Thermodynamics

Thermodynamics is the study of the flow of heat or any other form of energy into or out of a
system as it undergoes a physical or chemical transformation.
In studying and evaluating the flow of energy into or out of a system it will be useful to
consider changes in certain properties of the system.
 Scope of Thermodynamics

 It tells whether a particular physical or chemical change can occur under

a given set of conditions of temperature, pressure and concentration.
 It also helps in predicting how far a physical or chemical change can
proceed until the equilibrium conditions are established.
 Limitation of Thermodynamics

 Thermodynamics is applicable to macroscopic systems. It ignores the

internal structure of atoms.
 Thermodynamics does not bother about the time factor. It is concerned
only with the initial and final states of the system.
 Basic Thermodynamic Terms

 System is that part of the universe which is under thermodynamic study

 The rest of the universe is surroundings.
 The real or imaginary surface separating the system from the surroundings
is called the boundary.
 Thermodynamic Systems

Three types of thermodynamics systems.

I. Isolated system: It is one that can transfer neither matter nor energy to and
from its surroundings.
II. Closed system: It is one which can’t transfer matter but can transfer energy
in the form of heat, work and radiation to and from its surroundings.
III. Open system: It is one that can transfer both matter and energy to and
from its surroundings.
Thermodynamic Systems
Heat Flow

 Exothermic process: Heat flows out of system to surroundings (q < 0).

 Endothermic process: Heat flows into system from surroundings(q > 0).
 Sign convention of the system:
 If energy enters the system, its sign is positive.(+q)
If energy leaves the system, its sign is negative.(-q)
If work is done on the system, its sign is positive.(+w)
If work is done by the system, its sign is negative (-w)
Heat:
• Energy transferred between objects because of a
difference in their temperatures.
Work: w = F × d
• Work (w) is done when a force (F) moves an
object through a distance (d).
Two types of Energy:

 Potential energy
 Potential energy is stored energy and the energy of position.
 Example: Chemical Energy, Mechanical energy, Nuclear energy

 Kinetic energy
 Kinetic energy is the motion of waves, electrons, atoms, molecules,
substances, and objects.
 Example: Radiant energy, Thermal energy, Motion energy
 Potential: due to position or composition:
 • Can be converted to work: PE = m × g × h
 » m = mass, g = force of gravity, and h = vertical distance

 • Chemical energy = a form of potential energy

 Kinetic: due to motion of the object
 • KE = 1/2 mu2

 (m = mass, u = velocity)
 Example: 2 kg hammer is 0.4 m up. What is it's PE?
 PE =m g h
 =2 kg × 9.8 m/s2 × 0.4 m
 =7.84 kg m2/s2
 =7.84 J
 Example: What is the KE of a 1500 kg car going at suburban speed of 14
m/s ?
 KE = ½ m v2
 KE = ½ × 1500 kg × (14 m/s)2
 KE = 147,000 kg m2/s2
 KE = 147 kJ
The same car is now going at highway
speed of 28 m/s…. What is the K.E?

A 1 kg meteorite strikes the Moon at 11

km/s. How much KE is that?
 We drop this 0.1 kg apple 1 m. What is the
P.E?
 Thermodynamic State

 A thermodynamic system is said to be in a certain state when all its properties are
fixed.
 The fundamental properties which determine the state of a system are pressure (P),
temperature (T), volume (V), mass and composition.
 For pure gas, the composition is fixed and so the equation of the state is-
PV=nRT,
n=mole number.
 Thermodynamic Process

The operation is called a process when a thermodynamic system changes from one
state to another. There are various types of processes
o Isothermal process
The process in which the temperature remains fixed is called the isotherm process.
So for the isotherm process,
dT=0
o Adiabatic Process
The process in which no heat flows into or out of the system is called the adiabatic
process. So for the adiabatic process,
dq=0
 Thermodynamic Process

o Isobaric process
The process in which the pressure remains fixed is called the isobbaric process. So the
isobaric process,
dp=0
o Adichoric Process
The process in which the volume remains fixed is called the isochoric process. So the
isochoric process,
dV=0
o Cyclic Process
The process that goes through several different processes and finally returns to its initial
state is called a cyclic process. So for the cyclic process,
dE=0
 Reversible Process: A thermodynamic process (state i → state f ) is said to
be reversible if the process can be turned back to such that both the
system and the surroundings return to their original states, with no other
change anywhere else in the universe.
 Example:
 extension of springs
 the frictionless motion of solids
 slow isothermal compression or expansion of gases
 Irreversible Process: An irreversible process can be defined as a process in
which the system and the surroundings do not return to their original
condition once the process is initiated.

Example:
The friction that converts the energy of the fuel to heat energy
Mixing of two different substances that cannot be separated
 Equilibrium State: A system in which the state variables have constant
values throughout the system………

 Non Equilibrium State: A system in which the state variables have different
values in different parts of the system……..
Criteria of equilibrium:

 Temperature of the system

 Mechanical Properties
 Chemical composition
Internal Energy:

 The total of all the possible kinds of energy of a system, is called its internal
energy.
 The internal energy of a system is determined by the state of a system and
it is independent of the path by which it is obtained.
 Example: Heating of 1 mole of liquid water from o to 100 degree celcius
 First Law of Thermodynamics

 The total energy of an isolated system remains constant though it may change from one
form to another.
 When a system is changed from state A to state B, it undergoes a change in the internal
energy from EA to EB. Thus, we can write,
ΔE= EA – EB
➢ This energy change is brought about by the evolution or absorption of heat and/or by
work being done by the system. So the total energy must remain constant. We can write
the mathematical term of the first law as: the net energy change of a closed system is
equal to the heat transferred to the system minus the work done by the system
ΔE=q-w
Where q= the amount of heat supplied to the system
w= work done by the system
 The gas expands against an applied constant pressure by volume dv. So
the total mechanical work is done by given equation:
 W=PdV
 So from first equation we get
 dW=q-PdV
 Enthalpy:
 quantity of heat in a system.
 is equal to the sum of internal energy of such a system with the constant.
 The total heat content of a system, at constant pressure, is equivalent to
the internal energy E plus the PV energy
 H=E+PV
 Entropy:
 Thermodynamic state of quantity that is a measure of the randomness or
disorder of the molecules of the system.
 A process accompanied by an increase in entropy is spontaneous
process.
Second law of thermodynamics:

 Whenever a spontaneous process takes place, it is accompanied by an

increase in the total energy of the universe.
 One simple statement of the law is that heat always moves from hotter
objects to colder objects (or "downhill"), unless energy is supplied to
reverse the direction of heat flow.
 Another definition is: "Not all heat energy can be converted into work in
a cyclic process.“
 The second law of thermodynamics says, in simple terms, entropy always
increases. This principle explains, for example, why you can't unscramble
an egg.