1.

2 THE GAS LAWS 9

Table 1.2 The gas constant
R
8.314 47 J K1 mol1
8.205 74 102 dm3 atm K1 mol1
8.314 47 102 dm3 bar K1 mol1
8.314 47 Pa m3 K1 mol1
1 62.364 dm3 Torr K1 mol1
1.987 21 cal K1 mol1
Comment 1.3
For an object of mass mmoving at a
speed 1, the kinetic energy is EK 12 m12.
The potential energy, EP or V, of an
object is the energy arising from its
position (not speed). No universal
expression for the potential energy can
be given because it depends on the type
of interaction the object experiences.
behaving perfectly). However, a more accurate value can be obtained by measuring
the speed of sound in a low-pressure gas (argon is used in practice) and extrapolating
its value to zero pressure. Table 1.2 lists the values of R in a variety of units.
Molecular interpretation 1.1 The kinetic model of gases
The molecular explanation of Boyles law is that, if a sample of gas is compressed
to half its volume, then twice as many molecules strike the walls in a given period
of time than before it was compressed. As a result, the average force exerted on
the walls is doubled. Hence, when the volume is halved the pressure of the gas is
doubled, and p V is a constant. Boyles law applies to all gases regardless of their
chemical identity (provided the pressure is low) because at low pressures the average
separation of molecules is so great that they exert no influence on one another
and hence travel independently. The molecular explanation of Charless law lies
in the fact that raising the temperature of a gas increases the average speed of its
molecules. The molecules collide with the walls more frequently and with greater
impact. Therefore they exert a greater pressure on the walls of the container.
These qualitative concepts are expressed quantitatively in terms of the kinetic
model of gases, which is described more fully in Chapter 21. Briefly, the kinetic
model is based on three assumptions:
1. The gas consists of molecules of mass m in ceaseless random motion.
2. The size of the molecules is negligible, in the sense that their diameters are
much smaller than the average distance travelled between collisions.
3. The molecules interact only through brief, infrequent, and elastic collisions.
An elastic collision is a collision in which the total translational kinetic energy of the
molecules is conserved. From the very economical assumptions of the kinetic
model, it can be deduced (as we shall show in detail in Chapter 21) that the pressure
and volume of the gas are related by
pV nMc2 (1.9)
where M mNA, the molar mass of the molecules, and c is the root mean square
speed of the molecules, the square root of the mean of the squares of the speeds, v,
of the molecules:
c _v2_1/2 (1.10)
We see that, if the root mean square speed of the molecules depends only on the
temperature, then at constant temperature
pV constant
which is the content of Boyles law. Moreover, for eqn 1.9 to be the equation of
state of a perfect gas, its right-hand side must be equal to nRT. It follows that the
root mean square speed of the molecules in a gas at a temperature T must be
(1.11)
We can conclude that the root mean square speed of the molecules of a gas is proportional
to the square root of the temperature and inversely proportional to the square
root of the molar mass. That is, the higher the temperature, the higher the root mean
square speed of the molecules, and, at a given temperature, heavy molecules travel
more slowly than light molecules. The root mean square speed of N2 molecules, for
instance, is found from eqn 1.11 to be 515 m s1 at 298 K.
c
RT
M
/

1.2 THE GAS LAWS 9

Table 1.2 The gas constant
R
8.314 47 J K1 mol1
8.205 74 102 dm3 atm K1 mol1
8.314 47 102 dm3 bar K1 mol1
8.314 47 Pa m3 K1 mol1
1 62.364 dm3 Torr K1 mol1
1.987 21 cal K1 mol1
Comment 1.3
For an object of mass mmoving at a
speed 1, the kinetic energy is EK 12 m12.
The potential energy, EP or V, of an
object is the energy arising from its
position (not speed). No universal
expression for the potential energy can
be given because it depends on the type
of interaction the object experiences.
behaving perfectly). However, a more accurate value can be obtained by measuring
the speed of sound in a low-pressure gas (argon is used in practice) and extrapolating
its value to zero pressure. Table 1.2 lists the values of R in a variety of units.
Molecular interpretation 1.1 The kinetic model of gases
The molecular explanation of Boyles law is that, if a sample of gas is compressed
to half its volume, then twice as many molecules strike the walls in a given period
of time than before it was compressed. As a result, the average force exerted on
the walls is doubled. Hence, when the volume is halved the pressure of the gas is
doubled, and p V is a constant. Boyles law applies to all gases regardless of their
chemical identity (provided the pressure is low) because at low pressures the average
separation of molecules is so great that they exert no influence on one another
and hence travel independently. The molecular explanation of Charless law lies
in the fact that raising the temperature of a gas increases the average speed of its
molecules. The molecules collide with the walls more frequently and with greater
impact. Therefore they exert a greater pressure on the walls of the container.
These qualitative concepts are expressed quantitatively in terms of the kinetic
model of gases, which is described more fully in Chapter 21. Briefly, the kinetic
model is based on three assumptions:
1. The gas consists of molecules of mass m in ceaseless random motion.
2. The size of the molecules is negligible, in the sense that their diameters are
much smaller than the average distance travelled between collisions.
3. The molecules interact only through brief, infrequent, and elastic collisions.
An elastic collision is a collision in which the total translational kinetic energy of the
molecules is conserved. From the very economical assumptions of the kinetic
model, it can be deduced (as we shall show in detail in Chapter 21) that the pressure
and volume of the gas are related by
pV nMc2 (1.9)
where M mNA, the molar mass of the molecules, and c is the root mean square
speed of the molecules, the square root of the mean of the squares of the speeds, v,
of the molecules:
c _v2_1/2 (1.10)
We see that, if the root mean square speed of the molecules depends only on the
temperature, then at constant temperature
pV constant
which is the content of Boyles law. Moreover, for eqn 1.9 to be the equation of
state of a perfect gas, its right-hand side must be equal to nRT. It follows that the
root mean square speed of the molecules in a gas at a temperature T must be
(1.11)
We can conclude that the root mean square speed of the molecules of a gas is proportional
to the square root of the temperature and inversely proportional to the square
root of the molar mass. That is, the higher the temperature, the higher the root mean
square speed of the molecules, and, at a given temperature, heavy molecules travel
more slowly than light molecules. The root mean square speed of N2 molecules, for
instance, is found from eqn 1.11 to be 515 m s1 at 298 K.
c
RT
M
/

1 THE PROPERTIES OF GASES

Surface
of possible
states
Pressure, p
Volume, V
Temperature, T
Pressure, p
Temperature, T
Volume, V
pT
isochore

p 1/V
isotherm

VT
isobar

Fig. 1.8 A region of the p,V,T surface of a

fixed amount of perfect gas. The points
forming the surface represent the only
states of the gas that can exist.
Fig. 1.9 Sections through the surface shown
in Fig. 1.8 at constant temperature give the
isotherms shown in Fig. 1.4 and the isobars
shown in Fig. 1.6.
npVT
Initial
Final
Same 100 300
Same ? 500
Same
Same
2
The surface in Fig. 1.8 is a plot of the pressure of a fixed amount of perfect gas
against its volume and thermodynamic temperature as given by eqn 1.8. The surface
depicts the only possible states of a perfect gas: the gas cannot exist in states that do not
correspond to points on the surface. The graphs in Figs. 1.4 and 1.6 correspond to the
sections through the surface (Fig. 1.9).
Example 1.2 Using the perfect gas equation
In an industrial process, nitrogen is heated to 500 K in a vessel of constant volume.
If it enters the vessel at 100 atm and 300 K, what pressure would it exert at the
working temperature if it behaved as a perfect gas?
Method We expect the pressure to be greater on account of the increase in temperature.
The perfect gas law in the form PV/nT R implies that, if the conditions
are changed from one set of values to another, then because PV/nT is equal to a
constant, the two sets of values are related by the combined gas law:
(1.12)
The known and unknown data are summarized in (2).
Answer Cancellation of the volumes (because V1 V2) and amounts (because
n1 n2) on each side of the combined gas law results in
which can be rearranged into
p
T
T
2p
2
1
1
p
T
p
T
1
1
2
2

pV
nT
pV
nT
11
11
22
2 21 THE PROPERTIES OF GASES
Surface
of possible
states
Pressure, p
Volume, V
Temperature, T
Pressure, p
Temperature, T
Volume, V
pT
isochore

p 1/V
isotherm

VT
isobar

Fig. 1.8 A region of the p,V,T surface of a

fixed amount of perfect gas. The points
forming the surface represent the only
states of the gas that can exist.
Fig. 1.9 Sections through the surface shown
in Fig. 1.8 at constant temperature give the
isotherms shown in Fig. 1.4 and the isobars
shown in Fig. 1.6.
npVT
Initial
Final
Same 100 300
Same ? 500
Same
Same
2
The surface in Fig. 1.8 is a plot of the pressure of a fixed amount of perfect gas
against its volume and thermodynamic temperature as given by eqn 1.8. The surface
depicts the only possible states of a perfect gas: the gas cannot exist in states that do not
correspond to points on the surface. The graphs in Figs. 1.4 and 1.6 correspond to the
sections through the surface (Fig. 1.9).
Example 1.2 Using the perfect gas equation
In an industrial process, nitrogen is heated to 500 K in a vessel of constant volume.
If it enters the vessel at 100 atm and 300 K, what pressure would it exert at the
working temperature if it behaved as a perfect gas?
Method We expect the pressure to be greater on account of the increase in temperature.
The perfect gas law in the form PV/nT R implies that, if the conditions
are changed from one set of values to another, then because PV/nT is equal to a
constant, the two sets of values are related by the combined gas law:
(1.12)
The known and unknown data are summarized in (2).
Answer Cancellation of the volumes (because V1 V2) and amounts (because
n1 n2) on each side of the combined gas law results in
which can be rearranged into
p
T
T
2p
2
1
1
p
T
p
T
1
1
2
2

pV
nT
pV
nT
11
11
22
22

1.2 THE GAS LAWS 11

Table 1.3 The composition of dry air at sea level
Percentage
Component By volume By mass
Nitrogen, N2 78.08 75.53
Oxygen, O2 20.95 23.14
Argon, Ar 0.93 1.28
Carbon dioxide, CO2 0.031 0.047
Hydrogen, H2 5.0 103 2.0 104
Neon, Ne 1.8 103 1.3 103
Helium, He 5.2 104 7.2 105
Methane, CH4 2.0 104 1.1 104
Krypton, Kr 1.1 104 3.2 104
Nitric oxide, NO 5.0 105 1.7 106
Xenon, Xe 8.7 106 1.2 105
Ozone, O3: summer 7.0 106 1.2 105
winter 2.0 106 3.3 106
Substitution of the data then gives
Experiment shows that the pressure is actually 183 atm under these conditions, so
the assumption that the gas is perfect leads to a 10 per cent error.
Self-test 1.3 What temperature would result in the same sample exerting a pressure
of 300 atm? [900 K]
The perfect gas equation is of the greatest importance in physical chemistry because
it is used to derive a wide range of relations that are used throughout thermodynamics.
However, it is also of considerable practical utility for calculating the properties of a
gas under a variety of conditions. For instance, the molar volume, Vm V/n, of a perfect
gas under the conditions called standard ambient temperature and pressure
(SATP), which means 298.15 K and 1 bar (that is, exactly 105 Pa), is easily calculated
from Vm RT/p to be 24.789 dm3 mol1. An earlier definition, standard temperature
and pressure (STP), was 0C and 1 atm; at STP, the molar volume of a perfect gas is
22.414 dm3 mol1. Among other applications, eqn 1.8 can be used to discuss processes
in the atmosphere that give rise to the weather.
IMPACT ON ENVIRONMENTAL SCIENCE
I1.1 The gas laws and the weather
The biggest sample of gas readily accessible to us is the atmosphere, a mixture of gases
with the composition summarized in Table 1.3. The composition is maintained moderately
constant by diffusion and convection (winds, particularly the local turbulence
called eddies) but the pressure and temperature vary with altitude and with the local
conditions, particularly in the troposphere (the sphere of change), the layer extending
up to about 11 km.
p2
500
300
(100 ) 167 K
K
atm atm1.2 THE GAS LAWS 11
Table 1.3 The composition of dry air at sea level
Percentage
Component By volume By mass
Nitrogen, N2 78.08 75.53
Oxygen, O2 20.95 23.14
Argon, Ar 0.93 1.28
Carbon dioxide, CO2 0.031 0.047
Hydrogen, H2 5.0 103 2.0 104
Neon, Ne 1.8 103 1.3 103
Helium, He 5.2 104 7.2 105
Methane, CH4 2.0 104 1.1 104
Krypton, Kr 1.1 104 3.2 104
Nitric oxide, NO 5.0 105 1.7 106
Xenon, Xe 8.7 106 1.2 105
Ozone, O3: summer 7.0 106 1.2 105
winter 2.0 106 3.3 106
Substitution of the data then gives
Experiment shows that the pressure is actually 183 atm under these conditions, so
the assumption that the gas is perfect leads to a 10 per cent error.
Self-test 1.3 What temperature would result in the same sample exerting a pressure
of 300 atm? [900 K]
The perfect gas equation is of the greatest importance in physical chemistry because
it is used to derive a wide range of relations that are used throughout thermodynamics.
However, it is also of considerable practical utility for calculating the properties of a
gas under a variety of conditions. For instance, the molar volume, Vm V/n, of a perfect
gas under the conditions called standard ambient temperature and pressure
(SATP), which means 298.15 K and 1 bar (that is, exactly 105 Pa), is easily calculated
from Vm RT/p to be 24.789 dm3 mol1. An earlier definition, standard temperature
and pressure (STP), was 0C and 1 atm; at STP, the molar volume of a perfect gas is
22.414 dm3 mol1. Among other applications, eqn 1.8 can be used to discuss processes
in the atmosphere that give rise to the weather.
IMPACT ON ENVIRONMENTAL SCIENCE
I1.1 The gas laws and the weather
The biggest sample of gas readily accessible to us is the atmosphere, a mixture of gases
with the composition summarized in Table 1.3. The composition is maintained moderately
constant by diffusion and convection (winds, particularly the local turbulence
called eddies) but the pressure and temperature vary with altitude and with the local
conditions, particularly in the troposphere (the sphere of change), the layer extending
up to about 11 km.
p2
500
300
(100 ) 167 K
K
atm atm

1 THE PROPERTIES OF GASES

In the troposphere the average temperature is 15C at sea level, falling to 57C at
the bottom of the tropopause at 11 km. This variation is much less pronounced when
expressed on the Kelvin scale, ranging from 288 K to 216 K, an average of 268 K. If we
suppose that the temperature has its average value all the way up to the tropopause,
then the pressure varies with altitude, h, according to the barometric formula:
p p0eh/H
where p0 is the pressure at sea level and H is a constant approximately equal to 8 km.
More specifically, H RT/Mg, where M is the average molar mass of air and T is the
temperature. The barometric formula fits the observed pressure distribution quite
well even for regions well above the troposphere (see Fig. 1.10). It implies that the
pressure of the air and its density fall to half their sea-level value at h Hln 2, or 6 km.
Local variations of pressure, temperature, and composition in the troposphere
are manifest as weather. A small region of air is termed a parcel. First, we note that a
parcel of warm air is less dense than the same parcel of cool air. As a parcel rises, it
expands adiabatically (that is, without transfer of heat from its surroundings), so it
cools. Cool air can absorb lower concentrations of water vapour than warm air, so the
moisture forms clouds. Cloudy skies can therefore be associated with rising air and
clear skies are often associated with descending air.
The motion of air in the upper altitudes may lead to an accumulation in some
regions and a loss of molecules from other regions. The former result in the formation
of regions of high pressure (highs or anticyclones) and the latter result in regions of
low pressure (lows, depressions, or cyclones). These regions are shown as H and L on
the accompanying weather map (Fig. 1.11). The lines of constant pressurediffering
by 4 mbar (400 Pa, about 3 Torr)marked on it are called isobars. The elongated
regions of high and low pressure are known, respectively, as ridges and troughs.
In meteorology, large-scale vertical movement is called convection. Horizontal
pressure differentials result in the flow of air that we call wind (see Fig.1.12). Winds
coming from the north in the Northern hemisphere and from the south in the
Southern hemisphere are deflected towards the west as they migrate from a region
where the Earth is rotating slowly (at the poles) to where it is rotating most rapidly (at
the equator). Winds travel nearly parallel to the isobars, with low pressure to their
left in the Northern hemisphere and to the right in the Southern hemisphere. At the
surface, where wind speeds are lower, the winds tend to travel perpendicular to the
isobars from high to low pressure. This differential motion results in a spiral outward
flow of air clockwise in the Northern hemisphere around a high and an inward counterclockwise
flow around a low.
The air lost from regions of high pressure is restored as an influx of air converges
into the region and descends. As we have seen, descending air is associated with clear
skies. It also becomes warmer by compression as it descends, so regions of high pressure
are associated with high surface temperatures. In winter, the cold surface air may
prevent the complete fall of air, and result in a temperature inversion, with a layer of
warm air over a layer of cold air. Geographical conditions may also trap cool air, as
in Los Angeles, and the photochemical pollutants we know as smog may be trapped
under the warm layer.
(b) Mixtures of gases
When dealing with gaseous mixtures, we often need to know the contribution that
each component makes to the total pressure of the sample. The partial pressure, pJ, of
a gas J in a mixture (any gas, not just a perfect gas), is defined as
pJ xJp [1.13]
p0 Pressure, p
0
Altitude, /kmh
6
10
15
20
30
0
H
L
H
H
H
Fig. 1.10 The variation of atmospheric
pressure with altitude, as predicted by the
barometric formula and as suggested by the
US Standard Atmosphere, which takes
into account the variation of temperature
with altitude.
Exploration How would the graph
shown in the illustration change if
the temperature variation with altitude
were taken into account? Construct a graph
allowing for a linear decrease in
temperature with altitude.
Fig. 1.11 A typical weather map; in this case,
for the United States on 1 January 2000.
L
L
Wind
Rotation
N
S
Fig. 1.12 The flow of air (wind) around
regions of high and low pressure in the
Northern and Southern hemispheres.

1.2 THE GAS LAWS 13

where xJ is the mole fraction of the component J, the amount of J expressed as a fraction
of the total amount of molecules, n, in the sample:
n nA nB [1.14]
When no J molecules are present, xJ 0; when only J molecules are present, xJ 1.
It follows from the definition of xJ that, whatever the composition of the mixture,
xA + xB + 1 and therefore that the sum of the partial pressures is equal to the total
pressure:
pA + pB + (xA + xB + )p p (1.15)
This relation is true for both real and perfect gases.
When all the gases are perfect, the partial pressure as defined in eqn 1.13 is also
the pressure that each gas would occupy if it occupied the same container alone at
the same temperature. The latter is the original meaning of partial pressure. That
identification was the basis of the original formulation of Daltons law:
The pressure exerted by a mixture of gases is the sum of the pressures that each one
would exist if it occupied the container alone.
Now, however, the relation between partial pressure (as defined in eqn 1.13) and total
pressure (as given by eqn 1.15) is true for all gases and the identification of partial
pressure with the pressure that the gas would exert on its own is valid only for a perfect
gas.
Example 1.3 Calculating partial pressures
The mass percentage composition of dry air at sea level is approximately N2: 75.5;
O2: 23.2; Ar: 1.3. What is the partial pressure of each component when the total
pressure is 1.00 atm?
Method We expect species with a high mole fraction to have a proportionally high
partial pressure. Partial pressures are defined by eqn 1.13. To use the equation, we
need the mole fractions of the components. To calculate mole fractions, which are
defined by eqn 1.14, we use the fact that the amount of molecules J of molar mass
MJ in a sample of mass mJ is nJ mJ/MJ. The mole fractions are independent of the
total mass of the sample, so we can choose the latter to be 100 g (which makes
the conversion from mass percentages very easy). Thus, the mass of N 2 present is
75.5 per cent of 100 g, which is 75.5 g.
Answer The amounts of each type of molecule present in 100 g of air, in which the
masses of N2, O2, and Ar are 75.5 g, 23.2 g, and 1.3 g, respectively, are
These three amounts work out as 2.69 mol, 0.725 mol, and 0.033 mol, respectively,
for a total of 3.45 mol. The mole fractions are obtained by dividing each of the
n( )
.
.
.
.
Ar
g
g mol
mol
13
39 95
13
1 39 95
n( )
.
.
.
.
O
g
g mol
2 mol 1
23 2
32 00
23 2
32 00

n( )
.
.
.
.
N
g
g mol
2 mol 1
75 5
28 02
75 5
28 02

14 1 THE PROPERTIES OF GASES

Separation
Potential energy
0
Contact
Attractions
dominant
Repulsions dominant
Fig. 1.13 The variation of the potential
energy of two molecules on their
separation. High positive potential energy
(at very small separations) indicates that
the interactions between them are strongly
repulsive at these distances. At
intermediate separations, where the
potential energy is negative, the attractive
interactions dominate. At large separations
(on the right) the potential energy is zero
and there is no interaction between the
molecules.
above amounts by 3.45 mol and the partial pressures are then obtained by multiplying
the mole fraction by the total pressure (1.00 atm):
N2 O2 Ar
Mole fraction: 0.780 0.210 0.0096
Partial pressure/atm: 0.780 0.210 0.0096
We have not had to assume that the gases are perfect: partial pressures are defined
as pJ xJp for any kind of gas.
Self-test 1.4 When carbon dioxide is taken into account, the mass percentages are
75.52 (N2), 23.15 (O2), 1.28 (Ar), and 0.046 (CO2). What are the partial pressures
when the total pressure is 0.900 atm? [0.703, 0.189, 0.0084, 0.00027 atm]
Real gases
Real gases do not obey the perfect gas law exactly. Deviations from the law are particularly
important at high pressures and low temperatures, especially when a gas is on the
point of condensing to liquid.
1.3 Molecular interactions
Real gases show deviations from the perfect gas law because molecules interact with
one another. Repulsive forces between molecules assist expansion and attractive forces
assist compression.
Repulsive forces are significant only when molecules are almost in contact: they are
short-range interactions, even on a scale measured in molecular diameters (Fig. 1.13).
Because they are short-range interactions, repulsions can be expected to be important
only when the average separation of the molecules is small. This is the case at high
pressure, when many molecules occupy a small volume. On the other hand, attractive
intermolecular forces have a relatively long range and are effective over several molecular
diameters. They are important when the molecules are fairly close together but not
necessarily touching (at the intermediate separations in Fig. 1.13). Attractive forces
are ineffective when the molecules are far apart (well to the right in Fig. 1.13).
Intermolecular forces are also important when the temperature is so low that the
molecules travel with such low mean speeds that they can be captured by one another.
At low pressures, when the sample occupies a large volume, the molecules are so far
apart for most of the time that the intermolecular forces play no significant role, and
the gas behaves virtually perfectly. At moderate pressures, when the average separation
of the molecules is only a few molecular diameters, the attractive forces dominate
the repulsive forces. In this case, the gas can be expected to be more compressible than
a perfect gas because the forces help to draw the molecules together. At high pressures,
when the average separation of the molecules is small, the repulsive forces dominate
and the gas can be expected to be less compressible because now the forces help to
drive the molecules apart.
(a) The compression factor
The compression factor, Z, of a gas is the ratio of its measured molar volume, Vm
V/n, to the molar volume of a perfect gas, Vom
, at the same pressure and temperature