMINABY StTBVEY
31
phenomena.
When
consumed, this
==
to an accuracy of within 1 part in 1 000.* Thus the abovementioned 9648-9 electromagnetic units are equal to
3
The
ber of molecules
N
This
is
it
contains
is
accordingly
0-00008987 x 2-987 x 10 23
Loschmidt's number.
N^ can
be made from observations on the Brownian movements in the
way already explained. Pen-in, who first developed the method,
obtained values uniformly larger than those given above. Later
16. Another, although far less exact, determination of
Birge, Nature, 137 (1926), p. 187; Phys. Rev. 241 (1937), p. 241;
Reports on Progress in Physics, 4, Physical Society
(1938), p. 216; Nature, 23 July 1938, p. 159.
H. R. Robinson,
A PRELIMINARY SURVEY
32
R=
1-36 x 10~ 16
we can deduce
2-67 x 10 19
Combining
as the value
agreement between
17.
whence we can
xlO 3
3-34
xlO 19
allowed to evaporate
it every second, the
time required for the whole drop to evaporate will be 3-34 x 10 13
seconds, which is more than a million years.
Again, a man is known to breathe out about 400 c.c. of air at
each breath, so that a single breath of air must contain about
10 22 molecules. The whole atmosphere of the earth consists of
about 10 44 molecules. Thus one molecule bears the same relation
to a breath of air as the latter does to the whole
atmosphere of the
is
Ann.
PKELIMINABY SURVEY
33
(2-685
centimetres apart.
Molecular Masses
As there are 2
987
The
Specific Heats of a
Gas
As we have
20.
gas;
it
may be measured
Equation
namely
dQ = NdE + pdv,
(23)
tells
JKT
A PRELIMINARY SURVEY
34
(2)
is
open to
dv
The specific heat at constant volume, OV9 which is the heat r^quired to raise unit mass of the gas through a temperature change
of 1 C., is given by
-*Q
r"~
dT'
Cv =
or again
by
N
Nm
N dE
...
where
so that if
Gv
is
measured in heat-units,
its
value
is
is
given by
pv = NET,
so that
when
entiation
the pressure
is
,
differ-
A PRELIMINARY SURVEY
and equation
(20)
dQ =
whence the
heat-units,
specific
is
NdS + NRdT,
given by
difference
and
Cp measured
,
in
r = idQ =
The
35
fdS
given by
be
7?
......
yY =
Cv
^ i + _l_.
(26)
...... (27)
dEjdT
is fRT,
If the molecules are hard elastic spheres, the value of
and the value of Op /Gv becomes If.
Relation (26) is obeyed by most gases throughout a substantial
range of physical conditions (Carnot's law). Also the ratio of
E is
now given by
we
find
3-2
A PRELIMINARY SURVEY
36
in which
/?
Cp
The relation
which
(27)
is
Gv =
still
jD
-=
we have
(30)
proper place.
Maxwell's
So
22.
kinetic
Law
far
many
problems,
it is
necessary to
know how
the velocities of
it
moves from point to point under the forces of gravity or the other
permanent field of force, and will also change discontinuously
each time it collides with another molecule.
Let us now fix our attention on a small group of molecules
which occupies a small volume of space dxdydz, defined by the
A PRELIMINARY
SURVEY
37
condition that the ^-coordinate lies within the small range from
xtox + dx, while the y- and ^-coordinates lie within similar ranges
z to z
+ dz. We
selves with all the molecules inside the small element of volume,
du dv dw dx dy dz.
It
is
unit
"density", which specifies the number of molecules per
range lying within the range in question. This factor naturally
on the particular values of x y, z and of u, v, w. Let us
depends
suppose that, whatever these values
are, it is
f(u,v,w,x,y,z),
so that the
tion
number
is
(31)
f(u,v,w,x,y,z)dudvdwdxdydz.
and
x',y',z',u',v',w'
respectively.
and
where X, Y,
'
u'
molecule at x y,
}
= x + udt,etc.
= u + Xdt, etc.,
z.
(32)
......
(33)
mass on a
38
PRELIMINARY SURVEY
......
f(u',v',w',x ,y',z'}du'dv'dw'dx'dy'dz',
(34)
',
',
is
differentials in
we must
= f(u', v
f
,
which we
is
clearly
then
f(u,v,w,x,y,z)~E
a solution of equation (35). A more general solution
f(u,v,w,x,y,z)
where &(E)
square or
molecule,
<l>(E),
(36)
is
......
(37)
is
its
is
......
given by
E=
where % is the potential energy of a molecule in the field of force,
so that the forces acting on the molecule are given by
SURVEY
A PRELIMINARY
39
We
now found that if the law of distribution
given by equation (37), where
represents any function
whatever, the distribution of velocities will not be altered by
the natural motion of the gas, so long as no collisions take
is
place.
As we
189),
collisions
equation
(3)
or (19), namely
pRT
If the gas
is
variations in this pressure hold the gas at rest against the forces
exerted by the external field. As we have supposed these forces
or, inserting
m
*
<->
ex
___
m ox
/->
cuo,
edn.),
A PRELIMINARY SURVEY
40
common integral,
well
known
in hydrodynamical theory,
ETlogp =
X+a
constant,
or
p=
where
Be~xIRT
......
(39)
B is a constant.
equation.
/ expresses
= A Be
is
RT
The two
x,y
z)
B and e~2^
A PRELIMINARY
SURVEY
41
which
is
we know that
pro-
42
PRELIMINARY SURVEY
jectiles
is
velocities of
below),
and
is
found to be
3
=--
2hm
or 3
R
m T: In
a similar way.
J the
found to be -
two gases
2
.
C, so
that
O= l-086c
A PRELIMINARY SURVEY
43
',
u
this second
law
Vm ,u
/
etc.,
As a
so that the average molecular energy is the same in the two gases,
the result already obtained in 11.
i.e.
successive collisions.
Let us
call
fix
. . . .
. . .
may
think of
it
as pushing its
is TTVCT*.
enclose the centre of one of the molecules B, G, Z>,
in
still
...
all
were
If the molecules B, C, D,
space,
standing
. . .
44
A PRELIMINARY SURVEY
it
ex
1
77TCT
This calculation reproduces the essential features of the freepath problem, but is generally in error numerically because it
treats the molecule A as being in motion while all the other
molecules stand still to await its coming. Thus it gives accurately
the free path of a molecule moving with a speed infinitely greater
Fig. 7
PRELIMINARY SURVEY
45
Viscosity
27.
is
of special interest.
Q to P, so that, on balance,
\
.
at this point.
0,
free
path
PQ
with
to Q. If the free
momentum
0.
for
which u
is
positive,
and
as
on the two
sides of this
A PRELIMINARY SURVEY
46
plane.
viscosity.
A
and
if
the
velocities of
streaming
du
-7-5
dz
momentum mu is that
Q by an amount
appropriate to
it is
in
appropriate to
_^,du
= rOCA.
-^
^,du
x mA
-Tdz
dz
each free path had the same projection A' on the axis of z. If
the free paths are distributed equally in all directions in
space and
of average length A, we easily find that the
value
of A'
average
is |A. Inserting this value for A' into the formula
just obtained,
we find that the transfer of momentum is
if
_,
The theory
of viscosity
tells
du
is
du
Tz>
where
TJ
is
(47)
A PRELIMINARY SURVEY-
47
more exact
Conduction of Heat
28.
as
momentum.
8 with energy
may be regarded as transporting energy
If
mean energy at is equal to that at Q,
the
Q.
this transfer of energy will be equalised by another in the opposite
fig.
E from P to
of energy
dE
rfJ
is
dE
ivcA^.
_
-^,dE
vcX-,
or
......
(48)
is
where
vcXdE
*-272T-
......
/crm
(50)
coefficient of viscosity)
fj (the
(the specific heat at constant volume)
77
i-pcA,
J_dJ
JmdT'
A PRELIMINARY SURVEY
48
Using these
relations,
equation (50)
?jCv
......
(51)
this equation
can all
which they satisfy the equation provides a test of the truth of our
the equation is satisfied
theory. We shall see in Chapter vn that
with very fair accuracy; the relatively small discrepancies are
such as can be ascribed to the simplifying assumptions we have
made and to the fact that molecules have more complexity of
structure than our theory has allowed for.
29. Finally, if we regard the moving molecules of a gas as
a theory of gaseous diffusion,
transporters of mass, we arrive at
course.
in
due
which will be discussed
Of the
we have
seen
quantities
how
to calculate
c,
We
A PRELIMINARY SURVEY
49
Molecular Diameters
31. Having estimated the free path from an experimental
determination of the coefficient of viscosity, we may proceed
to estimate the molecular diameter from the relation
We find
(
152) that the diameter of a molecule of air is about
3-75 x 10~ 8 cm., while that of a molecule of hydrogen is only
about 2-72 x 10~ 8 cm.
50
A PRELIMINARY SURVEY
(146 ff.).
Chapter III
PRESSURE IN A GAS
AN IDEAL GAS
32. Leaving our general survey, we now turn to a more de
tailed study of various special problems. The present chapter will
CALCULATION OF PRESSURE
isr
that
>-'
move
Fig. 9
PRESSURE
52
I3ST
A GAS
This cylinder has dS for its base, and its height is u^dt, where u
the velocity of molecules of the first shower in the direction
normal to dS, which we shall take to be the axis of x. Thus the
volume of the cylinder is u^dtdS, and the number of molecules
of the first shower inside it is v^u^dtdS.
Each of these molecules brings to dS momentum mu^ in a
direction normal to the boundary. Thus in time dt the whole
shower brings momentum mv^u^dtdS, ,and all the showers
is
is
positive.
The pressure between the boundary and the gas first reduces
this x -momentum to zero, and then creates new momentum in
the opposite direction (u negative).
The pressure which, acting steadily for a time dt, will reduce
the original momentum to zero is Zmv^u^dS, where the sum
mation
is
again over
all
is
positive.
momentum
after
pdS = Smv^ldS,
where the summation
(52)
p = mvu 2
As we have seen
==
pu
2
.
(53)
12) that
mu 2
mv 2 =
mw
2 ==
^mC 2 = RT,
(54)
new forms
(55)
PRESSURE IN A GAS
53
p =
(56)
(v + v'+...)RT.
volume v of homogeneous gas contains
molecules in all,
then (v + v'+...)v = N, and equations (55) and (56) may be
combined in the single equivalent equation
If a
pv^NRT.
(57)
in
direc
lg "
the true law, it is easily seen that when molecules are reflected
from a minute area of the inner surface of a sphere, the number
which would strike any area of the sphere would be propor
tional simply to the area. Knudsen has tested this by reflect
ing molecules from a small area of a glass sphere which was
PRESSURE IN A GAS
54
contact with a
solid,
place; the molecule, so to speak, ends one life when it strikes the
boundary and after an interval starts out again on a new existence.
have
PRESSURE IN A GAS
an
55
for
of an ideal gas.
mation which will depend only on the nearness to the truth of the
assumptions just referred to.
In point of fact the laws are found to be true (as they ought
to be) for the osmotic pressure of weak solutions. They are
also true for the pressure exerted by free electrons moving
about in the interstices of a conducting solid, and also for the
"
pressure exerted by the atmosphere" of electrons surrounding
a hot solid. Each of these pressures p may be assumed to be given
by formula (55), where v is the number of free electrons per unit
volume.
...... (58)
C=
C=
1-086 times
c,
PRESSURE IK A GAS
56
0C.
Molecular Velocities at
We
4
oxygen E/m = 259-6 x 10 while the value
24
found, as in 19, to be 53-12 x 10~ grammes. Hence,
of
by
multiplication,
is
This quantity
is
B=
1-379
xlO-16
(60)
whatever at a temperature of
is
P=
absolute
2-068 x 10- 16
(61)
PKESSTJRE
The
1ST
A GAS
57
atom
RT =
Q
where T =
273-2
3-767 x 1C- 14 ,
aTQ =
5-651 x 1C)- 14
C.)
the molecules, just as, for instance, news which is carried by relays
of messengers spreads with a velocity comparable with the mean
rate at which the messengers travel. The propagation of a dis
turbance in the gas is, however, nothing but the passage of a wave
of sound, whence we see that the mean molecular velocity in any
gas must be comparable with the velocity of sound in the same
gas. Actually the velocity of sound a is given by the well-known
hydrodynamical formula
222 below).
becomes
a
If, so
that
...... (62)
shewing the actual relation between the velocity of sound and the
PRESSURE IN A GAS
58
air,
Effusion of Gases
is
nothing
else
tionally.
In
fig.
dS
remained
closed. If each
vcdSdt,
so that the rate of efflux, measured in terms of mass per unit
time per unit area of aperture, would be
mvc=pc.
(63)
Ipc.
efflux is the same as if the whole gas of
out
of the aperture with a uniform velocity Jc.
streamed
density p
PRESSURE IN A GAS
c obtained in
24, we find that
59
the formula
RT
.(64)
shewing that
more
directly
40. In 1846
11).
Efflux of Gases
Ann.
d.
60
PRESSURE
Iltf
A GAS
it is
sion".
plug
PRESSURE IN A GAS
61
from
to
Formula
(64)
The
pA pB
,
is
accordingly given
-
by
...... (66)
by equation
(66).
* Phil. Trans.
170, II (1879), p. 727.
PRESSURE IN A GAS
62
Cohesion of Gases
42.
fig.
B in
gas kept at
temperature TA This gas will flow through the plug or orifice into
the chamber B, and its temperature as it arrives in the chamber
B, say TB could be measured by a thermometer placed in B.
.
Suppose that the molecules of the gas had been held together
by strong forces of cohesion, so that each molecule was attracted
gas, or at least
by those
in its
im
temperature
TB
ments of
gas. Experi
and conducted by
any temperature
change in the gas, shewing that the forces of cohesion in a
gas
were at least small. In the more elaborate
experiments of Joule
and Kelvin, slight faUs of temperature were
observed; for in
stance, in an experiment in which air passed
by transpiration
from a pressure of about four
of one
atmospheres to a
pressure
atmosphere, the change of temperature observed was a fall of
0-9 C. In general it was found that for air
and many of the more
*
The
*6
'
>
PRESSURE IN A GAS
63
another,
this
When the
PRESSURE IN A GAS
Van
We
except
shall face
when
in actual contact.
molecules A,
C, ... in a volume v, and
a* is drawn round the
of
radius
a
that
as
before,
sphere
imagine,
centre of each of these mole
Let there be
cules
(fig. 12).
great
1
the difference .between
and write this total
and
volume in the form f-ZVTrcr 3
We
proceed on the
supposition that this total
volume is only a small frac
tion of the total volume v of
F'
12
the gas. In this case we may
disregard the possibility of two of the spheres of radius cr inter
secting, and so suppose that the space outside the spheres
is of volume v-^Nrror 3 This is, then, the space available for the
centre of molecule A. Thus the chance of finding the centre of
molecule A inside a specified volume dv is nil if this volume lies
inside one of the spheres, and otherwise is
shall
dv
(67)
PHESSTJBE IK A GAS
65
separately of this
1 spheres of radius
element of volume lying within one of the
<r, and of its not so lying.
We can imagine each sphere divided into two hemispheres by a
plane through its centre parallel to dS; we may describe these as
the nearer and farther hemispheres. Each point in the farther
hemisphere is farther from dS than the centre of the sphere, so
that no such point can ever be at a distance less than \& from the
boundary. Since the element of volume is only at a distance Jcr
from the boundary, it can never lie in one of the farther hemi
it.
spheres, but all points in the nearer hemispheres are open to
The total volume of the farther hemispheres is $(N l)7rcr3
1 and N> is
or, again disregarding the difference between
fNTTO-*. Thus the chance of dv lying inside one of the spheres is
,
is
p-fjfrro^
...... (6g)
(67),
Ndv
...... (69)
Ndv
TKT
PRESSURE IN A GAS
b = f Nrr<T*,
66
where
and so
is
all
(70)
with
v,
we may
Ndv
v
b'
We accordingly see that when b/v is small i.e. when the aggre
gate volume of the molecules is small compared with the space
occupied by the gas the effect of the finite size of the molecules
is adequately allowed for by replacing v by v
b, i.e. by re
of
the
the
the
vessel
four
times
volume
total
volume of
by
ducing
p(v-b)
(57),
= NKT.
(71)
may be put
PV = NRT(I+?\,
which
in the
(72)
but this is hardly found to agree better with observation than the
simpler equation (72).
45.
second correction
is
necessitated
by the
forces of
51.
PRESSURE
I IT
A GAS
67
simple pressure p.
Hence equation
(71)
in
the form
or again, replacing p
2
by Nm/v, and putting cN
a,
......(73)
This
as
we
is
mass of
gas,
T. So long
a and b are
5-2
PBESSUBE IN A GAS
68
Van
Equation
is,
as in equation (39),
f
= p e-Mx,
where p
is
boundary p
where
p'
is
given
and x
are
by
of the gas.
* Wied.
Ann. 65
(1898), p. 826
and 69
(1899), p. 685.
PRESSURE IN A GAS
69
Thus the
field
form
NRT e-*IRT
RT
p=
r
^ =
e -a!NRTv
......
(74)
The
There
these
is,
Mag. Aug.
1870.
PRESSURE IN A GAS
70
To
this
we now
turn.
The Virial
of Clausius
etc.,
(75)
d 2z
dx
<fe\n
*) J
where
c,
as before,
is
proceeds,
2
-j- (a;
+ y2 + z2
ct/t
continually
first
(76) disappears,
and we have
= -$Z(xX + yY + zZ).
......
(77)
we see that it is
the molecules.
(2)
(3)
made by
may
all
boundary
PRESSTJBE IK A GAS
71
(3)
it is
through
on
I,
z,
and the
m, n. If p
is
vessel, the
direction-cosines of
forces
exerts
has components
dS
Let
dS
(fig. 13).
Then
If
is
all
points of the
all parts of
made by
surface,
equal to
where v
(77)
is
and
this is
now becomes
),
......
(79)
PRESSURE
72
when
except
in actual contact.
IM"
A GAS
When
lision,
is nil.
make
to
which
is
2
pv = Z|rac
ideal gas.
(79),
which
......
(80)
made up
inside
coordinates x, y, z are
*
all
Principia, Prop,
xxm, theorem
xvni.
PRESSURE IN A GAS
73
We
We next proceed to calculate the contribution of the intermolecular forces to the virial. Let us assume that the force be
tween two molecules is a repulsive force <j)(r), which depends only
on the distance r they are apart. If the centres of the molecules
r
are at x, y, z, x', y', z', and if X, T Z, X', Y Z are the com
ponents of the forces acting on them, then
51.
two
particles
is
xX + x'X' = ^(x-x')*.
r
The contribution
Thus equation
(80)
to
2(xX + yY + zZ)
is
therefore
may be replaced by
pv = P7wc* + JZ2>0(r),
all
...... (81)
pairs of molecules.
\N(N\)
pairs of
cules
PRESSURE IN A GAS
74
and
+ cZr from
^*,
......
(82)
would be
(83)
between
......
(84)
*s
e work which must be done in bringing the two
molecules together from an infinite distance, so that
where x
/*00
X
Making this correction to expression (83), the
of molecules at a distance r apart will be
number of pairs
Multiplying this by
fyr<f>(r)
all
values of
r,
2-77 AT 2 poo
r*<j>(r)
J
or, since
<f>(r)
fl
dv
-~,
CM*
e~^x dr,
......
(85)
FRESStTBE IN A
Replacing %Zmc* by its value
NRT,
75
G-AS
the
equation (81) assumes
form
T}?;
Qp
J.V
-tl/
JL
JL "1
(86)
V
'
(87)
where
B = 2nN rr z (l-e-*h*)dr.
......
we
(88)
Jo
elastic spheres,
53. If the molecules approximate closely to hard
into
come
play when r is very
the forces between molecules only
nearly equal to
cr\
r3
by
cr
in equation (87)
and
find
(72).
is
PRESSURE IN A GAS
76
must
be replaced by
and
independent of the
temperature. Or again this last equation may be written
where
c is
45,
is
NBT(I+l
agreeing with Van der Waals' equation (73) as far as the first
order of small quantities.
is easily evaluated when the repulsive
54. The quantity
force <j)(r) varies as an inverse power of the distance, say
<p (r)
ftr~
so that
We then have
ZStfr)
It follows that
^ r^e-dr
v
Jo
r8 3
_ftriyvafri\A
~
2hv \a-l)
-!/'
where
3
cr is
given by
.(90)
PBBSSUEE IN A GAS
the values of B and a at
77
the general
C.,
T are given by
c-oh
V273:
The evaluation of
for
series
.i ({(*-!)
..
n=l ttl
where u
is
72,- 3}
in contact,
Keesom has
B when
for
B the value
where
1 \
-^Zl-
r(m-l)~3\
/
Leiden, Supp. 24
Amsterdam Akad. 15
(1912), p. 1406.
(1924), p. 463.
% Proc. Roy. Soc. 106
See
149 below,
P&ESSTTRE IN A GAS
78
GAS THERMOMETRY
In spite of
56.
its
stant,
Let us
first
TQ to
T.
Van
tells
us that
...... (92)
...... (93)
By
subtraction
we get
where KP
is
a "pressure-coefficient" given by
NB
or,
from equation
(92),
by
(n
1
ffl
.)=-.
eyZ} ijj
(95)
x
'
PRESSURE IN A GAS
79
Values of KP
gives the following values for the pressureto 100 C. at initial pressure 1000 mm.) of three
Callendar
coefficients (0
Air
0-00367425,
Nitrogen
0-00367466,
Hydrogen
0-00366254,
while for neon and argon, Leduc^f has .found the values:
Neon
Argon
T =
T =
5-47
C. to
T =
29-07 C.,
KP
31-87 C.,
KP
11-95 C. to 2\
=
=
0-003664,
0-003669.
pv = NRT exactly
*
Mem.
denoted by
Phil.
ft*.
Mag.
The
f Pp. 234r-40.
PBESSTJBE IN A GAS
80
gas, a
= 0,
=
so that /o
^
2iiO'*j
and
(93) of
57 are
(97)
is
is
given by
a "volume-coefficient" given
by
NR
On
eliminating
(96),
we
obtain
AU .......
(99)
PRESSURE IN A GAS
This
is
81
more complicated than the formula for the pressuredepends both on the volume and the
pressure.
Values of KV
Further values
will
Evaluation of a and b
59.
From an
pressure-
*
j
E.g.
KT
PRESSURE IN A GAS
82
~ = 0-003660.
while
-*o
At
^ = pQ T
x 0-000013
At
sphere,
v2
0-00260 atmosphere.
Air
0-0026,
Carbon-dioxide
0-0030,
0-00069,
Hydrogen
* Phil.
Mag. 2
Hydrogen
(1901), p. 130.
10-73.
PRESSURE
1ST
A GAS
83
0-00209,
Nitrogen
0-00255,
0-00096.
Hydrogen
Helium
0-000432.
The value
at
of b
is,
determine
<r
2-69 x 10 19
15),
and so
immediately.
The values of
^cr
follows:
ISOTHERMALS
61. One of the most instructive ways of representing the rela
tion between the pressure, volume and temperature of a gas is
by drawing isothermals or graphs shewing the relation between
fi
' '
8.
6-2
PRESSURE IN A GAS
84
For an
pv
To
is
= NET.
(100)
fig.
14.
These are
Fig. 14
Van
63.
Van
(v-b)
= NST.
(101)
is
equation
p(v
- b)=NRT,
(102)
PBESSUEE IK A GAS
85
a/v parallel to the axis of p, we shall obtain the system of isothermals represented by Van der Waals' equation (101).
The isothermals are found to lie as in fig. 15 in which the thick
2
line
is the curve p =
a/v while the line BCD is v = 6.
AB
Fig. 15
lie
we may
v-&) =
const.,
(103)
86
PRESSURE IN A GAS
are seen to be given by
at which dp/dv =
a(v~2b)
p=
V3
-c-
and
The isothermals
AB
by the molecules.
Now V Q
by
is (cf.
equation (70))
pTTrcr
ABGD in fig.
=
0,
two
2-96^.
......
(105)
lines
PEESSTJRE IN A GAS
87
The isothermals
Dieterici's equation
NP
O
Fig. 16
If
we neglect the
PRESSURE
88
1ST
A GAS
=
so that the points at which p has its
values on any isothermal are given by
*
const.,
so that
is
every
....... (106)
Continuity of the Liquid and Gaseous States
66. According to Van der Waals' equation, the temperature
determined by equation (104),
_
T~
has the special property that at all temperatures above this
temperature a decrease of volume is always accompanied by an
increase of pressure, but below it every isothermal contains
stretches in which the pressure and volume decrease together.
yard
it retreats.
The equation of
PRESSURE IN A GAS
Let us
89
is
P PP
liquefy
67.
it.
while
PP
X is
liquid states.
It remains to
vapour
states,
is
positive. If
common
PBESSUBE IN A GAS
90
until the point
condensation sets
in;
some of the substance is in the state Zi but some also is in the state
F. As the ratio of these amounts changes, the representative
point moves along the straight line ZXUY until, by the time the
point Y is reached, the whole of the matter is in the liquid state.
After this the substance, remaining wholly in the liquid state,
moves through the series of changes represented by the path
TQ'N.
There is of course an element of arbitrariness in this, for instead
of describing the path
the substance might equally well
SZUYN
is,
definite
XRY
dynamics that
* Collected
rrff)
\~ =
Works,
0,
where dQ
2, p. 425.
is
f Wied.
Ann. 9
(1880), p. 337.
PBESSUBE IK A GAS
91
the substance in any small part of the cycle and the integral
is
taken round the whole closed path representing the cycle. Since
the temperature is constant throughout the motion, this equation
becomes
dQ =
0,
is nil.
As
in
12, this
and therefore
Fig. 17
68. The figure which is obtained from fig. 16 upon replacing the
curved parts of isothermals such as ZQXB, Y by the straight line
ZXY is represented in fig. 17. This figure ought accordingly to
represent the main features of the observed systems of isothermals
of actual substances.
and 167
(1876), p. 421.
PRESSURE
92
A GAS
The next
lower
isothermal,
corresponding
to
temperature
90
80
As the representative
moves over this range,
70
60
50
spheres.
point
48-1
Fig. 18
The
Critical
more pronounced
Point
P in fig.
16 is generally described
as the "critical point". Just as there are points in England at
which three counties meet, so here is a point where three states
70.
PRESSURE
1ST
A GAS
93
meet the liquid, the vapour and the gaseous. And, because of
this, a substance at the critical point possesses certain remarkable
properties.
pressure
T p
We
is
The last column is of interest from the fact that NB TJpc vc is, on
any theory, a pure number, having no physical dimensions at all.
If Boyle's law still held at the critical point, this number would
of course be equal to unity; we see how far the critical point is
from the regions in which Boyle's law holds.
Actual observations of critical data are recorded in the table
p. 94 overleaf.
These data shew that the properties of different gases vary
widely, and that for most gases neither the equation of Van der
Waals nor that of Dieterici comes particularly near to the truth.
Generally speaking, however, the equation of Dieterici appears
on
94
to
PRESSURE IN A GAS
be more accurate than that of Van der Waals,
particularly for
so that,
NETv
= log
NRT
and
NRT~
According to
sides,
bs
2v
whence we obtain
a
NBT\
pv
NRTv 2\NRT
PRESSURE IN A GAS
If
and
95
we
b,
vloi(NET\
,
Ann.
d. Phys.
(1901), p, 58.
c.c.
per gramme.
PRESSURE IN A GAS
96
(NJRT\
is
all
The
72.
so that
its critical
is
all gases,
t,
p and
t)
are given
by equations
(106)
and on substituting
97
PRESSURE IN A GAS
Tc p
v c in Dieterici's equation,
corresponding "reduced" equation of state is
c,
we
l)
= te^ "^.
......
(109)
Corresponding States
73. If either of these equations could be regarded as absolutely
true for all gases, it appears that when any two of the quantities
are known, the third would also be given, and would be the
same for all gases. In other words, there would be a relation of the
form p =/(t,t)), in which the coefficients in / would be inde
t,
t)
same two as
in the equation of
cohesion-factor.
For
if
a and
and the
Van
between the
be a
five quantities
p, v,
The
in fac t
critical
point
J? =
and -
is
dv z
dv
fixed
by two more
0,
critical
quanti-
T pc and v
ties
c,
as well as a
l>=/(t,i>),
(no)
special equations of
Van
der Waals
and
Dieterici.
in the form
Assuming that the gas-equation can be expressed
and
t) are said
values
same
the
have
oft, J)
(110), two gases which
two
for
states.
to be in "corresponding"
gases to be in
Clearly
J
KT
PRESSURE IN A GAS
98
corresponding states,
quantities
t,
and
i)
it is sufficient
to be the
same
for
for both.
quantity will necessarily also be the same, and this supposed law
called the "Law of Corresponding States". This law will, how
ever, only be true if the reduced equation of state can be put in
the form of equation (110), and this in turn demands that the
is
that
that graphs in which logp, log/? and logT are plotted against
one another will be the same for all gases.
of State of Kamerlingh
Onnes
With
this notation,
Van
K must be
PBESSUEE IN A GAS
99
1-1
JL/^iU
64 1/ 64*1,
bjz\8
64t)
+-4096&I;
(112)
40768&I;
is
where
33,
(,
...
form
--"
an expansion which contains no fewer than twenty -five adjustable
coefficients.
*
Encyc. d. Math. Wissenschaften, 5 (1912), 10, p. 729, or
Lab. Leiden, 11, Supp. 23(1912), p. 115.
Comm. Phys.
7-2
PRESSURE IN A GAS
100
The circumstance
NRTb-a SNRTb*
which is simply Van der Waals' equation adjusted by the inclusion
of Boltzmann's second-order correction (44). It must however
be noticed that the value of Tc for helium is very low, about 5-3
range of temperatures studied by Prof. Kamer
about from t = 10 to t == 70, and for these high
values of t it is inevitable that Van der Waals' equation should in
any case give a good approximation.
abs., so that the
lingh Onnes
is
One of the
Clausius,
best
known
is
that of
namely
PRESSURE IN A GAS
101
the values of a', b and c which are found by Sarrau* to give the
best approximation to the observations of
Amagat:
77.
were
We
true, the
The equation of
constants, a', b
PEESSTJBE IN A GAS
102
and
C. to
0- 184
state,
Chapter IV
LAW
n+
1, 71
+ 2, n+ 1,
n,
n+1,
n,
nl
1,
}
n,
n
n+1,
n,
1,
n,
2,
n1,
104
LAW
is often a statable
properties of the gas vary; a cubic millimetre
volume. The number of molecules contained in an element of this
of the element, will give the mole
kind, divided by the volume
is
if
In such a
sufficiently large, the fluctuations are inappreciable.
think of
we
and
a
as
may
be
treated
case v may
steady quantity,
a
in
volume
unit
specified region
it as the number of molecules per
of the gas.
If each molecule
is
of mass m,
p =
will
and
mv,
it is
The Law
81
of Distribution of Velocities
move
at the
values.
23).
they are distributed according to Maxwell's law
To discuss the velocities of a great number of molecules, let
us take any point as origin, and draw from it a number of separate
both in
lines, each line representing the velocity of one molecule,
of
the
at
The
and
direction.
any such
extremity
point
magnitude
(
components of velocity
of points ob
distribution
The
molecule.
of the corresponding
of
distribution
the
as
the
same
tained in this way is of course
a
at
the molecules would be in space if they all started together
point and each moved for unit time with its actual velocity.
The number of points of which the coordinates lie between the
limits
-t-
LAW
105
v,
w) du dv dw.
u-\-du, v
and
106
vf(u,v,w)dudvdwdxdydz,
where /
(115)
Collisions
when
the
107
u',
respectively.
Any additional velocities the molecules
tions of Oy
u',
collision, since
Fig. 19
there
is
if
the molecules
had
w',
w and u
v',
w'
and
lie
u'
v'
108
We now
components before
collision,
is
So far the collision has been supposed to take place with its line
of impact along the axis of x, the relative velocity being u' u.
In such a case we obtain the velocities after the collision by super
posing the relative velocity along the line of impact (taken with
its appropriate
sign) on to the velocities before impact. Now as
this rule makes no mention of the special direction
(namely Ox)
that we have chosen for the line of impact, it must be of universal
application. So also must the other result we have obtained
that the total spread dudvdwdu' dv f dw of the velocities before
collision is equal to the total
spread after collision.
85. Let us now remove the restriction that the line of
impact is
r
to be in the direction
collision,
define
(i)
is
to be a molecule of
class
lie
(iii)
The
cosines l,m,n,
and
is
to
lie
impact
is
to
have direction-
angle do).
If the molecules
radius
We
da)
2
(iii), thus obtaining an area cr dot, in a direc
tion from the centre of the sphere of direction-cosines I, m, n.
Clearly a collision of type a will occur every time that the centre
of a molecule of class B comes upon this area cr 2 da).
specified in condition
LAW
109
20).
fig.
Fig. 20
its
V<r*eos6do)dt.
into play,
shall
of class
the interval dt
lie
is
(116)
of time
dt.
110
LAW
Each
dt.
(117)
v*f(u,v,w)f(u',v',w')Vcr*cos6dudvdwdu'dv'dw'da}dt
(p. 108).
w and u', v', w' with spreads dudv dw and du' dv' dw'.
dt is
v 2f(u,
2
w') Fcr cos 6 dudv dw du' dv dw' da> dt.
f
v,
w)f(u',
v',
(118)
and formula
(118)
v f(u,
v,
w)f(u',
v',
2
w') Fcr cos 6 du dv
LAW
111
State
number of
collisions of
f(u, v, w)f(u',
If,
v',
v,
w)f(u',
v',
).
then,
f(u, v, w)f(u', v
w') >f(u,
w)f(u v
v,
r
,
w'),
collisions of type
If
r
f(u,v,w)f(u',v',w'}
=f(u,v
w}}(u',v','w
),
(120)
types a and
then
collisions of
log/(^^) + log/(w>W)
(121)
LAW
112
v,
w)
= a1 m(^ 2 + v 2 + w z
) -j-
(122)
or, if
we
still
v,
w)
= a^m^u - U Q )* +(v- v
2
)
Ae-
+ (w- w
(w -w
^\
2
)
-f
a6
......
(123)
i.e.
when
u=u
VQ
w=w
^-^ = U,
v-
WQ
= V,
= W,
113
We may speak
* c
is
W) = ^ e -^(u +vHw^
2
/(U, V,
......
12 4)
V + cZV,
W and W-f dW
is
U=
ooto-j-oo,
V=
oo to
H-
oo
and
W=
oo to -f co,
integral is easily
p, 306), so that
A
I
KT
found to be
114
Any one
of the
to the total
is
2
2
e-^< u2 + v2 + w2 dU dV dW.
%mNA(V* + V +
Summing this over all values of U V, W, we find the total thermal
>
energy of the
N molecules to be
\rnNA
{(
f(U
+ V 2 + W2
e-
GO
integral is easily
found to be
is
is
accordingly
89.
slightly more complex problem arises when the gas
consists of a mixture of molecules of two different kinds. Let us
suppose that the molecules of both kinds are hard smooth spheres
ml3 <rl3 V-L, /x refer to the first kind of molecule, while 2 cr2 v2 /2
refer to the second kind. We proceed as before and obtain, in
place of formula (117),
;
let
cos 6 du dv dw du' dv
dw
da> dt
LAW
115
is
found to be that
Vw') =fi(u,v,w)fi(u'
v' 9 w'),
......
(in
(125)
and we
momentum,
finally
f2 (u, v, w)
=
=
where
To be more precise,
if
(127)
8-2
116
W)
f(l
J\^y
is
VW
\A^
V /
^-to(U 3 +V 2 +W 2) '
7T
0(U)
/I
\*-
\ 7T /
e~hm[J \
oo\
jQ>
is
(129)
there
LAW
we
obtain
all
is
given in
Appendix IV
(p. 301).
Thermal Motions
91.
W of
transformation of coordinates
The law
The
of distribution
direction of U, V,
now assumes
the form
of the
any solid angle is exactly proportional to the magnitude
solid angle. In other words, all directions are equally likely, as
indeed
we
law of
distribution becomes
nAe-hmc2 c*dc.
In
fig.
......
y
while the thick line
is
p-X* ,
Z
(130)
118
LAW
1-0
0-8
0-6
0-4
1-
0-2
0-2
0-4
0-6
1-0
0-
1-2
1-4
-6
1-8
2-0
2-2
2-4
Fig. 21
On
/*o
Jo
and so
is
oo
/
/Jo
represented
by the ordinate
_
(rrhm)*
of x
m
0-5642 in
fig.
21.
Molecules with more than four times this velocity are represented
by the area of that part of the thin curve which lies to the right
of the ordinate x = 2-257, and this is seen to be very small indeed.
Thus it is very rare for any component of molecular velocity to
have as much as four times the average value.
The thick curve exhibits the distribution of o among the mole
cules of the gas and here the maximum ordinate is that of x = 1,
so that the most frequent value of c is I/ (hm)*. The graph shews
119
that values of c which are more than 2 J times the most frequent
value of c are very rare. The average value of c, which we shall
denote by c, is
I /*oo
/*co
=
and
c3
e- n
*dc I
c 2 e-h
dc
U,
1-1284
any
single coordinate
--
2hm
hm
'
so that
0-921(7
and
C=
1-0865.
With C defined
2
molecule
is
We
and
since
Z\J
- TV = TW =
0,
we have
+ V -f v Q 2 +
(
where p
is
W+
by p = mv.
120
vessel,
cular energy
is
An
so as
domain of pure
121
solutions is
naturally to be looked for in the differences of the assumptions
made. The conception of the perfect non-viscous fluid postulated
by hydrodynamics is an abstract ideal which is logically incon
Fig. 22
93, Maxwell's
The marksman tries, in firing each shot, to make both the x and
the y coordinates as small as possible. Subject to certain assump
tions, which we need not discuss here. Gauss shewed that the two
122
efforts
-e-KX *dx,
(131)
7T
where
is
If the
When
fig.
22, the
7T
r, 6, is
7T
If the target
is
becomes
\7T/
which
fig.
is
now
22) the
identical
r, 6,
<f>,
marksman aims
0,
0;
-7=
rr-
is
LAW
123
94.
its
tion
of the curve
is
x--
1-225.
sometimes required to
is
of the mole
cules of a gas have a speed greater than or less than a given speed
c
Out of a total of molecules the number which have a speed
in excess of c
is,
by formula
(130),
~V f
and, on integrating by parts, this becomes
o
AT
,a.V
I
*
\ T7
xj
III
/
Ame2 /7/
/*
o
C
vM/ _i_
T t/
Uco
/*
co
-^-
^KJx
this
e~xZdx,
number becomes
N(erx + -^-xe-**\
where
(hm)*c Q
/5
/>,.\
J- \^
(132)
124
COLLISIONS
A35TD
MAXWELL'S LAW
Law
By putting various
retarding
on the escaping
potentials
* Phil.
t
t
Mag. 16
Ann.
d.
125
The
accuracy.
and
finally
series of
experiments
its
At
lg
heavily coated with silver. Surcontaining a narrow slit S 9
rounding this is a cylindrical drum
and still farther out another concentric drum PP'. The whole
apparatus can be rotated as a rigid body about W.
*
is
*
Phys. Rev. 15 (1925), p. 795.
t Zeitschr.f. Phys. 2 (1920), p. 49; 3 (1920), p. 417,
21 (1920), p. 582.
and Phys.
Zeitschr.
126
COLLISIONS AND
MAXWELL
LAW
Fig. 24
An
would, on each of these occasions, pass through the slit and form
a deposit on the point of the drum opposite to the slit. If, how
ever, the drum rotates so fast that the speed of its surface is com
parable with that of the molecules, the drum has turned through
an appreciable angle before the molecule strikes its farther side,
so that the point of deposition of the molecule is displaced by a
distance which will be inversely proportional to the velocity of
* See Loeb, Kinetic
Theory of Gases (2nd ed. 1934), pp. 132, 136.
COLLISIONS AND
the molecule. If the
MAXWELL
LAW
127
times per second, the speed of its surface is 314 feet per second,
and a molecule which is travelling at 1000 feet per second will
take y^o second to cross the drum. In this interval the surface of
the
drum
will
move
|^| feet or 7| inches,
so that the point of deposition will be displaced this far from the
point opposite the slit. In this way we obtain a sort of velocityspectrum of the speeds of the molecules of the vapour.
10
3-0
2-0
i-o
Displacement
Fig. 25
I.
F.
Zartman* and
C. C.
Kof experimented
with bismuth
expected
molecules of Bi, Bi 2 and Bi 3 in the proportion at 827 C. of
44 54 2, the molecules of each kind obeying Maxwell's law. In
a rather indirect proof of Maxwell's law is obtained.
this
,
way
128
99.
temperature of the
beam
a magnetic field; the atoms, being charged, had their paths curved
by the field, the radius of curvature being exactly proportional
electrically
129
speeds are either too late or too early to get through. By running
the wheels at different speeds, it is possible to pick out the mole
cules which travel at any desired speed; these are allowed to form
a deposit on a transparent screen, and from the density of this
deposit the number of molecules can be estimated. In this way
Lammert shewed that Maxwell's law was satisfied to a con
siderable degree of accuracy.
\J
Fig. 26
130
will
dX
T=
v
c'
Chapter
Number of
Collisions
by making a somewhat
which occur in a gas when this is
where
= u2 + v 2 -f w2
du dv dw du
dv'
dw' do}.
we
'dv'dw'dv.
(134)
Here V
is
132
AB
We may in
at right angles to V.
fact replace cr 2 cos$<fo>
an element of area in
by d8,
this plane
we then
is
obvious.
Fig. 27
be rewritten in the
may
form
(135)
When
is
by Maxwell.
106. Integrating expression (134) with respect either to dS or
and <j>, we replace cr2 cos6da> by Trcr2 and find that the
to 6
number
7TV
of collisions at
all
angles of incidence
is
'
dv' dw'
......
(136)
This
is
gas in
and
Lret
u'
us
4-
du
fix
and
lie
133
',
moment on
the ^-components
......(137)
fig.
-,
J=>
=-
we
ordinates,
find that
Fig. 28
'
'
fof
2jp
(J>
(138)
in
which
ij
~j^(v
t?),
etc.
The reason
V^
of coordinates
new
is
72
so that
= U _ U )z +
>
',??','.
7T
V in the
134
This
in
limits
We
and
collision.
V,
(140)
number of
as the total
lies
between
to
QQ,
we
collisions in
F and F + d V.
number of
collisions of all
kinds
2n
.(141)
Since (91) c
These results
will
2(jrAm)-*, this
be required
may
later.
be replaced by
135
Free Path
108.
The
free
molecule travels
seen that the v
pression, or
V27n>V2 c.
The total length of all these free paths is of course the total
distance travelled by the v molecules in unit time, and this is vc*
Hence by division we find that the average length of a free path is
(142)
This
we
is
free
path in a gas.
p, q
when in
collision.
#12
As
in
89,
we
Obviously
= ifo + tra),
Sn =
cr^ etc.
unit time
and
85)
f
136
where V
is
found to be
......
(143)
this expression
by new
variables, u, v,
w, a, /?, y given by
?_ e tc.; a
^
__i
=u
u, etc.,
......
,T
<\
(144)
so that u, v,
are the components of velocity of the centre of
gravity of the two molecules, and a,/?,y are as usual the com
ponents of the relative velocity V. Writing
u 2 -f v 2 + w 2 = c2
we
a2 + /? 2 + y 2 = F 2
find that
xc
-f
w c' =
2
(m 1 + m 2 )c 2 +
-M
- F
+
2
wij_
We
dudu'
2.
m%
WJf^*-^
......
(145)
On
(146)
137
THE FREE PATH IN A GAS
to c = cc, the number of collisions for
Integrating from c =
which V lies between V and V + dF is found to be
number
molecules of types
and
is
found to be
/ITT"!
(149)
of this.
The
by
v^
molecules of the
first
kind
is
(150)
138
When
is
We may now
put
This
is
velocity.
139
<j>
<f>
The
When c,
c are
being given by
whence we obtain by
differentiation,
VdV =
still
keeping
c, c'
constant,
cc'sin#d#.
(153)
by
..,...(154)
are
F is
F.
The
limits for
c -h c'
/2
fc(c*4- 3c )
/2
c'(c
when c >c,
when
c'
If we
to
c'
< c,
f y2
f2 V^A
^ e-^^Vfc +
61
'
(c'
3c /2 ) dc',
(155)
3c 2 ) dc'
(156)
-f
140
or less than c), we obtain, as the aggregate chance per unit time
of a collision between a given molecule of the first type moving
with velocity
velocity
c,
c',
r f "V((c 2 -f
vTT
The former of the two integrals inside the square bracket can
be evaluated directly. To integrate the second integral, we
2
2
replace hm 2c' by y After continued integration with respect to
2
^ we find as the sum of the two integrals in expression (157),
.
(158)
If
we
introduce a function*
i/r(x)
expression (158)
xe~- x2 ~f
i/r(x)
(2#
defined
4- 1)
Jo
by
e~ y *dy
(159)
(157)
by @ 12s
its
value
is
found
to be
With
The value of
|
141
is
(162)
The mean
free path
with velocity
c 9 is
Ac
moving
accordingly
(163)
ze.IS
When
there
is
(164)
r z T/r(c
V Am)
to c
c,
from
oo.
c/c
We notice
found.
hmc 2
AC /A
A/A C
-\/2A ?
as previously
142
Probability of a Free
115. It
is
shall describe
further distance
dl,
without collision
/(i) (i
is
-di;\).
~
Ac
SI
'
is
f(l)
e-**s
...... (165)
number to
Ne~ ^c
l
(166)
N being taken to be
100:
0-01
0-02
0-1
0-2
0-25
0-33
0-50
99
98
90
82
78
72
61
AC
100
1234
37 14 5
4-16
1
12*
A GAS
which
is
it is
of the form
t
where
i Q is
-*x
9
i^ e
i
(167)
speed
is
approached, the
mean
free
* H. F.
Mayer, Ann. d. Phys. 64 (1921), p. 451. C. Ramsauer, Ann. d.
Phys. 64 (1921), p. 513. R. B. Brode, Phys. Rev. 25 (1925), p. 630.
M. Ruseh, Ann. d. Phys. 80 (1926), p. 707. R. Kollath, Phys. Zeitschr.
31 (1930), p. 986.
f Phys. Zeitscfcr. 21 (1920), p. 578.
144:
in the ratio
In this way, Born found the free path of silver atoms moving
5
through air at atmospheric pressure to be about l-3x 10~ cm.
the
same method, has
More recently Bielz,* using a refinement of
found the free path of silver atoms moving through nitrogen at
5
atmospheric pressure to be about 1-29 x 10~ cm.
P. Knauerf has tested the formula for the scattering of a
beam of complete molecules, shot both into the same gas as the
On
differentiating
e-V*<~.
......
(168)
The
7T
VA m ;/;
3
;
(169)
v
Zeitechr.f. Phys.
t Zeitschr.f. Phys.
32 (1925),
80
p. 81.
(1933), p. 80
and 90
(1934), p. 559.
1<04/ A which
by more than about 1 per cent, from e~
the value for molecules moving with velocity l/+jhm.
At any instant a fraction
not ever
is
145
differ
of the whole
is
given by
r-c
Jo 6
This integral can only be evaluated by quadrature. The evalua
tion has been performed by Tait* and Boltzmann,f who agree in
assigning to
is
it
in
It
different
LAW
f Wien. Stizungsber.
J
KT
96
p. 74.
146
2
velocity c should collide with a molecule of type
f
moving with a
volume moving
hm\* _h
number we
this
Multiplying expressions (155) and (156) by
time per unit
unit
of
collisions
per
obtain, as the total number
within
velocities
volume between molecules having specified
ranges dc, dc
f
>
^
when
J/
/| 2 A 7/l|m|e-
A< m
(170)
(171)
S)
< c,
when K>
1,
^2
when/c<
1,
(173)
On
=
c'
whenl,
,
/c (/c
-f 3)
d/c.
The
77/1
may
to
(176)
when/c>l,
5
-
when/c<l,
5
-
m\ml
*
-fl)
/c(3/c
J u ,_
mSmi
/c (/c
^dx,
......(1/7)
2
-f-3)~
define the value of K for a collision in this case as the ratio of the
2+
y*
V2(l K
4-
(179)
)*
to K
oo is unity,
148
moment
and
let
P'
P'
be the images of P,
RQ
space.
We
in that direction.
149
123. Let us now average over all possible directions for the
velocity of the second molecule, keeping the magnitude of this
as before represent the
velocity constant. In fig. 30 let OP,
OQ
point of
PQ,
two
colliding molecules,
so that
any two
Fig. 30
Thus the
POQ
PQ
component
ON is therefore
fn
ON.
Jo
ON = ^-^
\
Jo
(180)
PQ&nddd
OP =
so that
OQ =
c,
F2 =
c2
c\
PQ =
+ c /2 -2cc'cos0.
V,
(181)
150
Then
ON =
i(0P + 0Jtf) =
|(c
+ c'cos0) =
By
VdV =
......
(182)
......
(183)
we have
cc'sin&dd,
JFW
4c
c'
+ c.
,-henoc',
whence',
......
(185)
and
we
is definitely in
same
also
is
true of the
If we denote
first
When/C>1
'
'
......
(186)
......
(187)
QK? -4- 5
151
/c,
the
ratio of velocities:
~=
oo
1J
~=
4oo
now
collisions.
Each
collision involves
entirely interchangeable.
so that
in
any one
10/c 2 (3*2 -f
and
The mean
collision,
25**+
-
...... (188)
152
persistence
oc
!U.
......
(189)
to |, the value
velocities.
Persistence
Different
Masses
are
all similar.
153
relations (182),
/cog
.......
So long as c and
The
as before.
c'
first
iu
(c
>
to
equal
^
is
already found in
-f-
c'
cos 6)
4-
-j-
m M-
mass
/m 2 and
c'/c.
we assume
(192)
very small.
When
priate value to
From equation
assume for
(191)
(a/c) e is J, this
corresponding to K
oo.
1-=^=r-^^\
193 >
154
is
and I-
\ c it
is
^^^...^
J.
The approximate
now
(194)
large')
knocks the
The
result
is
(195)
when p =
12
+
T^
4
~ OK
/^ "^ ^rmS ^ /^
is large,
the expansion
e^ C ->
is
/a\
,
x
etc.
(195)
and
(191),
155
calculated:
TQ
10
oo
"} =0-333 0-335 0-339 0-360 0-406 0-432 0-491 0-498 0-500
1-000 0-879 0-779 0-573 0-406 0-243 0-152 0-086 0-000
is
may have any value whatever, according to the ratio of the masses
of the molecules.
131. For laws of force between molecules different from that
between elastic spheres, the persistence of velocity will obviously
be different from what it is for elastic spheres. Clearly, however,
everything will depend on our definition of a collision. If we sup
pose that a very slight interaction is sufficient to constitute a
collision, then the mean free path will be very short, while the
persistence will be nearly equal to unity. If, on the other hand,
we require large forces to come into play before calling a meeting
of two molecules a collision, then the free path will be long, but
the persistence will he small, or possibly even negative. In fact,
is
Chapter VI
VISCOSITY
132. At a collision between two
molecules, energy, momentum
and mass are all conserved.
Energy, for instance, is neither
selves
we study
diffusion.
which
is
to the axis of x at
every point as in
being different for different values of
layers parallel to the plane of xy.
z,
is
in
VISCOSITY
157
"
\|P R
0,
(i)
v,
Let
QP in fig.
axis of z.
which
per unit volume having relative molecular- velocities for
VISCOSITY
158
c
and 6
lie
may
therefore be
taken to be
......
where
Jo
to
/(c) dc
1,
(196)
v.
The number
...... (197)
We
The
2-co-ordinate of
is
ZQ
A,,
cos 0,
is less
than that at
P by an
amount
(198)
in excess of that appropriate to the point P, where A c is the
mean free path for a molecule moving with velocity c.
The total excess of $ which these molecules carry across the
plane 2
(198),
= 2^
is
namely
limits for
between
which cross
and
+ dc, whatever
their direction.
The
are
to
TT,
values of
VISCOSITY
those which cross the plane from above.
gration
The
is
....... (199)
where cAc denotes the mean value of cAc averaged over
molecules of the gas.
In the foregoing argument
all
the
similar argument,
PQ = Ac
We may put
^=
cZ,
is
also five.
...... (200)
VISCOSITY
160
by any of the known values of the mean free path. At the same
time the mean values calculated in different ways will not greatly
differ from one another, and as our present calculation is at best
examined
136.
later.
per unit of time across a unit area of a plane parallel to the plane
of tfz/is
Ivcl^-.
......
tz
If
we replace /i by
of
momentum is
its
value mu,
/Z
becomes
(201)'
seen to be
......
(202)
moving with the same velocity as the gas at every point, would
exert a viscous drag
1
dx
TJ
given by
ip3.
...... (203)
suppose that their velocities are divided into two parts, namely,
u
for the first,
and
u v>w and %, 0,
u^ v, w and uQ3 0,
,
VISCOSITY
161
explains
why
Corrections
it is
accompanied by a
rise of
temperature in the
to be Elastic
Spheres
From want
between two
We may
assumption of equation
(200).
cAc
cA^,
to replace the
fee
f(c)Xc cdc.
(204)
j o
^ given by equation
m
we
tt
4(Am)*c
Jo
where x
_
\hm =
fr(c \Jirn)
j
==
V2C
JKT
-*"*;2
,
'
find
-
clearly
(164),
and
VISCOSITY
162
Thus
if
is
defined
by equation
(200),
we must take
(205)
mean
more
free
108.
path calculated in
by neglecting
(206)
has>
+-
r
distance
of
its
Q undisturbed,
and at each
collision
a certain amount
(7
excess of
liding molecule.
momentum
will
col
possible, the
to
momentum above
original molecule*
Making
this
VISCOSITY
163
Thus we must
W)
in the integrand of
by quadratures,
I find
is
......
(208)
......
(209)
given by
'fl~C
lpcl
= 0-461-^-.
2
V27TCT
(203), is still
......
this,
by an
entirely different
(210)
method.
VISCOSITY
164
number
through a viscous
fluid is
given
by
are the radius and mass of the sphere, and g the mass
of fluid displaced. Since ij is, by Maxwell's law, independent of
the density, it follows that, within the limits in which Stokes 's law
is true, the final velocity of a sphere falling through air or any
where a,
M M
To
VISCOSITY
165
As
up
+ O8000 + 0-7614-,
v
where
2-
This formula
The minimum
in yip
is
clearly
it
ought to occur,
is
0-87266,
reached at
VISCOSITY
166
C.) at
Pressures
liigli
At the other
* Comm.
Phys. Lab. Leiden, 134a (1913). See
Handbuck der Physik (nte auL), pp. 1399, 1406.
t Phil. Trans.
also
Winkelmann's
VISCOSITY
167
when gas
section.
When
and as
over
its
whole
amount
is
Dividing throughout by
27rrLy
and
integrating,
we obtain
a constant of integration.
no slip between the gas and the walls of the tube,
v must be zero when r = R. Determining A from this condition,
equation (211) becomes
where
is
If there
is
r*).
.,.,..(212)
VISCOSITY
168
The
total
unit time
is
(213)
that a
slip
We
so that
The constant
in equation (211)
when
We
accordingly find, as
i%
and, instead of equation (213), for the flow per unit time,
* Wien.
Sitzungsber. 40 (I860), p. 607.
f Pogg. Annalen, 155 (1875), p. 337.
J Coll.
Works, 2 p. 703.
t
VISCOSITY
We
with ?;,, it
?;/e, but when R is small compared
takes control of the whole process, and results in the flow being
comparison with
The quantity
on
yje,
itself to
I/
purely random
may
CO2 on
0-92
oil
Air on glass
Air on fresh shellac
145,
0-89
0*79
(214)
is
found to
VISCOSITY
170
comparable with, or
greater than, the diameter of the tube. In this ease it is re
markable that the rate of flow is independent of both the
is
path
is
thus
as in
|/e>c,
39.
The average
is
The
time
is
total
--_
accordingly!
(215)
power of JR.
We
146.
turn next to examine how the viscosity of a gas
varies with its temperature.
Since c is proportional to the square root of the absolute
if
p. 593,
'
is less
tests agree
it
with this
171
VISCOSITY
will
We
F2
VISCOSITY
172
V cos
is
2
fC'
The
kinetic energy which has been destroyed by the interfield of force when the molecules are, on the average,
molecular
is
or is
accordingly
6J
-=
R dT
dcr
-CT*~
da-'
giving on integration
<
Here
216)
Thus equation
VISCOSITY
173
This agrees with (216) except for the numerical factor, and agrees
completely, as it ought, for elastic spheres (s = oc). We see that
molecules which are point centres of force may be treated as
elastic spheres, both as regards pressure and viscosity, but the
spheres must be of different sizes in the two cases, except of course
when the molecules really are spheres.
appears that
will
vary as
T6 ~
l
,
so that
77
will
vary as
Tn
where
......(218)
n
(219)
C.
is of course the coefficient of viscosity at
7]
is helium; the agreement between the observed
instance
good
values of y for this gas and the values given by formula (215)
is exhibited in the table on p. 179 below.
where
VISCOSITY
174
law
where s
is
given by
equation (218).
If a gas is constituted of molecules which are not of this type,
it will still be possible to represent the viscosity-coefficient by
a formula of the type of (219), through any small range of
temperature we please. For the value of n is at our disposal,
and may be chosen so as to give the right value to dr/ldT, the
slopeof the viscosity-coefficient, through this small range. But this
value of n will not usually satisfy the experimental data through
another range; for this some other value of n must be chosen.
The following table gives the values of n for a number of
G., together with the
gases through ranges which include
pLJr
* Authorities:
1.
2.
3.
4.
5.
6.
Kamerlingh Onnes and Weber, Verslag. Kon. Akad. van Wetenechappen, Amsterdam, 21 (1913), p. 1385.
Trautz and Binkele, Ann. d. Phys. 5 (1930), p. 561.
Markowski, Ann. d. Phys. 14 (1904), p. 742.
Values given by Chapman and Cowling (The Mathematical Theory
of Non-uniform Gases, Cambridge, 1939), calculated from data
of various experimenters.
Ann. d. Phys. 5 (1901), p. 163 and 6 (1901), p.
8. Trautz and Winterkorn, Ann. d. Phys. 10 (1931), p, 522.
148, below.
t See
7.
Schultze,
30L
VISCOSITY
175
We
?/.
We
have
...... (220)
where
A is a numerical constant.
-^
A=
A
where /2 (s)
is
a pure
_-
5\to
...... (221)
s,
its
actual
value being
-*r
Jo
where 6' and VL have the meanings assigned to them in
196
below. This integral was introduced by Maxwellf in 1866. He
calculated that when s = 5 its value is 72 (5) = 1-3682, and
5 formula (221)
* Phil. Trans.
Roy. Soc.
t Coll Works, 2, p. 42.
211
is
exact.
A (1912),
p. 433.
VISCOSITY
176
5 to 1-01485
1
J per cent, and as this is smaller than experimental errors of
observation, it is hardly worth carrying the approximation
in the
form
just quoted.
a type
as this.
may be.
A
* PhiL Trans.
Roy. Soc. 216
(1915), p. 279.
f Kinetische Theorie der Vorgdnge in mdssig verdiinnten Gasen (Inaug.
Dissertation, Upsala, 1917). Enskog's analysis is given by Chapman and
Cowling, in a somewhat different form, in their book The Mathematical
VISCOSITY
177
<r
at temperature
T is
where C, cr^ are constants, cr^ being the value of a when T = oc,
and therefore being the diameter of the hard kernel of the mole
2
cule, while G is the temperature at which cr = 2cr|.
As the temperature
as
cZ,
and
T*
T*
so as -y, or again as
~.
Thus
if
??
is
the coefficient
of viscosity at
C. (T = 273*2), the general coefficient of vis
at
cosity 7}
temperature T will be given by
C
6 + 273-2
r
As an
fa
Ethylene
0-00009613,
0-00013879,
C=
225-9)
Carbon-dioxide
* Phil.
JKT
Mag. 36
(1893), p. 507.
C=
Ann.
239-7)
d.
178
VISCOSITY
Helium
Neon
C=
Argon
Krypton
C=
C=
C=
Xenon
Hydrogen
different
252 (Rankine).
'
Carbon-monoxide
C=
C=
Air
C=
Nitric oxide
Chlorine
Nitrous oxide
Carbon-dioxide
Ethylene
Methyl chloride
(Smith).
225-9 (Breitenbach), 272 (Sutherland).
454 (Breitenbach).
Nitrogen
(Sutherland).
Oxygen
Authorities
CC=
274
Ann.
Schmitt, Ann.
d.
d.
Markowski, Ann.
d.
We
On
VISCOSITY
179
taking
C-
78-2.
Viscosity of
Helium
* This
entry, which was obviously wrong in the original table, has
been recalculated.
of Force
f
J
ISO
VISCOSITY
ture. This
'
rn
_.m
r
Hasse and Cook* have calculated the resulting formula for the
5.
and
They
the
the experiments well for hydrogen,
nitrogen and argon, but could not be made to fit for helium,
carbon-dioxide and neon. The agreement of their formula with
observation for hydrogen and argon is shewn in the two tables
beJow.
formula could be
made
to
/*,
fit
Viscosity of Hydrogen
Here the second column gives the best observed value of the
viscosity coefficient, while the third column gives the value
calculated by Hasse and Cook. The last column
gives the value
calculated by Kamerlingh Onnes for a
simple repulsive force
11 2
and it will be seen that the agreement with
varying as r'
observation
not enormously
complex law of Hasse and Cook.
*
is
less
Soc. 125
(1929), p. 196.
VISCOSITY
Viscosity of
181
Argon
from 1
to
1, the coefficient of viscosity of the mixture will
of course also change, starting from the coefficient of
viscosity
of the first gas, and ending at the coefficient of
of the
:
viscosity
?/
*-
2L
Tram. Roy.
Soc.
136
of
(151),
^-T-
Pi
* Phil.
coefficient
(1846), p. 573.
......
(222)
VISCOSITY
182
where T/^
TJ Z
reduces of course to
Thus
if
?/ 2
>
T^;
7/^4^42,
when p 2/pi
is
small, it is
maximum as p 2 p
with elastic spheres, the formulae being corrected for the phe
nomenon of "persistence of velocity " explained in Chap, v; while
Verhand.
Ann.
(1902), p. 238.
183
VISCOSITY
the necessary formula
is
type
* Authorities:
6.
7.
1.
2.
3.
4.
5.
p. 162.
t L<c. ante.
%
Ann.
d.
VISCOSITY
184
We
molecules
may
cannot be expected
146.
will
be clear
Chapter VII
CONDUCTION OF HEAT
Elementary Theory
zQ
cos 6.
and
this
may be
taken to be
r,
z
.,....(223)
where
and
evaluated at z = z
The number of molecules which cross the unit area in question
in a direction making an angle between 6 and 6 + dQ with the axis
of z per unit time is (c formula (197))
if
is
CONDUCTION OF HEAT
energy given by formula (223), the total flow of energy across the
unit area of the plane will be
f
cz
J0
......
(224)
there
is
de
creasing.
If k is the coefficient of conduction of heat, the flow of heat
across unit area of the plane z = ZQ in the direction of z
increasing
dT
is
ST
is
Jk -^- where J
QZ
is
the
from which
it
is
_i>&dS
3~JdT'
......
(225)
--L^
c*~~
JmdT*
where
77
Using these
relations,
&
= ?*.
.....
(226)
CONDUCTION OF HEAT
The flow of energy
154.
Jk
of
dT
-cz
the plane z
ZQ
+ dz,
187
is
z increasing.
at the rate
Across
is
GZ*
lies
and
......
(227)
between
Z Q 4-
Jk~~dz
"
C Z"
per unit area, which must increase the temperature of the slab.
To raise the
the temperature
at a rate
dT
-=-dt
area equal to
dT
Equating
we
obtain
dT
which
which
is
(228);
Exact Theory
CONDUCTION OF HEAT
188
187).
first
'
4(a-l)(lls-13)
when
5.
EXPERIMENTAL VALUES
156. We proceed to examine the relation between k and //
which is found experimentally.
Monatomic Gases. The following table of recent determinations
of k >/f V the quantity we have denoted by e, is given by
EnskogrJ
?
=
=
e =
2-40,
2-23,
2-02.
2-49,
= 2-57.
e = 2-501.
* Phil.
Trans. Roy. Soc,.
279.
t See footnote to p. 182.
211
(1912), p. 433
and 216
(1915), p.
J L.c. p. 104.
CONDUCTION OF HEAT
189
* Authorities:
1.
2.
3.
and
mean
of determinations
by Winkelmann
Wiillner.
t Determined by Vogel, and quoted by Eucken. The value of <? for helium given by the
formula (25) is, however, 0-767.
*
Calculated from formula (25). Eucken takes C, - 0-177, Pier gives C, =0-175.
The mean
of values given
by Winkelmann
(Pogg.
Ann, 159
(1876), p. 177)
and Wiillner
The
An
by formula
(25) is 0-7G7.
** Ann. d.
Phys. 11 (1903), p. 303.
Eucken (Phys* Zeitechr. 14, p. 328) states that Schwarze gives too
high a value for helium owing to miscalculation of the value Cv .
JJ Proc. Roy. Soc. 95 A (1918), p. 190.
ff
CONDUCTION OF HEAT
190
place
......
(229)
We
_
{0
by (approximately)
formula (229)
may
carried.
we
......
(230)
flow,
CONDUCTION OF HEAT
191
is
If all the molecules of the gas moved with the same velocity c,
the number of molecules impinging on the area dS in unit time
would
be, as in
39,
2
|rac to the wall, so that
the gas to the element dS
would be
If the molecules do not all
c 3 in this
average
expression. If the speeds are distributed
to
Maxwell's
law, we find (c Appendix vi, p. 306)
according
that the average value of c 3 is 4/\/(7r& 3 3 ) and the total transfer
of energy from gas to "wall, per unit area and unit time, becomes
2BT= \p
2/
nm
where p
If the wall
Ann.
papers.
CONDUCTION OF
192
HJBAT
per unit area per unit time) from the wall to the gas of
rarefied gas
TQ
be jointly proportional to the temperature difference T 1
and to the pressure p.
158. Experiment confirms this law of proportionality, but
generally speaking, does not confirm the multiplying factor in
formula (231). The actual transfer of heat is substantially less
than that predicted by formula (231), as though the interchange
of energy between the solid wall and the adsorbed molecules of
will
an explanation suggested by
1898, and again by Soddy and Berryf in
Smoluchowski*
in
1010.
>
......
(232)
194 C.
steadily to 0*025 as the temperature was lowered to
* M. v.
Smoluchowski, Wied, Ann. 64 (1898), p. 101.
f Proc. Roy. Soc. 83 A (1910), p. 254 and 84 A (1911), p. 576.
J .4nn.d.P%.34(1911), p. 593,36 (1911), p. 871, and 6 (1930), p. 129.
For a full discussion of the subject see Loeb, Kinetic Theory of Gases
(2nd ed., 1934), pp. 321 ff.
Proc. Roy. Soc. 129 A (1930), p. 146 and 135 A (1932), p. 192.
CONDUCTION OF HEAT
193
2mrn'
This
is
equal to
\i
\m rm
j
This value of a
less
* J. M.
Jackson, Proc. Camb. Phil. Soc. 28 (1932), p. 136; C. Zener,
Phys. Review, 37 (1931), p. 557 and 40 (1932), pp. 178, 335; Jackson and
Mott, Proc. Roy. Soc. 137 A (1932), p. 703.
f Proc. Roy. Soc. 142 A (1933), p. 447.
13
J KT
CONDUCTION OF HEAT
194
by formula
(232).
namely
which all the quantities refer to the free electrons in the solid,
so that v is the number of free electrons per unit volume, I is their
average free path as they thread their way through the solid, and
in
so on. Taking
E=
fjB T, this
&
becomes
vclR.
2tJ
......
(234)
Conduction of Electricity
161. Drude's theory supposes that the free electrons also act
as carriers in the conduction of electricity. If there is an electric
force Tin the direction of the axis of x, each electron will be acted
on by a force Se, and so will gain momentum in the direction Ox
at a rate Se per unit time. The time required to describe an average
*
Ann.
Ann.
d.
d.
CONDUCTION OF HEAT
195
free path
Ed
me
parallel to the axis of x. It follows that at any instant the free
electrons have an average velocity u parallel to the axis of x,
,
given
by
ISel
The
veuQ
= ~1 EveH
2
me
and
or is
defined
by the rela
so that
<rS>
is
we may put
f?#(c)
%JRT,
by
...... (23o)
This
is
162.
(234)
law.
By comparison of equations
CONDUCTION OF HEAT
196
which
tion
it
is
'cr.
t
From
this
equa
np
*
......
(236)'
v
in
For
elastic
spheres
(s
oo)
CONDUCTION OP HEAT
197
-=
4-31 x 1010 at 18 C.
cr
namely
-=
6-46
xlO 10 at
18 C.
cr
=
=
k/cr
=
k/<r
for silver,
6-86 x 10 10 3
for
7-27, 7-09
x 1C10
x 10 10
The
factor 1011
Chapter VIII
DIFFUSION
ELEMENTARY THEORIES
164. The difficulties in the way of an exact mathematical
treatment of diffusion are similar to those which occurred in the
problems of viscosity and heat conduction. Following the pro
cedure we adopted in discussing these earlier problems, we shall
begin by giving a simple, but mathematically inexact., treatment
of the question.
We imagine two gases diffusing through one another in a
direction parallel to the axis of z, the motion being the same
at all points in a plane perpendicular to the axis of 2. The
The simplest
point.
by WQ, and let the molecular densities of the two gases be v^ v%.
Then v^ vt and w are functions of z only.
We assume that, to the approximation required in the problem,
the mass- velocity of the gas is small compared with its molecularvelocity, and we also assume that the proportions of the mixture
do not change appreciably within distances comparable with the
average mean free path of a molecule. We shall also, to obtain a
rough first approximation, assume that Maxwell's law of dis
tribution of velocities obtains at every point, and that h is the
same for the two gases.
199
DIFFTTSIOH
165.
plane z
increasing,
cross the
per unit area per unit time in the direction of z
now
is
~)
f f vie^^'+^v-^wdudvdw,
oo to
4-
oo as regards
......
u and
(238)
v.
and
"i
-A cos <?.
<"i)
...... (239)
becomes the
(238) with
at z
...... (240)
first
kind.
The second
integral
is
......
multiplier
A -^
\ cz f
(241)
this expression
*w*,
Bvi\ (hmA*
fffe~hm
hm<
1
_i
i<*
dudvdw,
,
Sz/\
in
all
TT
JJJ
all
values of u and
v,
and over
DIFFUSION
200
taken over
or
c,
and
is
7J}
c
oz]
(f*<ji
molecules, in a gas having no mass -motion. This
all
average value
is
therefore \c v
Hence expression
in
we
equal to
which
This
(241)
is
all
is
is
F we have
19
cons.,
gas, so
DIFFUSION
201
Eliminating
tv
_ r1 = r2 =
The number
cross -section
z,
cz
of molecules of the
first
and
z Q + dz, is
is
also
found
dt
o ri
to be
planes.
~dz^ by
two boundary
Hence we have
dvi
_
"~
8Fi
dz'
dt
_
"
dt
where
12
1
= ^1
3
1,
......(SM4)
Equation
diffusion.
*
The
actual value of
D 12
DIFFUSION
202
Coefficient of Self-diffusion
166.
Formula
25
Comparing
this
= Uc.
(245)
we
77
(246)
176).
(1937), p. 516.
0, in
which m x
DIFFUSION
Thus the
203
two
ratio
of <25 12 on
J>i/V2 .
to
2)
JAc
...... (248)
(249)
Actually,
two sources of
is
all
first arising
DIFFUSION
204
169.
cities.
""-
i-o*
Here 6
is
JAc/>
accordingly
Putting 6
(249)
found
in
must be
126, this
1-342^.
becomes
......
(250)
tween the
DIFFUSION
205
it is
more difficult
to
z-.
&
...... (251)
When
we
...... (252)
.,
where p,
q, r, ...
lisions.
We have
P = X+pX+pqX+pqrX + ...,
Ps =
sX -f psX +pqsX -f
. .
DIFFUSION
206
m
In this the
first
collisions
first
J3
:l-fr so that
I-/?
which again
is
sistence,
(254)
and there
^_
A>i2
yjPsCg +
7;
+
;
^1
ml~~ #12^2
^ 4- m2
DIFFUSION
207
__i
fo)
/r/T"
^ m
n ( V l + "2) ^12 ^
**
(256)
When v2 is small,
replaced by a 23L
Vv% varies is
Thus, when
171,
Equation (243)
out of the gas of the first kind, similar to the progress and spread
ing out of heat in a problem of conduction. The larger 2) is, the
more rapidly this progress takes place; 2) is largest when the free
paths are longest, and vice versa. Long free paths mean rapid
diffusion, as
we should
expect.
Now the formula for the mean path Aj in a mixture of two gases
was found
in
111 to be
Al
......
(257)
* This was
pointed out in a valuable paper by Kuenen ("The diffusion
of Gases according to O. E, Meyer", Supp, 28 to the Comm. Phys. Lab.
Leiden, Jan. 1913). Kuenen took a uniformly equal to 0*188, its value
assumed the number of collisions to be in the ratio
when t% =
vj : ViV& so that his result is different from mine, but the principle was
essentially the same. In a later paper by the same author {Comm. Pkys.
Lab. Leiden, Supp. 38) the mass difference was taken into account.
v ^d
DIFFUSION
208
where $I2
sion.
first
collisions should
equations
(258)
in place of equation (257). Using these values for the free paths,
Wien.
Sitzungsber.
63
[2]
(1871),
p.
63,
and 65
(1872),
p.
323.
f CoU. Scientific Papers, 1, p. 392, and 2, pp. 57 and 345. See also
Boltzrnann, Wien. Sitzungsber. 66 [2] (1872), p. 324, 78 (1878), p. 733,
86 (1882), p. 63, and 88 (1883), p. 835. Also Vorlesungen uber Gastheorie,
1,
p. 06.
DIFFUSION
or, in
209
If the
size, this
becomes
......(261)
which
of viscosity,
7;
0-499
-../**
',
1-336^,
(262)
obtains
namely
and
same value
p. 298).
is
JKT
14
DIFFUSION
210
by the factor
128. Thus the
may
be
A first approximation,
When 5 =
5, this is
exact,
195 below,
fa=oc
4?r
J a=0
and reduces
A = 7^5) =
where
cos 2 |#'
to
2-6595,
...... (
'
DIFFUSION
211
Multiplier
1-000
1-004
5=
17
1-008
oo
1-015
is
0*1520
1-200-.
......(266)
was given
as 0-151.
14-2
DIFFUSION
212
Diffusion in a Mixture
1-fib
where
original memoirs.^
The principal interest of these general formulae lies in the
which
This
may
^2
Uml+IGm^
12mf +
be compared with the value
/m 1 predicted by
* Phil.
Trans. 217
(1916), p. 166.
t L.c. ante (see footnote to p. 182).
J
Chapman,
(168)ff.
I.e.
ff.;
Enskog,
I.e.
L.c.p. 103.
equations
DIFFUSION
213
Meyer
Meyer (corrected for persistence)
Chapman-Enskog
10-000
1-324
1 -072
evidence as to
R. Schmidt, Ann.
214
DIFFUSION
of S) 12
is
values of
observed values.
The degree of
variation in
at least of the
176.
it is
determination.
DIFFUSION
215
of
23>
cr1? cr 2 , 0*3.
'
Pairs of gases
13,
23)
(12,
14,
24)
(13,
14,
(12,
13,
23)
1-35
(12,
14,
34). .....1-26
(23,
24,
24)
34)
0-193
0-190
0-183
Mean
0-189
Mean
Gases
(1)
Os
(2)
CO
C0 8
(4)
(3)
Pairs of gases
(12,
13,
(13,
14,
(23,
24,
Pairs of gases
n
1-32
(12,
1-31
34)
T)^
0-169
0-175
0-178
Mean
0-174
23)
34)
Pairs of gases
14,
24)
14,
(13,
34)
(12,
(23,
24,
X)^
0-106
0-111
34).. ,...0-109
Mean
0-109
<
Hydrogen
Nitrogen
0-203
Carbon-monoxide
0-211
Nitrous oxide
0- 1 07
Carbon-dioxide
0-121
A (1937),
p. 511.
BIFFUSIOK
177. It remains to test the numerical
multiplier.
tions of
The calcula
in predicting
1-200^
P
for elastic spheres, while Maxwell's
theory given in Chap, ix
below predicts the relation (exactly)
$=
1-504 ?
P
for molecules
repelling according to the inverse fifth-power of the
distance.
In the following
sumed
for
?i
217
DIFFUSION
theories of
Spheres
on
viscosity as
$12
p. 183.
sets of values of Sn
is
as
good
agreement
above, as
is still
is
DIFFUSION
218
diffusion
154
in a gas in the
while in
165
of conduction of heat
form
(243))
~ ^M ^i
3z 2
dt
Replacing
this
12
by the value
ij/p
'
becomes
'
dt
*
- J?a2j 1
-p~3*'
......
mm
(270)
f Phil. Trans.
217 A (I916),p.
164.
$ Phil.
DIFFUSION
We notice at
is
219
The
is
"i=4 e ~^>
......(271)
now
and
(270).
We
shall
how
Random, Motions
Let us consider the random motion of a single molecule
about by collisions with other molecules. As we are
concerned with general principles rather than numerical exacti
tude, let us simplify the problem to the extreme limit by supposing
181
as
it is
hit
that all free paths are of the same length I, and that all are
described parallel to the axis of 2; we shall further suppose that
for each free path the directions of z increasing and of z decreasing
are equally likely.
Any
will
ZZZ...
(to
N terms).
free paths
DIFFUSION
220
so that
Each of the signs in this series may be either -f or
there are 2 N possibilities in all. For some arrangements of signs,
the molecule will have advanced a distance si along the axis of z.
,
For
signs,
must be p
positive
and q negative
p + q = N,
p-q =
s.
(272)
of course
is
Nl
PW-'
so that the chance
distance
si after
P that
N free paths is
to the value of nl
when n
is large.
p.
From
equations (271)
we
find
Using
this relation,
equation
DIFFUSION
P=
so that
-j
large, the
-(274)
rr^r
rsrr/
221
q 4-
=e~^,
and
as given
by formula
(274),
value
/~^~
a*
(275)
This
is
Formula
gressed.
(275)
becomes
P= VA?L
e -SS,
net
which
is
in
all essentials
(276)
= pc =
^,
(277)
where
?/
Thus the
and so
forth.
Its true
importance
is,
however, that
it
presents
222
DIFFUSION
we now
see
is
The maximum
(p. 306),
we
readily find
Brownian Movements
184. The foregoing ideas are applicable to the Brownian
movements, although in a somewhat modified form. Each
Brownian particle will perform a sort of random walk, but as its
mass is much greater than that of the particles it encounters,
persistence of velocities becomes all important.
Following Einstein* and Smoluchowski,f we may treat all
collisions with other molecules as forming a statistical
group,
and regard the Brownian particle as ploughing its way through
a viscous fluid. We accordingly suppose the particle to ex
perience a viscous drag in the direction opposite to its motion.
We may suppose this viscous force to have components
dz
dy
- dx
er
>Tt>
-^di*
~ er}
dt'
now
dx
d*x
-T-e^-m^.eto.,
*
......(278)
223
DIFFUSION
d
)
= *w
d*
2
(a;
t,
4- 1/
-f
z2
)-mc
2
.
finally,
^
...... (279)
7]
......
(280)
(cf.
16, above).
dt
where
3 2"
dy
dz*
jri&v.
=A
x s -r ^$z -r ^~s
I
\dx*
diffusion.
DIFFUSION
224
where
is
= ~e
we
&+&+#
......
(282)
2
2
2
readily find that the average value of x + y + z is 6Kt. The
solution (282) is appropriate to a group of particles starting at
x 2 + */ 2 -f-2 2 to be
et]
we
find
X-**.
the value of K in the equation of diffusion (281),
This, then,
and with this value of K formula (282) will give the distribution
7/
is
Chapter
IX
186.
in
is
and
shall
f(u v,w,x,y,z),
}
22.
We
first fix
ij,
and bounded by
105) which
be
vf(u,
v,w,- $dx,
7j 9
dydzdudvdwudt*
vf(u, v,
w,
4-
\dx,
?},
dydzdudvdwudt.
&x [*/(
JKT
tfj
w)]dxdydzdudvdwudt,
15
226
in
which the
77,
The net
therefore
Gx
(u-zr-
+ v-~ + w~
oy
[vf(u> v,
w)]dudvdwdxdydzdt.
...(283)
cz/
dt.
\u
where w
VQ
x,y>z\ this
w)dudvdw = u
v,
etc.,
of the gas at
(284)
is
ip +
-^-dt\
t is,
however,
fo
-=-dtdxdydz.
Uit
Equating
dv
we
obtain
....... (285)
If we multiply throughout
replace
vm by p,
dp
d
o)
= ....... (286)
There
momentum
is
is
conserved, or
external forces.
class
carries
227
^-momentum
of
amount
to the element
mu, so that the loss of a molecule of class
The number
mu.
a
to
of
involves
loss
^-momentum
dxdydz
equal
in time dt is
the
which
are
lost
to
element
of molecules of class
mdxdydzdt
This
lu z
JJJ\
&x
-\-uv
cy
cz )
ex
(g
u2
where
uv
so that
+ uw~^-\ \yf(u,
u 2 uv
,
vy
|^ /(w,
\uuf(u, v,
the
w)]dudvdw.
+ r (vuv)+-^-(vuw)
cz
/
etc. are
(iw*)
v,
-;
......
(287)
dy
w)dudvdw,
w)dudvdw,
mean values of ^ 2
etc.,
x,y,z-
forces
...... (288)
where
-=-
(VU Q ) mdxdydzdt,
(jit
and on equating
i
we
obtain
eft
(289)
15-2
228
In
189.
u=
momentum
is
us write
UQ + U,
etc.,
thus dividing the motion into the mass motion of the gas as a
whole, and the thermal motions of the molecules. We have
u = ?/ and U = 0, so that uv = ^ t' 4-UV, and similarly for u 2
and uw.
,
becomes
a
= ZX -
() + <- (^UV) +
i*JV/)mdxdydz.
......
(290)
X will be
Smv dxdydz.
......
(291 )
UK
ZX
We
molecules such that one is inside and the other outside the
element dxdydz, that is to say, intermolecular forces which act
across the boundary of this element.
229
Let the sum of the components of all such forces across a plane
perpendicular to the axis of x be wxx ,wy}f ,mxz per unit area,
and let us adopt a similar notation as regards forces acting across
planes perpendicular to the axes of y and z. Then the contribution
to
from forces acting across the two planes x
fydx is
EX
On
-^r dxdydz.
C.X
0;
Combining
we
find,
ZX
this contribution to
expression (291),
and there
8y
ZY and ZZ.
Inserting this value for
ZX
.This
may be compared
mv by />, we obtain
equation,
We
fluid
-f/?UV, etc.J
230
Oas in a Steady
State
= pu =
as in
88,
_ _
_
uv = vw = wu =
and
o.
have
~* ^w
Pxy = P
=0v
* xs = P
==
-*-yz
j;
r~
"*
"
(80).
When we
188,
187,
we
arrived at the
When we
discussed the
1,
231
be denoted by
x, y, z
<?,
so that
Q=
II \f(u, v,
w) Qdudvdw.
ZQ =
vQdxdydz.
......(294)
dxdyv dz dt\ u
\
element
=-
dx
+ V -=- -h w TT-
amount of Q
1 (
vf
* } du dv dw,
dzj
dy
lost
is
^
^
*
j j* rrrr/
+ v-^dxdydzdt \\\\ \u^y
jjj L\ &
T
If we write
\uQf(u
v,
w) dudvdw
uQ,
etc.,
so that iiQ is the mean value of uQ averaged over all the molecules
in the neighbourhood of the point x> y, z, this loss of Q can be put
in the form
r~
dxdydzdt\
~z~~
'
(vuQ)
-I-
T^
~~s\\
\yvtyj
&
~\~~^~
.x.
\w}*&j
j
!
/oofc\
...... (>-<yvj
_
~~
dt
where
du dt
X,Y
__
dv dt
dw
dt
GENERAL THEORY OF
232
A GAS
all
molecules.
If
is
in the element
dxdydz by
collisions in
time dt by
dxdydzdtAQ.
Then the
......
(297)
molecules in dxdydz
is
233
tion of
A Q. Maxwell gave a
On
identifying
u,
and
?,
The numerical
Time
of Relaxation
= Z = 0. If the
=
forces act, so that
distribution of velocities is the same throughout the gas, the
where r
is
molecules* Similarly,
AQ =
TV2 uv,
GENERAL THEOBY OF
234
where r
v2
u*
is
A GAS
and uv both
satisfy
it
appears that
shews that
that
it is
Maxwell
<j>
..... (300)
reduced to
calls this
must
P^P^etc.
Maxwell shewed that r is related to the coefficient of viscosity rj
by the
relation
where p
vRT,
is
this relation
becomes
.....
To take a
0-000172, and
RT =
.(301)
is
~=
1
TV
seconds.
a x Vno
6
10 9
is.,
free path.
equation (300) has already become very small, so that the gas
almost in the state specified by Maxwell's law,
is
235
many
When
Y
dt
The number
Y dw = 7
'
'
<ft
of molecules which at
dt
vf(u, v,
w, x, y,
z,
t)dudvdwdxdydz.
(302)
Let these molecules pursue their natural motion for a time dt,
At the end of this interval, if no collisions have taken place in the
meantime, the u, v, w components of velocity of each molecule
will
*
Theory of Electrons, Note 29, Teubner, Leipzig (1906) and David
Nutt, London (1909).
f Kinetische Theorie der Vorgdnge in mdssig verdtinnten Gaaen (Inaug.
Dissertation, Upsala, Almquist, 1917).
n and in.
$ Vorlesungen vbet Gastheorie, I, Chaps,
however,
vf(u -f
dt,
v + Ydt,
and
if
no
t -f
dt)
......
(303)
...... (304)
colL
in
(vf),
we
<305)
by
No
progress can be
made with
U- (vf)\
L<^
and
this unfortunately
Jcoll.
237
......
-x-
L ci
(306)
(vf)
Jcoll.
We fix
v,
w and u',
?;',
In
in
32
let
MNP
and let
represent the path
described relatively to O by the second
molecule before the encounter begins.
u, v, w,
MNS,
the plane
Let
MNPO.
ROP
be a plane through
MN
Fig. 32
ROP
238
......
(308)
is
w and w + dw is
yf(u, v, w)dudvdw,
number per unit volume of collisions of the kind
consideration
f
is
ceeding precisely as in
86,
we
......
(310)
<r
JJJJJ^F-//')
1, 2, ...,
we
obtain in a similar
and
is
239
/ = ^e-^"-^^-^-^-*^,
......
(313)
and vf is independent of #, y,
found in
87,
On substituting
we again
z.
hn
/ = Ae- **+*x>,
......
(314)
find that the second term vanishes, while the first does not.
The case in which & VQ , w0y h and v vary only slightly
,
where
is
is
first
/ = ^e^^*"^^*"^
a solution when UQ v
order,
1
"*"^"" 11
and
^.
...... (316)
Since / = / is
w& h and v do not vary
from point to point, equation (315) must necessarily provide a
solution when these quantities vary to the first order of small
,
quantities.
240
"1*2/1/2
/01/02
so that
v lVz (]J'z-fJ'z )
momenta
at
an encounter give
......
/01/025
J J'oz (0i +
v iV
(319)
'i-$i-<P't).
On
we retained terms in
/a
(a
*S+
^
^ +z ^ +
a\
*a^^
......
(320)
where
i-#i-#i) Vdn'dv'dw'pdpde,
......
an equation
in
of the
is
first
(321)
order of small
quantities.
On
dividing out
by
/a
i-^+-5: ^-+
cu
\dt
/01 by
its
value from
becomes
a\
ov
dw
ox
cy
ozj
v +^
y
^^o-+^o-+^o-+^^-
x {log vA
hm[(u - uQ f +(v- z;
2
)
+ (w - ^
2
)
]}
/.
......
(322)
momentum
\
\p
in the direction
Ox
is
readily
(323)
w vA
241
rf
0dudvdw =
(324)
0,
,(325)
With
restricted in this way, the equation of continuity
again given by equation (285), so that
d
_
is
UQ ^- are
uX
We now
o
(
+ (v - v
where 7
2
)
2
)
Z]
It will
242
z
mu, mv, mw, mc
which
satisfies
equation (327)
C, D, E>
the five necessary conditions.
may
We therefore suppose
that the molecules are centres of force repelling according to the
where
r,
orbit,
orbit
is
is
_
_ /"/TO r*
r2
1 \ Z.SK
TTi^Tftg \s
in
is
'
i j /^
The method
of
196
is
identical with
is
avoided by
2, p. 36.
NOT
1ST
A STEADY STATE
243
d"
==,
(328)
.(329)
dr/S9
0,
and therefore by
0.
is
given by
51 la/
allel
are of course
V sin d
'.
F.
Except
a
members
tion of
3^ 33
* This
42. I am in
figure is given by Maxwell, Collected Works, 2, p.
debted to the Cambridge University Press for the use of the original block.
244
In
fig.
34.
OR,
GXR
lie
as centre.
Fig. 34
F2 =
and the
(u
- uY + (v - v)* + (w - w;) 2
f
From
w and u
f
,
v' y
it/.
G'X =
we have
in which
'
(u'
cos
cos
G'X = -
~-
cos
GX = ^1
e,
so that
.(330)
-V =
XGY
&> 2
(' - u) (v -
o) z
and
XGZ by <y3
we have, in a
(v
To determine
and
XGT by
245
et>
2,
),
OX Y, X Y = %n
thus
1>)
0,
(w'
cos
0.
6> 3
m^u + m^u' =
determine the velocities after
m^ + m^u',
...... (331)
collision.
- u) cos 2
W+VF 2
(u
we
obtain
197.
and the
we have
of /
From equation
(329)
so that
where
Zv^ [(MI
4-
2 ) /t/w^
wij-
J,
J=
ff
Jffei
In
this integral,
it
will
be remembered that
as yet undetermined, of u, v
and
w?; <&% is
is
,(333)
a function,
246
We
=
With
u^(c).
(333) be denoted by
J=
as defined
by equation
J(u),
where
Then a
solution
(lu
+ mv + nw)$i(c)
......(334)
Now
(335)
direction
value of
(I,
m,
/ given by
J=
J(lu + mv + nw),
(336)
-f
mv 4- nw)
U(u)
mJ(v)
nJ(w)
0,
Vartrage, iiber die Kinetische Theorie der Materie und der Elektrizit&t
(Leipzig, 1914), p. 185.
f Kineti&che Theorie der Vorgdnge in mdssig verdunnten Gasen (Inaug.
Disaertation, Upsala, 1917).
it
J(u)
uxi(c), etc.
U$i(c)
J=
uxi(c).
while a solution
leads to
Thus the
198.
will
be
^ + ^2 -+^3 4-^4
......(337)
where
^ ^4
1?
and
^2 ^3
only.
2
terms. Their expansion for a series of powers of c has been con
numerical
results.^
sidered by Enskog,f wno has also calculated
are now in a position to apply the analysis of the present
chapter to the exact solution of physical problems.
We
*
}
f L.c. Chaps,
n and
in.
248
Viscosity
dh
Bx
_ c*_f*
~~
~~
^-
3v
^oy
tix
We may
gas so that
'
cz
dy
3v
so that
0.
cz
X - T = Z = 0.
As a consequence of this,
i/rl9
^2 ^3 are
,
all
= ^4
The law
of distribution
now becomes
(cf.
equation (315))
The
Lamb, Hydrodynamics,
p. 512.
f L.c. pp. 88
ff.
NOT
1ST
STEADY STATE
249
Condition of Heat
200. Consider next a gas which is in a steady state, and devoid
of mass-motion, but which is not at a uniform temperature. For
simplicity suppose that the gas is arranged in parallel strata of
equal temperature, so that the temperature is a function of z
= Y=
0.
only, and that no external forces act, so that
The
and
must be found from the
ex
ex
condition that there shall be no mass-motion, i.e. the process of
conduction must not be complicated by the addition of con
relation
vection.
To
between
we must have
On
^ in
substituting for
integrations,
&
Using
we obtain a
this relation,
is
0.
this equation,
linear relation
ex
and
r~.
ex
given as a multiple of ex or of
,
ST
155.
Diffusion
To
discuss the
GENERAL THEORY OF
250
A GAS
The
expression,
172.
and
is
tvjcx in this
u and
motion parallel to the axis of a;. On putting Q
this
becomes
the
inverse
equation
fifth-power law,
assuming
for steady
--_
2hm l
ex
--
Vm
9
mz
~^-
-AI(UM
2
1V
UM).
01/J
(341)
v
;
The
251
Chapman
in the
proportions.
*
252
Hot bulb
H
H
2;
2;
CO 2
CO 2
The
may
be regarded as being
verified.f
The steady
state
interest in that
it
Elliott
Roy. Soc. 99
(C.
258.
J Phil.
Mag. 34
(1917), p. 146.
PhiL Mag. 38
(1919), p. 182.
Chapter
Degrees of Freedom
The
total
254
is
equal to the
sum
stituent systems.
If atoms are regarded as points, each atom has three degrees
of freedom. A diatomic molecule must therefore have six degrees
coordinates to specify
its
<?i>fe
The
......
2n>
(342)
by
tells
us that,
if
these quanti-
THERMODYNAMICS
ties are
255
all
it
experiences
and
define
P*
Pn
by the equations
Ordinarily
are x, y
z,
its
is
energy
E
so that the
momenta
are
dE =
mx,
ex
.
-TT-T
momenta reduce
moving mass, mu, mv, mw.
In
simplification
(342)
and
(343)
by
etc.
to the ordinary
momenta
of a
Pi*
When
4P.__!^.
~
dt
which it
q's and p's.
in
is essential
dq,'
that
^=M
dt
.....
(345)'
(
3p,'
E is expressed as a
function of the
256
spaces of three dimensions, for the spaces we use exist only in our
imagination. If the configuration and motion of a dynamical
system are specified by the 2n quantities (344), we can imagine
these quantities represented as the coordinates of a space of 2n
is
called a "phase-space".
Each point
of the system. The rates at which the point moves in the different
directions of the phase-space Le, the components of velocity of
the point are given by equations (345). The ratios of these com
ponents give the direction of motion at the point, and we see that
this
AND THERMODYNAMICS
257
We
moving
are
at a rate
p-^ 4- ?
moving apart at a
There
is
rate
particles
dt, this
dP t
becomes
.......... (346)
From
these
we
(345).
so that the
similarly for every other pair of coordinates,
and the ex
to
is
zero,
coefficient of <ft in expression (346)
equal
and
JKT
..,,
In other words,
I7
258
first
is
generally
is
found in
be for either of two reasons: either that the points in the phasespace tend to crowd into those regions of the space for which
the property is true, or else that the property is true for the whole
of the space. Liouville 's theorem excludes the first alternative,
so that the second must be the true one. We must now examine
this in
some
detail.
Let
system by a
W W
cordingly
WJW.
AND THERMODYNAMICS
259
WJW
W W
it is
260
may
arise
W W
in
it is easily
gas to be zero.
One property which can never be changed in a conservative
system is that of having a certain value for the energy. Thus in
discussing the normal state, we need only consider systems having
specified amount of energy. In the same way, if the system has
other quantities or properties which are invariable, account must
be taken of this invariability in specifying the normal state. The
AND THERMODYNAMICS
261
. . .
energy of oxygen
-f energy of nitrogen
E = # + #2 +... = /1 (0
1
1,
2 , ...
s )+f*(0
0^
...
0.*)
+ ....
is
Ez
Then the property
E
E2
to
to Ez
-f
dEl9
+ dE2
etc.
#2
>
^H.
t ) lies
and so on.
The volume W^ throughout which the property
written in the form
holds,
(347)
.(348)
may be
is
(349)
262
where the
first
integral is
the second integral within the limits (348), and so on. The
first integral can depend only on El and dEl9 and so must be of
the form F^EJdE^ Similarly the second must be of the form
F%(E2 )dEfr and so on. Thus W^ must be of the form
(347),
W,
- F^EjFdEJ ...dEidE^. =
Ji(^) Ji(^)
-. *.
...... (350)
WL has its
we
maximum
value.
slightly
values of
E E
dE2
dE,
==
jfir
j_
and equation
0-^2
^-^3
*^-^4
* * *
(351) becomes
If : is to have
values of 8E& 8E&
its
...,
maximum
so that
value, this
must vanish
dE2
The solution
for all
we must have
....... (
263
AND THERMODYNAMICS
Equipartition of Energy
21 1
where m
mu^mv^mw^mu^mv^mw^
tion (349), so that
..d0idff t ...dff9
l9
......
62
. . .
(353)
98 for which
EI
lies
..
6/1+01+
or
...
which
is
On differentiating
this in respect to
range dE-^
all
values which
make J^
lie
within a
is
C is
jP(
1)
dElt so that,
264
"
2'
~~_ J_
_ dlogF(E z _
)
~~
by the equations
E = $sT,
1
EZ
\tRT,
etc.,
......
(356)
where
$,t, ...
equations (356) is not only the most likely partition, but also
expresses a "normal" partition in the sense of 208; that is to
say, this partition is infinitely more probable than any other.
We have accordingly shewn that those parts of a system, say
in which the energy is of quadratic type, will necessarily
JEj, J72
tend to the partition of energy specified by equations (356). These
,
. . .
AND THERMODYNAMICS
265
f(u, v,
(357)
of distribution of coordinates
. .
is
Ce-^dxdydzdudvdwdtfridfit
is
...,
$!,
$2
. . .
$8
<j>
260
of
/Mi
V 7T e-Wdtdfa
(360)
the constant being determined from the condition that the inte
gral, taken from $5
cQto$5 = -foc, shall be equal to unity.
to the energy is
The mean value of the contribution from
<j>
of course jr or
^RT,
as before,
and we have
_
expressing the theorem of equipartition of energy in a
new form.
THEBMOBYNAMICS
213. Let us suppose that our gas, containing vessel, etc. are
in their
most probable
stat-e,
specified
by the equations
dlogFM^dlogfiJJSJ^
~
"
dEz
dE^~
_
"
"
'RT
..... ~ (6 * L)
Let the gas now be heated from outside, and suppose that, after
the gas has again attained its most probable state, we find that
Et ... have been increased to E^ + dJE^ z + dE2 ...
J5J
13
With
defined by equation (350), let us put
. .
.}
+a
P by an amount
Thus
2E = RdP.
AND THERMODYNAMICS
267
where S
is
the entropy.
S=
We accordingly
see that
E^Efr....
We
>
different temperatures
given by
the
268
has reached
its
maximum
value.
The
restriction.
make
attached to them,
possible to
remove
this
S = RlogW^ + a.
But
it
(363)
S by equation (363),
Here H is the volume of that part of the generalised space
which represents systems having the partition in question. This
volume measures, in a sense, the probability that this special
entropy
"An
is
proportional to the
increase of entropy
probability.
We have so far thought of the steady state and the final state
as the
same
thing,
but we
probability,
which corresponds to the steady state is far larger than that which
corresponds to any other state. If the number of molecules in the
gas were infinite, it would be infinitely larger. With the number
of molecules in the gas enormously large,
it is
enormously
larger,
AND THEBMOBY^AMICS
but not infinitely
269
maximum
so.
If W^
entropy, and
infinite time, it is
When applied to
first
it is infinitely
And
moreover, if we attempt
to boil the water a sufficient number of times, it is infinitely
probable that the water will, on some occasions, freeze instead of
boil. The freezing of the water, in this case, does not in any way
imply a contravention of the laws of nature: the occurrence is
merely what is commonly described as a "coincidence", exactly
similar in kind to that which has taken place when the dealer in
a game of bridge finds that he has all the cards of one suit in his
water
own hand.
The analogy of the
distribution of a
pack of cards
will help
us
270
up,
AND THERMODYNAMICS
271
ink.
composed
by red, and the other solely by blue ink. And from the dynamical
standpoint it is no less probable that this should occur, than that
we should be able to start stirring inks which were separated
initially as
217.
regards colour.
With reference
to this subject,
This
is
it is
undoubtedly
true so long as we can deal with bodies only in mass and have no
power of perceiving or handling the separate molecules of which
they are made up. But if we conceive a being whose facilities are
so sharpened that he can follow every molecule in its course, such
A and B, by a division in
and that a being, who can see the
individual molecules, opens and closes this hole, so as to allow
only the swifter molecules to pass from A to J5, and only the
which there
is
a small
hole,
to
come about
if left
272
FLTJCTrATIONS
Formula (358) or (359) shews that when no external
forces act on a gas, the normal state is one in which the density is
uniform throughout. In this state, and no other, the entropy is
218.
a maximum.
Nevertheless, we saw in 80 how the number of molecules in
any small volume of the gas must continually fluctuate as
molecules enter or leave the volume. The entropy, then, can
never be permanently equal to its maximum value; there must
at
any
A,B,C,
are
...
selected molecules
all outside, is
/ 1 VP /
Np
molecules
Vv
*)
AH
pl(N-p)l~
N(N- 1) (N- 2)
pi
...
(N-p+ 1)
AND THERMODYNAMICS
273
inside Q,
/ 1
Y1
_ IV*
Q becomes
......(365)
log<2
= log V 27771
t
so that
2tTl
Q = <j2nne~2Z.
j
.....
.(366)
18
274
This gives the chance that the number of molecules in the volume
Q shall differ by 8 from the average value n. Or, if we divide up
the whole gas into "cells" of volume Q, it gives the proportion
of the whole number in which there are n + S molecules.
value of S 2
is
*Jn.
108
(1933), p. 634.
Chapter
XI
problem in more
detail.
Calorimetry
is
known
in terms
P=f(>T)As
in
12,
(367)
is
dQ = NdE+pdv.
(368)
dQ - NdE.
Nm
dT will
be
JCv NmdT,
_j_dE
~~
JmdT'
is
con
T change, so that
is
276
so that
when dp =
*-()"+(&)*
0,
cpjcv
0),
is
cp/Sv
If Cp is the specific heat at constant
JCp NmdT, so that
P
n _n
Specific
is
pressure, this
is
equal to
perfect,
find
that
~
dp/dv
~ NR
p
'
become
20.
Molecular Structure
222. Experiment shews that for many gases C and Cv are
p
approximately independent of the temperature through a con
siderable range of temperatures and pressures in which the gas
is shewn by a
must mean that dEjdT is a constant,
CALORIMETBY
A2TD
MOLECULAR STE^CT^T EE
217
and therefore that the mean energy of a molecule of the gas stands
a constant ratio to the translational energy. As in 21, let us
denote this ratio by (1 -}-/?), so that /? is the ratio of internal to
translational energy. Then
in
(371)
dS
=
gy
so that
i-B(l+^)-
(372)
R
(374)
C/ //&
whence, on
division,
r*
\
<>
/,
(375)
others:*
Values of 7 for
air at
0=
0=
100 C.,
=
B=
500
900
6
*
0C.,
C.,
G.,
1-405,
7=1-404,
7=1-403,
7 = 1-399,
V = 1-39/f
278
(376)
as
is
and
for the
it is
Ann.
d.
279
280
is
n
3'
n=
so that
column on
3/#.
This
is
p. 279.
why
3/?,
values.
Monatomio Gases
The
collision.
six
is
the atom.
281
n=
y=
giving
Diatomic Gases
226. After
possible
is
n=
n=
2,
0,
giving
y=i|.
*
282
methane
CH
CH C1
CH C12
Methane
Methyl chloride
1-313
1-279
1-219
1-154
1-130
4
3
Methylene chloride
Chloroform
CHCl*
Carbon tetrachloride
We
derivatives:
CC14
6-4
7-2
9-0
13-0
15-4
atoms
7=
mately
tt
1-4,
and
7=
Bromine, Iodine 7 =
Chlorine
+3 =
Chlorine iodide
7=
7=
have approxi
5,
1-333
1-293
Bromine iodide
all
n+3 =
n+ Z =
and
6,
6-8.
chlorine,
1-33
n-\-
1-317
^+3 =
6,
6-3.
These figures shew that one halogen can be put in the place
of hydrogen without producing any difference in the values of 7
* Phil. Trans. 186
(1895,, p. 564; 185 (1894), p. 1.
f Wiedemann's Annalen, 13 (1881), p. 20 and 17 (1882), p. 85.
283
MOLECULAR AGGREGATION
The discussion of the physical properties of gases given in
and
the preceding chapters has been based upon the supposi
this
a gas can be regarded as a collection of separate
that
tion
dynamical systems, namely molecules, each of which retains its
identity through all time. As a close to this discussion, we may
examine what changes are to be expected if the supposition is
regarded as an approximation to the truth only, and not as being
wholly true. We shall first consider what complications are intro
duced by the possibilities of molecular aggregation, leaving the
228.
We
Ae-hm*dudvdwdxdydz,
......(377)
A and B in
where
expression becomes
W being a function of
u=
r.
If
we
a=
u'
109,
u, etc.,
and write
*d^
7rf
.(378)
284
The
A 2 expresses
shews that
wF
%mV 2 + 2*F
285
we
find for vt
which \mV* + 2^
The
V and
negative.
total number of constituent molecules per unit
r for
is
volume
is
...,..(381)
AL
Eliminating
is free,
rr
e-
from equations
form
we obtain a
'
...... (
where
286
v^
+ 2^.
where q
is
......(384)
The foDowing
g calculated in this
N0 2
'
287
v 2 to v\ ought to be
readings at the same temperature. We have from
all
this equation
so that
=Z
Vl
iQ- 1)
2,
s=1 +
llrv
Vl
^ [Zvrfm
2v$(T).
ET
shewing that the ratio
~-
we obtain
'
same temperature,
The following table, calculated from the observations in the
table of p. 286, will shew to what extent this prediction of theory
is borne out by experiment:
at the
ion of
NO a
equations (383).
From
^=
(
f fe
we
find
.....
(385)
will
288
appreciable,
it
falling
temperature.
where
o)
2
replaces the integral 4;r r dr,
I
"
77
...... (386)
that
tween the
effected,
in
which
limits
and we
Rfi,
find
iP is negative.
W=
is
289
dissociation.
An
Aggregation of
XQ 2
At very high
term, so that q
to its
temperatures, the series (381) reduces
in permanent
1, and there are no molecules
combination.
At lower temperatures k is greater, so that not only is A greater,
mV
but the exponential e-^ ^^\ in which it will be remembered
that the index is always positive, is also greater. The relative
the series (381) is therefore
importance of the later terms of
the temperature for which h
of
values
reach
we
greater. Finally,
has so great a value that the series (381) becomes divergent.
tend to form into clusters
According to our analysis the molecules
at this point, each containing an infinitely great number of mole
cluster absorbing all the
cules, and, ultimately, into one big
molecules. By the time this stage is reached the analysis has
ceased to apply, as the assumption that the molecular clusters are
It is, however, easy to
small, made in 230, is now invalidated.
* Trans. Connecticut Acad. 3 (1875), p. 108 and (1877), p. 343;
SiUiman Journal, 18 (1879), p. 277. Also CoU. Works, 1, pp. 55 and 372.
237.
f Oomptes Kendus, 64 (1867), p.
JKT
**
290
molecular clusters
The series
is
a saturated vapour.
(381)
A
.
increases,
and
accompanied by a
increase of pressure
is
conversely, so that an
rise in the boiling-point
of the substance.
Since
values A
the form
f(v>
T)
Q,
(388)
T at the boiling-point of a
liquid.
The
233.
Critical Point
become
identical, so
that the series (381) cannot become divergent. Thus for very high
values of T equation (385) can have no root corresponding to a
Pressure, Density
234. It will
now be
perature which
clear that
and Temperature
291
same meaning as
is
. . .
given by
...).
Promt a comparison of
. . .
235.
fect
The
just
The
is
We
have therefore, in
and the present chapter, examined their effect with the
Chap,
help of two separate simplifying assumptions. In Chap, in,
following Van der Waals, we regarded the gas as a single molecular
cluster containing an infinite number of molecules; and in re
placing the whole system of the forces of cohesion by a permanent
mathematical treatment to be
possible.
large cluster
account
altogether. The former treatment, because it failed to take
of the formation of small clusters, led to the erroneous result
(equation (71) and 45) that the internal pressure is proportional
292
summed up by
considers
saying that the treatment of Chap,
that
while
the
of
to
the
mass-clustering,
present
tendency
only
chapter considers only the tendency to molecular-clustering
So long as the deviations from the behaviour of a perfect gas
are small, the two tendencies may be considered separately, and
the total deviation regarded as the sum of the two deviations
caused by these tendencies separately. On the other hand, as we
approach the critical point the phenomena of mass-clustering and
.
Calorimetry
236. The formulae which have been obtained for the specific
heats will be affected to a greater or lesser degree by the possi
bilities of molecular aggregation. For in raising the temperature
of the gas work is done not only in increasing the energy of the
various molecules, but also in separating a number of molecules
from one another's attractions. This latter work will involve an
addition to the values of Cp and Cv such as was not contemplated
in the earlier analysis of
220-223. We should therefore expect
the values of Cp and Cv to be in excess of the values obtained from
our
Op
by Berthelot and
Ogier,*
who
293
From
27
27
27
27
27
to
to
to
to
to
67
C =
C.,
100,
150,
200,
300,
1-62,
1-46,
1-115,
0-85,
0-64.
NO
NO
somewhat
different
that 3 +
3/?
we should come
for
to the conclusion
6-6 for
dry
steam.
The
DISSOCIATION
treatment similar to the foregoing may be applied to
must be re
the problem of dissociation. The former molecules
molecules
of
clusters
by single
former
the
and
placed by atoms,
237.
molecules.
are each
Let us consider a gas in which the complete molecules
2. As in
suffixes
the
1,
composed of two atoms, distinguished by
* Butt. Soc.
p.
916; Ann.
93 {1882),
Chimie [2], 37 (1882), p. 434; Comptes Rendu*,
te
Chim. & de Phy*. [5], 30 (1883), p. 382; Recued
d.
294
=
=
where ^P
is
m m
......
and
9)
ft
m +m
*
docdftdy^r^dr.
......
(390)
This latter law is arrived at in the same way as the law (378),
except that the scheme of transformation of velocities must now
be taken to be
-.
m*u
_i + mu
*__
a=*u
m^ -f wi 2
u, etc.,
109.
is
limited to
T72
r
dissociation
is practically
unlimited.
205
we have imagined.
been encountered in
Appendix
Nf(v) dv, and the number for which w lies between w and w-\-dw will be
Nf(w) dw f where / always stands for the same function.
"Now the existence of the velocity u does not in any way affect that of
the velocities v or w, since these are all at right angles to each other and
independent, so that the number of particles whose velocity lies between
t* and u+du, and also between v and v-f dv and also between w and
w-\-dw is
Nf(u)f(v)f(w) dudvdw.
If we suppose the
particles to start from the origin at the same instant,
then this will be the number in the element of volume dudvdw after unit
of time, and the number referred to unit of volume will be
Nf(u)f(v)f(w).
is
we
find
wz =
)
Appendix II
THE H-THEOREM
In Chap, iv ( 87) we discovered certain steady states for a
gas, but it
was not proved that a gas would necessarily attain to one of these steady
states after a sufficient time. The following proof of this was
originally
given by Boltzmann and Lorentz.
H be defined by
H = I jlflogfdudvdw,
..... (a)
is
general case.
After an interval dt, the value off log/ corresponding to
values of u, v, w will of course have changed into
or,
what
is
Hence the
any specified
increase in
~^~
dt f will
U,
or, substituting
be given by
...... (6)
e dudvdwdu'dv'dw'dv.
Since
formula
(c)
We
(JJ'-ff'}V<r*
cos&dudvdwdu'dv'dw'du.
APPENDIX
300
III
Thus the whole value of the integral (y) comes from a small range
of values surrounding the values 1 = ea = ... = 0; i.e. the values of
JElf JStr ... given by equations (a). Thus the integral (g) reduces to the
right-hand member of equation (/), the small range dE being comparable
with <js.RT the small range dEt being comparable with *jt,RT, and so
on. These small ranges are of course small in comparison with the whole
values of E^ E^ ...; thus dE is comparable with E^^'s, dE% with E 2 <\t,
f
and so on.
With such values for the small ranges dEl9 dE2 ..., the value of
Wi+Wi given by equation (g) becomes identical with the value of "R^
given by equation (/). Thus we have WJW2 infinite, shewing that the
,
partition of energy
Appendix IV
consisting of
<
the state (i.e. velocity and positional coordinates) of the molecule. The
states of all the molecules can be represented by a collection of points in
this space, one point for each molecule. We want to find the law according
to which these points are distributed in the space.
Let T denote the density of points in this space the quantity which we
are trying to find so that
..
will
<j>i
d^ tj
...... (a)
lies
between
on.
Let us now suppose the whole of this space divided up into n small
rectangular elements of volume, each of equal size tt), and let these be
identified by numbers 1, 2, 3, .... Let us fix our attention on a special
distribution of points, which is such that the number of points in
elements 1, 2, 3, ... are respectively a^, o^, o^, .... Let any distribution of
be spoken of as a
points giving these particular numbers G^, Oj, %,
distribution of class A. Similarly any distribution of points giving
another set of numbers blf b%* &a * ro&y he spoken of as a distribution
of class B, and so on.
Each point in the original generalised space will correspond, as in 206,
to a complete distribution of points in the space now under consideration.
The distribution corresponding to some of these original points will be
a distribution of points of class A, corresponding to others it will be a
distribution of class B, and so on. We proceed to evaluate the volume,
say WA, of the original generalised space which is such that the points
in it represent systems for which the distribution of coordinates is of
. . .
A.
This volume
class
is
by
APPEHDIX IV
302
In this expression the
number of ways in which
it is
The remaining
factor,
say A, given by
for a
etc.,
WB = A#s, etc.
= XO^
TF4
system of class B,
Stirling,
(e)
the value of pi
when
Lt />!=</!
On
Lt log p
log
and using
this value
*"
log 04
= log -V! -:
s
=
If
(d) t
log a t
(JY-f J) log
A'- J (n-
1)
log
2w-(a, + 4) log r
n.
we put
6A
(a.
+ i) log
',
...... (/)
...... (g)
WA proportional to er yx
The most probable partition of energy
ob\*ioiisly obtained bv
making WA a maximum, and therefore K a minimum, for different values
Since
WA = A^,
etc., it is
clear that
is
*.
is
of
j,
2,
a,
as given
by equation
(/),
we
find
The variations &zz 3a& ... are not independent. They are
necessarily
connected by two relations, and in some cases by more. Of the two
relations whrjh ore certain, the first
expresses that the total number of
,
APPEKDIX
IV
303
number
and
is
therefore
...... (0
o,
***!
while the second relation expresses that the total energy of the A'
molecules is equal to the allotted amount E^ Let % denote the energy
associated with a molecule represented by a point in cell 1, so that e l is
a function of X , <^2 ... Zpr the coordinates of the first cell. Let e 2 be the
energy associated with a molecule represented by a point in cell 2, and
so on. Then the total energy of the
molecules, when the distribution
of coordinates is of class A, will clearly be al l + a t
..., so that we
,
<f>
e^
must have
relation
0.
...... (j)
*-l
/i t a s
AT,
***i
relation
...
be
In many problems there will be six equations of this type, the different
three components of linear momentum, and three com
frfs representing
ponents of angular momentum. We may, however, be content to take
one relation as typical of all, and shall suppose it to be given by the
equations just written down.
Following a well-known procedure, we now multiply equations (/),
and add corresponding mem
0"), (&) by undetermined multipliers p, q, r,
bers of these equations
and equation
Since a^ a 2
...
We
obtain
now given by
+ lo g ^+^-fge,-f r/ =
+ ^L
+.n
0,
the equations
{*=
1,
2, ... n).
o-\
may
is
(h).
are
all
APPENDIX
304
IV
which
is
for every
e -n+n e -ifftf/o
na>
values of &, &, ... ^ 2jf since equation (Z) was true
Changing the constants, this equation may be rewritten
true for
cell.
be
all
T *Jt **"
>,
now
in
fi is
Ce-'^e-^^"*^
-'dfadfa
. . .
d^.
From the result obtained in Appendix in, it follows that this distri
bution of co-ordinates is infinitely more probable than any other, and so
expresses a normal state of the system.
If there is no potential energy, there will be three co-ordinates x, y, z
in space, and these will not occur
fixing the position of the molecule
the chance of finding a
except through the differential dxdydz. Thus
molecule in a email element of volume dxdydz, however chosen, will be
the justification for the
proportional simply to dxdydz. This provides
82.
in
introduced
chaos
of
molecular
assumption
V
TABLES FOR NUMERICAL CALCULATIOXS
Appendix
The following tables will be found of use for the various numerical
calculations which are likely to be needed in connection with kinetic
theory problems. The values of y(x) are from a table by Tait in the paj>er
already referred to (p. 145).
KT
Appendix VI
ju
e-**du,
(i)
where n
finite
.(ii)
The
to
u=
oo,
the results
occurrence that
Each
above
it
INDEX OF SUBJECTS
^-coefficient of Van der Waals, 67, 81
Absolute scale of temperature, 26
Boundary,
effect of,
of,
66, 82
on law of distribu
292
Brownian movements, 7,
point, 274
Charles' law, 29, 54
affinity,
259
70
237 7 242
in
assumed
by
Maxwell,
99
222
Chemical
absence
190
tion, 64, 68
density at, influenced by cohesion,
67,
vm
42
Dissociation, 293
Distribution, laws of, *e*
Law
Dynamics of collisions,
Effusion of gases, 58
in solids,
Electricity, conduction
of,
INDEX OF SUBJECTS
308
solid, 55,
Low
194
temperature phenomena:
duction of electricity, 197
specific heats of gases, 279
15,
267,
Gas-thermometry, 78 if.
Gaseous medium, statistical mechanics
of a,260fif.
Gaseous state, 9, 289
Generalised space, 256
jET-theorem, 297
56
Ideal gas, 54
Internal energy of atoms and molecules,
Osmotic pressure, 55
Heat,
35,
con
279
Normal
Normal
properties, 258
259
state,
Number
Isothermals, 83 ff.
(experimental) of C0 2 , 91
(experimental) of isopentane, 95
Joule-Thomson
Planetary atmospheres, 42
effect,
63
Law
233
Liquid, superheated, 90
72,
290
Pressure-coefficient,
78
Pressure-diffusion, 251
Probability
Random
Random
in,
INDEX OF SUBJECTS
Reduced equation of state, 98
Reflection of molecules from a solid
21, 52, 169
from
and
of,
viscosity, 183
Solid state, 4
Solids, conduction of heat
in,
and
electricity
194
Superheated
liquid,
25
thermodynamical, 20
Self-diffusion of
Size
Temperature,
300
14,
of,
Wiedemann-Fraaz law,
1%
90
INDEX OF NAMES
Amagat, 101
Bieiz, 144
Andrade, 2
Binkele, 174
Birge, 31
9,
24
Andrews, 91
Blankenstein, 169
Aristotle, 2
Avogadro, 30
Bohr, N.,
Bannawitz, 188
Baumann, 178
Beatty and Bridgeman, 102
Behn and Geiger, 279
Bernoulli, D., 3
Berry, 192
Berthelot and Ogier, 293
INDEX OF NAMES
310
Erode, R. B., 143
Heraclitus,
Herapath, 3
Hercus and La by, 189
Hilbert, 211
Callendar, 79
Capstick, 282
Carnot, 25
Hooke, 3
Howarth, 193
Chapman,
Ibba, 252
250
Chapman,
Chapman,
S.
S.
Chappuis, 79
Charles, 29
Clausius, 3, 4, 69, 90, 100
Kalahne, 277
Kamerlingh Onnes,
Dalton, 29
Democritus, 1
Deutech, 213
183, 277
68 ff.
Dooteon, F. W., 218, 251
Dorsman, 166, 174, 179
Brude, 194
Dunoyer, L., 10
192, 194
Dieterici,
182,
Epicurus, 2
Frank, 196
Gabriel, 178
Gassendi, 2, 3
Gauss, 121
Gay-Irussac, 62
Gerl&ch, 11
Germer, 125
Gibbs, Willaxd, 270, 289
Gibson, 165
Graham, 59, 181
Hall, E. E., 126
Hartek, 202
Hass4
ISO, 181
188,
Lammert, 128
Langevin, 209, 210
Langmuir, 54, 128
Leduc, 79, 279
Lees, C. H., 196
Lennard-Jones, 77, 179
Leucippus, 1
Liouville, 258
Loeb, 30, 54, 126, 191, 193
Lonius, 213
Lorentz, H. A., 196, 235, 246, 297
Lorenz, 196
Lummer and
Pringsheim, 279
Maas, 174
Makower, 279
Markowski, 174, 178
Masson, 250, 279
Maxwell, J. Clerk,
Mayer, H.
F., 143
INDEX OF NAMES
Meissner, 128
Meyer, 0. E., 141, 201, 209
Michels and Gibson, 165
MiUikan, R. A., 169
Mott, 193
8,
72
Niemeyer, 279
Onnes, Kamerlingh, 83, 98, 99, 100,
166, 174, 178, 179, 180
Ornstein, 130
Perrin, J., 8, 31, 223
Pidduck, 211
Piotrowski, 168
Poiseuille, 168
Ramsauer,
G.,
Thiessen, 182
Sir J. J., 165, 283
Thomson,
Thomson,
62,
Pospisil, 32
Poynting, J. H., 165
143
311
Sciiroer, 182
Schultze, 174
Schwarze, 189
Sih Ling Ting, 124
Smith, C. J., 178, 183
W. (Lord
Sir
Kelvin),
214
169,
Waterston, 3
Weber, 166,
174, 179
Wiedemann, 196
Wild, 202, 215
Sarrau, 101
Scheel and Heuse, 279, 281
Scheffers, 128
Yoong,
Zener, 193
Wood, R. W., 54
S., 95,
Zartmann, 127
99
279
26,
102727