58 Pressure

Example 6.2
What is the volume occupied by one mole of ideal gas at standard
temperature and pressure (STP, dened as 0

C and 1 atm)?
Solution:
At p = 1.01325 10
5
Pa and T = 273.15 K, the molar volume V
m
can
be obtained from eqn 6.20 as
V
m
=
RT
p
= 0.022414 m
3
= 22.414 litres. (6.22)
Example 6.3
What is the connection between pressure and kinetic energy density?
Solution:
The kinetic energy of a gas molecule moving with speed v is
1
2
mv
2
. (6.23)
The total kinetic energy of the molecules of a gas per unit volume, i.e.
the kinetic energy density which we will call u, is therefore given by
u = n

0
1
2
mv
2
f(v) dv =
1
2
nmv
2
, (6.24)
so that comparing with eqn 6.15 we have that This expression is true for a non-
relativistic gas of particles. For an
ultra-relativistic gas, the correct ex-
pression is given in eqn 25.21.
p =
2
3
u. (6.25)
6.3 Daltons law
If one has a mixture of gases in thermal equilibrium, then the total pres-
sure p = nk
B
T is simply the sum of the pressures due to each component
of the mixture. We can write n as
n =

i
n
i
, (6.26)
where n
i
is the number density of the ith species. Therefore
p =

i
n
i

k
B
T =

i
p
i
, (6.27)
where p
i
= n
i
k
B
T is known as the partial pressure of the ith species.
The observation that p =

i
p
i
is known as Daltons law, after the
British chemist John Dalton (17661844), who was a pioneer of the
atomic theory.
Exercises 59
Example 6.4
Air is 75.5% N
2
, 23.2% O
2
, 1.3% Ar and 0.05% CO
2
by mass. Calculate
the partial pressure of CO
2
in air at atmospheric pressure.
Solution:
Daltons law states that the partial pressure is proportional to the num-
ber density. The number density is proportional to the mass fraction di-
vided by the molar mass. The molar masses of the species (in grammes)
are 28 (N
2
), 32 (O
2
), 40 (Ar) and 44 (CO
2
). Hence, the partial pressure
of CO
2
is
p
CO
2
=
0.05
44
1 atm
75.5
28
+
23.2
32
+
1.3
40
+
0.05
44
= 0.00033 atm. (6.28)
Chapter summary
The pressure, p, is given by
p =
1
3
nmv
2
,
where n is the number of molecules per unit volume and m is the
molecular mass.
This expression agrees with the ideal gas equation,
p = nk
B
T,
where V is the volume, T is the temperature and k
B
is the Boltz-
mann constant.
Exercises
(6.1) What is the volume occupied by 1 mole of gas at
10
10
Torr, the pressure inside an ultra high vac-
uum (UHV) chamber.
(6.2) Calculate u, the kinetic energy density, for air at
atmospheric pressure.
(6.3) Mr Fourier sits in his living room at 18

C. He de-
cides he is rather cold and turns the heating up
so that the temperature is 25

C. What happens to
the total energy of the air in his living room? [Hint:
what controls the pressure in the room?]
(6.4) A diuse cloud of neutral hydrogen atoms (known
as HI) in space has a temperature of 50 K. Calculate
60 Exercises
the pressure (in Pa) and the volume (in cubic light
years) occupied by the cloud if its mass is 100M

.
(M

is the symbol for the mass of the Sun, see Ap-

pendix A.)
(6.5) (a) Given that the number of molecules hitting unit
area of a surface per second with speeds between v
and v + dv and angles between and + d to the
normal is
1
2
v nf(v)dv sin cos d,
show that the average value of cos for these
molecules is
2
3
.
(b) Using the results above, show that for a gas
obeying the Maxwellian distribution (i.e. f(v)
v
2
e
mv
2
/2k
B
T
) the average energy of all the
molecules is
3
2
k
B
T, but the average energy of those
which hit the surface is 2k
B
T.
(6.6) The molecules in a gas travel with dierent veloci-
ties. A particular molecule will have velocity v and
speed v = |v| and will move at an angle to some
chosen xed axis. We have shown that the number
of molecules in a gas with speeds between v and
v +dv, and moving at angles between and +d
to any chosen axis is given by
1
2
nf(v) dv sin d,
where n is the number of molecules per unit volume
and f(v) is some function of v only. [f(v) could be
the Maxwellian distribution given above; however
you should not assume this but rather calculate the
general case.] Hence show by integration that:
(a) u = 0
(b) u
2
=
1
3
v
2

(c) |u| =
1
2
v
where u is any one Cartesian component of v, i.e.
v
x
, v
y
or v
z
.
[Hint: You can take u as the z-component of v with-
out loss of generality. Why? Then express u in
terms of v and and average over v and . You can
use expressions such as
v =
Z

0
v f(v) dv
Z

0
f(v) dv
and similarly for v
2
. Make sure you understand
why.]
(6.7) If v
1
, v
2
, v
3
are three Cartesian components of v,
what value do you expect for v
1
v
2
, v
1
v
3
and
v
2
v
3
? Evaluate one of them by integration to
check your deduction.
(6.8) Calculate the partial pressure of O
2
in air at atmo-
spheric pressure.
Biography 61
Robert Boyle (16271691)
Robert Boyle was born into wealth. His fa-
ther was a self-made man of humble yeo-
man stock who, at the age of 22, had
left England for Ireland to seek his fortune.
Fig. 6.6 Robert Boyle
This his father found or,
possibly more accurately,
grabbed and through
rapid land acquisition of
a rather dubious nature
Boyle senior became one
of Englands richest men
and the Earl of Cork to
boot. Robert was born
when his father was in
his sixties and was the
last but one of his fathers
sixteen children. His fa-
ther, as a new member of
the aristocracy, believed
in the best education for his children, and Robert
was duly packed o to Eton and then, at the age
of 12, sent o for a European Grand Tour, taking
in Geneva, Venice and Florence. Boyle studied the
works of Galileo, who died in Florence while Boyle
was staying in the city. Meanwhile, his father was
getting into a spot of bother with the Irish rebel-
lion of 16411642, resulting in the loss of the rents
that kept him and his family in the manner to which
they had become accustomed, and hence also caus-
ing Robert Boyle some nancial diculty. He was
almost married o at this time to a wealthy heiress,
but Boyle managed to escape this fate and remained
unmarried for the rest of his life. His father died in
1643 and Boyle returned to England the following
year, inheriting his fathers Dorset estate.
However, by this time the Civil War (which had
started in 1642) was in full swing and Boyle tried
hard not to take sides. He kept his head down, devot-
ing his time to study, building a chemical laboratory
in his house and worked on moral and theological es-
says. Cromwells defeat of the Irish in 1652 worked
well for Boyle as many Irish lands were handed over
to the English colonists. Financially, Boyle was now
secure and ready to live the life of a gentleman. In
London, he had met John Wilkins who had founded
an intellectual society which he called The Invisi-
ble College and which suddenly brought Boyle into
contact with the leading thinkers of the day. When
Wilkins was appointed Warden of Wadham College,
Oxford, Boyle decided to move to Oxford and set up
a laboratory there. He set up an air pump and, to-
gether with a number of talented assistants (the most
famous of which was Robert Hooke, later to discover
his law of springs and to observe a cell with a mi-
croscope, in addition to numerous other discoveries)
Boyle and his team conducted a large number of elab-
orate experiments in this new vacuum. They showed
that sound did not travel in a vacuum,and that ames
and living organisms could not be sustained, and dis-
covered the spring of air, namely that compressing
air resulted in its pressure increasing, and that the
pressure of a gas and its volume were in inverse pro-
portion.
Boyle was much taken with the atomistic view-
point as described by the French philosopher Pierre
Gassendi (15921655), which seems particularly ap-
propriate for someone whose work led to the path
for the development of the kinetic theory of gases.
His greatest legacy was in his reliance on experiment
as a means of determining scientic truth. He was,
however, also someone who often worked vicariously
through a band of assistants, citing his weakness of
health and of eyesight as a reason for failing to write
his papers as he wished to and to have read other
peoples works as he ought; his writings are, however,
full of criticisms of his assistants for making mistakes,
failing to record data and generally slowing down his
research endeavours.
With the restoration of the monarchy in 1660, the
Invisible College, which had been meeting for several
years in Gresham College, London, sought the bless-
ing of the newly crowned Charles II and became the
Royal Society, which has existed ever since as a thriv-
ing scientic society. In 1680, Boyle (who had been
a founding fellow of the Royal Society) was elected
President of the Royal Society, but declined to hold
the oce, citing an unwillingness to take the neces-
sary oaths. Boyle retained a strong Christian faith
throughout his life, and prided himself on his hon-
esty and pure seeking of the truth. In 1670, Boyle
suered a stroke but made a good recovery, staying
active in research until the mid-1680s. He died in
1691, shortly after the death of his sister Katherine
to whom he had been extremely close.
7
Molecular eusion
7.1 Flux 62
7.2 Eusion 64
Chapter summary 67
Exercises 67
Eusion is the process by which a gas escapes from a very small hole.
The empirical relation known as Grahams law of eusion [after
Thomas Graham (18051869)] states that the rate of eusion is inversely
proportional to the square root of the mass of the eusing molecule.
Example 7.1
Eusion can be used to separate dierent isotopes of a gas (which cannot Isotopes (the word means same place)
are atoms of a chemical element with
the same atomic number Z (and hence
number of protons in the nucleus) but
dierent atomic weights A (and hence
dierent number of neutrons in the nu-
cleus).
be separated chemically). For example, in the separation of
238
UF
6
and
235
UF
6
the dierence in eusion rate between the two gases is equal to

mass of
235
UF
6
mass of
238
UF
6
=

352.0412
348.0343
= 1.00574, (7.1)
which, although small, was enough for many kilogrammes of
235
UF
6
to be extracted for the Manhattan project in 1945 to produce the rst
uranium atom bomb, which was subsequently dropped on Hiroshima.
Example 7.2
How much faster does helium gas euse out of a small hole than N
2
?
Solution:
mass of N
2
mass of He
=

28
4
= 2.6. (7.2)
In this chapter, we will discover where Grahams law comes from. We
begin by evaluating the ux of particles hitting the inside walls of the
container of a gas.
7.1 Flux
The concept of ux is a very important one in thermal physics. It
quanties the ow of particles or the ow of energy or even the ow
of momentum. Of relevance to this chapter is the molecular ux, ,