C HA P T E R 1 9

The Physics of Gases

19.1 The Nature o f Gases are bodies and there is void in which these bodies
are placed and through which they move
Early Concepts
about. . . . " Ordinary matter is composed of these
two realities: solid, everlasting particles and, on
From the time of the earliest recorded philo
the other hand, the void, or what we might
sophical speculations to the present day, the
loosely call the vacuum.
human mind has been haunted by some para
Note that by their very definition these
doxical propositions: On the one side we can with
atoms are not directly perceptible, and until
our hands cut or subdivide gross matter-a rock
about 150 years ago there were very few fruit
or a quantity of water-into smaller and smaller
parts, until the crudeness of our tools or te
ful and unambiguous consequences that could be
drawn from the atomic hypothesis to serve as
deficiency of our sight, but never the matenal
experimental tests of this challenging sp:culative
itself, calls a halt to our experiments. Consequent
idea. Even at the beginning of the twentieth cen
ly, we might conclude that matter is inherently
tury when such confirmation was at hand, there
wer important scientists who still rejected the
infinitely subdivisible. But on the other hand, our
imagination encounters difficulty when ,!,e
concept of atoms as too convenient a fable,
demand that it present to us matter as a collectlon
unworthy of serious consideration by " hard
of truly infinitely small parts, and this view
boiled" investigators.
makes for logical problems as well. So where our
It is therefore not surprising that the struc
senses tend to one view of mattel; our reason per
ture of matter was for a long time the subject of
suades us of another.
inconclusive discussions, whether the atomistic
The great compromise was formulated about
view was rejected (as by Plato, Aristotle, and their
2400 years ago by the Greek philosophers Leu
diverse followers) or in some form accepted (by
cippus and Democritus, and later extended by
Galileo, Gassendi, Bacon, Descartes, Newton,

Epicurus. It is of course the atomistic idea (Sec
Leibniz and many of their contemporaries) . We
tion 3.2). Our senses and our reason would both
might s eculate that the idea of small particles
rest satisfied if we assumed that matter is indeed
became more convincing as a consequence of
divisible far beyond immediate experience, but
Newton's work, in which, as we have seen, the
that there does exist an ultimate substructure of
postulates leading to the law of universal grav
infinitely hard, uncuttable, indivisible particles,
itation provided that the particles of matter are
which we might provisionally name corpuscles
the agencies of mutual attraction. Of course,
or atoms.
these are not necessarily identical with ultimately
The Roman poet Lucretius, whose book
De Rerum Natura (The Nature of the Universe) indivisible particles or atoms. Yet the surpassing
success of the treatment of gravitation in terms
was cited before in connection with the origins
of the mechanics of particles could turn the
of the law of conservation of mass, exemplified
thoughts again to the idea that the mechanics of
the teaching of those now-largely-lost Greek
small discrete bodies is the key to all phenomena.
original works. He gave a summary of this atom
Newton himself wrote in the introduction to
istic science, which (according to George Sarton)
the Principia:
marked the climax of Roman scientific thought.
We have noted, of course, that Lucretius' work Then the motions of the planets, the comets,
is not to be regarded as primarily a science text. the moon, and the sea are deduced from these
His leading theme is "All nature then, as it [gravitational] forces, by propositions that are
exists by itself, is founded on two things: There also mathematical. If o nly we could derive
266 I The Physics of Gases
the other phenomena of nature from mechan
ical principles by the same kind of reasoning!
For many things lead me to have a suspicion that
all phenomena may depend on certain forces by
which the particles of bodies . . . either are
impelled toward one another and cohere in
regular figures, or are repelled from one another
and recede. Since these forces are unknown,
philosophers have hitherto made trial of nature
in vain. But I hope that the principles set down
here will shed some light on either this mode of
philosophizing or some truer one.
Later, in the Opticks (published 1704), we find
this visionary, yet still unformalized opinion on
atomism:
All these things being considered, it seems
probable to me that God in the Beginning
formed Matter in solid, massy, hard, impene
trable, movable Particles, of such Sizes and
Figures, and with such other Properties, and in
such Proportion to space, as most conduced to
the end for which he formed them; and as
these primitive Particles being Solids, are incom
parably harder than any porous Bodies com
pounded of them; even so very hard as never
to wear or break in pieces; no ordinary Power
being able to divide what God himself made
one in the first Creation . . . . And therefore that
Nature may be lasting, the Changes of cor
poreal Things are to be placed only in the
various Separations and new Associations,
and Motions of these permanent Particles;
compound Bodies being apt to break, not in the
midst of solid Particles, but where those Par
ticles are laid together . . .
God is able to create Particles of Matter of
several Sizes and Figures and in general Pro
portion to the space they occupy, and perhaps
of different Densities and Forces . . . . Now, by
the help of these Principles, all material Things
seem to have been composed of the hard and
solid Particles above mentioned-variously
associated in the first Creation by the Coun
sel of an intelligent Agent. For it became him
who created them to set them in order. And if
he did so, it's unphilosophical to seek for any
other Origin of the World, or to pretend that
it might arise out of a Chaos by the mere Laws
of Nature; though being once form'd, it may
continue by those Laws for many Ages.
Part of Newton's preoccupation here is the
ological, and for a most excellent historic reason
that we must not pass over if we wish to under
stand fully the development of the atomistic
view. Ever since its early inception, atomism has
generally been regarded as atheistic; as the excerpt
from Lucretius (Section 1 5 . 1 ) indicated, the
atomist openly professed to give an explanation
of matter and events not in terms of impenetra
ble designs of an ever-present Creator and Ruler,
but by means of the interplay and structure of
material bodies. In the seventeenth century,
philosophers such as Pierre Gassendi had
attempted to remove the taint of atheism by
proposing that atoms are not self-animated, but
are inert pieces of matter that required a divine
agency to set them into motion at the creation
of the world.
In the "mechanical philosophy, " as it was
advanced especially in England by Robert Boyle,
God was assigned the role of designer and cre
ator of the world machine, which, once set in
motion, could run from then on by His pleasure
without continual active intervention; all observ
able events should then be ultimately explainable
by the configurations, sizes, and shapes of the
eternal particles or by the mathematical laws of
force and motion ruling among them.
As we have seen in the previous chapter,
Newton himself did not accept the extreme ver
sion of the world-machine theory that would
forbid God to take constantly an active part in
the physical world. Yet the above quotation
from the Opticks shows that in formulating the
principles of his own system of the world, New
ton was primarily concerned with specifying the
results of God's initial creative acts, so that in
practice the Newtonian system could easily be
interpreted as a world machine.
Some of Newton's other remarks on the
properties of atoms did give support to those who
were dissatisfied with the mechanistic philosophy
advocated by Descartes (Section 6.1). The Carte
sians rejected the hypothesis of " action at a dis
tance," preferring to believe that all apparent
long-range forces, such as gravity, could be
explained by contact actions propagated through
an intervening material medium (the ether) .
Newton, while rejecting in principle the possibility
of true action at a distance (see his letter to
Bentley, quoted in Section 1 1.10), did explain
many phenomena in terms of attractive and
repulsive forces acting between atoms.
These remarks encouraged scientists like
Boscovich and Priestley in the eighteenth century
to develop an atomic theory of matter that relied

more on the atoms' attractive and repulsive
forces than on their hardness and impenetrabil
ity. The concept of an atom as a point center of
attractive and repulsive forces survived into the
twentieth century, a long with the alternative
concept of the atom as something like a billiard
ball that could interact with other billiard balls
only by contact.
1 9 .2 Air Pressure
In the meantime the atomistic view of matter was
extended from an entirely different direction
the research on gases.
Gal ileo, in his Two New Sciences ( 1 63 8 ) ,
noted that a suction pump cannot lift water
more than about 1 0 . 5 meters. This fact was
presumably well known by the time Galileo
wrote his book; pumps were a lready being
used to obtain drinking water from wells and
to remove water from flooded mines, so their
limitations must have become evident to many
workmen.
One important consequence of the limited
ability of pumps to lift water was that some
other method was needed to pump water out of
deep mines, and this need provided the initial
stimulus for the development of steam engines,
wruch allowed water to be conveyed out in buck
ets. Another consequence was that physicists in
the seventeenth century became curious to dis
cover the reason why the suction pump worked
at all, as well as why there should be a limit on
its ability to raise water.
If you remove air from a container and cre
ate a vacuum, there is a tendency for things to
be sucked in. The Aristotelian phil osophers
explained this fact by saying that "Nature abhors
a vacuum." It is unnatural, they said, for space
not to be filled with matter, and therefore mat
ter will move so as to fill up any empty space. Trus
is an example of a teleological explanation, one
based on an "ultimate cause" (another one would
be: " Rain falls because crops need water" ). One
of the basic goals of the new mechanical phi
losophy of the seventeenth century was to elim
inate such teleological expla nations, and to
explain phenomena instead in terms of immediate
physical causes.
The Aristotelian theory seemed especially
weak in this particular case: Even if one accepts
the assertion that Nature abhors a vacuum, one
finds it difficult to explain why this abhorrence
1 9 .2 Air Pressure / 2 6 7
Evacuated spaces
I
1
Fig. 19. 1. Torricel l i barometer (two forms). The mer
cury col u m n in each vertical g lass tube is balanced
by the pressu re of the atmosphere on the free mer
cury surface in the trough. Usually h is about 0.76 m
at sea level.
is j ust sufficient to raise water by 1 0.5 m by
means of a pump, no more, no less!
Evangelista Torricelli ( 1 608-1 647), once
briefly the pupil o f Galileo, realized that the
atmosphere exerts a pressure at the surface of the
earth, and suspected that this air pressure might
be sufficient to account for the phenomena pre
viously attributed to Nature's abhorrence of a
vacuum. He made the fortunate guess that mer
cury, a liquid nearly fourteen times as dense as
water, might be a more convenient medium for
laboratory experiments; indeed, it turned out
that the same vacuum pump that could raise a
column of water 1 0 . 5 m could lift a column of
mercury only 1114 as rugh, 0 . 76 m.
The pump itself is not even necessary to
hold up a column of liquid in the simple instru
ment that came to be known as the Torricelli
barometer. One takes a straight glass tube some
what more than 0.76 m long, open at one end
and sealed at the other; a bowl; and enough
mercury to fiji the ulbe and the bowl. Fill the tube
to the brim, close the open end with your finger,
rum it upside down in the bowl, and remove your
finger, and you will find that the mercury runs
down into the bowl, but only until the difference
between the level in the tube and the level in the
bowl is about 0.76 m. The result is shown in Fig.
1 9 . 1 (the left tube). There is now found to be an
evacuated space at the top of the tube above the
mercury. Torricelli then repeated the same pro
cedure with a tube that had a large bulb at the
closed end, thereby making available an evacu
ated space of larger size in which small objects
could be fastened.
268 / The Physics of Gases
The announcement of Torricelli's experi
ments in 1 643 prompted other scientists (Otto
von Guericke and Robert Boyle were among
the first) to develop better vacuum pumps for
experimenting on vacuum phenomena and the
properties of gases at low pressures. 1 With a pump
and a glass j ar, one could prepare an experi
mental space in which to discern the effect of
light, sound, and magnetic or electric forces
within an atmosphere rarefied in varying degrees.
One could attempt to discover, by the difference
in weight of a hollow vessel before and after "ex
suction" (sucking out), the weight of the gas
within. Conversely, one could also pump gases
into a vessel at higher pressures.
According to Torricelli and other followers of
the mechanical philosophy, the force that holds the
column of mercury up in the tube is simply the
pressure of the atmosphere, transmitted through
the mercury in the bowl. The air pushes down on
the surface of the mercury, and since there is
practically no gas in the space at the top of the
tube, the mercury rises until its weight is sufficient
to balance the force exerted by the air outside on
the top surface of the pool of mercury.
In France, the scientist-philosopher Blaise
Pascal ( 1 623-1 662) reasoned that if the pressure
of the atmosphere is indeed the force that sup
ports the column of mercury in the Torricelli
barometer, then the height of that column should
be less if the pressure of the atmosphere is
reduced. He assumed that the atmospheric pres
sure at the earth's surface results from the weight
of the rest of the atmosphere above it, just as the
pressure one experiences under water increases
at greater depths. Conversely, then, by taking the
barometer to the top of a mountain one should
find a lower atmospheric pressure, and conse
quently the height of the mercury supported by
that pressure should be reduced. The experi
ment proposed by Pascal was successfully per
formed in 1 648 by his brother Florin Perrier. It
is often called the Puy de Dome experiment,
after the mountain on which it was conducted.
lThese pumps were relatively crude and could not pro
duce what we would now call a vacuum. For that matter,
the complete removal of every trace of gas from a closed ves
sel is impossible even today. But considerable advances in
the construction of vacuum pumps in the second half of the
nineteenth century made possible evacuation good enough
to allow, on the one hand, the discovery of subatomic par
ticles (Section 25.5) and, on the other, the development of
the incandescent electric light bulb.
While the height of the mercury in the tube
depends on (and thus allows one to measure) the
local atmospheric pressure, it does not depend on
the diameter of the tube or the size of the bowl.
This might at first seem rather strange, since the
force exerted by the mercury depends on how
much of it there is-that is, on its total volume,
not just its height. Similarly, the force of the air
outside will be greater on a large bowl than on
a small one. Nevertheless, the mercury always
rises to the same height whether the tube is thick
or thin and whether the bowl is large or small.
This fact is explained if we recognize that it is the
balance of pressure, not force, that determines the
height of the mercury column (and the equilib
rium of fluids in general).
It is important to distinguish dearly between
pressure and force. Pressure is defined as the
amount of force acting perpendicular to a sur
face, divided by the area of the surface:
p= FlA. (19.1)
A large force may produce only a small pressure
if it is spread over a large enough area; for
example, if you wear large snowshoes, you can
walk on snow without sinking in. On the other
hand, a small force may produce a very large pres
sure if it is concentrated in a small area; when
spike heels were used on ladies' shoes some years
ago, many wooden floors and carpets were dam
aged because the pressure at the place where
the heel touches the floor-a very small area
can be greater than that exerted by an elephant's
foot!
It is instructive to calculate the numerical
value of the pressure exerted by the atmosphere,
to see how large it is and why it does not depend
on the diameter of the tube in the barometer. The
column of mercury stands 0.76 m high (the aver
age height of the barometer column at sea level at
OC). If this column has a cross-sectional area of
1 m2, the volume of the column is 0.76 m3 A cubic
meter of mercury has a mass of 13,600 kg. The
mass of the mercury in the column is therefore
m= 0.76 m3 x 13,600 (kglm3 ) = 10336 kg.
The force exerted by this amount of mercury is
F = mg = 10336 kg x 9.8 mlsec2
= 1.013 x lOS N.
(Remember that N is the abbreviation for the
newton, the unit of force in the SI system. )

Since the pressure is defined as PIA,
= 1 m2, we find that
Atmospheric pressure = 1 .0 1 3 x 1 05 N/m2.
Note that we had to multiply by the cross-sec
tional area to calculate the force and then divide
by this same area to calculate the pressure, so that
the final result is i ndependent of the value
assumed for the area.
The actual height of the mercury column in
a barometer is not precisely 0.76 m; it varies from
one day to the next and from one place to
another, being itself an index of changing climatic
conditions. It is now customary to define the
"standard atmosphere" as 1 .0 1 3 x 1 05 N/m2. The
unit of pressure in the 51 system is the pascal,
abbreviated Pa, which is defined as 1 N/m2; so
atmospheric pressure is approximately 105 Pa. In
common units this is about 15 Ib/in.2. Weather
reports in the United States still use an older
unit for atmospheric pressure, the bar, defined as
1 05 Pa. Weather maps usually give local atmos
pheric pressures in terms of millibars ( 1 bar
1 000 millibars).
The expression "gauge pressure" is some
times used to indicate the excess of the actual
pressure over atmospheric pressure. For example,
if you inflate your tires and then check the pres
sure with a gauge and it shows 30 Ib/in.2, the
actual pressure inside the tires is about 45 Ib/in.2
It was hard for many people to believe that
the atmosphere really exerts a pressure as great
as 15 Ib/in.2. A famous experiment, conducted
by Otto von Guericke in Magdeburg, Germany,
in 1 654, helped to dramatize the magnitude of
atmospheric pressure. Two large hollow bronze
hemispheres were fitted carefully edge to edge,
and the air was removed from the inside of this
space by a vacuum pump. A team of eight horses
was harnessed to each hemisphere and the two
teams were driven in opposite directions; they
were j ust barely able to pull the hemispheres
apart against the force with which the external
atmospheric pressure pressed them together.
The properties of air and of atmospheric
pressure were thoroughly investigated by the
British scientist Robert Boyle ( 1 627-1 69 1 ), who
heard a bout Guericke's experiments in 1 657.
Using an improved vacuum pump built for him
by Robert Hooke, Boyle was able to obtain a
large evacuated space in which several new
experiments could be done. In one rather macabre
test, he found that small animals became uncon
scious and eventually died when deprived of air.
1 9.2 Air Pressure / 269
and A
Fig. 19.2. Robert Boyle ( 1 627- 1 69 1 ), B ritish physicist
=
and chem ist who advocated the mechanistic "clock
work u niverse" p h i l osophy a n d estab l ished by his
experiments that suction is due to a i r pressure rather
than the Aristotelian " natu re's abhorrence of a vacu
u m . " Note in the background one of his p u m ps, set
up to evacuate a g lass g lobe.
In another experiment, Boyle placed a Tor
ricelli barometer inside a closed container and
then removed the air from the container. The level
of the mercury in the tube fell as the air was
removed from the container, until finally i t
reached the same level as the mercury in the
bowl. Boyle realized that this result proved it was
the pressure of the atmosphere outside that had
been holding up the mercury in the tube, rather
than the vacuum itself exerting some pull on
the top of the tube. He had essentially done
Pascal 's experiment without leaving his own
laboratory.
Soon after Boyle p ublished his experiments
in 1 660, his conclusions were challenged by
Franciscus Linus, a Jesuit scientist and professor
of mathematics and Hebrew at the University of
Liege, in Belgium. Linus asserted that the appar
ently empry space above the mercury really con
tains an invisi ble cord or membrane, which he
called the funiculus (a Latin word meaning
"small rope " ) . According to Linus, when a ir is
stretched or rarefied, the funiculus exerts a vio
lent attractive force on all surrounding objects,
and it is this attraction that pulls the mercury up
270 / The Physics of Gases
the tube. He would argue that if you put your
finger over the end of the tube from a vacuum
pump (or a modern vacuum cleaner), you can
actually feel the funiculus pulling in the flesh of
your finger. (Try it! )
The funiculus theory sounds like a fantastic
idea, which no scientist would take seriously
nowadays. But this kind of pseudomechanical
explanation of physical phenomena was quite
popular in the early days of modern science.
Boyle did not simply ignore Linus, perhaps real
izing that the new idea of air pressure needed fur
ther justification before it would be generally
acceptable. Along with his refutation of the
funiculus hypothesis, Boyle published in 1662
some quantitative measurements of the relation
between pressure and volume of air, in support
of what is now called Boyle's law, to be dis
cussed in the next section.
While it is for his pressure-volume law that
Boyle is chiefly famous, we should not forget that
in his own time his work in establishing the
qualitative importance of air pressure was more
significant.
19.3 The General Gas Law
The compressibility of air, a fact realized gener
ally for some time, was put on a quantitative basis
through Boyle's celebrated experiments, from
which it appeared that for a given mass of air
trapped in a vessel at a constant temperature, any
decrease of volume raises the gas pressure pro
portionally; conversely, any increase in pressure
decreases the volume. In modern terminology, we
write this result
P x V = constant
(at constant temperature) ( 19.2)
where P refers to the actual pressure of the gas
considered (for example, in N/m2 ) and V to the
volume of the gas (for example, in m3 ). 2
Following Boyle's work, continued effort
was made to discover the effect of changes in tem-
2The complicated history of the discovery of Boyle's law has
only recently been disentangled by historians. It appears that
the law was first proposed by two other British scientists,
Henry Power and Richard Towneley, on the basis of their
experiments, begun in 1653. They did not publish their
results immediately, but after Boyle's first experiments on
air pressure had been published in 1 660, Power sent a
paper describing the results of their joint work to his ftiend
perature on the pressure or the volume of a gas.
In the eighteenth century, Guillaume Amontons
and Jacques Charles suggested that if a constant
pressure is maintained in a sample of gas, its vol
ume would increase proportionately to the rise
in temperature (A V oc AT at constant Pl. This law
was definitely established by extensive experi
ments on a number of gases conducted by the
French chemist Joseph Louis Gay-Lussac, around
1 800, and confirmed shortly afterward in Eng
land by John Dalton. For brevity we shall call it
Gay-Lussac's law, as Gay-Lussac seems to have
had the greatest share in establishing its validity,
but recognizing that, just as in the case of Boyle's
law, several scientists made important contri
butions by proposing and testing it.
To visualize the meaning of Gay-Lussac's law
in an actual experiment, think of a quantity of
gas contained in a very thin, easily stretched
balloon. The pressures inside and outside tend to
be the same-if the pressure were higher inside,
the balloon would expand, thereby reducing the
inside pressure until it was the same as the out
side pressure; if the pressure were lower inside,
the balloon would be squeezed down to a smaller
size, and its inside pressure would increase. So
we can assume that the pressure inside is equal
to atmospheric pressure (about 105 Pa l .
A s we now proceed to heat the surroundings
(AT), the balloon expands (A V). What is so very
startling is the fact that the fractional increase in
volume per degree rise in temperature is exactly
the same for all gases, even though their chem
ical constitutions are different.
To appreciate the unexpectedness of this
finding, recall that on heating a solid or a liquid
one ordinarily also obtains a length or volume
expansion that is proportional to the tempera
ture change; but there is a great difference in the
relative amount of volume expansion per degree
of temperature among different solids or liq-
William Croone, in London. The title of the paper was
"Additional experiments made at Towneley Hall, in the years
1660 and 1661, by the advice and assistance of that Hero
ick and Worthy Gentleman Richard Towneley. " But Power
neglected to put his own name on the paper. Croone sent
the paper to Boyle, forgetting to mention that Power was
the author. Boyle was very careful to give proper credit for
the information he had received, and in his monograph of
1662 replying to Linus, he stated that he had not realized
that the simple relation PV constant applied to his own
=
data until Richard Towneley pointed it out. Later scientists,
who read Boyle's works carelessly or not at all, assumed that
Boyle had made the discovery all by himself.

uids (about 0.01 % for ice, 0.0025 % for quartz,
0.02 % for mercury and for wateJ; and 0.15% for
acetone) .
But under normal conditions, almost all
gases expand roughly 1/273 (that is, 0.37% ) of
their volume when heated from 0 to 1 C. The
same volume change is also observed at much
lower temperatures, provided that the pressure
of the gas is sufficiently low. (If a gas is contin
ually cooled at a constant pressure, it will even
tually condense to a liquid, and then, of course,
cease to obey Gay-Lussac's law. ) We can thus
define an ideal gas as a gas that obeys both
Boyle's law and Gay-Lussac's law with complete
precision; the behavior of real gases approaches
this as a limit at low pressures.
Assume that an ideal gas could be cooled to
273 below the ice point (that is, to Tc = -273);
then since by Gay-Lussac's law-if it holds over
such a large range-it should contract 1/273 of
its volume at Tc = 0 for each degree of cooling,
it would eventually have no volume at all. While
this condition cannot be realized experimen
tally, it suggests that we should recognize the spe
cial temperature Tc = -273 ( more precisely,
-273.15) as the absolute zero of temperature, in
the sense that no lower temperature can ever be
reached. 3 Consequently, we can simplify the law
8 V oc 8T (at constant P) by writing V OC T at con
stant P if T is measured on a new temperature
scale, that is, the absolute or Kelvin scale, where
T = Tc + 273.15. The unit of temperature is the
kelvin, abbreviated K. Thus a temperature 5
degrees above absolute zero would be written T
= 5 kelvins or T = 5 K.
Comparing the two scales, we see that for
example, OC is equivalent to 273 K; room tem
perature (about 20C) is 293 K; water boils at
373 K. Note that the size of the degree-the
kelvin-is the same on both the Celsius and the
Kelvin scale. However, in the SI system of units
the degree symbol " 0 " is no longer used for K,
but it is still used for Celsius degrees (0C).
The letter K was chosen in honor of William
Thomson, Lord Kelvin, who first proposed this
scale in 1 848, and showed that it is consistent
with the second law of thermodynamics. [Recall
that the definition of entropy, given by Clausius
3According to the third law of thermodynamics, proposed
by Walther Nernst in 1906, all thermal properties approach
zero values as the absolute zero of temperature is
approached, and as a consequence it is never possible to
reach this temperature.
1 9.3 The General Gas Law 1 27 1
I
1rernperature
t t
-273C or O K OC or 273 K
Fig. 19.3. Relation between volume and temperatu re
for a gas at constant pressu re. The dotted l i ne rep
resents a n ideal gas.
in 1 865, uses this temperature scale (see Sec
tion 18.4).]
Problem 1 9 . 1 . Figure 1 9.3 is a hypothetical plot
of experimental data for a sample of gas at con
sta nt pressu re; here the vol ume V is plotted
against the temperature T. The graph illustrates
!!. VI!!. T = constant (Gay-Lussac's law) . Show by
geometrical reasoning that if Gay-Lussac's law
holds, then also VOC T (at constant P) provided T
is measured on the absolute scale. Show that
the proportionality Voc Tis not true if Tis measured
on the Celsius scale.
What interests us most, however, is the obvi
ous next step: combining the two laws into one.
If for each gas, by Boyle's law, V oc 1/p, and by
Gay-Lussac's law, V OC T, then V oc TIP. This
implies that the quotient PVIT is a constant
(usually called r), whose value depends only on
the sample. Thus we can write:
PV = rT. ( 1 9.3)
We may call the last equation, which is of great
usefulness, the ideal gas law; it relates in a simple
way the three variables of interest in any given
sample of gas, and is approximately valid for all
real gases under ordinary conditions.
Problem 1 9.2. Find r in Eq. (1 9.3) for a sample of
hydrogen gas weighing 2 g and filling 22.4 L at OC
and 1 0 5 Pa pressure (approximately atmospheric
pressure) . Then determine the volume of this
sample at room temperature (20C) and a gauge
pressure of 1 07 Pa ( = 1 0 M Pa ) . ( Remember:
Gauge pressure is defined as the pressure above
atmospheric.)
272 I The Physics of Gases
At this point we may call attention to an
important temperature: the triple point of water,
the unique temperature at which all three phases
(gas, liquid, and solid) can coexist. The triple
point was found by experiment to be at 273 . 1 6
0. 0 1 K . A t the Tenth General Conference on
Weights and Measures in 1 9S4, it was decided
to establish a new absolute temperature scale
based on two fixed points: absolute zero and the
triple point of water, which was defined to have
the exact value T = 273 . 1 6 K. The new scale
agrees with the old one for nearly all practical
purposes, but has the advantage that the fixed
points are no longer quite so arbitrary. (Since the
melting and boiling points of a substance vary
with pressure, one had to specify a particular pres
sure, namely the average pressure of the atmos
phere at the earth's surface. The triple point,
however, occurs at a definite pressure, 6 1 1 .73 Pa.)
1 9.4 Two Gas Models
One is immediately tempted to interpret these
observations and the experimental gas law that
summarizes them in terms of some model or
structure. Even qualitatively, the great compressi
bility of all gases and their "springiness" (ten
dency to expand again when the external pressure
is reduced) seem to call for some explanation.
In 1 660 Boyle himself, while favoring one
model "without peremptorily asserting it, " pre
sented two opposing explanations by models,
both atomistic, for he and his time had begun to
accept atomism as part of the rising materialis
tic worldview. That view, expressed in his words,
is: "whatsoever is performed in the material
world, is really done by particular bodies, acting
according to the laws of motion. "
The two models that Boyle presents repre
sent respectively the static and the kinetic views.
If air consists of contiguous particles at rest, the
corpuscles must themselves be compressible,
rather like little springs or, as Torricelli had pre
ferred, like pieces of wool. If, on the other hand,
the corpuscles of the gas do not touch at all
times, they need be neither variable in size them
selves nor maintained by a static assembly, but
then they must be in violent agitation, being
whirled through all available space within a tur
bulent though "subtle" fluid. We recall that the
subtle-fluid theory, then recently proposed by
Descartes to account for the motion of planets,
had captured the imagination throughout Europe;
and indeed, it seemed to explain qualitatively the
behavior of gases well enough. (Boyle attempted
to find experimentally this subtle fluid, sepa
rated from the particles on which it supposedly
acted. This was the start of a 2S0-year-Iong
futile search for direct evidence of ethereal fluids.)
Having named the first of these the static
model of a gas and the second the kinetic model,
we must make a brief comment on each. As to
the first, a springlike compressibility of static
particles cannot easily account for one very con
spicuous property of gases-their ability to
expand infinitely in all directions, unless of
course we allow the improbable, namely, that
each atom itself can grow infinitely on expand
ing. For a pile of ordinary springs opposes com
pression, but does not disperse continuously
when put into the open. Therefore some fol
lowers of the static view found it necessary to con
sider that gas corpuscles do not change in size but
can repel one another at a distance. Evidently
some special new agency of repulsion, some new
force among gas atoms, would have to be
invented, because the well-known mutual grav
itational force between large bodies, also the
logical candidate for intercorpuscular forces,
was, unfortunately, always found to be a force
of attraction, as is evidently also the nature of
those forces that hold the particles together in
solids and liquids.
The distinguished authority of Newton
seems to lend some aid to the static picture, for
in the Principia he had shown, by way of a
mathematical demonstration, that if a sample of
gas were made of mutually repulsive particles,
and if a force of repulsion between any two par
ticles were inversely proportional to the distance
between their centers, then the gas pressure in this
sample would increase with a small decrease in
volume, just as found by Boyle's law.
Newton did not mean to prove that gases
really do correspond to this model; on the con
trary, he writes, " But whether elastic fluids do
really consist of particles so repelling each other,
is a physical question," in other words, one that
has to be settled by appeal to experience. And
indeed, this postulated type of force would cause
gases to exhibit different behavior for different
shapes of the container, which does not corre
spond to anything observed. Nevertheless, New
ton's was the first quantitative deduction obtained
for the behavior of gases on the basis of any
atomistic hypothesis, and it appears to have
been quite impressive.

Fig. 19.4. The pressu re on the piston exerted by the
weight P is balanced by the impact of high-speed gas
particles. From Da niel Bern o u l l i's Hydrodynamica,
1738.
The second or kinetic view of a gas might
well have been formulated without recourse to an
imponderable fluid (if it had not been for the
inescapable, almost hypnotic hold of that idea),
for it had been the opinion of Greek atomists, as
reported by Aristotle and Lucretius, that particles,
particularly those not joined in specific form,
are "ever passing about in the great void," just
as minute specks of dust can be seen dancing irreg
ularly in a sunbeam that pierces a dark room.
In fact, the Swiss physicist Daniel Bernoulli
in 173 8 did publish a prophetic, quantitative
development of a Lucretian type of kinetic model
for gases. Bernoulli thought of the "corpuscles"
of the gas as so minute as to be "practically
infinite in number" under ordinary conditions,
even in a small container. In their rapid motion
hither and thither these corpuscles collide with
one another and with the rigid walls of the
closed vessel. But the collisions can be assumed
to be perfectly elastic; therefore, as we would put
it, the kinetic energy of the particles is conserved
and the motion can continue undiminished. The
pressure that the gas is expected to exert against
all sides of the container is thus caused by the
incessant impact of millions of high-speed par
ticles-hence the name "impact theory of gas
pressure. "
Let u s say that the gas-filled container used
here is cylindrical, and that the top end can be
made to slide in like a piston (see Fig. 19.4). If
the volume is slowly decreased, the corpuscles are
more crowded in the progressively smaller space
and the number of collisions per second with the
1 9 .4 Two Gas Models 1 273
walls is larger, that is, the pressure should become
greater, as is actually observed. Bernoulli even cal
culated the magnitude of this expected increase
and found that it corresponds to Boyle'S exper
imental law. Then he continued:
The elasticity of air [the pressure in the con
tainer] is not only increased by the condensa
tion [decrease of volume] but by heat supplied
to it, and since it is admitted that heat may be
considered as an increasing internal motion of
the particles, it follows that if the elasticity of
the air of which the volume does not change
is increased [by heating the sample of gas], this
indicates a most intense motion in the particles
of air; which fits well with our hypothesis . . . .
(Hydrodynamica)
This model, this line of reasoning, and this
result, are all quite similar to the work that more
than a century later finally clarified simultane
ously the main problems of the nature of gases,
heat, and chemistry. But at the time, Bernoulli's
work was generally neglected. That lack of gen
eral attention and the long interval, are both
remarkable, and cannot be entirely explained
by pointing out that gases were not yet clearly
understood by chemists, that density measure
ments were lacking that would have been needed
to obtain the numerical values for the average
speed of the particles, and so forth.
The other model, the Boyle-Newton theory
based on repulsive forces between gas particles,
proved to be more congenial to the eighteenth
century scientists who adopted the caloric theory
of heat (Section 17.7). The repulsive force was
now attributed to atmospheres of caloric fluid
surrounding each atom. Heating a gas meant
pouring in more caloric, expanding the "atmos
phere" around each atom, and thereby intensi
fying the repulsive force. Although the caloric
theory did not completely exclude the notion that
heat might be associated with the motion of
particles, it did seem to be incompatible with
Bernoulli's hypothesis that heat is nothing but the
motion of particles.
The discovery of latent heat by Joseph Black
seemed to indicate that a simple proportionality
between heat and temperature could not be gen
erally valid, since a finite amount of heat must
be added to a liquid in order to change it to a
gas, without any change of temperature-as in
the case of liquid water, boiling away into vapor
at a steady 1 00C. This was one of several
274 1 The Physics of Gases
phenomena that were thought to be more easily
explicable by the caloric theory than by the
kinetic theory. Again, Bernoulli's theory, by pos
tulating free motion of the atoms through empty
space, ignored the ether, which was thought to
pervade all space; whereas caloric could easily be
identified as a special kind of ether.
Perhaps we may compare Bernoulli's aston
ishing insight to some quick, isolated, premature
stab from a general holding position, far through
enemy lines, bringing no strategically valuable
consequences until in time the whole main force
has moved ahead to link up with this almost for
gotten outpost. For Bernoulli, in effect, had
made two enormous j umps in his thinking for
which the great majority of scientists was not yet
ready: first, the direct equivalence of heat and
internal molecular motion, ignoring any inter
actions with the ether; and second, the idea that
a well-defined numerical relationship, such as
Boyle's simple law, could be deduced from the
chaotic picture of randomly moving particles. We
must postpone our account of the final victory
of these ideas to a later chapter, turning now to
examine some other ideas about atomic prop
erties that were being developed in the meantime.
RECOMMENDED FOR FURTHER READING
S. G. Brush (editor), Kinetic Theory, Vol. I, excerpts
from Boyle, Newton and Bernoulli, pages 43-65
J. B. Conant, " Robert Boyle's experiments in pneu
matics, " in Harvard Case Histories in Experi
mental Science (edited by J. B. Conant), pages
1-63
C. C. Gillispie, Dictionary of Scientific Biography,
articles by Marie Boas Hall on Boyle, Vol. 2,
pages 377-3 82, and by H. Straub on Daniel
Bernoulli, Vol. 2, pages 3 6-46
Marie Boas Hall, "Robert Boyle," Scientific Ameri
can, August 1 9 67, pages 97-1 02
S. Sambursky Physical Thought, excerpts from
Torricelli, Pascal, and Boyle, pages 256-263,
282-284
Martin Tamny, "Atomism and the mechanical phi
losophy," in Companion (edited by Olby), pages
597-609
Stephen Toulmin and June Goodfield, Architec
ture of Matter, Chapter 8