UNIVERSITY OF NAIROBI

COLLEGE OF BIOLOGICAL AND PHYSICAL SCIENCES

SCHOOL OF PHYSICAL SCIENCES

SCH 103; PHYSICAL CHEMISTRY 1

By:

Dr. John N. Wabomba

Department of Chemistry
University of Nairobi.

Email: jwabomba@uonbi.ac.ke.

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 COURSE OUTLINE.

1. THE GASEOUS STATE

1.1. Gaseous states of matter and the gas laws.

1. 2. Using the equation of the ideal gas law; Gaseous mixtures

1. 3. Kinetic theory of gases

1. 4. Behaviour of real gases

1. 5. Determination of molar masses of gases

2. SOLUTIONS

2.1. Classification of solutions; Properties of solutions of volatile (ideal) liquids

2.2. Colligative properties of solutions

3. CHEMICAL EQUILIBRIUM

3.1. Equilibria for gaseous and heterogeneous reaction

3.2. Using equilibrium constant

3.3. Changing the reaction conditions and choosing optimum conditions for reactions.

4. IONIC EQUILIBRIUM

4.1. Acid- Base Concepts

4.2. Acid-Base Equilibrium

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 INTRODUCTION

Physical chemistry can be defined as the study of macroscopic, atomic, subatomic, and

particulate phenomena in chemical systems in terms of laws and concepts of physics. It
applies the principles, practices and concepts of physics such as; 
 Motion
 Energy 
 Force 
 Time 
 Thermodynamics 
 Quantum physics 
 Statistical mechanics 
 Dynamics and 
 Equilibrium.

Physical chemistry can also be viewed as

the branch of chemistry concerned with the way in which the physical
properties of substances depend on and influence their chemical
structure, properties, and reactions

Investigations in physical chemistry combine tools of physics, chemistry and mathematics

to uncover information about processes ranging from for instance; the immune response of
the body to the structure and reactivity of semiconductor surfaces.

Some of the relationships that physical chemistry strives to resolve include the effects of:

1. Intermolecular forces that act upon the physical properties of materials

(plasticity, tensile strength, surface tension in liquids).
2. Reaction kinetics on the rate of a reaction.
3. The identity of ions and the electrical conductivity of materials.
4. Surface chemistry and electrochemistry of membranes.
5. Interaction of one body with another in terms of quantities
of heat and work called thermodynamics.

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 6. Transfer of heat between a chemical system and its surroundings during change
of phase or chemical reaction taking place called thermochemistry
7. Study of colligative properties of number of species present in solution.
8. Number of phases, number of components and degree of freedom (or variance) can
be correlated with one another with help of phase rule.
9. Reactions of electrochemical cells.

1.0 THE GASEOUS STATE

Under certain conditions of pressure and temperature, most substances can exist in any of the
three states of matter i.e. solid, liquid or gas (also plasma). Water for example exists in the
solid state as ice, liquid state as water and in the gaseous state as steam. The physical
properties of a substance often depend on the state of the substance.

Molecular motion in gases is totally random, and the forces of attraction between molecules
are so small/weak that molecules move freely and independent of each other. A gas subjected
to changes in temperature and pressure behaves according to much simpler laws than do
liquids and solids.

The laws that govern this behavior have played an important role in the development of the
atomic theory of matter and the kinetic molecular theory of gases.

1.1 Pressure of a gas

Gases exert pressure on any surface with which they come in contact, because gas molecules
are constantly in motion. Pressure can be defined as force per unit area. This is the force
exerted by a gas as a result of collisions that exert force which is experienced as a steady
pressure. Pressure exerted by the atmosphere is measured with a barometer.

1.2 Units of pressure.

Pressure is one of the most readily measurable properties of a gas. In order to understand the
units of measurement of gas pressure are derived, it is good to begin with velocity and
acceleration.
Velocity is the change in distance with time i.e.

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 Dis tan ce moved
Velocity= =m/s
Elapsed time
We know that force as defined by Sir Isaac Newton can be given as;
Force=Mass× Accaeleration
The SI unit for force is Newton, where;
2
1 N =1kg m/s
But since pressure is defined as force per unit area, then it follows that;
Force
Pr essure=
Area
The SI unit for pressure is the Pascal (Pa) which is defined as one Newton per square
meter;
2
1 Pa=1 N /m
1.2.1 Other units of pressure
1 atm=760 mmHg=760 torr
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1 atm=101 , 325 Pa=1 .01325×10 Pa
Because 1000 Pa = 1 kPa (kilopascal), then;
2
1 atm=1 .01325×10 kPa
A pressure of 1 x 105 Pa (1 bar) is the standard pressure for reporting data.

1.3 Atmospheric Pressure

Atoms and molecules of the gases in the atmosphere, like those of all other matter, are subject
to Earth’s gravitational pull. As a consequence the atmosphere is much denser near the
surface of the earth than at high altitudes. This implies that the force experienced by any area
exposed to Earth’s atmosphere is equal to the weight of the column of air above it.
The atmospheric pressure is thus the pressure exerted by Earth’s atmosphere. The actual
value of atmospheric pressure depends on location, temperature and weather conditions.

Atmospheric pressure is measured using a barometer. A 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. See Figure 1 bellow;

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 Figure 1: Mercury Barometer.

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 (76cm) high at 0 oC at sea
level. This implies that the standard atmosphere equals a pressure of 760mmHg, where mmHg
represents the pressure exerted by a column of mercury 1mm high. The mmHg unit is also
referred to as the Torr, named after Evangelista Torricelli, an Italian scientist who invented a
barometer. Thus;
1 torr=1 mmHg
Example 1
The pressure outside a jet plane flying at high altitude falls considerably below standard
atmospheric pressure. The air inside the cabin must be pressurized to protect the passengers.
What is the pressure in atmospheres (atm) in the cabin if the barometer reading is 688mmHg?

Solution;
We know that; 1 atm=760 mmHg

Therefore pressure in the cabin is given by;

1 atm
Pr essure=688 mmHg×
760 mmHg
=0 . 905 atm

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Example 2
The atmospheric pressure in Nairobi on a certain day was 732 mmHg. What was the pressure
in kPa?

Solution;
The pressure in kPa can be determined as;

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1. 01325×10 Pa
Pr essure=732 mmHg×
760 mmHg
=9.76×104 Pa
¿97.6 kPa
Exercise
1. Convert 746 mmHg into atmospheres.
2. Convert 295 mmHg into kilopascals.

1.4 Manometer
A manometer is a device used to measure the pressure of gases other than the atmosphere.
The principle operation of a manometer is similar to that of a barometer. There are two types
of manometers; (a). Closed tube manometer and (b). Open tube manometer.
The closed tube manometer is normally used to measure pressures below atmospheric
pressure whereas the open tube manometer is better suited for measuring pressures equal to or
greater than atmospheric pressure. See Figure below;

Figure 2: Closed-end manometer (a) and open-end manometers (b and c). In (b) gas
pressure is less than atmospheric pressure; in (c) gas pressure exceeds
atmospheric pressure.

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Nearly all barometers and manometers use mercury as the working fluid. The reason is that
mercury has a very high density (13.6 g/cm3) compared with most other liquids. This property
enables the construction of manageably small barometers and manometers.

1.5. The Gas Laws.

Gas laws as we know them today, are a product of many experiments that were carried out on
physical properties of gases over several centuries. Gas laws generally relate to the
macroscopic behaviour of gaseous substances. These laws have played a major role in the
development of many ideas in chemistry related to gases. The gas laws of particular interest
are;
1) Boyle's law,
2) Charles' and Gay-Lussac’s law, and
3) Avogadro's law.
The three laws are usually combined to form the equation of state which is very useful in
solving many problems involving gases.

In order to describe the states of gas, at least three of following variables must be specified i.e.

Table 1: Variables used in describing state of a gas

(i). The space occupied by a sample of a gas (Volume, V)
(ii). The number of molecules present in the sample (Moles, n)
(iii). Pressure (Pressure, P)
(iv). Temperature (Temperature, T)

1.5.1 Boyle’s Law; The Pressure - Volume Relationship

In the seventeenth century, Robert Boyles (British chemist) studied the behaviour of gases
systematically and quantitatively. Boyle investigated the pressure-volume relationship of a
gas sample using an apparatus like that shown in Figure 3 below.

Boyles noticed that when temperature is held constant, the volume (V) of a given amount (n)
of a gas decreases as the total applied pressure (P) is increased.

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Figure 3: Boyle's Experiment Using a J-Shaped Tube to Determine the Relationship
between Gas Pressure and Volume. 

The pressure-volume data recorded for such an experiment are consistent with these
mathematical expressions showing an inverse relationship. This relationship is known as the
Boyle’s law, which states that; “the pressure of a fixed amount of gas at a constant
temperature is inversely proportional to the volume of the gas”
The mathematical expression showing the inverse relationship between pressure and volume
can be given as;
I
Pα
V , temperature (T) is constant for a given amount
of gas (n).
This expression can be re-written as;
1
P=k 1 x
V
Where; k1 is a constant called the proportionality constant.
Rearranging the above equation, we obtain
PV =k 1 =cons tan t
Thus it follows from the Boyle’s law that the product of the pressure and volume of a gas at
constant temperature and amount of gas is constant. Thus, for example, doubling the pressure
reduces the volume by half.

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1.5.1.1 Graphical Representation of Boyle’s Law
The two conventional ways of expressing Boyle’s findings graphically are shown in Figure 4
below;

Figure 4: Boyle’s law findings (a) Graph of the equation PV =k 1 ; (b) Graph of the

equivalent equation P=k 1×1 /V

The equation of graph 4b is a linear equation of the form

y=mx +c , where b=0 and m=k 1
1
Hence it can be tested by plotting experimental values of V against P and seeing how
close the result is to a straight line.

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 gas does not change, P times
V is always equal to the same constant.

Therefore, for a given sample of gas under two different sets of condition at constant
temperature, we have;
P1 V 1=k 1 =P2 V 2

Or simply;
P1 V 1=P 2 V 2

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Where; V1 and V2 are the volumes at pressure P1 and P2 respectively.

One common application of Boyle’s Law is to use the above equation to predict how the
volume of a gas will be affected by a change in pressure, or how the pressure exerted by a gas
will be affected by a change in volume.
Example
The pressure in a 50L oxygen cylinder is 15.7atm at 21 0C, what volume of oxygen can we get
from the cylinder at 210C if the atmospheric pressure is 1atm?
Solution;
Let P1 and V1 be the initial pressure (15.0atm) and initial volume (50L), and P2 and V2 be the
final pressure (1atm) and final volume (?) respectively.

It then follows that; P2 V 2=P1 V 1

V 1×P1
V 2=
Therefore; P2

When we substitute the values into this equation, we get;

15 atm
V 2 =50 L× =750 L
1 atm

Exercise:
A sample of hydrogen gas at 0oC and 700 mmHg has a volume of 4.00L. What would be the
volume of the gas if the pressure was changed to 760 mmHg at the same temperature?

1.5.2 Charles’ and Gay-Lussac’s Law

We have already seen that Boyle’s Law depends on the temperature of the system remaining
constant. But suppose the temperature changes: How does this change affect the volume and
pressure of a given gas?

The earliest investigators of this relationship were French scientists, Jacques Alexandre
Charles and Joseph Louis Gay-Lussac. Their studies showed that, at constant pressure, the
volume of a gas sample expands when heated and contracts when cooled. The quantitative
relations involved in changes in gas temperature and volume turn out to be remarkably
consistent.
At any given pressure, the plot of volume versus temperature yields a straight line. See figure

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Figure 5: Plots of volume versus temperature (a) for equal-sized samples of H 2 at three
different pressures, (b) for different amounts of selected gases at 1atm
pressure, all the plots extrapolate to a value of V = 0 at −273.15°C, regardless
of the identity or the amount of the gas.

Note: The solid lines show the experimentally measured data down to −100°C, and the
broken lines show the extrapolation of the data to V = 0. The temperature scale is given in
both degrees Celsius and Kelvins. Although the slopes of the lines decrease with increasing
pressure, all of the lines extrapolate to the same temperature at V = 0 (−273.15°C = 0 K).

This is to say that, if the substance remain gaseous, the volume occupied will be zero at –
273.150C.

In 1948 Lord Kelvin realized the significance of this behaviour. He identified the temperature
–273.150C as absolute zero, theoretically the lowest attainable temperature. Then he set up an
absolute temperature scale, now called the Kelvin temperature scale with absolute zero as the
starting point. On the Kelvin scale, one Kelvin (K) is equal in magnitude to one degree
Celsius. The only difference between the absolute temperature scale and the Celsius scale is
that the zero position is shifted. A summary of the relationships between the two scales is as
follows:-

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Table 2: Relationship between Kelvin (Absolute Temperature) and Celsius Scale
Kelvin Scale Celsius Scale
Absolute zero 0K -273.15oC
Freezing point of water 273.15 K 0oC
Boiling point of water 373.15 K 100oC

By convention we use T to denote absolute (Kelvin) temperature and t to indicate temperature

on the Celsius scale. The dependency of volume on temperature is given by;

V α T , P is cons tan t
⇒V =k 2 T

V
=k
Or; T 2

Where; k2 is the proportionality constant.

This equation is known as Charles and Gay-Lussac’s Law, or simply Charles’s Law which
states that the volume of a fixed amount of gas maintained at constant pressure is directly
proportional to the absolute temperature of the gas.

Note: that the proportionality constant in the above equation (k2) is equal to nR/P .

Just as it was done for pressure-volume relationships at constant temperature, we can compare
two sets of conditions for a given sample of gas at constant pressure.
V1 V2
=k 2 =
We can write
T1 T2

V1 V 2
=
Or; T1 T2

Where; V1 and V2 are the volumes of the gas at temperatures T1 and T2 (both in Kelvins),
respectively.

Example
A quantity of gas at 100C and 1atm pressure occupied a volume of 200cm 3. What volume will
it occupy at –200C given that its pressure constant.

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Solution
V1 V
=k 2 = 2
We know that; T1 T2

Where; V1 = 200cm3, T1 = (10 + 273) K = 283K, T2 = (-20 + 273) K = 253K, V2 =?

V 1 T 2 200 cm 3×253 K
V 2= = =178 . 8 cm3
Hence; T 1 283 K

Another form of Charles’s law shows that at constant amount of gas and volume, the pressure
of a gas is proportional to temperature;
P α T , Vcons tan t
P=k 3 T
P
=k
Or; T 3

Note:
k 3 =nR /V ; and from the above equation, we can have;
P1 P2
=k 3 =
T1 T2
Or;
P1 P2
=
T1 T2
Where; P1 and P2 are the pressures of the gas at temperatures T1 and T2, respectively.

1.5.3 Avogadro’s Law; The Volume – Amount Relationship

The work of the Italian scientist Amedeo Avogadro complemented the studies of Boyles,
Charles and Gay-Lussac. In 1811 he published a hypothesis that stated that; “At the same
temperature and pressure, equal volumes of different gases contain the same number of
molecules (or atoms if the gas is mono-atomic)”.

It follows that the volume of any given gas must be proportional to the number of molecules
present, that is

Vαn , (at constant temperature and pressure)

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 V =k 4 n

Where n represents the numbers of moles and k4 is the proportionality constant (k4 = RT/P).
The above equation is the mathematical expression of Avogadro’s Law, which states that at
constant pressure and temperature, the volume of a gas is directly proportional to the number
of moles of the gas present.
According to this law it can be seen that when two gases react with each other, their reaction
volumes have a simple ratio to each other. For example consider the synthesis of ammonia
from molecular hydrogen and molecular nitrogen:
3H2(g) + N2(g) 2NH3(g)
3 mol 1 mol 2 mol

Because at the same temperature and pressure, the volumes of gases are directly proportional
to the number of moles of the gases present, we can now write
3H2(g) + N2(g) 2NH3(g)
3volumes. 1volume. 2volumes.

If we represent molar gas volume at some temperature and pressure by Vm, the volume

occupied by n moles of any gas at this temperature and pressure is

V =nV m Where V has
. m

the same value for all gases at a fixed temperature and pressure.

1.5.4 The Ideal Gas Equation

We have already seen that in;
1
V α , (at cons tan t n and T )
Boyle’s law: P

Charles’s law: V α T , (at cons tan t n and P )

Avogadro’s law: V α n , ( at cons tan t P and T )

All the three expressions above can be combined to form a single master equation for the
behaviour of gases:
nT
Vα
P
nT
V =R
P
Or; PV =nRT

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Where R, the proportionality constant, is called the gas constant while the equation
PV  nRT , which describes the relationship among the four experimental variables P,V,T
and n is called the ideal gas equation.

An ideal gas is a hypothetical gas whose pressure-volume-temperature behaviour can be

completely accounted for by the ideal gas equation. The molecules of an ideal gas do not
attract or repel one another, and their volume is negligible compared with the volume of the
container.

Although there is no such thing in nature as an ideal gas, discrepancies in the behaviour of
real pressure range do not significantly affect calculations. Thus we can use the ideal gas
equation to solve many gas problems. It is however important to note at this stage that before
we can apply the ideal gas equation to a real system, we must evaluate the gas constant R. at
0OC (273.15K) and 1atm pressure, many real gases behave like an ideal gas. Experiments
show that under these conditions, 1mole of an ideal gas occupies 22.414L. The condition 0 oC
and 1atm are called standard temperature and pressure (STP). We can obtain the value of R
from the experimental value of molar volume at (0oC, 1atm).

The data for evaluation of R are;

Variable Value
P 1atm
V 22.414 L
T 0OC = 273.15K
n 1 mol

We already know that;

PV
n=
RT
PV
⇒R=
nT ¿ =0.082057L.atm /( K .mol) ¿¿

(1mol) (273.15K ) ¿
=(1 atm) (22.414L)¿
¿

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