THERMODYNAMICS

Thermodynamics
• In physics, thermodynamics deals with
temperature, heat and their relation to energy,
radiation, work, and properties of matter.
• The energy can be of any forms such as
electrical, mechanical, or chemical energy.
William Thomson coined the term
thermodynamics in 1749.
• It is derived from two Greek words “thermes”
meaning heat, and “dynamikos” meaning
powerful.
 What is Thermodynamics?
• Thermodynamics is the branch of science which is concerned
with the relationship between other forms of energy and
heat. We can define thermodynamics as:
• The branch of science that deals with heat and temperature,
and their relation to energy, work, radiation, and 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.
• Thermal energy is the energy that comes from heat. This
heat is generated by the movement of tiny particles within
an object. The faster these particles move, the more heat is
 A System and Its Surroundings
• In thermodynamics, it is imperative to define a system and its surroundings
because that concept becomes the basis for many types of descriptions and
calculations.
• A primary goal of the study of thermochemistry is to determine the quantity
of heat exchanged between a system and its surroundings.
• The system is the part of the universe being studied, while the
• surroundings are the rest of the universe that interacts with the system.
• A system and its surroundings can be as large as the rain forests in South America or as
small as the contents of a beaker in a chemistry laboratory. The type of system one is
dealing with can have very important implications in chemistry because the type of
system dictates certain conditions and laws of thermodynamics associated with that
system.
• The system is the part of the universe we wish to focus our attention on. In the world of
chemistry, the system is the chemical reaction. For example:
• 2H2 + O2 ---> 2H2O
• The system consists of those molecules which are reacting.
• The surroundings are everything else; the rest of the universe. For example, say the
above reaction is happening in gas phase; then the walls of the container are part of the
surroundings.
 Open System
• An open system is a system that freely
exchanges energy and matter with its
surroundings.
• For instance, when you are boiling soup in an
open saucepan on a stove, energy and
matter are being transferred to the
surroundings through steam.
 The saucepan is an open system because it
allows for the transfer of matter (for example
adding spices in the saucepan) and for the
transfer of energy (for example heating the
saucepan and allowing steam to leave the
saucepan).
 Closed System
• Putting a lid on the saucepan makes the saucepan a
closed system. A closed system is a system that
exchanges only energy with its surroundings, not
matter. By putting a lid on the saucepan, matter can
no longer transfer because the lid prevents matter
from entering the saucepan and leaving the
saucepan. Still, the saucepan allows energy transfer.
Imagine putting the saucepan on a stove and heating
it. The saucepan allows energy transfer as the
saucepan heats up and heats the contents inside it.
• For example, when a lid is put a beaker, it becomes a
 This fog and mist is the steam which covers the sides of
the container because it cannot escape the beaker due
to the lid. The fact that the beaker is able to produce
this steam means that the beaker allows for energy
transfer. Thus, even though a closed system cannot
allow matter transfer, it can still allow energy transfer.
The methods of energy transfer in a closed system are
the same as those described for an open system above.
 Isolated System
• Now let's examine the type of system you have if you substituted a
thermos for the saucepan. A thermos is used to keep things either cold or
hot. Thus, a thermos does not allow for energy transfer. Additionally, the
thermos, like any other closed container, does not allow matter transfer
because it has a lid that does not allow anything to enter or leave the
container. As a result, the thermos is what we call an isolated system.
• An isolated system does not exchange energy or matter with its
surroundings. For example, if soup is poured into an insulated container (as
seen below) and closed, there is no exchange of heat or matter. The fact
that, in reality, a thermos is not perfect in keeping things warm/cold
illustrates the difficulty in creating an truly isolated system. In fact, there
are a few, if any, systems that exist in this world that are completely
isolated systems.
 FIRST LAW OF THERMODYNAMICS

• Energy cannot be created or

destroyed it can only be transformed
from one form to another i.e. energy
is conserved.
• The internal energy U of a system is
the sum of all kinetic and potential
energies of all its components.
• SYSTEM: an open system is one in which
matter and energy can be exchanged
with the surroundings.
• An isolated system is one in which
matter and energy cannot be exchanged
with the surroundings.
• Closed system is one that exchange
State Functions Affecting
Thermodynamics:

• Internal energy (U)

• Enthalpy (H)
• Entropy (S)
• Gibbs free energy (G)
 SOME TERMS IN THERMODYMANICS
• The change in internal energy ΔU is the difference
between U final and U initial
• A positive value ΔU indicates the system as gained
energy from its surrounding,
• A negative value of ΔU indicates that the system as lost
energy to its surroundings.
• ΔU = Q + W,
• Q is the heat absorbed or evolved by the system.
• U increases when work is done on a system or heat is
added to a system.
 SOME TERMS IN THERMODYMANICS

+Q = the system gains heat

—Q = the system losses heat
+w = work is done on the system
—w = work is done by the system
+ΔU = net gain of energy by the system
—ΔU= net loss of energy by the system An
 Energy, Heat, and Work

 In defining a system and its surroundings, words like energy and matter are
used very often. As a result, one's understanding of a system and its
surroundings can increase by understanding energy and matter. Energy is
the ability to do work. Work is when an object moves against a force and is
defined by the following equation:

with
 W representing work,
 F representing force, and
 D representing distance.
It can be as simple as picking up a tennis ball or as complicated as
pushing a car. When you are moving an object against a force (i.e.
gravity), you are doing work on that object.
 SOME TERMS IN THERMODYMANICS
• An endothermic process is one in which the system
absorbs heat while
• An exothermic process is one that losses heat
• A state function is the property of a system that is
determined by specifying the system’s condition like
temperature, pressure.
• The value of a state function depends only on the
present state and not the path the system took to
attain the state.
• Enthalpy H accounts for heat flow in processes
 A positive value of ΔH implies that the system
has gained heat and
 A negative value of ΔH means the system has
lost heat to the surrounding.
 When a reaction is carried out in a constant
value container, ΔV is zero.
 Enthalpies of Reactions
• The enthalpy change that accompanies a reaction is called the enthalpy of
reaction.

• A negative ΔH value means the reaction is exothermic; a positive ΔH value

means the reaction is endothermic.
• Enthalpy is an extensive property.
• The magnitude of ΔH is directly proportional to the amount of reactant
consumed in the process.
• The enthalpy for a reaction is equal in magnitude, but opposite in sign, to ΔH for
the reverse reaction.
• The enthalpy change for a reaction depends on the state of the reactants and
 What is thermodynamic process?
• A thermodynamic process is a passage of a thermodynamic system from
an initial to a final state of thermodynamic equilibrium.

• Thermodynamics Timeline:
• Thermodynamics has many sections under it and is considered as a broad
subject because it deals with topics that exist all around us and thus
classification becomes necessary.
• Classical Thermodynamics:
• In this section, the behaviour of matter is analyzed with a macroscopic
approach. Units such as temperature and pressure are taken into
consideration which helps the individuals to calculate other properties and
to predict the characteristics of the matter that is undergoing the process.
• Statistical Thermodynamics:
• In this section, every molecule is under the spotlight i.e. the properties of
each and every molecule and ways in which they interact are taken into
consideration to characterize the behaviour of a group of molecules.
• Pure Component Thermodynamics:
• As the name itself states, this section tries to describe the behaviour of a
system that has an unadulterated or pure constituent.
• Solution Thermodynamics:
• This section attempts to describe the behaviour of a system that contains
more than one chemical in the mixture.
What are Laws of Thermodynamics?

The laws of thermodynamics define the

fundamental physical quantities like
energy, temperature and entropy that
characterise thermodynamic systems at
thermal equilibrium.
The laws represent how these quantities
behave under various circumstances.
How many laws of thermodynamics are
There are four laws of
thermodynamics and are given
below:
Zeroth Law of Thermodynamics
First Law of Thermodynamics
Second Law of Thermodynamics
Third Law of Thermodynamics
 Zeroth Law of Thermodynamics
 The Zeroth Law is the basis for the measurement of temperature. It states
that:
 Two bodies which are in thermal equilibrium with a third body are in
thermal equilibrium with each other.
 Zeroth Law Of Thermodynamics Examples: consider two cups A and B with
boiling water.
 When a thermometer is placed in cup A, it gets warmed up by the water
until it reads 100°C.
 When it read 100°C, we say that the thermometer is in equilibrium with
cup A.
 Now when we move the thermometer to cup B to read the temperature, it
continues to read 100°C.
The thermometer is also in equilibrium with cup B.
• From keeping in mind the zeroth law of
thermodynamics, we can conclude that cup A and
cup B are in equilibrium with each other.
• The zeroth law of thermodynamics enables us to
use thermometers to compare the temperature of
any two objects that we like.
 First Law of Thermodynamics
• The first law of thermodynamics which is
also known as the conservation of energy
principle states that:
• Energy can neither be created nor destroyed,
but it can be changed from one form to
another.
• This law may seem abstract but if we look at
a few examples of the first law of
thermodynamics, we will get a clearer idea.
 First Law Of Thermodynamics Examples:
• Fansconvert electrical energy to
mechanical energy.
• Plants convert the radiant energy of
sunlight to chemical energy through
photosynthesis.
• We eat plants and convert the chemical
energy into kinetic energy while we
swim, walk, breathe and when we scroll
 Second Law of Thermodynamics
• The second law of thermodynamics states that:
• Energy in the form of heat only flows from
regions of higher temperature to that of lower
temperature.
• Many individuals take this statement lightly and
for granted, but it has an extensive impact and
consequence. This is why it costs money to run
an air conditioner. The human body obeys the
second law of thermodynamics too.
• Many individuals take this statement lightly and for granted, but it has an
extensive impact and consequence. This is why it costs money to run an
air conditioner. The human body obeys the second law of thermodynamics
too.
• Second Law Of Thermodynamics Examples
• One of the examples of the second law of thermodynamics can be
sweating in a crowded room. Assume yourself to be in a small room full of
people. You are very likely to feel warm and start sweating. Sweating is a
mechanism the human body uses to cool itself. Here, the heat from your
body is transferred to sweat. As the sweat absorbs more and more heat
from the body it evaporates and transfers heat to the surrounding air,
thereby, heating up the temperature of the room.
 Third Law of
Thermodynamics
• The Third Law states that:
• The entropy of a perfect crystal is zero
when the temperature of the crystal is
equal to absolute zero (0 K)
• Entropy is sometimes called “waste
energy” i.e., the energy that is unable to
do work, and since there is no heat
energy whatsoever at absolute zero, there
 Third Law Of Thermodynamics Examples:
• Let us consider steam as an example to illustrate the third law of
thermodynamics step by step:
• We know that steam is a gaseous state of water at higher temperatures. In this
state:
1. The molecules within it move freely and have high entropy.
2. If one decreases the temperature below 100°C, the steam gets converted to
water, where the movement of molecules is restricted, decreasing the entropy of
water.
3. When water is further cooled below 0°C, it gets converted to solid ice. In this
state, the movement of molecules is further restricted and the entropy of the
system reduces more.
4. As the temperature of the ice further reduces, the movement of the molecules in
them are restricted more and the entropy of the substance goes on decreasing.
5. When the ice is cooled to absolute zero, ideally the entropy should be zero. But in
• References
• Petrucci, et al. General Chemistry Principles & Modern
Applications. 9th ed. Upper Saddle River, NJ: Pearson
Prentice Hall, 2007
• Gonick, Larry; Criddle, Craig. The Cartoon Guide to
Chemistry. 1st ed. New York, NY: Harper Collins
Publishers Inc., 2005
• Moore, John T.;Langley, Richard. Chemistry for the Utterly
Confused. New York, NY: McGraw-Hill, 2007