GET 206 – FUNDAMENTALS OF THERMODYNAMICS

LECTURE NOTE 3

1. Reversible and Irreversible Processes

Reversible processes and irreversible processes are fundamental concepts in thermodynamics that
describe how energy and matter behave within a system.
❖ Reversible Processes:
Definition: Reversible processes are idealized processes that can be reversed at any point without
leaving any impact on the surroundings or the system itself. A reversible process occurs when a
system changes its state and passes through a continuous series of thermodynamic states such that
both the system and its surroundings can be restored to their original state.
For a system to undergo a reversible process, it must have passed through a series of
thermodynamic equilibrium state points that can be joined up to form a continuous line on a
diagram of properties.
They are characterized by minimal entropy generation and are often used as theoretical
benchmarks in thermodynamics.
Examples:
• Ideal Gas Expansion: When an ideal gas expands or compresses slowly enough that it can
be considered in equilibrium at every stage, it approximates a reversible process.
• Isothermal Expansion of an Ideal Gas: In this process, the gas expands at a constant
temperature, and if it's done infinitely slowly, it approaches reversibility.
• Reversible Electrical Work: Reversible electrical processes in circuits without resistance,
where there are no energy losses due to heat dissipation.
• Reversible Chemical Reactions: Certain chemical reactions can be considered reversible
under specific conditions, such as the reversible reaction between hydrogen and iodine to
form hydrogen iodide.
• Ideal Heat Transfer: Heat transfer processes that occur at infinitesimally small
temperature differences between the system and its surroundings, resulting in reversible
heat exchange.
 ❖ Irreversible Processes:
Definition: Irreversible processes are real-world processes that cannot be reversed completely
without leaving a change in the system or its surroundings. They are characterized by entropy
generation, energy dissipation, or irreversible changes.
Examples:
• Free Expansion of a Gas: When a gas expands rapidly into a vacuum, it undergoes an
irreversible process because the expansion is not controlled, and no work is done on the
surroundings.
• Frictional Heating: Mechanical processes involving friction, such as rubbing hands
together, generate heat that cannot be completely recovered as useful work, making it an
irreversible process.
• Chemical Combustion: Combustion reactions, such as burning fuel, release energy in a
way that cannot be fully converted back into the original chemical energy, making it
irreversible.
• Heat Transfer Across a Finite Temperature Difference: Heat transfer between two
bodies at different temperatures through a finite temperature gradient result in
irreversibilities due to heat loss or gain.
• Mixing of Different Substances: Mixing of substances can lead to entropy increase and
irreversible changes, as seen in mixing hot and cold water.
Understanding these concepts helps in analyzing the efficiency of processes, predicting energy
losses, and designing systems for optimal performance.

2.1 Ideal and Real Gases

Pure Substance: A pure substance is one that has a homogeneous and invariable chemical
composition.
It may exist in more than one phase but the chemical composition is the same in all phases.
Sometimes the mixture of gases, such as air is considered a pure substance as long as there is no
change of phase. Further, our emphasis will be on simple compressible substances
Early experiments on the variables of state (such as T, P, V, and n) showed that only two of these
variables of state need to be known to know the state of a sample of matter.
Extensive variables: depend on the amount of substance present. Examples include the volume,
energy, enthalpy, and heat capacity, oxygen gas (O2)
Intensive variables: do not depend on the amount of substance present. Examples include
temperature and pressure.
2.2 Pressure
The pressure is the force exerted by a fluid per unit area.
𝐹𝑜𝑟𝑐𝑒 𝑁
𝑃𝑟𝑒𝑠𝑠𝑢𝑟𝑒 = = 2 = 𝑃𝑎
𝐴𝑟𝑒𝑎 𝑚
In fluids, gases, and liquids, we speak of pressure; in solids this is stress. For a fluid at rest,
the pressure at a given point is the same in all directions.
𝑊𝑒𝑖𝑔ℎ𝑡 𝑜𝑓 𝑙𝑖𝑞𝑢𝑖𝑑
𝑃=
𝐴𝑟𝑒𝑎
z h 𝑚𝑔 𝜌Ah𝑔
𝑃= =
P(z) 𝐴 𝐴

Area = A 𝑃= 𝜌h𝑔
A

Fig. 8: Pressure of a fluid at rest increases with depth (due to added weight), but constant
in horizontal planes.

The actual pressure at a given position is called the absolute pressure, and it is measured
relative to the absolute vacuum.
gauge pressure = absolute pressure ‐ atmospheric pressure

𝑃𝑔𝑎𝑢𝑔𝑒 = 𝑃𝑎𝑏𝑠 − 𝑃𝑎𝑡𝑚 𝑃 > 𝑃𝑎𝑡𝑚

𝑃𝑔𝑣𝑎𝑐 = 𝑃𝑎𝑡𝑚 − 𝑃𝑎𝑏𝑠 𝑃 < 𝑃𝑎𝑡𝑚

P
𝑃𝑔𝑎𝑢𝑔𝑒

𝑃𝑣𝑎𝑐 𝑃𝑎𝑡𝑚 𝑃𝑎𝑏𝑠

Fig. 9: Absolute, gauge, and vacuum pressures. Absolute (vacuum) =0

In thermodynamics calculations, always use absolute pressure. Most pressure measuring devices
are calibrated to read zero in the atmosphere (they measure Pgauge or Pvac). Be aware of what you
are reading!
A device that measures pressure using a column of liquid is called a Manometer. The cross-
sectional area of the tube is not important. The manometer measures the gauge pressure.

Fig. 10: Basic manometer, P2=P1.

𝑃1 = 𝑃𝑎𝑡𝑚 + 𝜌𝑔ℎ (𝑘𝑃𝑎)

Bourdon Tube is a device that measures pressure using mechanical deformation. Pressure
Transducers are devices that use piezoelectric to measure pressure.
very accurate and robust
can measure from 10‐6 to 105 atm
can measure Pgauge or Pabs
The barometer is a device that measures atmospheric pressure. It is a manometer with a near
vacuum on one end
Fig. 11: Burdon gauge.

Example 1: Pressure
The piston of a cylinder‐piston device has a mass of 60 kg and a cross‐sectional area of 0.04 m 2,
as shown in Fig. 12. The depth of the liquid in the cylinder is 1.8 m and has a density of 1558
kg/m3. The local atmospheric pressure is 0.97 bar, and the gravitational acceleration is 9.8 m/s 2.
Determine the pressure at the bottom of the cylinder.

Solution: the pressure at the bottom of the cylinder can be found from the summation of the forces
due to atmospheric pressure, piston weight, and the weight of the liquid in the cylinder.

𝑊𝑏𝑜𝑡𝑡𝑜𝑚 = 𝑃𝑎𝑡𝑚 𝐴 + 𝑊𝑙𝑖𝑞𝑢𝑖𝑑 + 𝑊𝑝𝑖𝑠𝑡𝑜𝑛

𝑚𝑔
𝑃𝑏𝑜𝑡𝑡𝑜𝑚 = 𝑃𝑎𝑡𝑚 + + 𝜌𝑔ℎ
𝐴

(60𝑘𝑔 𝑥 9.8 𝑚⁄𝑠 2 ) 𝑘𝑔⁄

𝑃𝑏𝑜𝑡𝑡𝑜𝑚 = 0.97(𝑏𝑎𝑟) + { + (1558 𝑚 (1.8 𝑚)}
0.04𝑚2 𝑚2 ) (9.8 ⁄𝑠 2 )
 1 𝑁⁄𝑚2 1𝑏𝑎𝑟
⌊( )( ) = 1,3918 𝑏𝑎𝑟𝑠⌋
𝑘𝑔⁄ 102 𝑁⁄
1 𝑚𝑠 2 𝑚2

𝑃𝑎𝑡𝑚 = 0.97 𝑏𝑎𝑟

𝑚𝑝𝑖𝑠𝑡𝑜𝑛 = 60𝑘𝑔

𝐴 = 0.04 𝑚2 ℎ = 1.8𝑚
P=?

Fig. 12: Sketch for example 2.

2.3 Equations of State

An equation of state is an equation that relates the variables of state (T, P, V, and n). It's particularly
useful when you want to know the effect of a change in one of the variables of state

Solids and Liquids: If the pressure on a solid or liquid is increased, the volume does not change
much. If the temperature is increased, the volume doesn't change much either. Therefore, an
appropriate equation of state describing such systems would be: V(T, P) = constant.

Gases: In contrast, changing the pressure or temperature of a gas will have an easily observable
effect on the volume of that gas. For an ideal gas (no intermolecular interactions and no molecular
volume) n appropriate equation of state would be: V(T,P,n) = (nRT)/P.

There are many equations of state describing real gases. These equations take into consideration
molecular volume and interactions. The most well-known such equations are probably the Van der
Waals equation.
Ideal and real gases
An ideal gas is one that follows the ideal gas equation of state, namely
PV = (m/M) (MR) T = n Ru T
The universal gas constant has a value of 8.314 J/mol K or kJ/kmol K and is related to the specific
gas constant by the relation Ru = (R /M)

The ideal gas equation of state can be derived from the kinetic theory of gases where the following
assumptions are made:
1. The molecules are independent of each other. In other words, there are no attractive forces
between the molecules.
2. The molecules do not occupy any volume. That is the volume occupied by the molecules is quite
negligible compared to the volume available for the motion of the molecules.

The internal energy of an ideal gas is a function of temperature only and is independent of pressure
and volume. That is,
u= u(T)
 (∂u/∂P)T =0, (∂u /∂v)T = 0

2.6 Enthalpy and specific heat

h = u+ Pv
For an ideal gas u = u(T) only and PV = mRT and hence h = h(T) only.

The specific heat at constant volume is defined as the amount of energy transferred as heat at
constant volume, per unit mass of a system to raise its temperature by one degree. That is,

Cv = (ɗq/ɗT)v
The specific heat at constant pressure is defined as the energy transferred as heat at constant
pressure, per unit mass of a substance to raise its temperature by one degree. That is

Cp = (dh/dT)P
For a constant pressure process
dq = du + dw
= du + Pdv
= du+ Pdv +vdP
(since dP=0 for a constant pressure process)
Or
dq= du+d(Pv)
= d(U+ Pv) = dh
or
dq=dh
CP = (∂h/∂T)P
The ratio of specific heat (γ) is given by
γ= C P/Cv

For mono-atomic ideal gases γ = 1.67 and diatomic gases γ= 1.4.

Relation between two specific heats:
The two specific heats are related to each other.
Relationship between C v and C p

C v - Specific capacity of constant volume

C p - Specific capacity at constant pressure

C p = Cv + R Eqn. (1)

PV = C Eqn. (2)

Cp
 = Eqn. (3)
Cv

C p =  Cv Eqn. (4)

Cp
Also, CV = Eqn. (5)


C p =  Cv Eqn. (6)

Substitute Eqn. (6) into Eqn. (1)

C p = Cv + R

Cv = C v + R

Cv − Cv = R

Cv ( − 1) = R

R
Cv =
 −1
From Eqn. (5)

Cp
Cv =


R Cp
=
 −1 
R = C p ( − 1)

R
Cp =
( − 1)

Real gases:
The ideal gas law is only an approximation to the actual behavior of gases.
At high densities, that is at high pressures and low temperatures, the behavior of actual or real
gases deviates from that predicted by the ideal gas law. In general, at sufficiently low pressures or
at low densities all gases behave like ideal gases.
FIRST LAW OF THERMODYNAMICS
The first law of thermodynamics states that energy cannot be created nor destroyed it can only be
changed from one form to another. Another name for this law is the law of conservation of energy.
This means that the total energy of a system plus its surroundings is constant and does not change.
Energy can, however, be transferred in or out of the system and to or from the surroundings through
work or heat.

Conservation of Energy
Energy may be defined as the capacity to do work or to cause heat to flow. In the system term,
energy may be defined as the property of a system that changes by an amount equal to the work or
heat transferred across the system boundary. The total amount of energy that a system contains
cannot be determined. We are accustomed therefore to measuring energy above some arbitrary
datum. Energy is a scalar quantity with no direction relative to the frame of reference. It can exist
in different forms, in principle, all forms of energy are mutually convertible. There is a transfer or
flow of energy when a change in form takes place.

The first law of thermodynamics is the thermodynamic expression of the law of conservation of
energy.

Corollaries of the First law

1. Exist Property of a system is equal to the difference between the heat and workdone in a
system.
∫dQ from system= ∫dW on system or ∫dQ from system- ∫dW on system = 0
2. In an isolated system, there is no heat or work transfer therefore there’s no change in the
internal energy of the system.
dE = ∫dQ -∫dW
This is called internal energy because Kinetic and potential energy are negligible.
An isolated system does not exchange energy with the surroundings in the form of work as well
as heat.
Hence dQ = 0 and dW = 0. Then the first law of thermodynamics reduces to dE = 0 or E2 = E1 that
is energy of an isolated system remains constant.
3. It’s impossible for a system to perform work without any heat transfer into the system
(Perpetual Motion machine).
An imaginary device that delivers work continuously without absorbing energy from the
surroundings is called a Perpetual Motion machine of the first kind. Since the device has to deliver
work continuously, it has to operate on a cycle. If such a device does not absorb energy from its
surroundings ∫dQ =0. From the first law, it can be observed that ∫dW =0, if ∫ dQ = 0. Therefore
such a device is impossible from the first law of thermodynamics.

3.2 First law analysis of non-flow processes

The first law of thermodynamics can be applied to a system to evaluate the changes in its energy
when it changes state while interacting with its surroundings. The processes that are usually
encountered in thermodynamic analysis of systems can be identified as any one or a combination
of the following elementary processes:
(i) Constant volume (isochoric) process
(ii) Constant pressure (isobaric) process
(iii) Constant temperature (isothermal) process.
(iv) Adiabatic process.

3.5 Constant volume process

Suppose a gas enclosed in a rigid vessel is interacting with the surroundings and absorbs energy Q
as heat.
Since the vessel is rigid, the work done W due to expansion or compression is zero. Applying the
first law, we get
dU = dQ or Q = U2 –U1
That is, heat interaction is equal to the change in the internal energy of the gas. If the system
contains a mass m equal to an ideal gas, then

Q = ΔU = mCv (T2 –T1)

The path followed by the gas is shown on a P-V diagram. Now consider the fluid contained in a
rigid vessel as shown. The vessel is rigid and insulated. Shaft work is done on the system by a
paddle wheel.
Constant volume process involving electrical work:
- Ws = U2- U1

Since the vessel is rigid, the PdV work is zero. Moreover, the vessel is insulated, and hence dQ =
0.
Application of the first law of thermodynamics gives
dU = dQ – dW
= dQ – (dWpdv + dWs)
or

dU = -dWs or – Ws = ΔU = U2 –U1

Where dWpdv is the compression /expansion work and dWs is the shaft work. That is increase in
internal energy of a system at a constant volume, which is enclosed by an adiabatic wall, is equal
to the shaft workdone on the system.

3.6 Constant pressure process

Several industrial processes are carried out at constant pressure. A few examples of constant
pressure processes are: (a) reversible heating/cooling of a gas (b) phase change (c) paddlewheel
work (d) electrical work. For a constant pressure process, the work done W is given by
W = ∫PdV = P (V2-V1)

Application of the first law of thermodynamics gives

2
𝑊 = 𝑃 ∫ 𝛿𝑉
1

𝑊 = 𝑃[𝛿𝑉]12
𝑊 = 𝑃(𝑉2 − 𝑉1 )
From the first law,
𝛿𝑢 = 𝛿𝑄 − 𝛿𝑊 = 𝛿𝑄 − 𝑃𝛿𝑉
\or dQ = dU + d(PV) = d(U + PV) = dH

or Q = ΔH

That is in a constant pressure process, the heat interaction is equal to the increase in the enthalpy
of the system. Now consider the constant pressure processes in which the system is enclosed by
an adiabatic boundary. Application of the first law gives:
dU = dQ – dW = dQ – (PdV + dWs)
Here, the net work done (dW) consists of two parts – the PdV work associated with the motion of
the boundary and (-dWs), the shaft work (or electrical work) done by the surroundings. Since the
system is enclosed by an adiabatic boundary, dQ = 0 the equation can be written as

-dWs = dU + d(PV) = dH
That is, the increase in the enthalpy of the system is equal to the shaft work done on the system.

3.7 Constant temperature process

Suppose a gas enclosed in the piston-cylinder assembly is allowed to expand from P1 to P2 while
the temperature is held constant. Then an application of the first law gives:

dU = dQ – dW = dQ –PdV
It is not possible to calculate work and heat interactions unless the relationships between the
thermodynamic properties of the gas are known. Suppose the gas under consideration is an ideal
gas
(which follows the relation Pv = RT and u = u(T) only) then for an isothermal process,

2
W =  Pdv − − − − − (1)
1

PV = C − − − −(2)
c
P = − − − − − (3)
v
Sub eqn (3) into (1)
2
c
W =  dv − − − (4)
1
v
2
1
W = c  dv − − − −(5)
1
v

Integrating eqn (5)

W = cIn(V )v12 − − − −(6)
v

  v 
W = c  In 2  − − − −(7)
  v1 
But, c = Pv
c = P1v1 = P2v2 − − − − − (8a)
P1 v1
= − − − − − (8b)
P2 v2
Sub eqn (8a) into (7)
  v    v 
W = P1v1  In 2  = P2v2  In 2  − − − − − (9)
  v1    v1 
Also, sub eqn (8b) into (9)
  P    P 
W = P1v1  In 2  = P2v2  In 2  − − − − − (10)
  P1    P1 
But, PV=RT
   v    P 
Therefore; W = RT  In 2  = RT  In 2  − − − − − (11) QED
  v1    P1 

3.8 Reversible adiabatic (Isentropic process)

Polytropic Process
2
W =  Pdv − − − − − − − (1)
1

Pv = c − − − − − − − − − (2)
n

c
P = n − − − − − − − − − (3)
v
Sub eqn (3) into (1)
2
c
W = n
dv − − − − − − − (4)
1
v
2
1
W = c dv − − − − − − − −(5)
1
vn

Integrating eqn (5)

v2 v2
 v − n +1   cv − n +1 
W = c  = W =  − n + 1 − − − − − −(6)
 − n + 1 v1   v1

 cv − n +1 − cv1− n +1 
W = 2  − − − − − − − (7 )
 − n +1 
But, c = Pvn--------------- (8a)
Pv1n= Pv2n------------------(8b)
Sub. Eqn (8b) into (7)
 P v − n +1 − P1v1− n +1 
W = 2 2  − − − − − − − (9)
 − n +1 
 P v − Pv 
W =  2 2 1 1  − − − − − − − (10)
 − n +1 
For reversible isentropic,
  P v − P1v1 
W = − 2 2  − − − − − − − (11a)
 − n +1 
 P v − P2 v 2 
W = 1 1  − − − − − − − (11b)
 n −1 
For heat supplied
u2 − u1 = Cv T2 − T1  = q − w − − − −(1)
RT2 − T1  p1v1 − p2v2
q= + − − − − − (2)
 −1 n −1
 1 1 
= RT2 − T1  −  − − − − − −(3)
 (n − 1) ( − 1)
p v − p2v2
= 11 − − − − − − − (4)
 − n 
n − 1 
  −1 
 − n 
q = w  QED
  −1 
Derive temp, volume and pressure under adiabatic process
From the First Law of Thermodynamics,

Q = W + (U 2 − U 1 )

Where,
Q = Heat transfer

W = Work done
U = Internal Energy
For Isothermal process;

U = (U 2 − U 1 ) = 0

Q =W

In adiabatic process;
Q=0

PV  = C -----Governing law
 Cp
 = Eqn. (1)
Cv

W =  Pu
2
Eqn. (2)
1

Since entropy is constant

C
P= Eqn. (3)
V
Substituting eqn. (3) into (2)

C
W =
2
V
1 V

1
W = C
2
V
1 V

W = C  ln V − V
2

2
V 1− 
W = C  Eqn. (4)
1 −   1

From the governing law

C = PV 

V   V 1− 
2
V 1− 
W = PV    
V  +1− = V 
1 −   1  
2
 PV 
W = 
1 −   1

P2V2 − P1V1
W= Eqn. (5)
1− 

For Adiabatic Process Q = 0

Q = W + (U 2 − U 1 )

0 = W + (U 2 − U 1 )

− W = U 2 − U1 Eqn. (6)
Substitute Eqn. (5) into (6)

 P V − P1V1 
− 2 2  = U 2 − U1 Eqn. (7)
  −1 

At constant volume,

U = Cv T

Relationship between Temperature & Volume

From the Ideal gas equation;

P1V1 P2V2
=
T1 T2

P1V1T2 = P2V2T1

V2 P1T2
= Eqn. (5)
V1 P2T1

Substitute Eqn. (5) into (4)

 −1
T1  V2 
= 
T2  V1 
 −1
T1  P1T2 
= 
T2  P2T1 

 −1  −1
T1  P1  T 
=    2 
T2  P2   T1 
 −1 − ( −1)
T1  P1  T 
=    1 
T2  P2   T2 

Collect like terms

 −1  −1
 T1   T1  P 
     =  1 
 T2   T2   P2 
  −1 
 P1  T 
  =  1 
 P2   T2 

Relationship between Pressure and Temperature

 −1
T1  P1  
= 
T2  P2 

Continuity,
 −1
 −1
T1  P1   V 
=  =  2 
T2  P2   V1 