Substances That Exist as Gases

Figure 1. Elements that exist

as gases at 25°C and 1 atm.
The noble gases (the Group
8A elements) are monatomic
species; the other elements
exist as diatomic molecules.
Ozone (O3) is also a gas.

Figure 1 shows the elements that are gases under normal atmospheric conditions. Note that hydrogen,
nitrogen, oxygen, fluorine, and chlorine exist as gaseous diatomic molecules: H2, N2, O2, F2, and Cl2. An
allotrope of oxygen, ozone (O3), is also a gas at room temperature. All the elements in Group 8A, the
noble gases, are monatomic gases: He, Ne, Ar, Kr, Xe, and Rn.
The behavior of molecular compounds is more varied. Some—for example, CO, CO2, HCl, NH3, and
CH4 (methane)—are gases, but the majority of molecular compounds are liquids or solids at room
temperature.
CO, NO2, O3, and SO2, are somewhat less toxic. The gases He, Ne, and
Ar are chemically inert; that is, they do not react with any other substance.
Most gases are colorless. Exceptions are F2, Cl2, and NO2. The dark
brown color of NO2 is sometimes visible in polluted air.
All gases have the following physical characteristics:
Gases assume the volume and shape of their containers.
Gases are the most compressible of the states of matter.
Gases will mix evenly and completely when confined to the same container.
Gases have much lower densities than liquids and solids.
 Pressure of a Gas
Gases exert pressure on any surface or container with which they come in contact, because gas particles are
constantly in motion.

The SI unit of pressure is the pascal (Pa), defined as one newton per square meter. 1 Pa = 1 N/m
 Atmospheric Pressure
The force experienced by any area exposed to Earth’s atmosphere is equal to
the weight of the column of air above it. Atmospheric pressure is the pressure
exerted by Earth’s atmosphere (Figure 2). The actual value of atmospheric
pressure depends on location, temperature, and weather conditions. Figure 2. A column of air
extending from sea level
How is atmospheric pressure measured? The barometer is probably the most to the upper atmosphere.
familiar instrument for measuring atmospheric pressure. A simple barometer
consists of a long glass tube, closed at one end and filled with mercury. If the
tube is carefully inverted in a dish of mercury so that no air enters the tube,
some mercury will flow out of the tube into the dish, creating a vacuum at the
top (Figure 3). The weight of the mercury remaining in the tube is supported
by atmospheric pressure acting on the surface of the mercury in the dish.
Standard atmospheric pressure (1 atm) is equal to the pressure that
supports a column of mercury exactly 760 mm (or 76 cm) high at 0°C at sea
level. In other words, the standard atmosphere equals a pressure of 760 Figure 3. A barometer for
measuring atmospheric
mmHg, where mmHg represents the pressure exerted by a column of pressure. Above the
mercury 1 mm high. The mmHg unit is also called the torr, after the Italian mercury in the tube is a
scientist Evangelista Torricelli, who invented the barometer. Thus, vacuum. The column of
mercury is supported by
the atmospheric pressure.
 1 torr = 1 mmHg
and
1 atm = 760 mmHg (exactly)
The relation between atmospheres and pascals is
1 atm = 101,325 Pa
= 1.01325 × 105 Pa
and because 1000 Pa = 1 kPa (kilopascal)
1 atm = 1.01325 × 102 kPa
A manometer is a device used to measure the pressure of
gases other than the atmosphere. The principle of
operation of a manometer is similar to that of a barometer.
There are two types of manometers, shown in Figure 4.
The closed-tube manometer is normally used to measure
pressures below atmospheric pressure [Figure 4(a)],
whereas the open-tube manometer is better suited for
measuring pressures equal to or greater than atmospheric
pressure [Figure 4(b)].
Nearly all barometers and many manometers use mercury Figure 4. Two types of
manometers used to measure
as the working fluid, despite the fact that it is a toxic
gas pressures. (a) Gas pressure
substance with a harmful vapor. The reason is that mercury may be less or greater than
has a very high density (13.6 g/mL) compared with most atmospheric pressure. (b) Gas
other liquids. Because the height of the liquid in a column is pressure is greater than
inversely proportional to the liquid’s density, this property atmospheric pressure.
enables the construction of manageably small barometers
and manometers.
The Gas Laws

Figure 5. Apparatus for studying the

relationship between pressure and volume
of a gas. (a) The levels of mercury are
equal and the pressure of the gas is equal
to the atmospheric pressure (760 mmHg).
The gas volume is 100 mL. (b) Doubling
the pressure by adding more mercury
reduces the gas volume to 50 mL. (c)
Tripling the pressure decreases the gas
volume to one-third of the original value.
The temperature and amount of gas are
kept constant.
Figure 6. shows two conventional ways of expressing
Boyle’s findings graphically. Figure 6(a) is a graph of the
equation PV = k1; Figure 6(b) is a graph of the equivalent
equation P = k1 × 1/V. Note that the latter is a linear
equation of the form y = mx + b, where b = 0 and m = k1.
Although the individual values of pressure and volume
can vary greatly for a given sample of gas, as long as the
temperature is held constant and the amount of the gas
does not change, P times V is always equal to the same
constant. Therefore, for a given sample of gas under two Figure 6. Graphs showing variation of the
volume of a gas with the pressure exerted on
different sets of conditions at constant temperature, we
the gas, at constant temperature. (a) P versus
have V. Note that the volume of the gas doubles as
P1V1 = k1 = P2V2 the pressure is halved. (b) P versus 1/V. The
or P1V1 = P2V2 (2) slope of the line is equal to k1.

where V1 and V2 are the volumes at pressures P1 and

P2, respectively.
The Temperature-Volume Relationship: Charles’ Law

Figure 7. Variation of the

volume of a gas sample with
temperature, at constant
pressure. The pressure
exerted on the gas is the sum
of the atmospheric pressure
and the pressure due to the
weight of the mercury.
Figure 8. Variation of the volume of a gas sample with
temperature, at constant pressure. Each line represents
the variation at a certain pressure. The pressures
increase from P1 to P4. All gases ultimately condense
(become liquids) if they are cooled to sufficiently low
temperatures; the solid portions of the lines represent
the temperature region above the condensation point.
When these lines are extrapolated, or extended (the
dashed portions), they all intersect at the point
representing zero volume and a temperature of −273.15°
C
The Volume-Amount Relationship: Avogadro’s Law
The Ideal Gas Equation
Density Calculations
 Dalton’s Law of Partial Pressures

Figure 9. Schematic illustration of Dalton’s law

of partial pressures.

where nT, the total number of moles of gases present, is given by n = nA + nB, and PA and PB are the partial pressures of
gases A and B, respectively. For a mixture of gases, then, PT depends only on the total number of moles of gas present, not
on the nature of the gas molecules.
Figure 10. Schematic illustrations of Boyle’s law, Charles’ law, and Avogadro’s law.
 The Kinetic Molecular Theory of Gases
The findings of Maxwell, Boltzmann, and others resulted in a number of generalizations
about gas behavior that have since been known as the kinetic molecular theory of gases,
or simply the kinetic theory of gases. Central to the kinetic theory are the following
assumptions:
1. A gas is composed of molecules that are separated from each other by distances far
greater than their own dimensions. The molecules can be considered to be “points”; that is,
they possess mass but have negligible volume.
2. Gas molecules are in constant motion in random directions, and they frequently collide
with one another. Collisions among molecules are perfectly elastic. In other words, energy
can be transferred from one molecule to another as a result of a collision. Nevertheless, the
total energy of all the molecules in a system remains the same.
3. Gas molecules exert neither attractive nor repulsive forces on one another.
4. The average kinetic energy of the molecules is proportional to the temperature of the gas
in kelvins. Any two gases at the same temperature will have the same average kinetic
energy. The average kinetic energy of a molecule is given by
 Application to the Gas Laws
The following examples illustrate the range of its utility.
Compressibility of Gases. Because molecules in the gas phase are separated by large
distances (assumption 1), gases can be compressed easily to occupy less volume.
Boyle’s Law. The pressure exerted by a gas results from the impact of its molecules on
the walls of the container. The collision rate, or the number of molecular collisions with
the walls per second, is proportional to the number density (that is, number of molecules
per unit volume) of the gas. Decreasing the volume of a given amount of gas increases
its number density and hence its collision rate. For this reason, the pressure of a gas is
inversely proportional to the volume it occupies; as volume decreases, pressure
increases and vice versa.
Charles’ Law. Because the average kinetic energy of gas molecules is proportional to
the sample’s absolute temperature (assumption 4), raising the temperature increases the
average kinetic energy. Consequently, molecules will collide with the walls of the
container more frequently and with greater impact if the gas is heated, and thus the
pressure increases. The volume of gas will expand until the gas pressure is balanced by
the constant external pressure.
 Distribution of Molecular Speeds
The kinetic theory of gases enables us to investigate molecular motion in more detail.

Figure 11. (a) The distribution of speeds for nitrogen gas at three different temperatures. At the higher
temperatures, more molecules are moving at faster speeds. (b) The distribution of speeds for three gases at
300 K. At a given temperature, the lighter molecules are moving faster, on the average.
Figure 11(a) shows typical Maxwell speed distribution curves for nitrogen gas at
three different temperatures. At a given temperature, the distribution curve tells us the
number of molecules moving at a certain speed. The peak of each curve represents
the most probable speed, that is, the speed of the largest number of molecules.
Note that the most probable speed increases as temperature increases (the peak
shifts toward the right). Furthermore, the curve also begins to flatten out with
increasing temperature, indicating that larger numbers of molecules are moving at
greater speed.

Figure 11(b) shows the speed distributions of three gases at the same temperature.
The difference in the curves can be explained by noting that lighter molecules move
faster, on average, than heavier ones.
Root-Mean-Square Speed
 Viscosity of gases
Viscosity is a measure of a fluid’s resistance to flow. The greater the viscosity, the
more slowly the liquid flows. The viscosity of a liquid usually decreases as
temperature increases; thus, hot molasses flows much faster than cold molasses.

The viscosity of a gas can be thought of as a measure of its resistance to flow and is
measured in the CGS unit Poise = dyne sec/cm2. The viscosity of gases near room
temperature are in the centiPoise range, so that is a commonly used unit. Gas
viscosity is only weakly dependent on pressure near atmospheric pressure.

Viscosity arises from jump of molecules from one layer to another in case of a gas.
There is a transfer of momentum of molecules from faster layer to slower layer or
vice-versa.
 Gas Diffusion and Effusion
Gas Diffusion
A direct demonstration of gaseous random motion is provided by
diffusion, the gradual mixing of molecules of one gas with molecules of
another by virtue of their kinetic properties.
Figure 12. The path traveled by a
For example, when a bottle of concentrated ammonia solution is single gas molecule. Each change
opened at one end of a lab bench, it takes some time before a person in direction represents a collision
at the other end of the bench can smell it. The reason is that a molecule with another molecule.
experiences numerous collisions while moving from one end of the
bench to the other, as shown in Figure 12.

Thus, diffusion of gases always happens gradually, and not instantly as

molecular speeds seem to suggest. Furthermore, because the
root-mean-square speed of a light gas is greater than that of a heavier
gas, a lighter gas will diffuse through a certain space more quickly than
will a heavier gas. Figure 13 illustrates gaseous diffusion.

Figure 13. A demonstration of gas diffusion. NH3 gas (from a bottle containing
aqueous ammonia) combines with HCl gas (from a bottle containing hydrochloric
acid) to form solid NH4Cl. Because NH3 is lighter and therefore diffuses faster, solid
NH4Cl first appears nearer the HCl bottle (on the right)
In 1832, the Scottish chemist Thomas Graham state that under the same
conditions of temperature and pressure, rates of diffusion for gases are inversely
proportional to the square roots of their molar masses. This statement, now known
as Graham’s law of diffusion, is expressed mathematically as

(16)

where r1 and r2 are the diffusion rates of gases 1 and 2, and ℳ1 and ℳ2 are their
molar masses, respectively.
Gas Effusion
Whereas diffusion is a process by which one gas gradually
mixes with another, effusion is the process by which a gas
under pressure escapes from one compartment of a container
to another by passing through a small opening. Figure 14
shows the effusion of a gas into a vacuum. Although effusion
differs from diffusion in nature, the rate of effusion of a gas
has the same form as Graham’s law of diffusion [see Equation
(16)]. A helium-filled rubber balloon deflates faster than an
air-filled one because the rate of effusion through the pores of Figure 14. Gas effusion.
the rubber is faster for the lighter helium atoms than for the air Gas molecules move from
molecules. Industrially, gas effusion is used to separate a high-pressure region (left)
uranium isotopes in the forms of gaseous 235UF6 and 238UF6. to a low-pressure one
By subjecting the gases to many stages of effusion, scientists through a pinhole.
were able to obtain highly enriched 235U isotope, which was
used in the construction of atomic bombs during World War II.
 Real gases
Real gases are nonideal gases whose molecules occupy space and have interactions;
consequently, they do not obey to the ideal gas law. To understand the behavior of real
gases, the following must be taken into account:

compressibility effects;
variable specific heat capacity;
van der Waals forces;
non-equilibrium thermodynamic effects;
issues with molecular dissociation and elementary reactions with variable composition

For most applications, such a detailed analysis is unnecessary, and the ideal gas
approximation can be used with reasonable accuracy. On the other hand, real-gas models
have to be used near the condensation point of gases, near critical points, at very
high pressures, to explain the Joule–Thomson effect, and in other less usual cases.
The deviation from ideality can be described by the compressibility factor Z.
 Deviation from Ideal Behavior
The gas laws and the kinetic molecular theory assume that molecules in the gaseous state
do not exert any force, either attractive or repulsive, on one another. The other assumption
is that the volume of the molecules is negligibly small compared with that of the container. A
gas that satisfies these two conditions is said to exhibit ideal behavior.
Although we can assume that real gases behave like an ideal gas, we cannot expect them
to do so under all conditions. For example, without intermolecular forces, gases could not
condense to form liquids. The important question is: Under what conditions will gases most
likely exhibit nonideal behavior?
Figure 15. shows PV/RT plotted against P for three real gases and an ideal gas at a given
temperature. This graph provides a test of ideal gas behavior. According to the ideal gas
equation (for 1 mole of gas), PV/RT equals 1, regardless of the actual gas pressure. (When
n = 1, PV = nRT becomes PV = RT, or PV/RT = 1.) For real gases, this is true only at
moderately low pressures (≤ 5 atm); significant deviations occur as pressure increases.
Attractive forces operate among molecules at relatively short distances.
At atmospheric pressure, the molecules in a gas are far apart and the attractive forces are
negligible. At high pressures, the density of the gas increases; the molecules are much
closer to one another. Intermolecular forces can then be significant enough to affect the
motion of the molecules, and the gas will not behave ideally.
 Another way to observe the nonideal
behavior of gases is to lower the
temperature. Cooling a gas decreases
the molecules’ average kinetic energy,
which in a sense deprives molecules of
the drive they need to break from their
mutual attraction.
To study real gases accurately, then, we
need to modify the ideal gas equation,
taking into account intermolecular
forces and finite molecular volumes.
Such an analysis was first made by the
Dutch physicist J. D. van der Waals in
Figure 15. Plot of PV/RT versus P of 1 mole of a gas at 0°
1873. Besides being mathematically
C. For 1 mole of an ideal gas, PV/RT is equal to 1, no simple, his treatment provides us with
matter what the pressure of the gas is. For real gases, we an interpretation of real gas behavior
observe various deviations from ideality at high pressures. at the molecular level.
At very low pressures, all gases exhibit ideal behavior; that
is, their PV/RT values all converge to 1 as P approaches
zero.
 Consider the approach of a particular molecule toward the
wall of a container (Figure 16). The intermolecular attractions
exerted by its neighbors tend to soften the impact made by
this molecule against the wall. The overall effect is a lower
gas pressure than we would expect for an ideal gas. Van der
Waals suggested that the pressure exerted by an ideal gas,
Pideal, is related to the experimentally measured pressure,
Preal, by the equation

Figure 16. Effect of intermolecular forces on

the pressure exerted by a gas. The speed of a
molecule that is moving toward the container observed correction
wall (red sphere) is reduced by the attractive pressure term
forces exerted by its neighbors (gray spheres).
Consequently, the impact this molecule makes where a is a constant and n and V are the number of
with the wall is not as great as it would be if no moles and volume of the container, respectively. The
intermolecular forces were present. In general,
the measured gas pressure is lower than the correction term for pressure (an2/V2) can be understood
pressure the gas would exert if it behaved as follows:
ideally
The intermolecular interaction that gives rise to nonideal behavior depends on how frequently
any two molecules approach each other closely. The frequency of such “encounters” increases
with the square of the number of molecules per unit volume (n2/V2), because the probability of
finding each of the two molecules in a particular region is proportional to n/V. Thus, a is just a
proportionality constant.
Another correction concerns the volume occupied by the gas molecules. In the ideal gas
equation, V represents the volume of the container. However, each molecule does occupy a
finite, although small, intrinsic volume, so the effective volume of the gas becomes (V − nb),
where n is the number of moles of the gas and b is a constant. The term nb represents the
volume occupied by n moles of the gas.
Having taken into account the corrections for pressure and volume, we can rewrite the ideal gas
equation as follows:

corrected corrected
pressure volume

Equation (17), relating P, V, T, and n for a nonideal gas, is known as the van der Waals
equation. The van der Waals constants a and b are selected to give the best possible
agreement between Equation (17) and observed behavior of a particular gas.
 Critical Temperature and Pressure
The opposite of evaporation is condensation. In principle, a gas can be made to liquefy
by either one of two techniques. By cooling a sample of gas we decrease the kinetic
energy of its molecules, so that eventually molecules aggregate to form small drops of
liquid. Alternatively, we can apply pressure to the gas. Compression reduces the average
distance between molecules so that they are held together by mutual attraction. Industrial
liquefaction processes combine these two methods.

Every substance has a critical temperature (Tc), above which its gas phase cannot be
made to liquefy, no matter how great the applied pressure. This is also the highest
temperature at which a substance can exist as a liquid. Putting it another way, above the
critical temperature there is no fundamental distinction between a liquid and a gas— we
simply have a fluid.

The critical temperature (Tc) of a substance is the temperature at and above which
vapor of the substance cannot be liquefied, no matter how much pressure is applied.
Critical pressure (Pc) is the minimum pressure that must be applied to bring about
liquefaction at the critical temperature. The existence of the critical temperature can
be qualitatively explained as follows. Intermolecular attraction is a finite quantity for
any given substance and it is independent of temperature. Below Tc, this force is
sufficiently strong to hold the molecules together (under some appropriate pressure)
in a liquid. Above Tc, molecular motion becomes so energetic that the molecules can
break away from this attraction. Figure 11.37 shows what happens when sulfur
hexafluoride is heated above its critical temperature (45.5°C) and then cooled down
to below 45.5°C.
Table 11.7 lists the critical temperatures and critical pressures of a number of
common substances. The critical temperature of a substance reflects the strength of
its intermolecular forces. Benzene, ethanol, mercury, and water, which have strong
intermolecular forces, also have high critical temperatures compared with the other
substances listed in the table.
The pressure required to liquefy the gas at critical temperature is called critical
pressure (Pc). The critical pressure is the vapor pressure of a fluid at
the critical temperature above which distinct liquid and gas phases do not exist.
Critical Volume (Vc): The volume of the gas at critical temperature and pressure is
called critical volume (Vc). The volume occupied by a certain mass, usually one
gram molecule of a liquid or gaseous substance at its critical point: The numerical
value of the critical volume depends upon the amount of gas under experiment.