Dr.

Mohsen El-Tahawy
Lecturer of Physical chemistry,
Chemistry Department,
Faculty of Science, Damanhour University
PhD, Bologna University, Italy

Contents
✓ Chemical Equilibrium
✓ Chemical kinetics
❑ Principles of Thermodynamics →
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❑ The Colloidal State
Principles of Thermodynamics
Basic Concepts
What is Thermodynamics?
✓ Thermodynamics is a branch that deals with
heat, work and temperature, and their relation
to energy, radiation and physical properties of
matter.
✓ To be specific, it explains how thermal energy is
converted to or from other forms of energy and
how matter is affected by this process.
 The analysis of thermal systems is achieved
through the application of the governing
conservation equations,
✓ namely Conservation of Mass,
✓ Conservation of Energy (laws of
thermodynamics),
 Energy can be viewed as the ability to cause
changes.
Scope of Thermodynamics
(1) Most of the important laws of Physical
Chemistry, including the van’t Hoff law of
lowering of vapour pressure, Phase Rule and the
Distribution Law, can be derived from the laws
of thermodynamics.
(2) It tells whether a particular physical or
chemical change can occur under a given set of
conditions of temperature, pressure and
concentration.
(3) It also helps in predicting how far a physical or
chemical change can proceed, until the
equilibrium conditions are established.
Limitations of Thermodynamics
(1) Thermodynamics is a macroscopic science. This
means that it deals with the bulk system and
does not deal with the molecular constitution
of matter.
(2) It is not concerned about how and at what rate
the energy transformations are carried out.
(3) It is based on the initial and final states
undergoing the change.
THERMODYNAMIC SYSTEMS
➢A system is a specific quantity of matter or a
region definite boundary on which our attention
is focused.
✓ Boundary: the real or imaginary surface that
separates the system from its surroundings.
✓ The
boundaries of a system can be fixed or
movable.
✓ Mathematically,the boundary has zero thickness,
no mass, and no volume.
 Surrounding is the rest of the universe.
✓ we can consider the ‘Surrounding’ as the immediate
neighborhood of the system (the part of the universe at
large, with which the system ‘effectively’ interacts).
 Things that matter affects on the surrounding:
T, P, ability to:
do work, transfer heat,
transfer matter, etc.
Parameters for the system:
Internal energy, Enthalpy, T, P, mass, etc.
Work, heat, and energy:
 Work is motion against an opposing force, doing work
is equivalent to raising a weight somewhere in the
surroundings.
e.g. expansion of a gas that pushes out a piston and
raises a weight.
 The energy of a system is its capacity to do work.
✓ When work is done on an isolated system, the capacity
of the system to do work is increased so the energy of
the system is increased.
✓ While when the system does work, the energy of the
system is reduced, and it can do less work than before.
 When the energy of a system changes due to the
temperature difference between the system and
its surroundings, we say that energy has been
transferred as heat.
✓ Inthe exothermic process such as combustion
reactions energy is transferred 'as heat' to the
surroundings
✓ while in the endothermic process such as
vaporization of water energy is transferred 'as
heat' from the surroundings into the system
 Work (W) Heat (Q)
Interaction Mechanical Thermal
Force and
Requires Temperature difference
Displacement
Macroscopic pushes
Process Microscopic collisions
and pulls
Q > 0 when the
W > 0 when a gas is
environment is at a higher
Positive compressed. Energy
temperature than the
value is transferred into
system. Energy is
system.
transferred into system.
W < 0 when a gas Q < 0 when the system is at
Negative expands. Energy is a higher temperature than
value transferred out of the environment. Energy is
system. transferred out of system.
Energy and matter are the two ‘things’ may be
added/removed to a thermodynamic system :
 Energy
✓ energy may be transferred (‘added’) to the system as
heat, electromagnetic radiation etc.
✓ In thermodynamic the two modes of transfer of energy
to the system are considered Heat and Work.
✓ Note: Heat and work are modes of transfer of energy
and not ‘energy’ itself
✓ Inside the system, the part of energy which came via
work and that which came via heat, cannot be
distinguished
✓ From the above it is clear that, bodies contain internal
energy and not heat (nor work!).
 Matter.
✓ Matter is easy to understand and includes atoms,
ions, electrons, etc.
✓ when matter is added to a system, it brings
along some energy.
✓ The‘energy density’ (energy per unit mass or
energy per unit volume) in the incoming matter
may be higher or lower than the matter already
present in the system.
Types of systems
 Closed system or control
mass
✓ Itconsists of a fixed amount
of mass, and no mass can
cross its boundary,
✓ energy in the form of heat or
work, can cross the boundary,
✓ the volume of a closed system
does not have to be fixed.
(e.g. Refrigerator, a closed
water bottle in fridge).
 Open system or control volume
✓ Itusually encloses a device that
involves mass flow such as a
compressor.
✓ Both mass and energy can cross the
boundary of a control volume. (e.g.
an open beaker to which we can
add water, A steam turbine).
Important note
✓ Some thermodynamics relations that are applicable
to closed and open systems are different.
✓ Thus, it is extremely important to recognize the type
of system we have before start analyzing it.
 Isolated system:
✓A closed system that does not communicate with
the surroundings by any means. i.e. a system to
which neither matter nor heat can be
added/removed. a closed vacuum ‘thermos’
flask can be considered as isolated.
Properties of a System
 Any characteristic of a system is called a property.
 Intensive properties
✓ are those that are independent of the size (mass) of
a system, such as T, and density. They are not
additive.
 Extensive properties:
✓ values that are dependent on size of the system such
as mass, volume, and total energy U. They are
additive.
✓ Extensive properties per unit mass are called specific
properties, e.g. specific volume (v=V/m).
Processes in thermodynamics
 The state of a system is a complete description of a
system at a given time, including its temperature and
pressure, the amount of matter it contains, its
chemical composition, and the physical state of the
matter
 A state function is a property of a system whose
magnitude depends on only the present state of the
system, not its previous history. e.g. Temperature,
pressure, volume, and potential energy are all state
functions.
 Any change a system undergoes from one equilibrium
state to another is called a process,
 The series of states through which a system passes
during a process is called a path.

 Ata given state, all the properties of a system

have fixed values.
 Thus, if the value of even one property changes,
the system’s state changes to a different one.
 TheState of a thermodynamic system is
determined by four factors or preparties’:
1. Absolute Pressure P in Pascals.
2. Temperature T in Kelvins.
3. Volume V in cubic meters.
4. Number of moles n of working gas.
 In an equilibrium state,
✓ thereare no unbalanced potentials (or driving
forces) within the system.
✓ No changes in the value of properties occur when
it is isolated from its surroundings.
Types of thermodynamic equilibria:
 Thermal equilibrium:
✓ when the temperature is the same throughout the entire
system.
 Mechanical equilibrium:
✓ When there is no change in pressure at any point of the
system.
 Phase equilibrium:
✓ in a two-phase system, when the mass of each phase
reaches an equilibrium level.
 Chemical equilibrium:
✓ when the chemical composition of a system does not
change with time, i.e., no chemical reactions occur.
Thermodynamic Process
 A system undergoes a thermodynamic process when there
is some energetic change within the system that is
associated with changes in pressure, volume and internal
energy.
 There are four types of thermodynamic processes that
have their unique properties, and they are:
 Note: the Prefix iso‐ is refers to a process for which a
particular property is constant.
Isothermal process:
 A process in which no change in temperature occurs.
 Phase transformation occurs at constant temperatures, such as
melting, sublimation, and boiling
Isobaric process:
 A process in which no change in pressure occurs.
 e.g. heating of water in open air i.e. under atmospheric
pressure
Isochoric or isovolumetric process:
 A process where no change in volume occurs and the
system does no work.
 e.g. heating of gas in a closed container. When the
volume of a system doesn’t change, it will do no work on
its surroundings.
Adiabatic Process –
A process where no heat transfer into or out of
the system occurs.
Cyclic process:
A system is said to have undergone a cycle
process if it returns to its initial state at the end
via a process or a combination of processes