Scribd
Upload
25 views18 pages

THERMODYNAMICS

Uploaded by

N Nikisha
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
25 views18 pages

THERMODYNAMICS

Uploaded by

N Nikisha
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PPTX, PDF, TXT or read online on Scribd
You are on page 1/ 18

THERMODYNAMI

CS
S. VEDHA
P.G.ASSISTANT IN CHEMISTRY
Introduction
• 'Thermodynamics' means flow of heat.
• The study of the transformation of energy.
• The principles of thermodynamics based on three laws of
thermodynamics.
• The first two laws (First and second law) summarize the actual experience
of interconversion of different forms of energy.
• The third law deals with the calculation of entropy and the unattainability
of absolute zero Kelvin.
SYSTEM,SURROUNDING AND
BOUNDARY
The universe into two parts, the system and its
surroundings.
System
• The system is the part of universe which is under
thermodynamic consideration.
• It is separated from the rest of the universe by real or
imaginary boundaries.
Surrounding:
• Everything in the universe that is not the part of the
system is called surroundings.
Types of systems
• Isolated system: A system which can
exchange neither matter nor energy with
its surroundings is called an isolated
system.
• Closed system: A system which can
exchange only energy but not matter
with its surroundings is called a closed
system.
• Open system: A System which can
exchange both matter and energy with
its surrounding is called an open system.
Properties of the system:
• Extensive properties: The property that
depends on the mass or the size of the system is
called an extensive property.
• Examples: Volume, Number of moles, Mass,
Internal energy, etc.,
• Intensive properties: The property that is
independent of the mass or the size of the system
is called an intensive property.
• Examples : Refractive index, Surface tension,
density, temperature, Boiling point, Freezing
point, molar volume, etc.,
Types of
processes:
• Reversible process:
The process in which the system and
surrounding can be restored to the
initial state from the final state without
producing any changes in the
thermodynamic properties of the
universe is called a reversible process.
• Irreversible Process: The process in
which the system and surrounding
cannot be restored to the initial state
from the final state is called an
irreversible process.
Types of
processes
• Adiabatic process:
An adiabatic process is defined as one in which there is
no exchange of heat (q) between the system and
surrounding during the process.
Those processes in which no heat can flow into or out
of the system are called adiabatic processes. q = 0
• Isothermal process :
An isothermal process is defined as one in which the
temperature of the system remains constant, during the
change from its initial to final state.
dT = 0
Type of
processes
• Cyclic process :
When a system returns to its original state after completing a series of changes, then it is
said that a cycle is completed. This process is known as a cyclic process.
For a cyclic process dU = 0, dH = 0, dP=0, dV=0, dT=0
• Isobaric process :
An isobaric process is defined as one in which the pressure of the system remains constant
during its change from the initial to final state. dP= 0
• Isochoric process
An isochoric process is defined as the one in which the volume of system remains constant
during its change from initial to final state. dV= 0
State and path functions
• A state function is a property whose
value does not depend on the path
taken to reach that specific value.
Example : Pressure (P), Volume (V),
Temperature(T), Internal energy (U), Enthalpy
(H), free energy (G) etc.
• In contrast, functions that depend on
the path from two values are call path
functions.
Example: Work (w), Heat (q).
Internal energy
Internal Energy (U)
• The internal energy is a characteristic property of a
system which is denoted by the symbol U.
• The internal energy of a system is equal to the
energy possessed by all its constituents namely
atoms, ions and molecules.
• The total energy of all molecules in a system is
equal to the sum of their translational energy
(Ut ), vibrational energy (Uv), rotational energy (Ur ),
bond energy (Ub), electronic energy (Ue) and energy
due to molecular interactions (Ui ).
• U = Ut + Uv + Ur + Ub+ Ue+ Ui
Characteristics of internal energy
(U):
• The internal energy of a system is an extensive property.
It depends on the amount of the substances present in the system. If the amount is doubled,
the internal energy is also doubled.
• The internal energy of a system is a state function. It depends only upon the state variables
(T, P, V, n) of the system. The change in internal energy does not depend on the path by
which the final state is reached.

• The change in internal energy of a system is expressed as ΔU= Uf – Ui • In a cyclic process,


there is no internal energy change. ΔU(cyclic) = 0 • If the internal energy of the system in the
final state (Uf ) is less than the internal energy of the system in its initial state (Ui ), then ΔU
would be negative. ΔU=Uf − Ui = −ve (Uf < Ui )
• If the internal energy of the system in the final state (U f ) is greater than the internal energy
of the system in its initial state(Ui ), then ΔU would be positive. ΔU=U f − Ui = +ve (Uf > Ui )
Zeroth law of thermodynamics:
• The law states that `If two systems are separately in
thermal equilibrium with a third one, then they tend
to be in thermal equilibrium with themselves’.
• Application
Usage of thermometers
First Law of Thermodynamics:
• "Energy can neither be created nor
destroyed, but may be converted from one
form to another“.
Applications
• An electric light bulb transforms electric
energy into light energy.
• Plants convert the radiant energy of the
sunlight into chemical energy.
• The chemical energy stored in the body is
transformed into kinetic energy when we
walk, run and swim.
Hess’s law of constant heat
summation
• The enthalpy change of a reaction either at constant volume or constant pressure is
the same whether it takes place in a single or multiple steps provided the initial and
final states are same.

• Application of Hess's Law:


Hess's law can be applied to calculate enthalpies of reactions that are difficult to
measure.
Lattice energy (ΔHlattice)
• Lattice energy is defined as the amount of energy required to completely
remove the constituent ions from its crystal lattice to an infinite distance
from one mole of crystal. It is also referred as lattice enthalpy.
• NaCl(s) → Na+(g) + Cl–(g) ΔHlattice = + 788 kJ mol-1
Born - Haber cycle:
• The Born–Haber cycle is an approach to analyze reaction energies.
• Born–Haber cycle is primarily used in calculating lattice energy, which
cannot be measured directly.
Various statements of the second
law of thermodynamics
• Entropy
• Entropy is a measure of the molecular
disorder (randomness) of a system
• dS = dqrev / T
Kelvin-Planck statement:
• It is impossible to construct a machine that
absorbs heat from a hot source and
converts it completely into work by a cyclic
process without transferring a part of heat
to a cold sink
Various statements of the second
law of thermodynamics
• Clausius statement:
This statement recognizes that heat flows spontaneously from hot objects
to cold objects and to get it flow in the opposite direction, we have to
spend some work.
• Entropy statement: “whenever a spontaneous process takes place, it is
accompanied by an increase in the total entropy of the universe”.
Application
• Refrigerator and Air conditioner.
Gibbs free energy (G)
• One of the important applications of the second law of thermodynamics is to
predict the spontaneity of a reaction under a specific set of conditions.
• ΔG =ΔH – T ΔS
• Criteria for spontaneity of a process
• The spontaneity of any process depends on three different factors.
• If the enthalpy change of a process is negative, then the process is exothermic
and may be spontaneous. (ΔH is negative)
• If the entropy change of a process is positive, then the process may occur
spontaneously. (ΔS is positive).
• The gibbs free energy which is the combination of the above two (ΔH -TΔS)
should be negative for a reaction to occur spontaneously, i.e. the necessary
condition for a reaction to be spontaneous is ΔH -TΔS < 0

You might also like