Introduction and Principle of Thermodynamics

Introduction and Principle
of Thermodynamics
Zeroth Law of Thermodynamics
Provides a basis for thermodynamic temperature scales.
T K = T ℃ + 273.15
T R = T ℉ + 459.67
T R = 1.8T(K)
T ℉ = 1.8T ℃ + 32
First Law of Thermodynamics
The significance of this law is that every bit of energy should be
accounted for during a process. It also throws light in the concept
of internal energy.
𝑬𝒊𝒏 = 𝑬𝒐𝒖𝒕
Second Law of Thermodynamics
Asserts that processes occur in a certain direction.
Energy has quality as well as quantity.
Used in determining the theoretical limits for the performance of

commonly used engineering systems.
Third Law of Thermodynamics
Provides the basis for the calculation of absolute entropy of the
substances.
Entropy is a measure of the amount of energy which is unavailable

to do work.
Thermodynamic Processes
Isometric process: Constant volume process of a pure substance
Isobaric process: Constant pressure process of a pure substance
Isothermal process: Constant temperature process of a pure

substance
Thermodynamic Processes
Isentropic process: Constant entropy process of a pure substance.
No heat is transferred.
Isenthalpic or throttling process: Constant enthalpy process of a

pure substance. No work is done.
Adiabatic process: No flow of heat between system and

surroundings.
Polytropic process: Reversible process given by 𝑷𝑽𝒏

= 𝑪.
Property Diagrams
T-v diagram
P-v diagram
P-t diagram
T-s diagram
P-h diagram
T-v diagram
P-v diagram
P-t diagram
T-s diagram
P-h diagram
Thermodynamic Systems
Systems: a finite quantity of matter or a prescribed region of
space.
Boundary: the actual of hypothetical envelope enclosing the
system.
Thermodynamic Systems
Closed System: the boundary of the system is impervious to the
flow matter (i.e. mass of gas or vapor in an engine cylinder)
Open System: matter flows into or out of the system (i.e. gas
turbine, compressor, etc.)
Isolated System: a system which exchanges neither energy nor
matter with any other system or with environment.
Adiabatic System: a system which is thermally insulated from its
surroundings. It can however exchange work with its surroundings.
Phase
A quantity of matter which is homogeneous throughout in
chemical composition and physical structure.
Homogeneous System: Consists of a single phase (i.e. mixture of

air and water vapor)
Heterogeneous System: Consists of a two or more phases (i.e.

water plus steam)
Pure substance
Has a homogeneous and invariable chemical composition
even though there is a change of phase.
(i.e. liquid, water, mixture of liquid water and steam, mixture of

ice and water)
State
The condition of the system at an instant of time as described
or measured by its properties
Cycle
Any process or series of processes whose end states are
identical.
Quantities: Temperature
SI: Celsius, Kelvin
English: Fahrenheit, Rankine
T Kelvin = T(Celsius) + 273.15

T Rankine = T(Fahrenheit) + 459.67
T Rankine = 1.8T(Kelvin)
T Fahrenheit = 1.8T Celsius + 32
Quantities: Pressure
SI: Pascal, atm, bar
English: psi, psf
1 𝑎𝑡𝑚 = 14.7 𝑝𝑠𝑖 = 101.325 𝑘𝑃𝑎 = 1.01325 𝑏𝑎𝑟
1 𝑏𝑎𝑟 = 100 𝑘𝑃𝑎

Reversible and irreversible process
Reversible Process: can be stopped at any stage and
reversed so that the system and surroundings are exactly
restored to their initial states.
Irreversible Process: cannot return both the system and the

surroundings to their original conditions. (i.e. relative motion
with friction, diffusion, heat transfer, combustion, free
expansion, plastic deformation).
Energy, Work & Heat
Energy: can be energy in transition (heat and work) or stored
energy (mechanical and internal energy).
Work: Appears at the boundary while a change of state is

taking place within the system.
Heat: Appears at the boundary when a system changes its

state due to a difference in temperature between the system
and its surroundings.
Characteristic equation of state
At temperatures that are considerably in excess of critical
temperature of a fluid and also at very low pressure, the vapor
of fluid tends to obey the equation:
𝑷𝒗
=𝑹
𝑻
P = absolute pressure (Pa or kPa), v = specific volume (𝐦𝟑 /𝐤𝐠),

𝐤𝐉
R= gas constant ( ), T = absolute temperature (Kelvin, K)
𝐤𝐠−𝐊
Perfect Gas
Also called ideal gas, a gas that conforms to the general gas
law.
P = absolute pressure
v = specific volume
𝑝𝑣 = 𝑅𝑇 R= gas constant = 𝐮
𝐑
𝐌
T = absolute temperature
V = volume
𝑝𝑉 = 𝑚𝑅𝑇 m = mass
𝐤𝐉
𝐑 𝐮 = 𝐮𝐧𝐢𝐯𝐞𝐫𝐬𝐚𝐥 𝐠𝐚𝐬 𝐜𝐨𝐧𝐬𝐭𝐚𝐧𝐭 = 𝟖. 𝟑𝟏𝟒
𝐊 𝐦𝐨𝐥 − 𝐊
𝐌 = 𝐦𝐨𝐥𝐚𝐫 𝐦𝐚𝐬𝐬
Joule’s law
The internal energy of a perfect gas is a function of the
absolute temperature only.
𝑢 = 𝑓(𝑇)
𝑈 = 𝑚𝑐𝑣 𝑇
∆𝑼 = 𝒎𝒄𝒗 ∆𝑻
Specific heats
non-flow process at constant pressure

𝑑𝑄 = 𝑚𝑐𝑝 𝑑𝑇 → 𝑄 = 𝑚𝑐𝑝 ∆𝑇
non-flow process at constant volume

𝑑𝑄 = 𝑚𝑐𝑣 𝑑𝑇 → 𝑄 = 𝑚𝑐𝑣 ∆𝑇
Relationship between cp & cv
Consider a perfect gas being heated at constant pressure from 𝐓𝟏 to 𝐓𝟐 . According to
non-flow equation,
𝐐 = 𝐔𝟐 − 𝐔𝟏 + 𝐖
For constant pressure process,
𝑸 = 𝒎𝒄𝒑 (𝑻𝟐 −𝑻𝟏 )
Also for a perfect gas,
𝐔𝟐 − 𝐔𝟏 = 𝐦𝐜𝐯 (𝐓𝟐 −𝐓𝟏 )
For a constant pressure process, the work done by the fluid,
𝐖 = 𝐩(𝐕𝟐 −𝐕𝟏 ) = 𝐦𝐑(𝐓𝟐 −𝐓𝟏 )
Equating the two previous equations,
𝒎𝒄𝒑 (𝑻𝟐 −𝑻𝟏 ) = 𝒎𝒄𝒗 (𝑻𝟐 −𝑻𝟏 ) + 𝒎𝑹(𝑻𝟐 −𝑻𝟏 )
Thus,
𝒄𝒑 = 𝒄𝒗 + 𝑹
Ratio of specific heats
The ratio of specific heats at constant pressure to specific
heat at constant volume is given by
𝑐𝑝
𝑘=
𝑐𝑣
Approximated values of 𝒌 are as follows:

For monoatomic gases such as argon, helium = 1.6
For diatomic gases such as carbon monoxide, hydrogen, nitrogen, and oxygen = 1.4
For triatomic gases such as carbon dioxide = 1.3
Enthalpy
The sum of internal energy (𝒖) and pressure volume product
(𝒑𝒗),
𝒉 = 𝒖 + 𝒑𝒗
For a perfect gas,
𝒉 = 𝒄𝒗 𝑻 + 𝑹𝑻 = 𝒄𝒗 + 𝑹 𝑻 = 𝒄𝒑 𝑻

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Introduction and Principle

Energy has quality as well as quantity.

Used in determining the theoretical limits for the performance of

Entropy is a measure of the amount of energy which is unavailable

Isobaric process: Constant pressure process of a pure substance

Isothermal process: Constant temperature process of a pure

Isenthalpic or throttling process: Constant enthalpy process of a

Adiabatic process: No flow of heat between system and

Polytropic process: Reversible process given by 𝑷𝑽𝒏

Homogeneous System: Consists of a single phase (i.e. mixture of

Heterogeneous System: Consists of a two or more phases (i.e.

(i.e. liquid, water, mixture of liquid water and steam, mixture of

T Kelvin = T(Celsius) + 273.15

1 𝑎𝑡𝑚 = 14.7 𝑝𝑠𝑖 = 101.325 𝑘𝑃𝑎 = 1.01325 𝑏𝑎𝑟

1 𝑏𝑎𝑟 = 100 𝑘𝑃𝑎

Irreversible Process: cannot return both the system and the

Work: Appears at the boundary while a change of state is

Heat: Appears at the boundary when a system changes its

P = absolute pressure (Pa or kPa), v = specific volume (𝐦𝟑 /𝐤𝐠),

non-flow process at constant pressure

non-flow process at constant volume

Approximated values of 𝒌 are as follows:

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