LECTURE 1-INTRODUCTION TO PHYSICAL CHEMISTRY

1.1 WHAT IS PHYSICAL CHEMISTRY?

Physical chemistry is the branch of chemistry that establishes and develops the principles of the
subject. Its concepts are used to explain and interpret observations on the physical and chemical properties
of matter. Physical chemistry is also 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 behavior 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). That is, it includes study of the following scales of chemical
properties of materials: (IvyRose, 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.
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:
The study of Physical Chemistry generally involves using theories, measurements, and
techniques either from, or more usually associated with, physics – to study, understand and
explain chemical substances.
Hence, when asked the question “What is Physical Chemistry”, some people talk about the “physics of
chemicals”, which may be a helpful way to remember or work out a simple definition of physical chemistry.

1.2 THE NATURE OF PHYSICAL CHEMISTRY

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.
Purpose of physical chemistry:
• To collect the appropriate data required to define the properties of gases, liquids, solids,
solutions, and colloidal dispersions
• To systemize them into laws, and
• To give them a theoretical foundation

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

• Thermodynamics - relationship between energy interconversion by materials, and the molecular
properties.
• Kinetics - rates of chemical processes
• Quantum Mechanics - phenomena at the molecular level
• Statistical Mechanics - relationships between individual molecules and bulk properties of matter
• Spectroscopy - non-destructive interaction of light (energy) and matter, in order to study
chemical structure
• Photochemistry - interaction of light and matter with the intent of coherently altering molecular
structure

1.3 MATTER
Matter: 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
objects)
• 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

1.4 SYSTEM, STATES, AND EQUILIBRIUM

Systems
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

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 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 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

1.5. ENERGY
Energy: The capacity to do work (or to heat)
Work: Force causes mechanical displacement on a body.
For an infinitesimal amount of work, dw, done by a force F in the x- direction:
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.

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 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)

1.6 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)
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

1.7 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.

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 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.

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

1.8 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)

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EXERCISES:

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.
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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