Thermodynamics

 Lecture Objectives
Able to understand:
 First Laws of Thermodynamics, applications and limitations
 Second Laws of Thermodynamics, applications and limitations
Definition of Thermodynamics
Thermodynamics is the branch of Science (physics) that deals with the quantitative relationships
between heat and other forms of energy. In particular, it describes how thermal energy is converted to
and from other forms of energy and how it affects matter.
Thermodynamics is the study of the effects of work, heat, and energy on a system

Importance of thermodynamics
Thermodynamics is important for both Chemistry and Physics as it deals with the study of energy, the
conversion of energy between different forms and the ability of energy to do work.

Laws of Thermodynamics
The laws of thermodynamics are:
 First law of thermodynamics: Energy can neither be created nor be destroyed, it can only be
transferred from one form to another.
 Second law of thermodynamics: The entropy of any isolated system always increases.
 Third law of thermodynamics: The entropy of a system approaches a constant value as the
temperature approaches absolute zero.
 Zeroth law of thermodynamics: If two thermodynamic systems are each in thermal equilibrium
with a third, then they are in thermal equilibrium with each other.
→ Entropy is the measure of the number of possible arrangements the atoms in a system can have.
→ Enthalpy is the measurement of energy in a thermodynamic system.

The First Law

 energy can neither be created nor destroyed
It states that the total increase in the energy of a system is equal to the increase in thermal energy plus
the work done on the system. This states that heat is a form of energy and is therefore subject to the
principle of conservation.
 One form of work may be converted into another,
 or, work may be converted to heat,
 or, heat may be converted to work,
 but, final energy = initial energy

Prof. Dr. Bikash Chandra Sarker, ACH 101 L1S1_ Topic: Thermodynamics Page 1
The Second Law states that heat energy cannot be transferred from a body at a lower temperature to a
body at a higher temperature without the addition of energy. This is why it costs money to run an air
conditioner.
 naturally occurring processes are directional
The Third Law states that the entropy of a pure crystal at absolute zero is zero. As explained above,
entropy is sometimes called "waste energy," i.e., energy that is unable to do work, and since there is no
heat energy whatsoever at absolute zero, there can be no waste energy. Entropy is also a measure of the
disorder in a system, and while a perfect crystal is by definition perfectly ordered, any positive value of
temperature means there is motion within the crystal, which causes disorder. For these reasons, there can
be no physical system with lower entropy, so entropy always has a positive value.
The Zeroth Law states that if two bodies are in thermal equilibrium with some third body, then they are
also in equilibrium with each other. This establishes temperature as a fundamental and measurable
property of matter.

Objectives or application of Thermodynamics in Chemistry:

i) To predict the feasibility of a process: Whether or not, a process will occur under the given
set of conditions, can be predicted by applying the principles of thermodynamics
ii) To estimate the yield of product: Thermodynamic relationship help to predict the yield of
products obtainable in a process or a reaction. It is possible to know the extent upto which the
reaction takes place before attaining equilibrium.
iii) To deduce some important relationships in physical chemistry: it has been possible to deduce
some important and useful results such as Roult’s Law of lowering of vapour pressure and
expressions for depression in freezing point, elevation in boiling point, distribution law and
phase rule from the study of thermodynamics.
The Van 't Hoff equation relates the change in the equilibrium constant, Keq, of a chemical reaction
to the change in temperature, T, given the standard enthalpy change, ΔH⊖, for the process.

How is thermodynamics used in everyday life?

Thermodynamics has several types of applications in our daily life:
 all types of vehicles
 refrigerators and deep freezers
 evaporators
 radiators
 air-conditioning systems
 heat pumps
Limitations of thermodynamics
i) It deals with the properties like temperature, pressure etc. of the matter in bulk i.e., with
macroscopic quantities and not with the microscopic quantities. In other words, it deals with
large groups of atoms, molecules and ions than individual atoms, molecules or ions.
ii) It helps to predict the feasibility of a process but does not tell us anything about the time
taken for the process to complete or the rate at which the process would proceed.

Prof. Dr. Bikash Chandra Sarker, ACH 101 L1S1_ Topic: Thermodynamics Page 2
 iii) It concerns itself only with the initial and final states of a system and is not concerned with
the path by which the change is brought about i.e., throws no light on the mechanism of a
process.

Some common terms used in Thermodynamics

System
Is that part of the universe which is under thermodynamic study and the rest of the universe is
surroundings

Boundary
The real or imaginary surface separating the system from the surroundings is called boundary
bo

The 1.0 mole of oxygen confined in a cylinder fitted with a piston, is a thermodynamic system.
Thus cylinder, piston and all other objects outside the cylinder form the surroundings
Here
The boundary between the system (O2) and the surroundings (cylinder & piston) is clearly defined
Homogenous and Heterogenous system
Homogenous system
When a system is uniform throughout, it is called a homogenous system. A homogenous system is made
of one phase
Heterogenous system
Which consists of two or more phases.
hases. A heterogenous system is ink, milk, ice and water

Prof.
rof. Dr. Bikash Chandra Sarker, ACH 101 L1S1_ Topic: Thermodynamics Page 3
Types of thermodynamic system
1. Isolated 2. Closed and 3. Open

Prof. Dr. Bikash Chandra Sarker, ACH 101 L1S1_ Topic: Thermodynamics Page 4
What is meant by i) State of system ii) State variables iii) Thermodynamic equilibrium?
i) State of system
The state of a system implies a condition of the system when the various macroscopic
properties like pressure, volume, temperature, etc. of the system have definite values. The
first and the last state of the system are called initial state and final state, respectively.
ii) State variables
Macroscopic properties are called state variables. The four most common macroscopic properties
which are sufficient to define the state of a system are composition, pressure, volume, and
temperature. If these properties are fixed, all other physical properties of the system are
automatically fixed.
iii) Thermodynamic equilibrium
A system is aid to be thermodynamic equilibrium if the macroscopic properties of a system in
various phases do not undergo any change with time.
In fact, the thermodynamic equilibrium implies three different types of equilibria which must exist
simultaneously. These are;
a) Thermal equilibrium: This equilibrium demands that there should be no flow of heat from
one portion of a system to another. This can happen if the temperature of the system
remains constant.
b) Mechanical equilibrium: This equilibrium implies that no work should be done by one
part of the system over another i.e., no macroscopic movement of matter should occur
within the system or of the system with respect to its surroundings. This is possible if the
pressure of the system remains constant.
c) Chemical equilibrium: This equilibrium demands that no change in composition should
take place in any part of the system with passage of time.

Explain the following terms

i) Isothermal process
ii) Adiabatic process
iii) Isochoric process
iv) Isobaric process

i) Isothermal process
Isothermal process: when a process is carried out in such a manner that the temperature remains
constant throughout the process, it is called an isothermal process. Obviously, when such a
process occurs, heat can flow from the system to the surroundings and vice-versa in order to keep
the temperature of the system constant.

ii) Adiabatic process

When a process is carried out in such a manner that no heat can flow from the system to the
surroundings or vice-versa, i.e., the system is completely insulated from the surroundings, it is
called an adiabatic process.

iii) Isochoric process

It is a process during which the volume of the system is kept constant.

iv) Isobaric process

It is a process during which the pressure of the system is kept constant.

Prof. Dr. Bikash Chandra Sarker, ACH 101 L1S1_ Topic: Thermodynamics Page 5
Reversible and irreversible processes

A reversible processes is a process which is carried out infinitesimally slowly so that all changes
occurring in the direct process can be exactly reversed and the system remains almost in a state of
equilibrium at all times. In other words, a reversible process may be defined as a process which is
conducted in such a manner that at every stage, driving force is only infinitesimally greater than the
opposing force and which can be reversed by increasing the opposing force by infinitesimal amount.

Strictly speaking, a reversible process is almost impossible as it would require an infinite time for
completion. A process can be made very nearly reversible in some cases. For example, if an opposing
EMF is applied to a cell, then no current flows if the opposing EMF is exactly equal to that of the cell. If
the opposing EMF is very slightly (infinitesimally) less than that of the cell, a very small current is given
out by the cell. If the opposing EMF is slightly greater than that of the cell, a very small current flows in
the opposite direction.

A irreversible processes which does not meet the above requirements is called an irreversible
processes. In other words, an irreversible process is defined as that process which is not carried out
infinitesimally slow (instead, it is carried out rapidly) so that the successive steps of the direct process
cannot be retraced and any change in the external conditions disturbs the equilibrium.
It is interesting to note that all naturally occurring processes like the flow of water down a hill or flow
of heat from a hot end to a cold end of an iron bar etc. are thermodynamically irreversible.
Explain
i) Internal energy
ii) Change in internal energy
iii) Sign convention in energy
Internal energy: The evolution or absorption of energy in different processes clearly shows that every substance
must be associated with some definite amount of energy, the actual value of which depends upon the nature of the
substances (i.e., arrangement of atoms and electrons within the molecules) and the conditions of temperature,
pressure, volume and composition. The energy associated with a substance is called its internal energy and
usually denoted by the symbol E.
ii) Change of internal energy: It is not possible to find the absolute value of internal energy of a substance because
it involves certain quantities (like translational, vibrational and rotational kinetic energies) which cannot be
measured.
However, it is not required to know the absolute value of internal energy possessed by any substance (or a
system). What is required in different processes is simply the change of internal energy when the reactants change
into products or when system changes from initial state to the final state. This is easily measurable and is
represented by E.
Thus if the internal energy of a system in the initial state is E1 and in the final state, it is E2, then the change of
internal energy (E) may be given by
E= E2-E1
Similarly, in a chemical reaction it ER is the internal energy of the reactants and EP is the internal energy of the
products, then the energy change accompanying the process would be
E= Ep-ER

Prof. Dr. Bikash Chandra Sarker, ACH 101 L1S1_ Topic: Thermodynamics Page 6
Sign conventions in energy: Obviously, if E1>E2 (or ER>EP), the extra energy possessed by the system in the
initial state (or the reactants) would be given out, and E will be negative according to the above equations.
Similarly it E1<E2 (or ER<EP), energy will be absorbed in the process and E will be positive.
Hence E is negative if energy is evolved
and E is positive if energy is absorbed
Derivation of an expression for work of expansion against constant pressure.
The expression for such a work may be derived as follows: Consider a gas enclosed in a cylinder filtered with a
frictionless piston. (Figure ).
Area of cross-section of the cylinder = a sq cm
Pressure on the piston (which is slightly less than internal pressure of the gas so that the gas can expand) = P.
Distance through which gas expands= dl cm
As pressure is force per unit area, force (f) acting on the piston will be
f= P×a
Work done by the gas (i.e., the system)
= Force × Distance = f×dl
= P×a×dl
But a×dl=dV is a small increase in the volume of the gas. Hence, the small amount of work (δw) done the gas can
be written as
δw= P dV
If the gas expands from initial volume V1 to the final volume V2 then the total work done (w) will be given by
v1
w   PdV
v2
If the external pressure P against which the gas expands remains almost constant through the process, the
above result may be written as
v1
w  P  PdV  P(V  V )
2 1
v2
=P.V

where v = V2-V1 is the total change in the volume of the gas.

If the external pressure (P) is slightly more than the pressure of the gas, the gas will contract i.e., the work will
be done by the surroundings on the system. However, the same formulae will apply for the work done.

It may be mentioned here that P is the external pressure and hence is sometimes written as Pext So that

w=Pext ×v.

Prof. Dr. Bikash Chandra Sarker, ACH 101 L1S1_ Topic: Thermodynamics Page 7
Note: According to the latest SI conventions of sign, w is taken as positive it work is done on the system (i.e.,
wconstraction is positive) and it is taken as negative if work is done by the system (i.e., wexpansion is negative). Thus
wexp = -PV and wcontraction = +PV.

Prof. Dr. Bikash Chandra Sarker, ACH 101 L1S1_ Topic: Thermodynamics Page 8