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Topic One
Gas Law

CHE 1104-1
Basic Physical
Chemistry

Lecturer: Kehongo M.

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Introduction to physical chemistry

What is chemistry? -Chemistry is the study of matter and energy and the interaction between them.
What is physical chemistry? Physical chemistry is a branch of chemistry that deals with the physical
properties of chemical substances (matter). This explains how specific chemical substances behave at
differing conditions such as pressure and temperature changes among many.

Chapter one; Gases Law

1.0 Introduction

1.1 The state of matter

States of matter are the distinct forms that different phases of matter exist. In the physical sciences,
a phase is a region of space (a thermodynamic system), throughout which all physical properties of a
material are essentially uniform (Reichardt, 2007). Examples of physical properties include density,
index of refraction, magnetization and chemical composition. Matter exists in solid, liquid or gaseous
phase usually referred to as the tree states of matter. The three phases are clearly convertible as in
ice, water and steam, which represent the same substance in different phases.

But what makes them different?

1.1.1 Solids

In a solid the particles (ions, atoms or molecules) are closely packed together in the solid state, the
particles are fixed in a uniform manner, held in definite positions in a crystal lattice by strong forces
operating between them. As a result, solids are rigid, with definite shape and volume and can resist
compression or distortion. Only vibrational motion is allowed in solid particles. This vibrational
motion is dependent on temperature, thus the higher the temperature, the longer the vibrational
distance making the forces between the particles weaker. At a given temperature, these forces
become so weak that the solid structure breaks down and the solid melts to form a liquid.

1.1.2 Liquids

In the liquid state, the particles can move freely as they possess translation motion which has weak
forces operating between them as compared to the solids. However, these forces are not weak
enough to allow a complete separation of the particles from one another. A liquid is a nearly
incompressible fluid that conforms to the shape of its container but retains a (nearly) constant volume
independent of pressure. Therefore a liquid have definite volume with no definite shape but takes the
shape of the container that hold it. The forces holding the liquid particles together also depend on
temperature. The higher the temperature, the faster the particles become and therefore the weaker
the forces holding them together. At a certain temperature, the forces become so weak that the liquid
particles break down and the liquid particles evaporate after boiling.

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1.1.3 Gases

In the gaseous state, the restraining forces of attraction between the particles have been overcome
completely. The particles move in a completely random manner at high speeds. This because the
molecules have enough kinetic energy so that the effect of intermolecular forces is small and the
distance between neighboring molecules is much greater than the molecular size. As a consequence,
gases have no definite shape or volume, but occupy (or fills) the entire container in which it is confined
and therefore highly compressible.

A solid can be converted to liquid by heating and a liquid can be converted to a gas by heating at
constant pressure to the boiling point, or else by reducing the pressure at constant temperature. The
sensitivity to changes in volume with changes in pressure and temperature is therefore:-

Solid<liquid << gas

The relation between volume, temperature, and pressure is more on gaseous state hence will a subject
in this chapter.

1.2 Learning goals

By the end of this unit, students should be able to:-

• Describe how gases respond to changes in pressure, volume, temperature, and the quality of
gas.
• Use the ideal-gas equation to solve for any one variable (P, V, n, or T) given the other three
variables or information from which they can be determined.
• Use the gas laws, including the combined gas law, to calculate how variable of gas (P, V, n, or T)
responds to changes in one or more of the variables.
• Calculate the partial pressure of any gas in a mixture, given the composition of that mixture.
• Calculate the mole fraction of a gas in a mixture, given its partial pressure and the total pressure
of the system.
• Describe how the relative rates of effusion and diffusion of two gases depend on molar masses
(Graham’s law).
• Explain the origin of deviation shown by real gases from the relationship PV/RT=1 for a mole of
an ideal gas.
• Cite the general conditions of P and T under which real gases most closely approximate ideal
gas behavior.
• Explain the origins of the correction terms to P and V that appear in the Van Der Waals equation.
Describe how molecular velocities are distributed in a sample of gas.
1.2 The gas laws

Experiments with a large number of gases reveal that four variables are needed to define the physical
condition, or state, of a gas: temperature, T, pressure, P, volume, V, and the amount of gas, which is
usually expressed as the number of moles, n. The equations that express the relationships among T,
P, V, and n are known as the gas laws.

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1.3.1 The Pressure-Volume Relationship: Boyle's Law

The first person to investigate the relationship between the pressure of a gas and its volume was a
British chemist Robert Boyle (1627-1691). He used a J-shaped tube like that shown in Figure 1.

Figure 1 An illustration of Boyle's experiment.

In diagram a, the volume of the gas trapped in the J-tube is 60 mL when the gas pressure is 760
torr. When additional mercury is added, as shown in diagram b, the trapped gas is compressed.
The volume is 30 mL when its total pressure is 1520 torr, corresponding to atmospheric pressure
plus the pressure exerted by the 760-mm column of mercury.

A quantity of gas is trapped in the tube behind a column of mercury. Boyle changed the pressure on
the gas by adding mercury to the tube. He found that the volume of the gas decreased as the pressure
increased. He observed that by doubling the pressure (by adding 760 ml of mercury) it caused the gas
volume to decrease to one-half its original value.

From that, he developed the Boyle’s law which stated that:-

The volume of a fixed quantity of gas maintained at constant temperature is inversely proportional to
the pressure

Boyle's law can be expressed in mathematical terms as shown in equation1. The value of the constant
depends on the temperature and the amount of gas in the sample. A plot of P against V at a co nstant
temperature (isotherm) will give hyperbola as shown in figure 2 below.

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Figure 2 Graphs based on Boyle's law of volume versus pressure

Plot another with different temperatures

The figure shows that as the volume increases, pressure decreases. Another plot of V against 1/P was
done and is presented in figure 3.

Figure 3 Graphs based on Boyle's law of volume versus 1/P.

The results obtained gave a linear relationship which has a constant gradient as shown. The
results from the isotherm in Figure 2 show that when the volume of gas V 1 at pressure P1 is
changed to a new volume V 2, the new pressure P2 can be evaluated using Equation 2.

This is because PV must remain constant.

Thus equation 2 can be applied to calculate the volume of a gas at any required pressure, if the
volume and the other pressure are known.

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We see an application of Boyle's law every time we breathe. Between breaths, the gas pressure
inside the lungs equals atmospheric pressure. The volume of the lungs is governed by the rib cage,
which can expand and contract, and the diaphragm, a muscle beneath the lungs. Inhalation occurs
when the rib cage expands and the diaphragm moves downward. Both of these actions serve to
increase the volume of the lungs, thus decreasing the gas pressure inside the lungs. The
atmospheric pressure then forces air into the lungs until the pressure in the lungs once again
equals atmospheric pressure. Exhalation involves the reverse process: The rib cage contracts and
the diaphragm moves up, both of which decrease the volume of the lungs. Air is forced out of the
lungs by the increase in pressure caused by this reduction in volume.

1.3.2 The Temperature-Volume Relationship: Charles's Law

The relationship between gas volume and temperature was discovered in 1787 by the French
scientist Jacques Charles (1746-1823). He found out that the volume of a fixed quantity of gas
at constant pressure increases linearly with temperature. This implies that the change in volume
is directly proportional to temperature at a constant pressure. He came up with a law called the
Charles’s law which states that:-

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The volume of a fixed mass of any gas increases by the same fraction (δ V) for ever degree
rise in temperature.

Therefore, if V 0 is the volume of a given quantity of gas 0˚C (at a constant pressure) the volume V t
at any temperature t ˚C is given by equation 3 given below.

The fraction δ V which is also called the co-efficient of expansion was found to be

1/273 Therefore equation 3 can be re-written to read as equation 4 below.

If equation 4 expanded, it would read as V t=V0+V0t/273. It can be considered as a general linear

quadratic equation, y=mx + c. When a plot of volume against temperature gives rise to a straight line
with an intercept of V0 and a gradient V0/273. Figure 4 gives a plot of volume against temperature.

Figure 4 A plot of Volume of an enclosed gas as a function of temperature at constant pressure.

If the line is extrapolated it intercepts the temperature axis at -273˚C. Upon making that
intercept our new origin, we obtain a new temperature scale called the Kelvin scale referred to
as absolute temperatures (T Kelvin or T K). The relationship between the Kelvin scale and the
Celsius scale is done by adding 273 to the latter (T K=273+˚C).

It is assumed that gases have zero volume at this temperature. However, this condition is never
fulfilled because they liquefy or solidify before reaching that temperature.

Then two different volumes V 1 and V 2 at temperatures t1 and t2 respectively can be evaluated by
placing the respective values in equation 4 above.

Thus

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Since 273+˚C =T Which is the conversion of Celsius to Kelvin scale, the equation 7 can be re-written
as equation 8 below

From equation 9 shows an alternative of stating the Charles Law stating that:-

The volume of a given mass of a gas at constant pressure is directly proportional to the
absolute temperature increases by the same fraction (δ V) for every degree rise in temperature
V T.
In real life application, this is why hot-air balloons rise because air expands as it is heated. The warm air in
the balloon is less dense than the surrounding cool air at the same pressure. The difference in density
causes the balloon to ascend. Similarly, a balloon will shrink when it is cooled.

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1.3.3 The Quantity-Volume Relationship: Avogadro's Law

As gas is added in a balloon, the balloon expands. The volume of a gas is affected not only by
pressure and temperature but by the amount of gas as well. The relationship between the
quantity of a gas and its volume follows from the work of Joseph Louis Gay-Lussac (1778-1823)
and Amadeo Avogadro.

From that observation, Avogadro came up with a law stating that:-

The volume of a gas maintained at constant temperature and pressure is directly proportional to the
number of moles of the gas.

Thus, by doubling the number of moles of gas will cause its volume to double if temperature and
pressure remain constant. Experimentally, 1 mole of gas at the same temperature and pressure
occupies the same volume as any other gas at the same temperature and pressure. From that

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information, it was found that under standard temperature and pressure (STP) which are 0˚C (273 K)
and 1 atm., 1 mole of gas occupies 22.4 litres. Amadeo Avogadro hypothesized that:-
Equal volumes of all gases at the same temperature and pressure contain the same number of moles.
Hence volume is proportional to the number of moles (V α n) at constant temperature and pressure.
For 1 mole, this number is 6.023 x 10-23 molecules. This is called the Avogadro number.

How can we combine the three laws so far to obtain an equation of state?

1.4 The equation of state and the ideal gas equation

The results of Boyle, Charles and Gay-Lussac may be combined in an expression, which represents the
relationship between pressure P, and temperature T of a given mass of gas. Such an expression is called
the equation of state. The universe can be divided into two portions, according to the convenience of
person concerned namely the system and its surrounding. A system is the region separated from the
remainder of the universe by real or imaginary boundaries for the purpose of observing interchanges
of energy and matter between this region and the rest of the universe. The state of a system and its
description is given by specifying its composition, its pressure and temperature.
In the preceding section, we examined three historically important gas laws. Each was obtained by
holding two variables constant in order to see how the other variables affect each other. Using the
symbol ∝ which is read “is proportional to” we have

We can combine these relationships to make a more general law:

Consider a gas initially at a state where Volume V 1 pressure P1 and temperature T1. If the state changes,
such that the new variables are P2, V2 and T2 respectively, then how will the two states be related? If
initially the temperature T 1 is kept constant and the pressure changes to P2, the volume V 1 changes to
V’1 according to Boyle’s law. NOTE the temperature IS KEPT CONSTANT T1
According to Boyles law, the pressure change expression can be written as shown below.

According to Boyles law, the pressure change expression can be written as shown below.

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P1V1 = P2V’1 eq 13
And therefore,
V’1 = P1V1/ P2 eq 14

If the pressure is maintained at P2 and the temperature changes to T 2, then the volume changes to V 2
according to
Charles law.

V’1/T1 = V2/T2 eq 15

Substituting V’1 from equation 14 in equation 15

P1V1/ P2T1 = V2/T2 eq 16

Therefore, this equation can be rearranged to

P1V1/T1 = P2V2/T2 eq 17

Equation 17 is called the equation of state for gases that obey Boyle’s law Charles’ law and Gay-Lussac’s
law. This implies that, for a definite mass of gas, any change in temperature and pressure will be
accompanied by an adjustment of
volume so the PV/T = constant The Value of the constant depends upon the mass and nature of the
gas.
However according to Amadeo Avogadro which state that equal number of molecules of different
gases will occupy the same volume at a given temperature and pressure. Thus, applying Avogadro’s
law where for 1 mole of gas, if temperature and pressure are kept constant, all gasses occupy the
same volume, since V is proportional to the number of molecules then

(Eq 1.18)
Where R is the constant in equation 1.18, and is called the gas constant. This value is the same for 1
mole of all gases.

According to Amadeo Avogadro, that 1 mole of gas will have a volume V then n moles will have a total
volume of nV

Then for n moles, Equation 1.18 becomes; -

(Eq 1.19)
Equation 1.18 is called the ideal gas equation and is obeyed by all ideal gases. The concept of ideal gas
will be made clearer later. The ideal gas equation can be utilized in determining several other

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quantities involving gases eg concentration C. Concentration is defined as number of moles per given
volume i.e n/V. Therefore equation 1.19 can be expressed in concentration form to appear as shown
in equation 19 below.

(eq 1.20)

An ideal gas is a theoretical gas composed of a set of randomly moving, non-interacting particles. The ideal gas
concept is useful because it obeys the ideal gas law, a simplified equation of state and is amenable to analysis
under statistical mechanics.
An ideal gas is defined as one in which all collisions between atoms or molecules are perfectly
eleastic and in which there are no intermolecular attractive forces. One can visualize it as a
collection of perfectly hard spheres which collide but which otherwise do not interact with each
other. In such a gas, all the internal energy is in the form of kinetic energy and any change in
internal energy is accompanied by a change in temperature.

An ideal gas can be characterized by three state variables: absolute pressure (P), volume (V), and
absolute temperature (T). The relationship between them may be deduced from kinetic theory
and is called the Ideal gas PV = nRT

From equation 1.20, then equation 1.21 is derived as shown.

PV = CRT (eq 1.21)

Since number of moles n is given as mass of a gas as a fraction of it relative formular mass, m/M,
equation 20 can also be written as

(eq 22)
Equation 22 can be rearranged to read

Since mass divided by volume m/V is density ρ then equation 21 can be re-written as equation 23 below

(eq 23)
From equation 22, the relative formula mass (M) of a gas can be determined by rearranging equation
23

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(eq 23)
1.4.1 The gas constant R

The gas constant is a very important quantity and we need to work out its value and units. At STP, the
volume of 1 mole of an ideal gas is 22.4 l or 22.4 x 10 -3 m3. The pressure is 101325 N m-2 or 1 atm while
the temperature is 273
K. Hence in SI units

(eq 24)
While working with volume in litres and pressure in atm, equation 23 can be written as equation 24
below

(eq 24)

The value of R as can be seen depends on our units of volume and pressure

Numerical values of the gas constants R in various pressure values

Units Numerical Value

1-atm mol-1 K-1 0.0821
Cap mol-1 K-1 1.987
J mol-1 K-1 8.314
8.314
m3-Pa mol-1 K-1
L-tor mol-1 K-1 63.36

Point of emphasis

➢ But while working with gases, the most commonly used values of R are 0.82062 atm mol-1 K-1
and 8.314 J mol- K-1
➢ The standard condition for gas behaviours (0 ˚C) are not the same as the standard conditions
(STP) in thermodynamics and thermo chemistry (25˚C)

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➢ Any gas law can be derived from the gas equation

1.5 Mixture of gases: Dalton’s law of partial pressure

This law is concerned with pressure of a mixture of gases. Due to the nature of ideal gases, in a
mixture of one or more gases each gas exerts the same pressure as that which it would have
exerted if it was occupied alone in a container.

Dalton’s law of partial pressure states that the total pressure of a mixture of gases is equal to the
sum of the partial pressure of the constituent gases.

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Teaching notes
When explaining Dalton’s law, emphasize that each component is at the same temperature and occupies
t he same volume

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1.6 The kinetic molecular theory of ideal gases

Why does a gas obey Boyle’s law or Charles law? To understand the nature of gases, we develop
a physical picture of the gaseous state capable of explaining the various laws of gaseous
behaviour. We propose the hypothesis about the nature of the gas. Such hypothesis is referred
to as a “model” for a gas. The properties of the gas deduced from this model are then compared
to the experimental properties of the gas.

Having looked at the gas laws generally, it is important to try and understand them from the
molecular point of view. To develop our theory, we need to firstly define precisely a gas in a
container in the form of postulates. Thus the following (postulates) will hold for any ideal gas
for the moment at low pressure and moderate

➢ Gases are made of independent particles (atoms or molecules) moving in rapid motion and in
straight line.
➢ When the particles collide with others or with the surface of the container, there is no loss of
velocity (momentum conserved) thus the collision is perfectly elastic.
➢ The particles are viewed as being relatively far apart and their volumes relatively small
(negligible) compared to the total volume of the container. Thus, the gas only occupies about
0.03% of the total volume say for 1 mole of gas at STP.
➢ The particles exert no attractive or repulsive forces between (themselves) one another.
➢ The pressure (force per unit area) is due to the impact of the particles on collision with the walls
of the container

It is with these postulates that we want to represent mathematically in the molecular theory of gases
to obtain an equation of state.

Consider a gas contained in a cube of dimension 1 meter. See Figure 5. Focus on a single molecule
of mass m confined in an otherwise empty container of volume V (l3).

Figure 5 Gas in a container showing the movements in three dimensions

Although the molecules move randomly, assume that an average 1/3 (direction) move in the
paths parallel to each pair of opposite faces of the container. Then if N is the total number of
molecules, then N/3 molecules move along x, y or z directions. How do we calculate the pressure
which will be the force exerted per square meter?

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Consider a molecule of mass m, moving back and forth, along x direction. If u is the velocity of the
molecule per second, then the rate of collision with the side of the container is given by

This is because the molecule will have to travel 2l meters before collision. The momentum
before collision is mu and since the collisions are perfectly elastic, then the momentum after
collision will be the same but in the reverse direction i.e –mu.

This momentum is transferred to the wall of the container. The rate of change of momentum is called
force.

The total force exerted by N molecules moving in the x direction will be:-

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The kinetic theory and temperature

We need also to know the relationship between kinetic energy of the molecules with temperature.
The kinetic energy k per molecule is given by: -

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NB: It also implies that kinetic energy of a gas depends on the temperature of

that gas.

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(eq 44) t1
1
Where t and t2 are the time, it takes for equal volumes of two gases to diffuse under similar
conditions.

NB’: For all gases at the same temperature, the average kinetic energies are identical.
At a fixed temperature, the average speed of a lighter gas is greater than that of a heavier gas.

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1.7 Distribution of molecular velocities

We have already noted that gas molecules in a container do not move at the same speed. The
distribution of velocities was worked out using a probability theory by Maxwell Boltzmann to
yield what is referred to as Boltzmann-Maxwell distribution law. This mathematical law is
represented as: -

Where k is the Boltzmann-Maxwell distribution constant. The physical interpretation of this equation
is that

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Figure 6 Distribution of molecular speeds at different temperatures

Note that the curves are not symmetrical and hence the average speed is high er than the most
probable. Solving the equation for 1 mole of a gas yields the following:

1.7 Real gases

An ideal gas is one that obeys Boyle’s law. But few gases are ideal. In fact, if PV is plotted against
P, the gases deviate from ideal behaviour as pressure increases as shown in Figure 7.

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Figure 7 A plot of the product of the pressure and volume (PV) against P for samples of H 2, N2, CO2

What causes the deviation? Since Boyle’s law agrees with molecular theory of gases, then the
problem must lie in the postulates. Firstly, the molecules are said to have no attractive or
repulsive forces between them. This is not true at moderate to high pressures since these forcers
exist. Due to attractive forces, the pressure exerted by gas will actually be less than that is
predicted by theory. We need then a correction for pressure. Since the attractive forces as well
as the number of molecules striking the walls are directly proportional to the number of
molecules N, then a correction term must be proportional to N 2. The number of molecules
hitting the walls will be inversely proportional to the volume, hence force will vary as 1/V 2.
The correction term was then found to be a/V 2 for 1 mole. Where “a” is a constant. The pressure
becomes: -

Secondly, for one mole of gas, the postulate that molecules occupy (no space) negligible volume
ought to be modified. Thus molecules should be considered to have some (space) volume.
Therefore, the volume should be corrected to take into consideration of the volume occupied
by the molecules to give the effective volume. The correction term “b” (the co-volume) was
found to be four times the actual volume of the molecules. The correction factor is introduced
to give the actual volume as V-b for 1 mole or V-nb for n moles of gas.

The final equation of state for real gas becomes: -

Equation 50 is called the Van der Waals equation. It is found to give a better description of the state
of gas where a and b are constants determined experimentally.

Point of emphasis

Gases deviate from ideality at high pressure.

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Summary

To describe the state or condition of a gas, we must specify the variables: pressure, temperature,
volume and quantity of gas. Pressure is defined as force per unit area. It is expressed in SI units
as Pascals, Pa (1 Pa=101325 M m -2=1 kg m-1 s-2) or more commonly in torr or in atmosphere
(atm). One atm. Equals 101325 KPa or 760 torr.

The ideal-gas equation, PV= nRT, is the equation of state for an ideal gas. Most gases at pressures
about 1 atm. and temperatures of 300 K and above obey the ideal gas equation reasonably well.
We can use the ideal gas equation to calculate variations in one variable when one or more of
the others are changed. For example, for a constant quantity of gas at constant temperature,
the volume of the gas at constant pressure, the volume of a gas is directly proportional to
temperature (Charles’s law). Avogadro’s law states that at a constant temperature and pressure,
the volume of a gas is directly proportional to the quantity of gas, that is the number of
molecules.

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In gas mixtures, the total pressure is the sum of all the partial pressures that each gas would exert if
it were under the same conditions (Dalton’s laws of partial pressures).

The kinetic –molecular theory accounts for the properties of an ideal gas in terms of a set of
assumptions about the nature of gases.

The molecules of a gas do not have the same kinetic at a given instant. Their speeds are distributed
over a wide range; the distribution varies with molar mass of a gas and with temperature
Departure from ideal behaviour increases in magnitude as pressure increases and as temperature
decreases.

Van der Waals Equation

The behavior of real gases usually agrees with the predictions of the ideal gas equation
to within 5% at normal temperatures and pressures. At low temperatures or high
pressures, real gases deviate significantly from ideal gas behavior. In 1873, while
searching for a way to link the behavior of liquids and gases, the Dutch physicist
Johannes van der Waals developed an explanation for these deviations and an equation
that was able to fit the behavior of real gases over a much wider range of pressures.

Van der Waals realized that two of the assumptions of the kinetic molecular theory were
questionable. The kinetic theory assumes that gas particles occupy a negligible fraction
of the total volume of the gas. It also assumes that the force of attraction between gas
molecules is zero.

The first assumption works at pressures close to 1 atm. But something happens to the
validity of this assumption as the gas is compressed. Imagine for the moment that the
atoms or molecules in a gas were all clustered in one corner of a cylinder, as shown in
the figure below. At normal pressures, the volume occupied by these particles is a
negligibly small fraction of the total volume of the gas. But at high pressures, this is no
longer true. As a result, real gases are not as compressible at high pressures as an ideal
gas. The volume of a real gas is therefore larger than expected from the ideal gas
equation at high pressures.

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Van der Waals proposed that we correct for the fact that the volume of a real gas is too
large at high pressures by subtracting a term from the volume of the real gas before we
substitute it into the ideal gas equation. He therefore introduced a constant

constant (b) into the ideal gas equation that was equal to the volume actually occupied
by a mole of gas particles. Because the volume of the gas particles depends on the
number of moles of gas in the container, the term that is subtracted from the real volume
of the gas is equal to the number of moles of gas times b.

P(V - nb) = nRT

When the pressure is relatively small, and the volume is reasonably large, the nb term is
too small to make any difference in the calculation. But at high pressures, when the
volume of the gas is small, the nb term corrects for the fact that the volume of a real gas
is larger than expected from the ideal gas equation.
The assumption that there is no force of attraction between gas particles cannot be true.
If it was, gases would never condense to form liquids. In reality, there is a small force of
attraction between gas molecules that tends to hold the molecules together. This force of
attraction has two consequences: (1) gases condense to form liquids at low temperatures
and (2) the pressure of a real gas is sometimes smaller than expected for an ideal gas.
To correct for the fact that the pressure of a real gas is smaller than expected from the
ideal gas equation, van der Waals added a term to the pressure in this equation. This
term contained a second constant (a) and has the form: an2/V2. The complete van der
Waals equation is therefore written as follows.

This equation is something of a mixed blessing. It provides a much better fit with the
behavior of a real gas than the ideal gas equation. But it does this at the cost of a loss in
generality. The ideal gas equation is equally valid for any gas, whereas the van der
Waals equation contains a pair of constants (a and b) that change from gas to gas.

Prepared by Kehongo Moses; Maasai Mara University, MPS

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The ideal gas equation predicts that a plot of PV versus P for a gas would be a
horizontal line because PV should be a constant. Experimental data for PV versus P for
H2 and N2 gas at 0C and CO2 at 40C are given in the figure below. Values of the van der
Waals constants for these and other gases are given in the table below.

The magnitude of the deviations from ideal gas behavior can be illustrated by
comparing the results of calculations using the ideal gas equation and the van der Waals
equation for 1.00 mole of CO2 at 0oC in containers of different volumes. Let's start with
a 22.4 L container.

According to the ideal gas equation, the pressure of this gas should be 1.00 atm.

Substituting what we know about CO2 into the van der Waals equation gives a much
more complex equation.

Prepared by Kehongo Moses; Maasai Mara University, MPS

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This equation can be solved, however, for the pressure of the gas.

P = 0.995 atm

At normal temperatures and pressures, the ideal gas and van der Waals equations give
essentially the same results.

Let's now repeat this calculation, assuming that the gas is compressed so that it fills a
container that has a volume of only 0.200 liters. According to the ideal gas equation, the
pressure would have to be increased to 112 atm to compress 1.00 mol of CO 2 at 0C to a
volume of 0.200 L.

The van der Waals equation, however, predicts that the pressure will only have to
increase to 52.6 atm to achieve the same results.

P = 52.6 atm

As the pressure of CO2 increases the van der Waals equation initially gives pressures
that are smaller than the ideal gas equation, as shown in the figure below, because of the
strong force of attraction between CO2 molecules.

Prepared by Kehongo Moses; Maasai Mara University, MPS

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A plot of the product of the pressure times the volume for samples of
H2, N2, CO2 gases versus the pressure of these gases.

Let's now compress the gas even further, raising the pressure until the volume of the gas
is only 0.0500 liters. The ideal gas equation predicts that the pressure would have to
increase to 448 atm to condense 1.00 mole of CO2 at 0oC to a volume of 0.0500 L.

The van der Waals equation predicts that the pressure will have to reach 1620 atm to
achieve the same results.

P = 1620 atm

The van der Waals equation gives results that are larger than the ideal gas equation at
very high pressures, as shown in the figure above, because of the volume occupied by
the CO2 molecules.

Prepared by Kehongo Moses; Maasai Mara University, MPS

 lO M oARcPS D| 46219784

Analysis of the van der Waals Constants

The van der Waals equation contains two constants, a and b, that are characteristic
properties of a particular gas. The first of these constants corrects for the force of
attraction between gas particles. Compounds for which the force of attraction between
particles is strong have large values for a. If you think about what happens when a
liquid boils, you might expect that compounds with large values of a would have higher
boiling points. (As the force of attraction between gas particles becomes stronger, we
have to go to higher temperatures before we can break the bonds between the molecules
in the liquid to form a gas.) It isn't surprising to find a correlation between the value of
the a constant in the van der Waals equation and the boiling points of a number of
simple compounds, as shown in the fugure below. Gases with very small values of a,
such as H2 and He, must be cooled to almost absolute zero before they condense to form
a liquid.

The other van der Waals constant, b, is a rough measure of the size of a gas particle.
According to the table of van der Waals constants, the volume of a mole of argon atoms
is 0.03219 liters. This number can be used to estimate the volume of an individual argon
atom.

The volume of an argon atom can then be converted into cubic centimeters using the
appropriate unit factors.

If we assume that argon atoms are spherical, we can estimate the radius of these atoms.
We start by noting that the volume of a sphere is related to its radius by the following
formula.

Prepared by Kehongo Moses; Maasai Mara University, MPS

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V = 4/3 r3

We then assume that the volume of an argon atom is 5.345 x 10-23 cm and calculate the
radius of the atom.

r = 2.3 x 10-8 cm

According to this calculation, an argon atom has a radius of about 2 x 10 -8 cm.

Exercise one
1. During the course of a reaction, 0.25 moles of gas phase reactant become 0.50 moles of gas
phase product. The initial volume of the gaseous reactant is 125 cm 3. What is the volume of
the gaseous product?

2. 1 l of an ideal gas at 0.4775 atm and 12.2˚C undergoes a change in volume and pressure to
5.3 l and
1.22 atm. What is the new temperature of the gas?

3. A helium balloon has a volume of 2 l. How many moles of helium will the balloon hold if it is
filled to a pressure of 1.01 atm at a temperature of 24˚C? How many grams of helium does
it hold?

4. What is the density of carbon tetrafluoride at 1.0 atm and 298 K?

5. What is the pressure exerted by 100 moles of CO2 in a 22.4 l vessel at 273 K, a calculated
from Van der Waals equation? Compare your results with the pressure predicted by the ideal
gas equation given a=3.59 l2 and b=0.043 l mol-1.

6. What is the volume at STP, of 1.0 l of carbon tetrachloride?

7. 0.50 g of neon gas and 0.50 g of argon gas are placed in a 3.0 l flask at 27˚C. What is the
partial pressure of each gas and the total pressure of the mixture of the gases in the
atmosphere?

8. 150 g of neon and 100 g of oxygen are placed in a flask at a temperature such that the total
pressure is 1,22 atm. What is the mole fraction and partial pressure of each gas?

9. At a given temperature and pressure, a certain amount of argon requires 277 s to diffuse
through a porous plug. How long will it take an equivalent amount of nitrogen to diffuse
under the same conditions?

10. Calculate the pressure exerted by 40 g of oxygen enclosed in a 1 l flask at 25˚C. (RFM of
O=16)

Prepared by Kehongo Moses; Maasai Mara University, MPS