THERMODYNAMIC PROPERTIES

Thermodynamic properties are characteristics or attributes of a system that help

describe its state and behaviour in terms of temperature, pressure, volume, and
other relevant variables. These properties play a crucial role in the field of
thermodynamics, which is the study of energy and its transformations.
There are two sorts of thermodynamic properties.
1. Intensive properties
2. Extensive properties
1. Intensive properties: The properties which are independent of the mass of
the system is called intensive properties. Example: Temperature, pressure,
density, specific extensive properties are the intensive properties.
2. Extensive properties: The properties which are dependent of the mass of
the system is called extensive properties. Example: Total mass, total
volume, enthalpy, entropy etc.

Intensive properties Extensive properties

Temperature Mass
pressure Volume
density Enthalpy
specific extensive properties Entropy

Pressure: Pressure is a measure of the force exerted per unit area on the
boundaries of a substance (or system). The unit of pressure in SI units is Pascal.
1 Pa equals 1 N/m².
Gauge pressure
Atmospheric pressure (101.325 kPa/ 760 mm of Hg)
Absolute pressure
Temperature: Temperature is a measure of the average kinetic energy of the
particles in a substance. In simpler terms, it reflects how hot or cold a substance
is. In SI Units, temperature is measured in kelvin (K). The relationship between
temperature and kinetic energy is a fundamental concept in thermodynamics.
Absolute zero temperature
Absolute zero is the lowest temperature possible. At a temperature of absolute
zero there is no motion and no heat. Absolute zero occurs at a temperature of 0
degrees Kelvin, or -273.15 degrees Celsius
Enthalpy: Enthalpy is a thermodynamic quantity that represents the total heat
content of a system. It is the sum of the internal energy of the system and the
product of pressure and volume. Enthalpy is often used to describe the heat flow
in processes that occur at constant pressure.
H=U+ pv,
where U is the internal energy, ‘p’ is pressure, and ‘v’ is volume.
GAS LAWS
1. Boyle’s law. Boyle’s law states that the volume of a given mass of a perfect
gas varies inversely as the absolute pressure when temperature is constant.
1
P ∝ when T = c
𝑣
This can be expressed as: pv=constant

Or P1V1=P2V2
2. Charle’s law

Charles law states that the volume of a given mass of a perfect gas varies directly
as its absolute temperature when the pressure is constant.
V∝T
𝑉1 𝑉2
Or =
𝑇1 𝑇2

3. Joule's Law
Joule's Law states that, "The change of internal energy of a perfect gas is directly
proportional to the change of temperature."
Mathematically,
dU ∝dT
or
dU = m c dT
where
m = Mass of the gas, and
c = A constant of proportionality, known as specific heat.
4. Avogadro’s law
Avogadro's law states that "equal volumes of all gases, at the same
temperature and pressure, have the same number of molecules
𝑉
=C
𝑛
𝑉1 𝑉2
=
𝑛1 𝑛2
Characteristic Gas Equation (Derivation)

In actual practice, three thermodynamic variables (p, V & T) change simultaneously.

Therefore, Boyle's law & Charle's law are combined to get relationship between p, V & T.
So the equation derived is known as combined gas law. Let a given mass expands from
state-1 to state-2 according to Boyle's law. Further it expands from state-2 to state-3
according to Charle's law.
Apply Boyle's law to process 1-2.
p1V1 = p2V2 When T1 = T2
p1V1
or V2 = ………….… (1)
𝑝2

Apply Charle's law to process 2-3

V2 V3
= When p2 = p3
𝑇2 𝑇3

V3T2
V2 = ………… (2)
𝑇3
Combining equations (1) and (2)
p1V1 V3T2
V2 = =
𝑝2 𝑇3

Or
 p1V1 p2V3
= ……… (3)
𝑇2 𝑇3
But, T1 = T2 and p2 = p3
p1V1 p3V3
=
𝑇1 𝑇3

Or
p1V1 p2V2 p3V3
= =
𝑇2 𝑇2 𝑇3

Or
pV
= Constant,
𝑇
This equation is known as general gas equation and the constant depends upon the
mass of the gas.
pV
= R, Where, R is known as Characteristic gas constant
𝑇
Or
pV = RT (for unit mass)
pV = nRT (n= No. of moles) ……. Mole basis
pV = mRT (for m kg mass) …… Mass basis
Unit of R in SI units is kJ/kg K
SPECIFIC HEAT
It is the amount of heat energy required to raise the temperature of a unit mass of a
substance by (1 0C or 1K). Unit kJ/kg K
a. Specific heat at constant pressure (Cp)
It is the amount of heat energy required to raise the temperature of a unit mass of a
substance by (1 0C or 1K), when its pressure kept constant.
b. Specific heat at constant Volume (Cv)
It is the amount of heat energy required to raise the temperature of a unit mass of a
substance by (1 0C or 1K), when its volume kept constant.
RELATIONSHIP BETWEEN SPECIFIC HEATS
Mayer’s relation
If the specific heat is at constant pressure
(Cp) is greater than the specific heat at constant volume (CV) then the gas constant can
be expressed as Cp - CV = R and this relation are termed as Mayer's Formula
Relations

Cp - CV = R

Where R= Characteristic gas constant

Adiabatic index (γ)
Adiabatic index is defined as the ratio of the specific heat at constant pressure (Cp)
to the specific heat at constant volume (Cv).
𝐶𝑝
Mathematically, it is expressed as: γ=
𝐶𝑣

Since Cp is always greater than Cv and hence the value of γ greater than unity.
THERMODYNAMIC EQUILIBRIUM
Thermodynamic equilibrium is a concept in thermodynamics that describes a
state in which a system has reached a stable configuration with respect to its properties.
In a state of thermodynamic equilibrium, macroscopic variables such as temperature,
pressure, and chemical potential do not exhibit any net changes over time. The system is
in a balanced and unchanging condition.
There are three types of thermodynamic equilibrium:
1. Thermal Equilibrium: In a system in thermal equilibrium, there is no net flow of
heat between different parts of the system.
2. Mechanical Equilibrium: A system is in mechanical equilibrium when there is no
net movement of matter within the system.
3. Chemical Equilibrium: Chemical equilibrium occurs when there is no net change
in the composition of the system.
QUASI STATIC PROCESS
A quasi-static process, also known as a quasi-equilibrium process, is a concept used
in thermodynamics to describe an idealized process that occurs very slowly, allowing
the system to remain in equilibrium at each stage. In a quasi-static process, the
system passes through a sequence of equilibrium states, and the deviation from
equilibrium is minimized. While it's an idealization and may not be achievable in
practice, it is a useful concept for theoretical analysis.
WORK DONE, CHANGE IN INTERNAL ENERGY, HEAT TRANSFERRED, AND
CHANGE IN ENTHALPY IN THERMODYNAMIC PROCESS
1. Work done

2
Work done =∫1 𝑝 𝑑𝑉
 2. Change in internal energy
dU = m Cv (T2-T1)
where, m = mass of gas
Cv = Specific heat at constant volume
T1 = Initial Temperature
T2 = Final Temperature
3. Heat transferred
Q1-2 = Change in internal energy + Workdone
Q1-2 = dU + pdV
4. Change in enthalpy
dH = H1- H2
= m Cp T2 - m Cp T1
= m CP(T2-T1) [ For constant volume process, dH = m Cv (T2-T1)
Prob: 1.x
1 kg of an ideal gas is heated from 20° C to 100° C assuming, R=264 J/kgK and
γ = 1.18 for the gases. Find
(i) Specific heat at constant pressure and volume
(ii) Change in internal energy
(iii) Change in enthalpy.
(April 2023)

THERMODYNAMIC PROCESSES
In thermodynamics, a thermodynamic process refers to a series of changes that a
system undergoes as it transitions from one equilibrium state to another. These
processes are often described in terms of changes in various thermodynamic
variables, such as temperature, pressure, volume, and internal energy.
The following are the important types of thermodynamic processes:
1) Isochoric process
2) Isobaric process
3) Isothermal process
4) Adiabatic process
5) Polytrophic process

1. ISOCHORIC PROCESS (CONSTANT VOLUME PROCESS)

A thermodynamic process taking place at constant volume is known as the isochoric
process. It is also called an isometric process or constant-volume process.
In an Isochoric process volume of the system remain uncharged throughout (v1= v2)
 a. p,v,T relationship
𝑝 𝑝1 𝑝2
= C OR = (v= c)
𝑇 𝑇1 𝑇2
b. Work done
2
Work done =∫1 𝑝 𝑑𝑉
= p (V1-V2)
=0
c. Change in internal energy
dU = m Cv (T2-T1)
d. Heat transferred
Q1-2 = Change in internal energy + Workdone
Q1-2 = dU + pdV
= m Cv (T2-T1) +0
= m Cv (T2-T1)
e. Change in enthalpy
dH = m Cv (T2-T1)
Prob:
Certain gas occupies a space of 0.3m3 at pressure of 2 bar and at a temperature of 77℃. It
is heated at constant volume until the pressure is 7 bar. Determine
(i) temperature at the end of process
(ii) Mass of gas
(iii) Change in internal energy and
(iv) Change in enthalpy during the process.
Take CP=1.005 kJ/kgK, CV = 0.712 kJ/kgK. (Nov. 2022)
 2. ISOBARIC PROCESS (CONSTANT PRESSURE PROCESS)
An isobaric process is a thermodynamic process in which the pressure of the system
remains constant. In other words, during this process, the pressure of the system
does not change despite changes in the system’s properties (p1= p2)

a. p,v,T relationship
𝑉 𝑉1 𝑉2
= C or = (p= c)
𝑇 𝑇1 𝑇2
b. Work done
2
Work done =∫1 𝑝 𝑑𝑉
= p (V2-V1)
= m R (T2-T1)
c. Change in internal energy
dU = m Cv (T2-T1)
d. Heat transferred
Q1-2 = Change in internal energy + Workdone
Q1-2 = dU + pdV
= m Cv (T2-T1) + p (V2-V1)
= m Cv (T2-T1) + m R (T2-T1)
e. Change in enthalpy
dH = m CP (T2-T1)
Prob:1.x
One kg of an ideal gas is heated at constant pressure from 250C to 2000 C. The values of
specific heats at constant volume and constant pressure are 0.73kJ/kg K and 0.98 kJ/kg
K respectively. Find the following:
(i) Value of characteristic gas constant
(ii) The heat added
(iii) Ideal work done
(iv) Change in internal energy (November 2020)
3. ISOTHERMAL PROCESS (CONSTANT TEMPERATURE PROCESS)
An isothermal process is a thermodynamic process in which the system’s
temperature remains constant. The system can perform work and heat
transfer through its boundaries.

a. p,v,T relationship
pv = C Or p1 v1 = p2 v2 (T= c)
b. Work done
2
Work done = ∫1 𝑝 𝑑𝑉
2𝐶
= ∫1 𝑉 𝑑𝑉 [∵ pv = C, ∴ p = C/V]
21
= 𝐶 ∫1 𝑉 𝑑𝑉
𝑣
= 𝐶[𝑙𝑛 𝑉]𝑣21
𝑣
= 𝐶 𝑙𝑛 (𝑣2 )
1

𝑣 𝑣
= p1v1 𝑙𝑛 (𝑣2 ) = p2v2 𝑙𝑛 (𝑣2 )
1 1

𝑣
= m R T 𝑙𝑛 (𝑣2 )
1

c. Change in internal energy

dU = m Cv (T2-T1)
=0 [ ∵T2 = T1]
d. Heat transferred
Q1-2 = Change in internal energy + Workdone
Q1-2 = dU + p dV
= 0 + p dV
= p dV
𝑣 𝑣
= p1v1 𝑙𝑛 (𝑣2 ) = p2v2 𝑙𝑛 (𝑣2 )
1 1

𝑣
= m R T 𝑙𝑛 (𝑣2 )
1
 e. Change in enthalpy
dH = m CP (T2-T1)

Prob: 1.x
0.0001 m3 of air at 1000kN/m2 expands isothermally to a volume of 0.001m3, the initial
temperature is 25°C. Taking R = 0.297 kJ/kgK. Find the mass of air, the Final pressure
ADIABATIC PROCESS
An adiabatic process is one in which no heat is transferred to or from the fluid
during the process

4. .

a. p,v,T relationship
𝑝𝑣γ = 𝐶 Or p1 v1γ = p2 v2γ
b. Work done
2
Work done = ∫1 𝑝 𝑑𝑉
2
C γ 𝐶
=∫ ⅆV [∵pv = C, ∴ p = 𝛾 ]
Vγ 𝑣
1
2
1
=C ∫ ⅆV
Vγ
1
2
= C ∫1 𝑣 −𝛾 𝑑𝑉
2
𝑉 −𝛾+1
=C[ ]
−𝛾+1 1
−𝛾+1 −𝛾+1
𝑣2 −𝑣1
=𝐶 [ ]
−𝛾+1
1−𝛾 1−𝛾
𝑣2 −𝑣1
=𝐶 [ ]
1−𝛾
 𝐶 1−𝛾 1−𝛾
= [𝑣2 − 𝑣1 ]
1−𝛾
𝛾
𝑝1 𝑣1 1−𝛾 1−𝛾
=
1−𝛾
[𝑣2 − 𝑣1 ] [∵ 𝑝1𝑣1𝛾 = 𝑝2𝑣2𝛾 = 𝐶 ]
𝛾 1−𝛾 𝛾 1−𝛾
𝑝1 𝑣1 𝑣2 −𝑝1 𝑣1 𝑣1
=
1−𝛾
𝛾 1−𝛾 𝛾 1−𝛾
𝑝2 𝑣2 𝑣2 −𝑝1 𝑣1 𝑣1
=
1−𝛾
𝑝2 𝑉2 −𝑝1 𝑉1
=
1−𝛾
𝑝1 𝑉1 −𝑝2 𝑉2
=
𝛾−1
𝑇1 −𝑇2
= mR [
𝛾−1
]
c. Change in internal energy
dU = m Cv (T2-T1)

d. Heat transferred
Q1-2 = Change in internal energy + Workdone
= dU + pdV
=0
Or
dU = W1-2
𝑝1 𝑉1 −𝑝2 𝑉2
i.e. m Cv (T2-T1) = 𝛾−1

e. Change in enthalpy
dH = m CP (T2-T1)
Prob: 1.x
0.12 m3 of air at 1500 kPa and 1500°C expand adiabatically to 175 kPa. Find final
temperature and work done. Take Cp = 1.0035 kJ/kgK and Cv = 0.7165 kJ/kgK.
(April 2021)
Prob: 1.x
0.2 m3 of gas at 1 bar and 100° C is compressed adiabatically to 0.05 m 3.
Determine
(i) The mass of gas compressed
(ii) Final pressure and temperature of gas
(iii) Increase in internal energy.
Take γ=1.4 and R= 295 J/kgK. (April 2023)
5. POLYTROPIC PROCESS
A polytropic process is any thermodynamic process that can be expressed by the
following equation:
n
pV = constant
The polytropic process can describe gas expansion and compression, which include heat
transfer. The exponent n is known as the polytropic index, and it may take on any value
from 0 to ∞, depending on the particular process.
There are some special cases of n, which corresponds to particular processes:
• the case n = 0, p= constant, corresponds to an isobaric (constant-pressure)
process.
• the case n = 1, pV = constant, corresponds to an isothermal (constant-
temperature) process.
• the case n = , pV = constant, corresponds to an isentropic (constant-
entropy) process.
• the case n ➝ ∞ corresponds to an isochoric (constant-volume) process.
a. p,v,T relationship
pvn = C Or p1 v1n = p2 v2 n
b. Work done
2
Work done = ∫1 𝑝 𝑑𝑉
𝑝1 𝑉1 −𝑝2 𝑉2
=
𝑛−1
𝑇1 −𝑇2
= mR [
𝑛−1
]
c. Change in internal energy
dU = m Cv (T2-T1)

d. Heat transferred
Q1-2 = Change in internal energy + Workdone
Q1-2 = dU + pdV
𝑝1 𝑉1 −𝑝2 𝑉2
= m Cv (T2-T1) +
𝑛−1
𝑇1 −𝑇2
= m Cv (T2-T1) + mR [
𝑛−1
]
e. Change in enthalpy
dH = m CP (T2-T1)
Prob:
Certain amount of air has volume of 0.192 m3 at a pressure of 1 bar and temperature
43℃. It is compressed polytropically to a volume of 0.0142 m3. Find

(i) Pressure at the end of compression.

(ii) Mass of gas
(iii) Work done during compression and
(iv) Heat rejected during compression.

Take γ =1.4, R= 0.289KJ/KgK, n = 1.37. (Nov. 2022)

 THERMODYNAMIC PROCESSES- SUMMARY
Change in Change in
Thermodynamic p-v-T Work done Heat transferred
PROCESS internal energy enthalpy
condition Relationship W1-2 =(pdV) dU+ pdV
dU dH
𝑝
Isochoric Constant Volume =C 0 m Cv (T2-T1) m Cv (T2-T1) m Cv (T2-T1)
𝑇

𝑉 p (V2-V1) = m R (T2-T1) m Cv (T2-T1) +m R (T2-T1) m CP (T2-T1)

Isobaric Constant Pressure =C m Cv (T2-T1)
𝑇
𝑣 𝑣
p1v1 𝑙𝑛 (𝑣2 ) p1v1 𝑙𝑛 (𝑣2 )
1 1

𝑣 𝑣
Constant pv = C = p2v2 𝑙𝑛 (𝑣2 ) = p2v2 𝑙𝑛 (𝑣2 )
Isothermal 1 0 1 m CP (T2-T1)
Temperature
𝑣2 𝑣2
= m R T 𝑙𝑛 (𝑣 ) = m R T 𝑙𝑛 (𝑣 )
1 1

No heat transfers 𝑝𝑣γ = 𝐶 𝑝1 𝑉1 −𝑝2 𝑉2

= mR [
𝑇1 −𝑇2
]
Adiabatic W1-2 = -dU 𝛾−1 𝛾−1 m Cv (T2-T1) 0 m CP (T2-T1)

𝑝𝑣n = 𝐶 𝑝1 𝑉1 −𝑝2 𝑉2
= mR [
𝑇1 −𝑇2
] 𝑝1 𝑉1 −𝑝2 𝑉2
Polytropic ……… 𝑛−1 𝑛−1 m Cv (T2-T1) + m Cv (T2-T1) m CP (T2-T1)
𝑛−1
 THERMODYNAMIC LAWS
1. ZEROTH LAW OF THERMODYNAMICS
Zeroth law of thermodynamics states that ‘If two systems are each in thermal
equilibrium with a third system, then they are in thermal equilibrium with each other’.
If two systems are each in thermal equilibrium with a third system, they are
considered to be at the same temperature. This law establishes the concept of
temperature and allows us to define and measure temperature.

2. FIRST LAW OF THERMODYNAMICS

This law may be stated as follows:
(a) 'The heat and mechanical work are mutually convertible".
According to this law, when a closed system undergoes a thermodynamic
cycle, the net heat transfer is equal to the nett work transfer.
Mathematically,
∮ 𝑑𝑄 = ∮ 𝑑𝑤
(b) ‘The energy can neither be created nor destroyed though it can be transformed
from one form to another’.
According to this law, when a system undergoes a change of State (or a
thermodynamic process), then both heat transfer and work transfer takes
place. The net energy transfer is stored within the system and is known as
stored energy or total energy of the system.
Mathematically
dQ-dW = dE
First law of thermodynamics may also be stated as
“Heat and work are mutually convertible but since energy can neither be created nor
destroyed, the total energy associated with an energy conversion remains constant”.
 3. SECOND LAW OF THERMODYNAMICS
The second law of thermodynamics has been enunciated meticulously by
Clausius, Kelvin and Planck in slightly different words although both statements are
basically identical. Each statement is based on an irreversible process.

 The Clausius statement considers transformation of heat between two thermal

reservoirs
 Kelvin and Planck statement considers the transformation of heat into work.
a. Clausius statement
“Clausius statement `It is impossible for a self-acting machine working in a cyclic
process, to transfer heat from a body at a lower temperature to a body at a higher
temperature, without the aid of an external agency”.
In other words, heat cannot flow by itself from a cold body to a hot body
without receiving external work.

b. Kelvin Plank statement

“It is impossible to construct an engine which operating in a cycle will produce no effect
other than the exchange of heat from a single reservoir and produce an equal amount
of work”
In other words, no actual heat engine working on a cyclic process can convert the
whole of the heat supplied to it into mechanical work.
 It means that a part of the heat supplied to the heat engine must be rejected
to the surroundings and only the remaining part is converted into work. Hence, the
work done by a heat engine will be equal to the difference between heat supplied and
heat rejected.

ENTROPY
Entropy is a function of a quantity of heat which shows the possibility of
conversion of that heat into work. Entropy is a fundamental concept in
thermodynamics, and it relates to the amount of disorder or randomness in a
system.
The increase in entropy is small when heat is added at a high temperature
and is greater when heat addition is made at a lower temperature. Thus, for
maximum entropy, there is minimum availability for conversion into work and for
minimum entropy there is maximum availability for conversion into work.”