4.

J ldeal gases The gas laws

The mole and associated terms
Kinetic theory of gases
Pressure exerted by an ideal gas
Work done by a gas
First law of thermodynamics
The principal heat capacities
of a gas
Methods of producing changes
in gases
Self-assessment
1i.e. for a fixed mass of -gas at constant temperature.
the product of pressure and r-olume is constantl.
358 This equation can be used to calculate pressure or
361 volume changes whenever a fixed mass of gas is
362 either compressed into a smaller volume (at higher
362 pressure), or allowed to expand into a greater volume
367 by reducing the pressure, provided the temperature
369 remains constant throughout the change.
Thus if (pr) and (Vr) are respectively the pressure
370
and volume of a fixed mass of gas, at some initial
stage, and (f ) and (Vr) are the values measured
370
after expansion or compression at constant
373 temperature:

P1V, = prV,

A graphical view of the relationship between the

The 6as laws
When discussing the thermal behaviour of a gas, there
are three inter-dependent variables which need to be
considered. These are the volume (I/), temperature
(O, and pressure (p) of the gas. Experiments
performed by Boyle, Amontons and Charles in the
lTth and lSth centuries resulted in three gas laws
which relate these three variables.
Boyle's law
Boyle's law relates the pressure and volume of a gas
at constant temperature and states that:
pressure p and the volume Y of a fixed mass of
gas at constant temperature is shown inFigure 4.32
below.
In Figure 4.32(a), when (p) is plotted against (I.f a
curve called a rectangular hyperbola is obtained. In
Figure 4.32(b) (p) is plotted against (llV) to give a
straight line graph and in Figure 4.32(c) (pV) against
(p) produces a straight line parallel to the p-axis. By
investigating a fixed mass of gas at different
temperatures, a series of graphs can be obtained in
each. Each of the curves or lines is called an
isothermal (since the values plotted were obtained at
constant temperature).

The pressure (p) of a fixed mass of gas at Gharles'law

constant tem perature is inversely proportional Charles' law relates the volume (If and temperature
to its volume (V). (T) of a gas at constant pressure and states that:

This law may be stated mathematically as The volume (W of a fixed mass of gas at
constant pressure is directly proportional to its
L
.V Dq.: (at constant temperature) absolute (or kelvin) temperature (I).

or pY= constant

Equation I
'p
increasing
r"r I
il
rrI

(a) p/Vgtaph (b) p/V-r (c) pv/pglaph

eruph
Figure 4.32 Graphical illustrations of the relationship between pressure and volume of a of
Boyle's law
fixed mass gas -
 nl;\ De \iriei This iril be stateci mathematicaLlr as
p * T (at constant Pressure)
V - T (at constant pressure)

V
constant or !=
D
constant
T T

:-.:tation 2 Equation 3

lis equation is used to calculate changes in volume
: temperature whenever a gas expands or contracts at
constant pressure. Thus if (V,) and (7,) are
::.pectively the volume and temperature of a fixed
.:ress of gas at the start of some process, and (Vr) and
f. i are the values at the end, then if the pressure
..i'or" and after is constant:
(i.e. for a fixed mass of gas at constant volume the
ratio of the pressure of the gas to its absolute
temperalure is a constant).
This equation is used to calculate changes in pressure
or temperature whenever a gas is compressed or
rarefied at constant volume' Thus if (p,) and (Tr) are
respectively the pressure and temperature of a fixed
mass of gas at the start of some process, and
(pr) and

TT, (Tr) the values at the end, then

are if the volume
before and after is constant:
i,e. for a fixed mass of gas at constant pressure the
ratio of the volume of the gas to its absolute
Pr _ Pz.

iemperature is constant). Ti T2

Figure 4.33 below shows the relationship between the The graph of (p) against (D ("C) yields a straight line
volume and the temperature of a fixed mass of gas' which cuts the temperature'axis at approximately
- 213'C as before (see Figure 4.34).
In Figure 4.33(a) volume (V) is plotted against the
absolute temperature (I) in kelvins. This yields a
sraight line graph which passes through the origin
n hen it is extended backwards. In Figure 4.33(b) V is
plotted against Celsius temperature. This line cuts the
iemperature axis at approximately -213 'C (the
rbsolute zero of temPerature).

Pressure law
TTC
The pressure law relates the pressure and absolute
temperature of a gas and states that:
Figure 4.34 Graphical representation of the
The pressure (p) of a fixed mass of gas at relationship betw'een pressure and temperature of a
constant volume is directly proportional to its fixed mass of gas - Pressure law.
absolute (or kelvin) temperature (I).

(a) (b)

mass of gas -
Figure 4.33 Graphical illustrcttions of the relation between volume and temperature of a fixed
Charles'law
 fhe ideal gas equation Combrnrng til and iiil gires:
An ideal or perfect gas is one which obeys the gas
laws exactly. Real gas behaviour can be classed as
F,V,. P,V,
very nearly ideal so long as we are considering gases lL 12

at low pressures and at temperatures which are

-=-
Equation 5
significantly higher than those at which liquefaction
occurs. Thus, for an ideal gas each of the following This is called the combined gas equation. It is
applies. particularly useful for solving problems in
pV = constant (at constant f) which, volume, pressure and temperature vary
V/T = constant (at constantp) simultaneously. When using Equation 5 it does
not matter what units are used for p and V so
p/T = constant (at constant If long as they are the same on both sides of the
From which we have that: equation, but T must be in kelvins.
pV
_ = constant
T
The magnitude of the constant depends on the mass of
gas being considered. If, for example, one mole 1. A diver swims at a depth of 40 m where the
(defined on page 361) of gas is considered, the temperature of the water is 4.0 "C.
constant is the universal molar gas constant (R)
He inhales 1.2 x 10-s m3 of compressed air at a
(R = 8.31 J mol-r K-11. Thus for one mole of gas:
pressure of 7.0 x 10s Pa and suddenly he sees
pv something that panics him into rising to the
=R
T surface very rapidly without exhaling.
Calculate the new volume of the air which he
pV=RT
inhaled at 40 m, if the surface temperature and
So for n moles of gas: pressure are20 'C and 1.01 x 105 Pa
respectively.
Pa mol
"',IK
'pV = nRT, Guidelines
'I
The initial pressure, volume and temperature
m3' Jmol-1 Kr are given at a depth of 40 m. Use Equation 5
to calculate the new volume, given the new
Equation 4 pressure and temperature at the surface, but
remember that temperatures must be expressed
This is the equation of state of an ideal gas; in kelvins.
sometimes simply called the ideal gas equation.
You should note that: 2. A gas cylinder of volume 6.0 x 103 cm3
contains oxygen at a temperature of 20"C and
ions made in the a pressure of 3.0 x 106 Pa. Calculate:

(-n[b assumptions is that

(a) the equivalent volume of oxygen at
standard temperature and pressure
molecules and thi (i.e. 0"C and 1.0 x 105 Pa).
(b) the mass of oxygen in the cylinder if the
density of oxygen at standard temperature
For a gas of volume (Vr) at a pressure (f 1) and a and pressure (i.e. 0'C and 1.0 x tOs Pa) is
temperature (I,) Equation 4 gives: 1.4 kg m 3.

n.V.
l*] = rrR (i)
11 Guidelines
For the same mass of gas (i.e. same number of moles (a) Use Equation 5 * temperatures in kelvins;
of gas) whose volume has become (Vr) at a new (b) mass = density x volume - You must use
pressure (pz) and temperature (Zr) Equation 4 gives: the volume at s.t.p. obtained in (a) since
P,V, the density value is at s.t.p.
#lr = nR (ii)
The mole and associated
terms
(br the mass of gas if its molar mass is
32.Q x 10r kg
Cne mole is the amount of substance which
:ontains the same number of elernentary units (c) the mass of a single molecule of the gas.
,.e. atoms or molecules) as there are atoms in (Given that the universal molar gas
12 g al carbon-I2 (t2C). constant, R = 8.31 J mol-l K-l and the
Avogadro constant,
r.)
re number of atoms tn 12 g of carbon-12 (which is No = 6.92 x 1623 mol
.,tua1 to the number of elementary units per mole) is
,.iled the Avogadro constant No: Guidelines
\* = 6.02 x l02r mol-r (a) Use Equation 4 and the fact that the
number of molecules in 1 mole of
lre relative molecular mass {M.) of a substance is substance = No.

-eiined by: (b) Use Equation 8.

Mm
mass of a molecule of the substance (c)
l/- = x12 Iv{ass per molecule, ru =
,^
mass of the carbon-L2 atom

ELlutttion 6
2. An isotope of lead has a relative atomlc mass
,3
of 2g8 and a density of 11.3 x 1CI3 kg m
The molar mass (M*) of a substance is the mass per Calculate:
mole of the substance:
(a) the number of atoms in a lead sample of
v*= M,(in gram) = Mrx 1o-3 (in kg) volume 0.25 m3
(b) the distance between the centres of two
l,iuation 7
adjacent lead atoms if it can be assumed
",\'e
can use pV = nRT to calculate the volume of that they are perfect spheres in contact.
- mole (i.e. the molar volume V*) of a gas at standard (Given that the Avogadro constant'
.:nrperature and pressure (i.e. 0 oC = 213 Kand
I= Nt = 6.Oz x 1023 mol-1.)
- = 1.013 x 10s Pa):

(1 mol) x (8.31 J morr K-1) x (273 K)

Guidelines
=!!!_ (l.0l3x (a) Use Equation 7 to obtain the mass per
t) lOsPa)
mole. M..
= 22.4 x 10-3 m3
Then number qf moles per m3

- :e number of moles n in a given mass of gas can be mass perm3 _ density

. :ulated from: mass per mole M*

M (ks) Then multiply by the Avogadro constant

M. (kg mol-1) (No) to obtain the number of atoms per m3
Hence obtain the number of atoms in the
sample (M.
-..:rtrion 8
(b) Volume of atom (7) = volume of sample
'.:rc M mass of gas
= divided by the number of atoms (AI).
-.d ,U,, = molar mass of the gas.
Calculate the radius of the atom, assuming
it to be a perfect sphere.
Hence the distance between centres of
adjacent atoms is calculated.
3
1. -{ sealed container of volume 0.8 x 10 m3
contains a gas at a temperature of 320 K and a
pre\sure of 1.5 x 106 Pa. Calculate:
ra) the number of moles and molecules of the gas
Kinetic theory of gases
Up to now we have described gas behaviour mainly in
terms of large-scale, measurable quantities such as
mass, volume, pressure and temperature. The kinetic
theory tries to improve our understanding by explaining
the quantitative behaviour of gases in terms of a model
in which a gas is seen as alarge collection of particles
in continuous motion. Probably the first attempts to
give a microscopic explanation of gas behaviour came
from Boyle and Hooke who thought the pressure
exerted by a gas was due to the collisions of gas
particles with the container walls. Newton's laws of
motion, which came a short time later, gave the idea
some strong mathematical explanation. It was the work
of Boltzmann and Maxwell on the statistical treatment
of the distribution of energy among a large sample of
particles, however, which was to give the kinetic theory
its finishing touch.
The first step in this theory is to visualise a gas as a very
large number of molecules in a state of random and
perpetual motion. The diffusion of gases and Brownian
motion are two effects which give support to this idea.
The Brownian motion is the observed continual,
haphazard motion of any small particles which are
suspended in a fluid. The original observation was made
by a Scottish botanist called Robert Brown who noticed
that tiny pollen grains suspended in water were subject to
continual, jerky movements. The theory was developed
by Albert Einstein in 1905 and it gave one of the first
methods of measuring 1/o which convinced many
sceptics of the correctness of kinetic theory. The effect
can be clearly observed and studied using the
arrangement shown in Figure 4.35.
ffi
ffi
ffi
ffi
re
Wvdeocamera
I Bas
low-power
microscope
(eyepiece removed)
cover slip
AcA.hAam
beam
laser V= smoke particles
glass cell
Figure 4.35 Apparatus used for observing Brownian
motion
The glass cell is filled with smoke and quickly
covered with a cover slip. It is then brightly
illuminated as shown and a low-power microscope is
used'to view the motion of the smoke particles. These
appear on the TV screen as tiny light spots which are
continually jiggling about.
The observations can be explained by considering
what happens to a single smoke particle. The particle
is quite large compared to the air molecules which are
continually bombarding it from every direction. At
any given moment, the smoke particle is forced to
move in a particular direction because the number of
molecular impacts is greater in that direction than in
any other. A moment later the particle may be moving
in a new direction as the balance of air molecule
impacts changes. Thus the smoke particle is pushed
around haphazardly as shown in Figure 4.36.
invisible, colliding
air moleculesH
6"'---*
resultant randomd........ ..|ffi. .. .._*,
motion of smoke Y" * ;-
partictes %.
| K
i -.:&
*&......"r"
#
Figure4.36 Diagrammatic illustration of the
random motion of a smoke particle in air
Pressure exerted by an ideal
According to kinetic theory the pressure exerted by a
gas results from the impact of its molecules with the
walls of the vessel which contains the gas. We will
now use this idea to derive an expression for gas
pressure. The following assumptions are made:
[i . e gas consists of a large number of identical
i
1
\ *o
molecules.
Intermolecular collisions and those between
\ molecules and the container walls are perfectly
i elastic (i.e. there is no loss of kinetic energy).
ip Intermolecular forces are negligible (except during
,J collisions) and the effect of gravity is ignored. As a
f result the molecules move in straight lines at
i constant speed between collisions and their
'..*-direction of motion is random.
 Ll Tle collisron time is negiigit,ie compared ri.ith the
:rme spent b1' a molecule bet$'een collisions.
(l The voiume of the molecules is negligible
--.rmpared with that of the gas.
The number of molecules is large enough to allow
, meaningful statistical treatment.
| \e $'ton's laws of motion can be applied.
81 Neriton's second law the force erened on the
moiecule by the wall = the rate of change of
momentum of the molecule.
Rate of change of momentum of molecule
momentum change
time taken
Rate of change of momentum of molecule

1 ,sas consisting of a large number of identical -'1

:.rr1ecu1es in rapid, random motion is contained in a
= '*'*
2l/c, = I
:;bic box of side I (see Figure 4.37).
Also, according to Newton's third law, the force
exerted by the wall on the molecule is equal but
oppositely directed to the force exerted by the
molecule on the wa1l.
Force (-F) exerted by the molecule on the wall is
given by:
nc2
F =-=L
I

Since pressure = force/area, the pressure, (p), which

then acts on face 1 is given by:

p- .fttrce _ mcll *r1

=
atea PF
If the gas contains (N) molecules having x-
components of velocity cxt, cx2, ...t cxN, the total
pressure (p) on face 1 is given by:

m)222m
P= , (crt tCr2tc,.l*...C.,1,)=l
' ('- )
13 l'
Figure 4.37 Derivation of, the erpression for gas
?re s sure Nmz (i)
p =';r:
Consider a single moiecule of mass (m) moving
:.-rn'ards face 1 with an r-component of velocity (c,). where c,2 = the mean square speed of the gas
. . momentum in the x-directiorr = mcx molecules in the x-direction (i.e. the mean of the
squares of the speeds of all the molecules travelling
.\t face 1 the molecule has a perfectly elastic in the x-direction)
,'.rllision and its momentum is reversed so that after
and V= 13 = the volume of the gas.
, ollision:

n.\\. momentum in the r-direction = -ntCx Of course, the molecules in the container will be
moving in all possible directions. Very few will be
.'. momentum change in the r-direction
moving exactly parallel to the x-axis. However, we
- fficr- 1- mc*) - 2mc, can consider each molecule as having components
of velocity c*, c, and c. in each of the three co-
\ner colliding with face 1 the molecule travels a ordinate directions x, y and z. As can be done with
::stance (21) beforeit again collides with face 1 : two dimensions, the three components can be
combined into a resultant velocity (c), given by:
rime taken (r) to travel distance 2/ is given by:
,] 2t
/ r)))= c|+ c'+ c' (see Maths window on page 364)
| -- C,
iir
Similarly, the components of the mean square
flr 'i,': velocities can be combined:
are trying to derive an expression for the pressure
& -.used by these molecular collisions, so we need to ;222
$ +c +c
c-=c-{yz
l "-.k at the force exerted by this collision.
ii
 The collision time is neglgib'ie compared ri ith the
Lr
time spent b1 a molecule betu'een collisions.
{. The voiume of the molecules is negligible
compared with that of the gas.
Br \errton's second 1au' the torce ererted on rhe
molecule b5' the wall = the rate of change of
momentum of the molecule'
Rate of change of momentum of molecule

The number of molecules is large enough to allow momentum change

a meaningful statistical treatment. time taken
| \ewton's laws of motion can be applied. Rate of change of momentum of molecule

\ sas consisting of a large number of identical

2mc, *r1
nolecules in rapid, random motion is contained in a Zl/c, I
.-ubic box of side / (see Figure 4.37).
Also, according to Newton's third law, the force
exerted by the wall on the molecule is equal but
oppositely directed to the force exerted by the
molecule on the wall.
Force (O exerted by the molecule on the wall is
given by:
,,C2r
t-17-
I

Since pressure = force/area, the pressure, (p), which

then acts on face 1 is given bY:

^-Jitrce -mcll- *r:

areo l) 13

gas contains (Af molecules having x-

If the
components of velocity cxp cx2,...., cxN, the total
pressure (p) on face 1 is given bY:

m (c-,2 +c.+
2 2 m /^,J\
2 +....*)=;
p=+ c',
\^., /
l1 /' '
Figure 4.37 Derivation of the expression for gas
, re s sure
D=
Nm1 (i)
,VT
-C
Consider a single molecule of mass (m) moving
:!r\\'ards face 1 with an x-component of velocity (c-,). *h"re 7= the mean square speed of the
gas

molecules in the r-direction (i.e. the mean of the

.'. momentum in the x-direction = mcx
travelling
squares of the speeds of all the molecules
.\t face 1 the molecule has a perfectly elastic in the x-direction)
:o1lision and its momentum is reversed so that after and V= 13 = the volume of the gas.
: --,1lision:

::n. momentum in the r-direction = -mcx

Of course, the molecules in the container will be
moving in all possible directions. Very few will be
'. momentum change in the x-direction moving exactly parallel to the x-axis. However, we
- ffic,- (- mcx) - 2mc* can consider each molecule as having components
of velocity cr, c, and c- in each of the three co-
.:ier colliding with face 1 the molecule travels a ordinate directions x, y and z. As can be done with
lr>tance (2/) before it again collides with face 1: two dimensions, the three components can be
combined into a resultant velocity (c), given by:
rime taken (r) to travel distance 2l is given by:
,' = ,1* ,',* ,l (see Maths window on page 3641
2t
d C, Similarly, the components of the mean square
',i': velocities can be combined:
ilir are trying to derive an expression for the pressure
:.:sed by these molecular collisions, so we need to ))22
C.=C I}Z+C +C
lir

,,, i' at the force exerted by this collision.

AIso, since there are a large number of moiecules in
random motion we can assume that there will be equal Maths window
numbers moving in each of the three co-ordinate The direction of motion of the molecules is
directions: assumed to be totaiiy ranclom.

222 Consider a molecule whose speed (c) is resolved

(
dt:-( -t into x, y ard z components cr, cl and c- respectivL-ly
as shown below:
--l
c- = 3c'Ii from which: c- -
12
(,
-3
Ly
Substituting for c2 in Equation (i) we have:

l)=-
I Nm.
J V

from which:
kg
Pa
1-
pV =)Nmcz
crQ
ms I

Eqttation 9

You should note that:

Equation 9 links the macroscopic properties of gas )z
v
pressure and volume with the microscopic
properties of number, mass and speed of the
individual molecuies.
Applying Pythagoras's theorem tr.l triangle OMN:
Since Nnz = total mass of gas
OM-r=MN2+ON2
and V = totai volume of gas
c'-Lr.'+ON-
the density (p) of the gas is given by:
Applying Pythagoras's iheorem to triangle CNQ:
p- mass of gas _ Nnr
volume of gas V
ONr=OQ2+lrlQl
ON'= i',' + ...'
Then Equation 9 can be expressed as:
From which we have
kg
Pa
'n' .a1),
C" = c"+ c*+ c-
-!'1'.1

lr- ;51,-
pc'
This relationship also holds tnre for the mean
square velocities:
m s-l
.:)2
Equation 10 C-=('+('+(.'
The speed of gas molecules n'hereas the mean of the squares of the speeds is
given by:
-:; molecul'es in a gas have a ven,rvide range of
:.-:.rent speeds. This is illustrated in the graph shown z 52+ 102+ !52+202
.:. Figure 4.38. in u,hich number of molecules is = 187.5
4
:.::ied against molecular speed.
Make sure you appreciate the difference between the
- --ber of molecules two terms.

The term root-mean-square speed is most often used

to quantify the molecular speeds of a gas, but you
may also encounter mean speed. Although r.m.s.
speed (c,..) is of the same order of magnitude as the
mean speed of the gas molecules, they have totally
different meanings.

For example, if we consider four gas molecules

moving with speeds of 650, 700,750 and 800 m s-1.

Then the mean speed c is given by:

Figure 4.38 Distribution of molecular speeds

650+700+750+800
t,
- = 725 m s-1
4
\bu should note that: whereas the root-mean-square speed (c,-.) is given
; Few molecules move either very fast or very by'
f:
slowly, and none are at rest. rl r
cMS = !c- = otn' * roo' * r*' * u*
q The variation of gas molecular speed depends on ^l,4
temperature. The higher the temperature, the
greater is the proportion of high-speed molecules = 727.2m{1
and the lower is the proportion of low-speed
molecules. The difference is small, in this case, but important.
* Three specific molecule speeds are shown on the *. If the gas pressure and density are known, the
graph in Figure 4.38. They are: r.m.s. speed (c,-,) of the molecules.of a particular
gas can be obtained from a rearranged version of
(i) The most probable speed (co) - This is the
Equation 10.
speed at which the greatest number of
molecules are moving. l-
(iD The mean speed @ - This is the average
value of the speeds of all the molecules.
o," =
!#
(iiD The root-mean-square speed (c*,) - This is Equation 10(a)
the square root of the mean-square speed
;
(c') of the molecules.
For example, air has h density of about 1..2kgm-3 at
room temperature.
* The mean-square speea 1C) of the molecules,
which appears in Equation 10, cannot be obtained Thus the r.m.s. speed (c*,) of air molecules at
by merely squaring the mean speed of the standard atmospheric pressure (= 1.013 x 105 Pa) is
molecules. given by:

-, u'e consider four molecules having speeds of 5, 10, (3) x (1.013 x 10) Pa)
20 units. c*a = = 502.5 m s*1
--< and
(7.2ksm-3)
Then the mean speed is given by:
This is of the same order of magnitude as the speed of
-= (iillj llj lo) sound in air (about 340 m s1) and suggests that the
= r2.-S
4 kinetic theory assumptions are reasonable. This is because
.:d the square of the mean speed is: the speed of sound is the speed at which the disturbance is

-' = (j . loi-lli?o)' = t56.25 passed on from one air molecule to the next and it is
reasonable to expect this to be of the same magnitude as
the r.m.s. speeds of the molecules themselves.
 o You should spend some time familiarising yourself But'N/n is the number of gas molecules per mole (i.e.
with the terms used in these equations. Difficulties N/n = Nl., the Avogadro constant).
are usually caused by confusion between symbols.
In this text, n has been used for the number of kg J mol-l K-l
moles, while N represents the number of molecules
and No is the number of molecules in one mole.
The symbols, and their meanings, may look similar,
but they are totally different.
MS

Guided example (3) Equation ll

Calculate the root-mean-square speed of the gas
molecules in each of the following cases,
o R is the gas constant per mole of gas molecules
(i.e. the molar gas constant)
(a) Hydrogen of density 0.009 kg m-3 at a
pressure of 2.5 x l0s Pa
a II/N^ = k is called Boltzmann's constant - it is
the gas constant per moletule.
(b) Helium of density 0.18 kg m-3 at a pressure
of 3.0 x 105 Pa Thus Equation 11 can be written:
(c) Oxygen of density 1.43 kg m-3 at a pressure
of 1.01 x 10sPa.

Guidelines
Use Equation I0(a) in each case. Equation l2

which tells us that: the average translational kinetic

energy of a gas molecule is directly proportional to
Molecular kinetic energly and temperature the absolute temperature of the gas.

The equation of state for (n) moles of an ideal gas of The equation of state for ru moles of an ideal gas is:
volume (1) at a pressure (p) and an absolute pV = nRT.
temperature (7) is:
pV = nRT (i) This can also be expressed in terms of Boltzmann's
constant (k).
where (R) is the universal molar gas constant

From kinetic theory of gases we have that:

Since t= n 11r"nR=kNe.
NA

,y = -L Nmc2
-a
(ii) Substituting for R in pV = nRT gives: pV = n(kN)T
J
But nNo is the product of the number of moles of gas
where N = number of molecules in volume V of gas and the number of molecules per mole, i.e. it is
,n = mass of each molecule equal to the total number of molecules in the gas (N).
and 7 = the mean-square speed of the gas
molecules.
Equation 13
Combining Equations (i) and (ii) we obtain:
You should note that from Equation 12, the
J- N*7 = rnr relationship between mean-square speed and
3
temperature is:
This may be re-written as:
7*T
+ .(+ *?)=,nr From which the r.m.s. speed is related to temperature
by:
l

1 .' * trr
1- 3n Rr=1 R
-mc'=
2 - -
2N 2 N/n i.e. the root-mean-square speed of gas molecules is
proportional to the square root of the absolute
temperature of the gas.
Avogadro's law
Guided examqles (4)
ris Ia\\ states tnat -I-t{a S
I t'--t (b) the temperature at which the r.m.s. speed
Equal volumes of ideal gases at the same
of the molecules would become twice as
:emperature and pressure contain equal
rumbers of molecules.,''
r' , r;' -:1". ,1
great as that calculated in (a).

Guidelines
,- *e consider two ideal gases x and y we can write:
(a) Use Equation 10.
:..r-qasx: P*V*= N*kT* (b) Make use of the fact that r.m.s. speed is
Frrr -EIIS Yi PrV, = NrkT, proportional to the square root of the
absolute temPerature.
-l the gases have equal volumes and are at the same
:ressure, then: 3. A cylinder of volume 0.25 m3 contains
P*V* = PrV, nitrogen gas at a pressure of 1.5 x 105 Pa and a
'. temperature of 17'C. Assuming that the gas
N*kT* = NrkT,
behaves ideallY, calculate:
If two gases are also at the same temperature, then (a) the number of moles of gas in the cylinder
T Tr'and so: (b)
'= the r.m.s. speed of the gas molecules at
\=N' 17 "c
(c) the average translational kinetic energy of
i.e. the number of molecules in gas x = the number of
a nitrogen molecule
molecules in gas y.
(d) the total kinetic energy of the gas
contained in the cYlinder.
Gu,ided examplss f4l
(Molar mass of nitrogen = 0'028 kg mol-r;
1. The observed speeds of ten particles at a 1
molar gas constant, R = 8.31 J mol K-1;
parlicular instant were as shown in the table Nt = 6'02 x 1023 mol-1')
Avogadro constant,
helow.
Guidelines
number of
I 2 4 I 1
(a,) Use Equation 4.
particles
(b) Use Equation 10.
speed (m s-1) 5.0 7.0 9.0 t2.0 14.0 15.0
(c) Use Equation 12.
(d) Total kinetic energy = kinetic energy per
What is (a) the most Probable sPeed
of molecules'
molecule x total number
(b) the mean speed
The total number of molecules = number
(c) the root-mean-square sPeed of
of moles of gas x number of molecules per
these Particles?
mole.

Guidelines
(a) This is the speed at which the greatest
number of particles are moving. Work done bY a gas
(b) You must add all the speeds and divide by
Consider a mass of an ideal gas at a pressure (p)
the total number of particles. Remember
enclosed in a cylinder by a frictionless piston of
that at some speeds there is more than one
area (A). The piston is in equilibrium under the
particle.
action of an external force (O and the pressure
(c) The r.m.s. speed is the square root of the force (pA) which the gas exefrs (see Figure 4'39
mean of the squares of the sPeeds. overleaf).

2. Nitrogen gas is kept in a container at a If the piston is allowed to move outwardsa distance
temperature of 2l "C and a pressure of Ax which is small enough for the pressure to be
1.0 x 105 Pa. If the density of nitrogen is assumed constant, then:
1.25 kg m-3, calculate:
External work done (4140 by the expansion is given
(a) the root-mean-square speed of the nitrogen by:
molecules
[l\/ = pAA,x (since work - force x distance)
 Equation 15

This equation is valid for all relationships between p

andV.

For a process in which p is constant (called an

isobaric process) we have that:
lAxi
Figure 4.39 Work done by an ixpanding gas
lv, a,
W
uvdv=[V'z
=pl
v1
But AAr = AV (the small increase in volume resulting 1

from the piston's movement)

w= p(vr_vr)
_
T, N m-21pa;
\,/ Equation 16
naK
\, Generally if a pressure-volume graph is plotted for
^p= ,;: the gas (such a graph is called an indicator diagram,
Equation 14 as shown in Figure a.a\@)), then the work done (l4f
by the gas as the volume changes from (V,) to (Vr) is
i.e. when a gas expands at constant pressure, it does equal to the area enclosed by the p-V graph between
work (in J) on the surroundings, equal to the pressure the two V-values (shown shaded).
(in Pa) multiplied by the change of volume (in m3).
For an isobaric process the p-V graph is a horizontal
You should note that: line and so

o The same result can be obtained by considering a W = zraz enclosed by p-V graph
compression of the gas in which case work is done p(Vr* V)
=
on the gas rather than by it.
as shown in Figure 4.40(b).
o For a finite expansion in which the volume changes
from an initial value (y,) to some final vafue (Vr),
the total work done (I4r) is given by:

(a)

Figure 4.40 Pressure-volume graph for q gas

 Hrst law of thermodynamics rilierb pll-= the n'ork done lrn this case b1 the
system on the surroundings.,).
;;:modvnamics is a branch of phvsics u'hich deals
' -:h processes in w,hich heat flows into or out of a Changes of state such as melting, vaporisation and
,.. ::3m (e._e. the petroVair mixture in the cylinder of a sublimation can be described in terms of the first law
-.: enuine.l rvhile work is done on or by the system. of thermodynamics by stating that:
- :.: tlrst lau, of thermodynamics is a specific case of
.-.e principle of conservation of energy and may be A,l=Lu+LW
.."red as follows:
Eqwation 19
f0=AU+LW
where

ELiLtation l7 Ll = the latent heat energy supplied to cause

',',
here:
_\0 = heat energy supplied to a system, or
flowing out of it
-\U = change ofinternal energy ofthe system
-\17 = work done by or on the system
The sign convention we adopt here is that:
* AQ is positive when heat is supplied to the system
and it is negative when heat is transferred from the
system.
a LW is positive if the external work is done by the
system and it is negative if the external work is
done on the system.
: LU is positive if the internal energy of the system
increases.
If we consider the case of the gas expansion of Figure
-1..10(a), Equation 17 can be wrirten as;
the change of state
AU = increase in internal potential energy
resulting from the change of state
A I{ = the external work done as a result of the
change of state.
This term is most significant in the cases of
vaporisation (change from liquid to vapour) and
sublimation (change from solid directly to a vapour)
because these two processes involve large volume
increases and a large proportion of the latent heat is
used to do work in pushing back the atmosphere. AW
is taken as positive for an expansion (e.g. in melting
and vaporisation) and negative for a contraction (e.g.
in condensation).
The internal energy of a system can be increased by:
* supplying heat energy to the system and/or
* doing work on the system.

JJPa For example, if we consider the air in a bicycle pump

to be the system, its internal energy and hence its
LQ=LU+pLV,. temperature can be increased by supplying heat from
outside the pump or by pushing the plunger in with
-: the finger held over the nozzle. Figure 4.41 illustrates
Equation l8 the two methods.

atI

plunger movement

(a) Heat is supplied (the space around the pump (b) Work is done on the air by movement of the
is at a highel temperature than the air inside) plunger. Potential energy increases

Figure 4.41 Increasing the internal eruergy of the air in a bicttcle pump
This leads us to an alternative way of stating the
first law which is preferred by some examination
boards.
The increase in intemal energy of a system = Heat
supplied to the system + Work done on the system
i.e. A,u = LQ + LW
Equation 20
In the case of an isolated system (i.e. one on which
there are no external influences), no work is done on
or by the system and no heat is supplied to or
transferred from the system.
AW=O and AQ =Q
From which it follows that the change in internal
energy LU = 0.
Thus the internal energy of an isolated system is
constant.
Adiabatic processes
An adiabatic process is one in which there is no heat
energy flow into or out of the system. When a
system undergoes such a process, LQ = 0 and
Equation 20 becomes: AU = AW.
Thus when a system undergoes an adiabatic process:
the increase in the internal energy of the system is
equal to the work done on it.
The principal heat capacities
of a gas
Since only a relatively small expansion is produced
when a solid or a liquid is heated, most of the heat
energy supplied is used to increase the internal energy.
In the case of a gas, however, the expansion can be
much greater, enabling the gas to do external work.
Thus when a gas is heated the increase in its internal
energy and hence the temperature rise produced
depends on how much external work the gas is
allowed to do. Because of this a gas has an infinite
number of heat capacities. The most useful two gas
heat capacities, called the principal heat capacities,
which are used are those which relate to constant
volume and constant pressure conditions. They are
defined as follows:
The molar heat capacity at constant volume
(C,) is the heat enerry needed to produce a unit
temperature rise in one mole of a gas when the
volume is kept constant.
The molar heat capacity at constant prffire
(C*) is the heat energy needed to produce a unit
tepPerature rise in one mole of a gas when the
prqssure is,kepl contqnt. l
You should note that:
e The unit of molar heat capacity at constant volume
or pressure is J mol I K-1.
g If we are dealing with unit mass of gas instead of
one mole, we use the terms principal specific heat
capacity at constant volume and principal
specific heat capacity at constant pressure, and
these are denoted by the symbols cu and co.
e % , C - This can be explained in terms of the first
law of thermodynamics. When a gas is heated at
constant pressure some of the energy is used to raise
the internal energy (hence the temperature) of the gas
and some is used to do extemal work. If the gas is
heated at constant volume we are effectively not
allowing the gas to do any work and so all the energy
supplied is used to raise the internal energy and
therefore the temperature. Thus the amount of heat
needed to raise the temperature of a gas at constant
pressure is greater than that needed to produce the
same temperature rise at constant volume.
o The amount of heat AQ needed to raise the
temperature of 1" mole of an ideal gas by an
amount AZ at constant volume is given by:
LQ . C,, LT
' Lquation 2l (a)
c The amount of heat AQ needed to raise the
temperature of 1 mole of an ideal gas by an amount
AZ at constant pressure is given by:
aO= cp,ar
Equation 2l(b)
o It can be shown that for ideal gases:
C^_ v
P C,,= R
Lquation 22
e pv is denoted by y (= 1.67 for a
The ratio C^/C,.
monatomic gas, 1.40 for a diatomic gas and 1.33
for a polyatomic gas).
Methods of producing
Ghanges in $ases
The state of a gas (i.e. the values of p, V and 7) can
be changed by any of the following processes.
lsothermal process
I Occurs at constant temperature (7 constant).
a For an isothermal expansion or contraction of an
ideal gas,
pV = constant and p rV r = p 2V, (see Figure 4 .42) .
 r Since 11/ = 0. no u.ork is done and all the heat
entering the gas becomes internal energy.
The temperature rises from t to Trand the pressure
increases from prto pr.
LQ = LU = Cu(Tz- T).

lsobaric process
* Occurs at constant pressure.
a For an isobaric change of an ideal gas,
v,. v,
o = constanl and -
T1 T2

(see Figure 4.44).

Figure 4.42 Isothermal process

o Since the internal energy of an ideal gas depends
only on its temperaturc, LU = 0, and so AQ = A,W.
This means that if gas expands and does work AtrY
then an amount of heat AQ must be supplied to
keep the temperature constant.
o A reversible isothermal change is an ideal one
iij
lr'
which would require the gas to be contained in a
,ir
thin, highly conductive vessel, surrounded by a
ii
constant-temperature reservoir. In addition, the
change would have to occur very slowly.
ii

lsovolumetlic process Figure 4.44 Isobaric process

a Occurs at constant volume.

6 Some of the heat supplied to the gas increases the
internal energy (temperature rise ?, to 7r) and the
a For an isovolumetric change of an ideal gas, rest is used to do work.

V= constant urd
P, P,
= Adiabatic process
T, Tz
a Occurs with no heat entering or leaving the gas.
(see Figure 4.43).
o For an adiabatic change of an ideal gas, pVv =
constant (where y= CrlC,) and prVrv = p2V2v
(see Figure 4.45).

Figure 4.43 Isovolumetric change Figure 4.45 Adiabatic change

 o Since LQ = 0, LW = - AU. This means that for an
adiabatic expansion all the work is done at the
expense of the internal energy of the gas which
thus cools (Trto Tr). In the case of a compression
the gas heats up as the work done increases the
internal energy.
o A reversible adiabatic change is an ideal process
which requires the gas to be in a thick-walled,
poorly conducting vessel and the volume change
must be small and rapid.
Work done during a cycle
When a gas undergoes changes which eventually
return it to its original state, it is said to have gone
through a cycle of operations. The p-V (indicator)
diagram is then a closed loop whose area represents
the net work done by or on the gas. Consider, for
example, an ideal gas which undergoes the changes
shown in Figure 4.46.
Figure 4.46
Area enclosed by the closed loop
resultingfrom a cycle of changes on a gas = the net
work done
Work done by the gas as it expands from
Vlto V?= area6sfg = pr(Vr- V).
(This expansion results from an isovolumetric change
a to b followed by an isotraric change b to c.)
Work done on the gas in compressing it from
Vzto V1 = area aflfs = pr(Vr- V).
(This compression results from an isovolumetric
change c to d followed by an isobaric change d to a.)
Net work done by the gas = areabcfe - area adfe
= pz(Vz- Vr) - rr(Vr- Vr)
= (pz- p) (Vz_ V)
.'. Net work done by the gas = area abcd
(the area enclosed by the rectangle)
This can be applied to any cycle of operations.
Guided examples (5)
1. A sample of gas is enclosed in a cylinder
by a frictionless piston of area 60 cm2. The
cylinder is heated so that 400 J of heat
energy is supplied to the gas which then
expands against atmosphere pressure and
pushes the piston 20 cm along the cylinder.
Given that atmospheric pressure is
1.0 x 10s Pa, calculate:
(a) the external work done by the gas and
(b) the change in internal energy of the gas.
Guidelines
(a) Use Equation 16 - Remember SI units
throughout.
Altematively use the fact that the work
done by the gas = force exerted by gas
on piston x distance moved by piston.
(force exerted by gas on piston = force
exerted by atmospheric pressure acting
on piston).
(b) Use Equation 17.
2. When 0.60 kg of water is converted into steam
at 100"C at a pressure of 1.0 x 105 Pa the
amount of heat energy supplied is 2.9 x 106 J.
If during the vaporisation the water increases
its volume'by 2.2 m3, calculate:
(a) the work done against the extemal
pressure
(b) the increase in the internal energy of the
water.
Guidelines
(a) Use Equation 14.
(b) Use Equation 18.
3. When 22.4 g of nitrogen is heated from 293 K
to 393 K in an insulated and freely extensible
container, 2.33 x 103 J of heat is required.
When the same mass of nitrogen is contained
in an insulated, rigid container, 1.66 x 103 J of
heat energy is required to give the same
temperature rise. Calculate:
(a) the principal molar heat capacities of
nitrogen
(b) the value of the universal molar gas
constant.
(molar mass of nitrogen = 28.0 g mol-l)

Guidelines
Use Equation 8 to find the number of moies
of nitrogen in the sample.
Then use Equatior-r 21(b) to obtain the molar
heat capacity at constant pressllre. Cr, and
Equation 21(a) to obtain the molar heat
capacity at constant volume, C".
Use Equation 22.
p/ xtO5 Pa
The indicator diagram shows an energy cycle f'or
1 mole of an ideal gas. The gas is cooled at
SECTION A
Qualitative assessment
1. For each of the gas laws (Boyle's larv, Charles'
law and the pressure law):
(a) give a written statement of the law
(b) express the law as arr equation
(c) express the law on a graph relating
the
quantities involved.
2,
(a) Explain what is meant by an ideal gas.
(b) Write down the equation of state for N moles
of an ideal gas. Define each quantity in the
equation.
3. (a) Define the mole.
(b) How is the moie related to the Avogadro
constant?
lc) What is
(i) the relative molecular mass and
constant pressure (a to b). heated at con\Iani
vohrme (b to c) and then retumed to its onginal
state (c to a). Calculate:
(a) the gas temperature at a, b and c
(b) the heat removed frorn the gas during the
process a to b
(c) the heat supplied to the gas during the
process b to c, and
(d) the net rvork done in the cycle.
(universal molar gas constant,
R = 8.3 J mol rf I; C, for the gas = 5R/2)
Guidelines
(a) Use Equation 4 for 1 mole of gas - take the
values ofp and V for each point from the
indicator diagrarn.
(b) Obtain Equatior 22.
a value fcrr Co by using
Then use Equation 21(b) to find heat
removed during the isobaric process (a to b).
(c) [Ise Equation 21(a) to find heat supplied
during the isovolumetric process (b to c).
(d) Use net work done in the cycie = ore& of
triangle abc"
(ii) the molar mass of a substance?
(d) How many moles are there in M kg of a
1?
substance of rnoiar rnass M* kg mo1
(a) What is Brownian motion?
(b) How is it explained in terms of molecules?
(a) State the main assumptions made in the
kinetic theory of gases.
(b) Derive the equation.
! Nm-
P-g v "
for an ideal gas of volume (l.f at a pressure
(p) if the gas contains (A) molecules, each of
mass (ru) and with mean-square speed (c2).
Explain what is meant by
(a) most probable speed
(b) mean speed and
(c) root-mean-square speed of gas molecules.
 7. Derive the expression,
relating average molecular kinetic energy and
absolute temperature of a gas.
8. State Avogadro's law and prove your statement.
g.
(a) Consider an ideal gas enclosed in a cylinder
by a piston of area (A). What is the work
done when the piston moves over a small
distance Ax as a result of the gas pressure
(p)? Assume that the change in volume is so
small that the pressure remains constant.
What is the work done in terms of the volume
change of the gas?
(b) What is the expression for the total work
done by the gas for a finite expansion in
which the volume increases from Vrto Vr?
What is the expression if the expansion
occurs at constant pressure?
10. (a) State the first law of thermodynamics.
(b) Explain what is meant by internal energy in
the context of the first law.
(c) How can the internal energy of a system be
(i) increased, (ii) decreased?
(d) What is the alternative form of the first law
which is based on the change of internal
energy of a system?
11. (a) What is an isolated system?
(b) Why is the internal energy of such a system
constant?
(c) What is an adiabatic process?
(d) What do you conclude by applying the first
law of thermodynamics to a system which
undergoes an adiabatic process?
12. (a) Why can a gas have an infinite number of
, heat capacities?
(b) Define O the molar,heat capacity at
constant volume C"
and (ii) the molar heat capacity at
constant pressure Co, of a gas.
(c) Explain why % is greater than C,.
(d) Give an expression for the amount of heat Le
which must be supplied to n moles of an ideal
gas so as to produce a temperature rise AZ if
the heating is performed (i) at constant
volume, and (ii) at constant pressure.
S..-
13. The state of a gas can be changed by each of the
following processes: isothermal; isovolumetric;
isobaric; adiabatic. For each of these:
(a) State the condition under which the change occurs.
(b) Show the change on a pressure-volume graph.
SEGTION B
Quantitative assessment
(Answers: 1.5 x 10+; 2.7 x tOa; 2.1, x 7O-3;
8.6 x 10-3; 0.010; 0.026; 0.80; 1.3; 60;
L2O; 27O; 240; 24O;480; 480; 480; 480;
48O; 48O; 52O; 52O; 730; 830; 920;
1.6 x 1O3; 2.0 x 103; 2.5 x 7O3; 2.6 x !O3;
7.0 x 103; t.O x lOa; 2.7 x LOa; 2.3 x tOa
2.3 x LOs; 4.8 x 1023.)
1,. (u) A fixed mass of gas has a volume of
3000 cm3 at a pressure of 1.0 x 105 Pa.
Calculate its volume if the pressure increases
to 2.0 x 106 Pa with the temperature
remaining constant.
(b) A fixed mass of gas has a volume l/when the
temperature is 127'C. To what temperature
must the gas be raised so that its volume
increases to 2.75 lzwith the pressure
remaining constant?
(c) A fixed mass of gas has a volume of
0.02 m3 at a temperature of 44"C and a
pressure of 2.02 x 10s Pa. Find the new
volume of the gas at standard temperature and
pressure (i.e. 0 'C and 1.01 x 10s Pa).
*2. (a) At a particular instant five oxygen molecules
have speeds of 450, 475,480,495 and
510 m s-1.
Calculate their:
(, mean speed
(ii) mean-square speed and
(iii) root-mean-square speed.
(b) Calculate the r.m.s. speed for the molecules
of a gas of density 1.3 kg m-3 at a pressure of
1.0 x 10s pa.
3. A sealed can of volume 2 x 10a cm3 contains gas
at a pressure of 1 x 10s Pa and a temperature of
27 "C. Assuming the gas to be ideal, calculate:
(a) the number of moles of gas in the can (given
that the universal molar gas constant, R =
8.3t J mol-1 K-1)
{
frr

,b r the number of gas molecules in the can (given 7. An insulated, freely extensible vessel contains
that the Avogadro constant, 0.5 mol of oxygen at 273 K. If atmospheric
,\ = 6.OZ x 1023 mol-l) pressure is taken as 1.0 x lOs Pa and thc
,c) the mass of gas in the can if its relative principal molar heat capacity at constant pressure
molecular mass is 32 of oxygen is 29 J mol 1 K-l calculate:
rd) the gas density
temperature of the gas to 323 K
te ) the r.m.s. speed of the gas moiecules.
(b) the volume increase of the gas produced by
1. The total translational kinetic energy of a certain the temperature rise
mass of an ideai gas at a temperature of 57 "C is (c) the external work done by the gas
550 J. If the relative molecular mass of the gas is
(d) the increase in the internal energy of the gas
1.0, calculate:
(e) the heat energy needed to cause the same
(a) the total kinetic energy of the gas molecules
temperature rise at constant volume.
at a temperature of 280 "C
(Universal molar gas constant,
+(b) the mass of gas present and
R = 8.3 J mol-r K-r.)
(c) the r.m.s. speed of the molecules at 280 "C
(given that the universal molar gas constant, 8.
pressure/105 Pa
R = 8.3 J mol-l K-r;.

Pr = 1.0 x 105 Pe

area = 150 cm2

2
volume/1O m3

The diagram shows a sample of gas enclosed in a
cylinder by a frictionless piston of area 150 cm2.
When 300 J of energy is supplied to the gas, it
expands against a constant atmospheric pressure
of 1.0 x 105 Pa and pushes the piston out a
distance of 16 cm along the cylinder.
Calculate:
(a) the work done by the gas and
The indicator (pV) diagram shows an energy cycle
for one mole of an ideal gas which is: cooled at
constant pressure (a to b), heated at constant
volume (b to c), heated at constant pressure (c to
d) and finally returned to its original state by an
isothermal expansion (d to a).
Calculate:

(b) the increase in internal energy of the gas. (a) the gas temperature at a, b, c and d
(b) the heat energy removed or supplied during
6. When 10 cm3 of water is boiled at 100'C and at the processes a to b, b to c, and c to d
an almospheric pressure of 1.0 x 105 Pa,
(c) the net work done in 1 cycle (an estimate).
1.6 x 104 cm3 of steam is produced. Calculate:
(Universal molar gas constant,
(a) the mass of water boiled
R = 8.3 J mol-r K-1; molar heat capacity at
(b) the heat energy needed to produce the constant pressure of the gas,
vaporisation Cp=29Jmol rK-1.;
(c) the external work done during the
vaporisation
(d) the increase in internal energy.
(Density of water = 1.0 x 103 kg m-3;
specific latent heat of vaporisation of steam =
ry'
2.26x106Jkg-t.)