CHE 404 : PHYSICAL CHEMISTRY FOR CHE

MODULE
1
INTRODUCTION TO PHYSICAL CHEMISTRY

INTRODUCTION
This module gives an overview of what is physical chemistry. It discussed the physical properties
of many different types of substances on different levels. The nature of physical chemistry and the
relationship with other areas of discipline has covered in this chapter. It also provides an
introduction to various systems, states and equilibrium which will be discussed in detail for the
succeeding chapters.

INTENDED LEARNING OUTCOMES

At the end of the module, the students are expected to demonstrate understanding on concepts of
physical chemistry and chemical behaviour of matter.

CONTENT OVERVIEW
Indicative contents included the following topics:

1. Nature of physical chemistry

2. Matter
3. Systems, states and equilibrium
4. Energy
5. Perfect gases
6. Pressure
7. Temperature

END OF THE MODULE TEST

This is given to assess students understanding on the introduction to physical chemistry

Coursework : 7 items problem solving

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Table of Contents

MODULE 1. INTRODUCTION TO PHYSICAL CHEMISTRY ............................................................................ 3

1.1 NATURE OF PHYSICAL CHEMISTRY .............................................................................................. 3
1.2 MATTER....................................................................................................................................... 5
1.3 SYSTEM, STATES, AND EQUILIBRIUM .......................................................................................... 7
1.4 ENERGY ....................................................................................................................................... 8
1.5 PERFECT GASES ........................................................................................................................... 9
1.6 PRESSURE .................................................................................................................................. 10
1.7 TEMPERATURE .......................................................................................................................... 12
1.8 END OF THE MODULE TEST ....................................................................................................... 12

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MODULE 1. INTRODUCTION TO PHYSICAL CHEMISTRY

1.1 NATURE OF PHYSICAL CHEMISTRY

The following are the definitions of Physical Chemistry:

Physical chemistry is used to explain and interpret observations on the physical and
chemical properties of matter. It essential for developing and interpreting the modern techniques
used to determine the structure and properties of matter, such as new synthetic materials and
biological membranes (Atkins, 2006).

Physical Chemistry is 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
chemistry, statistical mechanics and dynamics, equilibrium (Bulthelezi, 2007).

Physical chemistry is the application of the methods of physics to chemical problems. It

includes the qualitative and quantitative study, both experimental and theoretical, of the general
principles determining the behaviour of matter, particularly the transformation of one substance
into another (The Lincoln Library of Essential Information, 2011).

Physical Chemistry includes study of the physical properties of many different types of
substances and on different scales (levels of physical detail).

It includes study of the following scales of chemical properties of materials (Ivy Rose,
2003).

1. Macroscopic:
Macroscopic properties of substances describe how relatively large quantities of the
substance behave as a group, e.g. melting points and boiling points, latent heats of fusion
and vaporization, thermal conductivity, specific heat capacity, coefficient of linear thermal
expansion, and many other “physical properties”.

2. Microscopic:
Microscopic properties of substances concern details of their physical properties
observable only using the magnification provided by microscopes. Microscopic physical
properties include, for example, the shapes and structures of crystal – which can have
important consequences for the behavior of large sections of the material of which they are
a part.

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3. Atomic:
Atomic properties relate to elements. (Recall that elements consist of many individual
atoms, whereas compounds consist of many molecules – which are, in turn, specific
combinations of atoms joined together via chemical bonds.) Examples of atomic properties
of elements include atomic numbers and atomic mass, e.g. the element Boron whose
chemical symbol is B, has atomic number 5 and atomic mass 10.81 (strictly for a free
neutral atom in ground state).

4. Subatomic:
Subatomic particle, also called elementary particle, any of various self-contained units
of matter or energy that are the fundamental constituents of all matter. Subatomic particles
include electrons, the negatively charged, almost massless particles that nevertheless
account for most of the size of the atom, and they include the heavier building blocks of
the small but very dense nucleus of the atom, the positively charged protons and the
electrically neutral neutrons.

Thus, from the definitions above it can be said that the area of chemistry which concerns
itself with the study of the physical properties and structure of matter, with the laws of chemical
interaction, and with the theories governing these is called Physical Chemistry. Its main purposes
are:
1. To collect the appropriate data required to define the properties of gases, liquids,
solids, solutions, and colloidal dispersions
2. To systemize them into laws, and
3. To give them a theoretical foundation

Physical chemistry can be organized into thermodynamics, kinetic theory,

electrochemistry, quantum mechanics, chemical kinetics, and statistical thermodynamics. (Laidler,
1999) Basic concepts of physics, including classical mechanics, are important to these areas. We
begin by developing the relation between work and kinetic energy. Our main interest is in the
system and its surroundings. It is not so much concerned with the description of the chemical
substances and their reactions – this is the concern of organic and inorganic chemistry – as it is
with theoretical principles and with quantitative problems.

Two approaches:

1. Systemic approach – the investigation begins with the very basic constituents of
matter – the fundamental particles – and proceeds conceptually to construct larger
systems from them. Microscopic (Greek micros, small) is used to refer to these tiny
constituents. In this way, increasingly complex phenomena can be interpreted on the
basis of the elementary particles and their interactions.

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2. Phenomenological approach – the study starts with investigation of macroscopic

material (Greek macros, large) that can be easily observed with the eye. Measurements
are made of macroscopic properties such as P and V.

Physical chemistry includes numerous disciplines such as the following:

1. Thermodynamics - relationship between energy interconversion by materials, and

the molecular properties.
2. Kinetics – study the rates of chemical processes
3. Quantum Mechanics - phenomena at the molecular level
4. Statistical Mechanics - relationships between individual molecules and bulk
properties of matter
5. Spectroscopy - non-destructive interaction of light (energy) and matter, in order to
study chemical structure
6. Photochemistry - interaction of light and matter with the intent of coherently altering
molecular structure

1.2 MATTER
Matter is composed of electrons and nuclei (neutrons and protons) - which can be further
divided into subatomic particles. All matter is made from atoms. Every substance (oxygen, lead,
silver, neon ...) has a unique number of protons, neutrons, and electrons. Oxygen, for example,
has 8 protons, 8 neutrons, and 8 electrons. Hydrogen has 1 proton and 1 electron. Individual
atoms can combine with other atoms to form molecules. Water molecules contain two atoms of
hydrogen H and one atom of oxygen O and are chemically called H2O. Oxygen and nitrogen are
the major components of air and occur in nature as diatomic (two atom) molecules. Regardless of
the type of molecule, matter normally exists as a solid, a liquid, or a gas. We call this property of
matter the phase of the matter. The three normal phases of matter have unique characteristics.
(NASA, 2015)

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Solid - In the solid phase the molecules are closely bound to one another by molecular forces. A
solid holds its shape and the volume of a solid is fixed by the shape of the solid.

Liquid - In the liquid phase the molecular forces are weaker than in a solid. A liquid will take the
shape of its container with a free surface in a gravitational field. In microgravity, a liquid forms a
ball inside a free surface. Regardless of gravity, a liquid has a fixed volume.

Gas - In the gas phase the molecular forces are very weak. A gas fills its container, taking both the
shape and the volume of the container.

Physical Properties:
 Mass- largely due to the nuclei; thermal properties
 Electric charge -atoms and molecules are bound together by electrostatic
interactions
 Magnetism- nucleus interacts with magnetic fields; little consequence for
atomic or molecular structure
 Spin- least “tangible” property; closest classical analogy: electrons and nuclei are
spinning like little planets

Quantifying Matter
 Substance: A pure form of matter
 Amount of substance: Reported in terms of moles
1 mol of a substance contains as many entities as exactly 12 g of carbon-12 (ca. 6.02
x 1023)
 Avogadro’s Number: NA = 6.02 x 1023 mol-1
 Extensive Property: Dependent upon the amount of matter in the substance (e.g.,
mass & volume)
 Intensive Property: Independent of the amount of matter in a substance (e.g., mass
density, pressure and temperature)
 Molar Property: Xm, an extensive property divided by the amount of substance, n:
Xm = X/n
 Molar Concentration: “Molarity” moles of solute dissolved in litres of solvent: 1.0
M = 1.0 mol L-1

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1.3 SYSTEM, STATES, AND EQUILIBRIUM

Physical chemists attempt to define very precisely the object of their study, which is called
the system. It may be solid, liquid, gaseous, or any combination of these. The study may be
concerned with a large number of individual components that compromise a macroscopic
system. Alternatively, if the study focuses on individual atoms and molecules, a microscopic
system is involved. We may summarize by saying that the system is a particular segment of the
world (with define boundaries) on which we focus our attention. Outside the system are the
surroundings, and the system plus the surroundings compose a universe.

In an open system there can be transfer of heat and also material. If no material can pass
between the system and the surroundings, but there can be transfer of heat, the system is said to
be a closed system. Finally, a system is said to be isolated if neither matter nor heat is permitted
to exchange across the boundary. This could be accomplished by surrounding the system with an
insulating container. These three possibilities are illustrated in Figure 2.1

Intensive and Extensive Properties

Physical chemists generally concern themselves with measuring the properties of a system,
properties such as pressure, temperature, and volume. These properties may be of two types. If the
value of the property does not change with the quantity of matter present (i.e., if it does not change
when the system id subdivided), we say that the property is an intensive property. Examples are
pressure, temperature, and refractive index. If the property does change with the quantity of matter
present, the property is called extensive property. Volume and mass are extensive. The ratio of
two extensive properties is an intensive property. There is a familiar example of this; the density
of a sample is an intensive quality obtained by the division of mass by volume, two extensive
properties.

Equilibrium
A certain minimum number of properties have to be measured in order to determine the
condition or state of a macroscopic system completely. For a given amount of material it is then

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usually possible to write an equation describing the state in terms of intensive variables. This
equation is known as an equation of state and is our attempt to relate empirical data that are
summarized in terms of experimentally defined variables. For example, if our system consists of
gas, we normally could describe its state by specifying properties such as amount of substance,
temperature, and pressure. The volume of gas is another property that will change as temperature
and pressure are altered, but this fourth variable is fixed by an equation of state that connect these
four properties. In some cases it is important to specify the shape or extent of the surface.
Therefore, we cannot state unequivocally that a predetermined number of independent variables
will always be sufficient to specify the state of an arbitrary system. However, if the variables that
specify the state of the system do not change with time, then we say the system is in equilibrium.
Thus, a state of equilibrium exists when there is no change with time in any of the system’s
macroscopic properties.

Thermal Equilibrium

Two objects are said to be in thermal equilibrium if

no change in state occurs when they are in contact with
one another.
A: Block of iron
B: Block of copper
C: Flask of water

Zeroth Law of Thermodynamics:

If A is in thermal equilibrium with B, and B is
in thermal equilibrium with C, then C is also in thermal
equilibrium with A. If B is a thermometer (glass
capillary with Hg), in contact with A the Hg column has
a certain length. If B is placed in contact with another object C, one can predict the change
of state when A and C are put in contact. Thus, the Hg column is used to measure the
temperatures of A and C.

Thermodynamic temperature scale (Kelvin): T/K = q/oC + 273.15

1.4 ENERGY

The energy is the capacity to do work (or to heat) while the Work are the force that causes
mechanical displacement on a body.

For an infinitesimal amount of work, dw, done by a force F in the x- direction:

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𝑑𝑤
= 𝐹𝑥 𝑑𝑤 = 𝐹𝑥 𝑑𝑥
𝑑𝑥
𝑥2
𝑤 = ∑ 𝐹 (𝑥 )𝑑𝑥 = ∫ 𝐹 (𝑥 )𝑑𝑥 = 𝐹 (𝑥2 − 𝑥1 )
𝑥1
For constant F:
The amount of work for finite displacement, w, is given by the sum of infinitesimal
displacements, which is equivalent to the integral above.

Energy is conserved - it is either created or destroyed: it can be transferred from one location
to another in the form of mechanical work (orderly) or heat (thermal motion, random)

1.5 PERFECT GASES

We shall consider a hypothetical perfect or ideal gas, which is a form of matter that
completely fills any container.
A perfect gas is pictured as a collection of molecules or atoms which undergo continuous
random motion (or Brownian motion):
 The speeds of the particles increase as the temperature is increased
 The molecules are widely separated from one another, with the only interactions
being with the side of the container and other molecules during infrequent collisions
 The molecules are unaffected by intermolecular forces (e.g., dipole-dipole, van der
Waals, etc.)

States of Gases

The physical state of a substance is designed by its physical properties.

The state of a perfect pure gas is defined by:
V- volume
n- amount of substances (moles)

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p- Pressure
T- temperature
Each substance is described by an equation of state, which correlates the variables
describing that state. For example, for a perfect gas:
𝑛𝑅𝑇
𝑝 = 𝑓(𝑇, 𝑉, 𝑛) = , 𝑅 𝑖𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝑉

1.6 PRESSURE

Pressure is the amount of equal force applied (measured in N) to a specific area

(measured in m2): p = F/A
Pressure from a gas is the result of countless collisions of rapidly moving molecules
with the walls of the container.

Pressure Exerted by Gases

Gases can be stored in two separate containers separated by a movable wall (i.e., piston).
The higher pressure gas will move the wall and compress the lower pressure gas, until an
equilibrium pressure is established. The piston is said to be in mechanical equilibrium at this point.
Pressures of the gases in a mechanical system involving a piston can be controlled via gas
entry and release valves, that are set or controlled to let gases in and out at certain pressure
thresholds.

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Measuring Pressure
One device used to measure pressure is a
barometer (by Torricelli). When the column of mercury
is in equilibrium with the atmosphere, the pressure at the
base is equal to that from the atmosphere - so the height
of the mercury is a measure of the external pressure.
A simple pressure measuring device is a
manometer, in which a non-volatile viscous fluid is
contained in a U-tube The pressure in the apparatus (a)
or from atmosphere (b) is directly proportional to the
height difference of the two columns, h:
p = ρgh
ρ = density of viscous fluid
g =gravitational acceleration, 9.8 m s-2

EXAMPLE
Compare the length of a column of mercury to that of a column of water required to indicate
a pressure of 1.000 bar. The densities of mercury and water at 0.00˚C are 13.596 cm -3 and 0.99987
g cm-3, respectively.

SOLUTION:
The pressure exerted by both liquids is given by 𝑃 = 𝜌𝑔ℎ. Since the length of both
liquids must exert the same pressure, we can set the pressures equal with the subscripts Hg and
w, denoting mercury and water, respectively.

𝜌𝐻𝑔 𝑔ℎ𝐻𝑔 = 𝜌𝑤 𝑔ℎ𝑤

The height of mercury column required to produce 1 bar pressure in mm is
0.986923 atm/bar x 760 mm/atm = 750.06 mm/bar

Substitution of this and rearrangement of the earlier equation gives

13.596
ℎ𝑤 = 750.06 𝑚𝑚 𝑥 = 𝟏𝟎𝟏𝟗𝟗𝒎𝒎 𝒐𝒓 𝟏𝟎. 𝟏𝟗𝟗𝒎
0.99987

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1.7 TEMPERATURE

Temperature is a property that describes the flow of

energy. Energy will flow between two objects in
contact, resulting in change of state of these two
objects. If objects A and B are touching, and A has a
higher temperature than B, energy flows from A to B
until some equilibrium condition is established.

Separatory boundaries:
Diathermic - if a change of state is observed
when two bodies are brought into contact with
one another (e.g., metal)

Adiabatic - if no energy flow is permitted

between the two objects in contact (e.g.,
styrofoam)

1.8 END OF THE MODULE TEST

1. The mercury level in the left arm of the J-shaped tube is attached to a thermostat gas-
containing bulb. The left arm is 10.83 cm and the right arm is 34.71 cm above the bottom
of the manometer. If the barometric pressure reads 738.4 Torr, what is the pressure of the
gas? Assume that temperature-induced changes in the reading of the barometer and J tube
are small enough to neglect.

2. The standard atmosphere of pressure is the force per unit area exerted by a 760-mm column
of mercury, the density of which is 13.595 11 g cm–3 at 0 °C. If the gravitational
acceleration is 9.806 65 m s–2, calculate the pressure of 1 atm in kPa.

3. At 100°C and 1.60 kPa, the mass density of phosphorus vapour is 0.6388 kg m−3. What is
the molecular formula of phosphorus under these conditions?

4. Determine the density, specific gravity, and mass of the air in a room whose dimensions
are 4 m x 5 m x 6 m at 100 kPa and 25°C.

5. A rigid tank contains 20 lbm of air at 20 psia and 70°F. More air is added to the tank until
the pressure and temperature rise to 35 psia and 90°F, respectively. Determine the amount
of air added to the tank.

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6. A manometer is used to measure the pressure in a tank. The fluid used has a specific gravity
of 0.85, and the manometer column height is 55 cm. If the local atmospheric pressure is 96
kPa, determine the absolute pressure within the tank.

7. The piston of a vertical piston–cylinder device containing a gas has a mass of 60 kg and a
cross-sectional area of 0.04 m2, as shown in Fig. 3–20. The local atmospheric pressure is
0.97 bar, and the gravitational acceleration is 9.81 m/s2. Determine the pressure inside the
cylinder.

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