Course Code: CHEM 1101

Fundamentals of Physical Chemistry

Course instructor: Dr. Umme Salma

Reference of Books:
1. General Chemistry (11th edition)
By D. D. Ebbing and S. D. Gammon

2. Chemistry (9th edition)

By Raymond Chang

3. Essentials of Physical Chemistry

By Arun Bahl, B.S. Bahl, G.D. Tuli
 Outline of the Course

 Chapter 1: Gaseous State

 Chapter 2: Liquid State

 Chapter 3: Solid State

 Chapter 4: Fundamental Concept of Solution

 Chapter 5: Colligative Properties

 Chapter 6: Chemical Kinetics

 Chapter 6: Chemical Equilibrium

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 The Ideal Gas Law
The discussed empirical gas laws in previous section can be combined into one equation, called
the ideal gas equation. Earlier we combined Boyle’s law and Charles’s law into the equation

This “constant” is independent of the T and P but does depend on the amount of gas.

For one mole, the constant will have a specific value, which we will denote as R. The molar
volume, Vm , is

According to Avogadro’s law, Vm is a constant at a specific value of T and P independent of the

nature of the gas, and this implies that R is a constant independent of the gas.

The molar gas constant, R, is the constant of proportionality relating the molar volume of a gas
to T/P. For n moles of gas the equation can be written by multiplying both sides by n.

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Because Vm is the volume per mole, nVm is the total volume V.

The equation PV = nRT, which combines all of the gas laws, is called the ideal gas law.

Molar gas constant ‘R’ has the dimension of work

From the ideal gas equation, we can write

PV = [R is called the molar gas constant]

For one mole of a gas the equation is reduced to

PV =

R= …………………………………………………………(1) 4
If the pressure is written as force per unit area and volume as area times length, from (1)

x
=

= x

Hence R can be expressed in units of work or energy per degree per mole. The actual value of R
depends on the units of P and V used in calculating it.

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The Numerical Value of R.
From the ideal-gas equation, we can write
……………………………………………………(2)

We know that one mole of any gas at STP occupies a volume of 22.4 litres. Substituting the values
in the expression (2), we have

It may be noted that the unit for R is complex; it is a composite of all the units used in calculating
the constant.

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Problem
How many grams of oxygen, O2, are there in a 50.0-L gas cylinder at 21°C when the oxygen
pressure is 15.7 atm?

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 Partial Pressures and Mole
Fractions
The pressure exerted by a particular gas in a mixture is the partial pressure of that gas.
According to Dalton’s law of partial pressures,
The sum of the partial pressures of all the different gases in a mixture is equal to
the total pressure of the mixture.

Figure 1. An illustration of Dalton’s law of partial pressures

The valve connecting the flasks and the valve at the funnel are opened so that flask A fills with mineral oil. The helium
flows into flask B (having the same volume as flask A), where it mixes with hydrogen. Each gas exerts the pressure it
would exert if the other were not there. 8
If you let P be the total pressure and PA , PB , PC , . . . be the partial pressures of the component gases
in a mixture, the law of partial pressures can be written as

The individual partial pressures follow the ideal gas law. For component A,
where nA is the number of moles of component A.

The composition of a gas mixture is often described in terms of the mole fractions of component
gases. The mole fraction of a component gas is the fraction of moles of that component in the
total moles of gas mixture.

Because the pressure of a gas is proportional to moles, for fixed volume and temperature (P =
nRT/V α n), the mole fraction also equals the partial pressure divided by total pressure.

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Problem
A 1.00-L sample of dry air at 25°C and 786 mmHg contains 0.925 g N2, plus other gases including oxygen,
argon, and carbon dioxide.
a. What is the partial pressure (in mmHg) of N2 in the air sample?
b. What is the mole fraction and mole percent of N2 in the mixture?

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 KINETIC MOLECULAR THEORY OF GASES
To explain the behaviour of gases and the gas laws Maxwell and Boltzmann (1859) developed a
mathematical theory based on the fundamental concept that a gas is made of a large number of
molecules in perpetual motion. Hence the theory is called the kinetic molecular theory or
simply the kinetic theory of gases. The kinetic theory makes the following assumptions.

(1) A gas consists of extremely small discrete

particles called molecules dispersed throughout
the container. The actual volume of the molecules
is negligible compared to the total volume of the
gas. The molecules of a given gas are identical and
have the same mass (m).

(2) Gas molecules are in constant random

motion with high velocities. They move in straight
lines with uniform velocity and change direction on
collision with other molecules or the walls of the
container.
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(3) The distance between the molecules are very large and it is assumed that van der Waals
attractive forces between them do not exist. Thus the gas molecules can move freely,
independent of each other.

(4) All collisions are perfectly elastic. Hence, there is no loss of the kinetic energy of a molecule
during a collision.

(5) The pressure of a gas is caused by the hits recorded by molecules on the walls of the
container.

(6) The average kinetic energy of the gas molecules is directly proportional to absolute
temperature (Kelvin temperature). This implies that the average kinetic energy of molecules is
the same at a given temperature.

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 How Does an Ideal Gas Differ from Real Gases ?

 An ideal gas
A gas that confirms to the assumptions of the kinetic theory of gases. It obeys the basic laws
strictly under all conditions of temperature and pressure.

The real gases as hydrogen, oxygen, nitrogen etc., are opposed to the assumptions (a), (b) and (c)
stated below. Thus :

(a) The actual volume of molecules in an ideal gas is negligible, while in a real gas it is
appreciable.
(b) There are no attractive forces between molecules in an ideal gas while these exist in a real gas.
(c) Molecular collisions in an ideal gas are perfectly elastic while it is not so in a real gas.

For the reasons listed above, real gases obey the gas laws under moderate conditions of temperature
and pressure. At very low temperature and very high pressure, the clauses (a), (b) and (c) of kinetic
theory do not hold. Therefore, under these conditions the real gases show considerable deviations
from the ideal gas behaviour.
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 DEVIATIONS FROM IDEAL BEHAVIOUR

An ideal gas is one which obeys the gas laws or the gas equation PV = RT at all pressures and
temperatures.
However no gas is ideal. Almost all gases show significant deviations from the ideal behaviour.
Thus the gases H2, N2 and CO2 which fail to obey the ideal-gas equation are termed nonideal or
real gases.

Compressibility Factor
The extent to which a real gas departs from the ideal behaviour may be depicted in terms of a
new function called the Compressibility factor, denoted by Z. It is defined as

The deviations from ideality may be shown by a plot of the compressibility factor, Z, against P.
 For an ideal gas, Z = 1 and it is independent of temperature and pressure.

 The deviations from ideal behaviour of a real gas will be determined by the value of Z being
greater or less than 1.

The difference between unity and the value of the compressibility factor of a gas is a measure
of the degree of nonideality of the gas.

For a real gas, the deviations from ideal behaviour depend on (i) pressure; and (ii)temperature.
This will be illustrated by examining the compressibility curves of some gases discussed below
with the variation of pressure and temperature.

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 Effect of Pressure Variation on Deviations
Fig. 10.23 shows the compressibility factor, Z, plotted against pressure for H2, N2 and CO2 at a
constant temperature.

 At very low pressure, for all these gases Z is approximately equal to one. This indicates that at low
pressures (upto 10 atm), real gases exhibit nearly ideal behaviour.
 As the pressure is increased, H2 shows a continuous increase in Z (from Z = 1). Thus the H2 curve lies
above the ideal gas curve at all pressures.
 For N2 and CO2, Z first decreases (Z < 1). It passes through a minimum and then increases
continuously with pressure (Z > 1).
 For a gas like CO2 the dip in the curve is greatest as it is most easily liquefied. 16
 Effect of Temperature on Deviations
Fig 10.24 shows plots of Z or PV/RT against P for N2 at different temperatures.
 The deviations from the ideal gas behaviour become less and less with increase of
temperature.
 At lower temperature, the dip in the curve is large and the slope of the curve is negative. That
is, Z < 1.
 As the temperature is raised, the dip in the curve decreases.

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 At a certain temperature, the minimum in the curve vanishes and the curve remains horizontal for
an appreciable range of pressures. At this temperature, PV/RT is almost unity and the Boyle’s law
is obeyed. Hence this temperature for the gas is called Boyle’s temperature. The Boyle
temperature of each gas is characteristic e.g., for N2 it is 332 K.

Conclusions
From the above discussions we conclude that :
(1) At low pressures and fairly high temperatures, real gases show nearly ideal behaviour and
the ideal-gas equation is obeyed.

(2) At low temperatures and sufficiently high pressures, a real gas deviates significantly from
ideality and the ideal-gas equation is no longer valid.

(3) The closer the gas is to the liquefaction point, the larger will be the deviation from the ideal
behaviour.

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 EXPLANATION OF DEVIATIONS – VAN DER WAALS EQUATION
van der Waals (1873) attributed the deviations of real gases from ideal behaviour to two erroneous
postulates of the kinetic theory. These are :
(1) The molecules in a gas are point masses and possesses no volume.
(2) There are no intermolecular attractions in a gas.

Therefore, the ideal gas equation PV = nRT derived from kinetic theory could not hold for real
gases. van der W aals pointed out that both the pressure (P) and volume (V) factors in the ideal
gas equation needed correction in order to make it applicable to real gases.

Volume Correction
The volume of a gas is the free space in the container in which molecules move about. Volume V of
an ideal gas is the same as the volume of the container. The dot molecules of ideal gas have zero-
volume and the entire space in the container is available for their movement. However, van der
Waals assumed that molecules of a real gas are rigid spherical particles which possess a definite
volume.
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The volume of a real gas is, therefore, ideal volume minus the volume occupied by gas
molecules (Fig. 10.25). If b is the effective volume of molecules per mole of the gas, the volume in
the ideal gas equation is corrected as :

For n moles of the gas, the corrected volume is :

where b is termed the excluded volume which is constant and characteristic for each gas.
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Pressure Correction
A molecule in the interior of a gas is attracted by other molecules on all sides. These attractive forces
cancel out. But a molecule about to strike the wall of the vessel is attracted by molecules on one side
only. Hence it experiences an inward pull (Fig. 10.27). Therefore, it strikes the wall with reduced
velocity and the actual pressure of the gas, P, will be less than the ideal pressure. If the actual pressure
P, is less than Pideal by a quantity p, we have

p is determined by the force of attraction between molecules

(A) striking the wall of container and the molecules (B)
pulling them inward. The net force of attraction is, therefore,
proportional to the concentration of (A) type molecules and
also of (B) type of molecules. That is,

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where n is total number of gas molecules in volume V and a is proportionality constant
characteristic of the gas. Thus the pressure P in the ideal gas equation is corrected as :

for n moles of gas.

VAN DER W AALS EQUATION
Substituting the values of corrected pressure and volume in the
ideal gas equation, PV = nRT, we have

This is known as van der W aals equation for n moles of a gas. For 1 mole of a gas (n = 1), van
der Waals equation becomes

Constant a and b in van der Waals equation are called van der W aals constants. These constants
are characteristic of each gas. 22
 Determination of a and b

From the expression (1), the value of a is given by the relation

If the pressure is expressed in atmospheres and volume in litres,

Thus a is expressed in atm litre2 mol–2 units.

Since nb is excluded volume for n moles of gas,

If volume is expressed in litres, b is expressed in litre mol–1 units.

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SI units of a and b. If pressure and volume are taken in SI units, we have

The values of (a) and (b) can be determined by knowing the P, V and T of a gaseous system under
two different conditions.

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 Limitations of van der W aals Equation
van der Waals equation explains satisfactorily the general behaviour of real gases. It is valid over a
wide range of pressures and temperatures. However, it fails to give exact agreement with
experimental data at very high pressures and low temperatures. Dieterici (1899) proposed a
modified van der Waals equation. This is known as Dieterici equation. For one mole of gas, it may
be stated as

Here the terms (a) and (b) have the same significance as in van der Waals equation.

Interpretation of Deviations from van der W aals equation

For one mole of gas, van der Waals equation is

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Now we proceed to interpret the deviations of real gases from ideal behaviour as depicted in Figs.
10.21 and 10.22.
(a) At low pressure. When P is small, V will be large. Thus both the terms Pb and ab/V2 in
equation (2) are negligible compared to a/V. Ignoring these,

Thus at low pressure, the compressibility factor is less than 1. This explains the initial portions of
Z/P curves of N2 and CO2 which lie below the ideal curve. As the pressure is increased, V decreases
and the value of Z increases. Hence the curves show upward trend.

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(b) At high pressures. When P is large, V will be small. Therefore the terms a/V and ab/V2 are
negligible in comparison with Pb. Hence equation (2) is reduced to

Thus at high pressures, Z is greater than 1 and Z/P lies above the ideal gas curve. With the increase of
pressure, the value of Z will be still higher. This accounts for the rising parts of the curves in Fig.
10.18.
(c) At extremely low pressures. At extremely low pressures, V becomes very large. Hence all the
terms Pb, a/V and ab/V2 in equation (2) are negligibly small. These could be ignored compared to RT.
Thus equation (2) reduces to

Hence, at low pressures real gases behave ideally.

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(d) At high temperatures. At high temperatures, volume will be large (V∝T). Hence P will be small.
Then in the equation (2) the term RT predominates the other terms and the equation is reduced to

Thus at extremely high temperatures real gases tend to show ideal behaviour. However, at low
temperatures, both P and V will be small and the net result of Pb, – a/V, and ab/V2 will be appreciable.
Therefore the deviations would be quite prominent.

(e) Exceptional behaviour of hydrogen. Because of the small mass of H2 molecule, the attractions
between the molecules are negligible. Hence the term ‘a’ is extremely small and the terms a/V and
ab/V2 in equation (2) can be ignored. The equation now becomes

Since Z is always greater than 1, the Z/

P curve throughout lies above the ideal curve.
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