Introduction and Basic Concepts

Thermodynamics can be defined as the science of energy. Energy can be

viewed as the ability to cause changes.

The name thermodynamics stems from the Greek words therme (heat)
and dynamics (power), which indicates the early efforts to convert heat
into power. Today the same name is used to include all aspects of energy
and energy transformations including power generation, refrigeration, and
relationships among the properties of matter.

There are different forms of energy such as:

- Kinetic energy: When all parts of a system move with the same
𝑚𝑉 2
velocity 𝑉 , the kinetic energy is expressed as: 𝐾𝐸 =
2

𝑉2
Per unit mass, 𝑘𝑒 =
2

- Potential energy: The energy that a system possesses as a result of its

elevation in a gravitational field. It is expressed as:

𝑃𝐸 = 𝑚𝑔𝑧

Per unit mass, 𝑝𝑒 = 𝑔𝑧

Where g is the gravitational acceleration and z is the elevation of the

center of gravity of a system relative to some arbitrarily selected
reference level.

- Internal energy: It is the form of energy that is related to the

molecular structure of a system and the degree of the molecular
 activity. It is independent of outside
reference frames. The sum of all the
microscopic forms of energy is called
the internal energy of a system and
is denoted by U.

The magnetic, electric, and surface

tension effects are significant in some
specialized cases only and are usually
ignored. In the absence of such effects,
the total energy of a system consists of
the kinetic, potential, and internal
energies and is expressed as:

𝑚𝑉 2
𝐸 = 𝑈 + 𝐾𝐸 + 𝑃𝐸 = 𝑈 + + 𝑚𝑔𝑧
2

Or per unit mass:

𝑉2
𝑒 = 𝑢 + 𝑘𝑒 + 𝑝𝑒 = 𝑢 + + 𝑔𝑧
2

The above forms of energy, which constitute the total energy of a system,
can be contained or stored in a system, and thus can be viewed as the
static forms of energy (these forms of energy are considered properties
of the system).

The forms of energy not stored in a system can be viewed as the dynamic
forms of energy or as energy interactions.
The dynamic forms of energy are recognized at the system boundary as
they cross it, and they represent the energy gained or lost by a system
during a process. The only two forms of energy interactions associated
with a closed system are heat transfer and work.

An energy interaction (transfer) is heat transfer if its driving force is a

temperature difference. Otherwise it is work,

As mentioned earlier, energy can cross the boundary of a closed system

in the form of heat or work. Therefore, if the energy crossing the
boundary of a closed system is not heat, it must be work. Heat is easy
to recognize: Its driving force is a temperature difference between the
system and its surroundings. Then we can simply say that an energy
interaction that is not caused by a temperature difference between a
system and its surroundings is work. More specifically, work is the
energy transfer associated with a force acting through a distance.

A moving piston (moving boundary work), a rotating shaft (shaft work),

and an electric wire crossing the system boundaries (electric work) are all
associated with work interactions. The electric work is not mechanical
work because it is not a force acting through a certain distance.

So, we can say that: Systems possess energy, but not heat or work.
In thermodynamics, energy is classified into two main categories:

1- Thermal energy
- The first type of thermal energy that refers to the sensible form of
internal energy (that causes change of temperature) and latent form
of internal energy (that causes change of phase without change of
temperature), it is the thermal content of the body.
- The second type of thermal energy is the heat transfer. Heat is
defined as the form of energy that is transferred between two
systems (or a system and its surroundings) by a temperature
difference

2- Mechanical energy

The mechanical energy can be defined as the form of energy that can be
converted to mechanical work completely and directly by an ideal
mechanical device such as an ideal turbine. Kinetic and potential
energies are the familiar forms of mechanical energy. Also, work is form
of mechanical energy.

The pressure of a flow (flowing fluid) is another form of mechanical

𝑃 𝑁 𝑚3
energy that is called flow work (or flow energy), 𝑃𝑣 = = 2
. =
𝜌 𝑚 𝑘𝑔
𝑁.𝑚 𝑗𝑜𝑢𝑙𝑒
= = 𝑒𝑛𝑒𝑟𝑔𝑦 𝑝𝑒𝑟 𝑢𝑛𝑖𝑡 𝑚𝑎𝑠𝑠
𝑘𝑔 𝑘𝑔

Since the total flow energy = KE + PE + flow work is mechanical energy

So the mechanical energy of a flowing fluid equals:

𝑉2 𝑃
𝑒𝑚𝑒𝑐ℎ = + 𝑔𝑧 +
2 𝜌
Thermal energy (internal energy or heat) is not mechanical energy,
however, since it cannot be converted to work directly and completely.

Energy

Static Energy Dynamic Energy

Internal Kinetic Potential Heat

Work
Energy Energy Energy Transfer

Mechanical Energy

Thermal Energy
System:

A system is defined as a quantity of matter or a

region in space chosen for study. The mass or
region outside the system is called the
surroundings.

The real or imaginary surface that separates the system

from its surroundings is called the boundary.

The boundary of a system can be fixed or movable.

According to the exchange (interaction) between the system and its

surrounding the system is classified into:

Closed system: It is a system where no mass can cross the system

boundaries; it is a fixed mass system. Only energy (heat, work) can cross
the system boundaries. Piston-cylinder device is an example for a closed
system.
Isolated system: It is a special case of closed system where even energy
is not allowed to cross the boundary.

Open system (control volume): It is a system where energy and mass can
cross the system boundaries. Ex. Devices that involve mass flow such as
a compressor, turbine, or nozzle.

PROPERTIES OF A SYSTEM

Any characteristic of a system is called a property, such as pressure,

temperature, volume and mass. Also, internal energy, velocity, elevation
and total energy are properties of the system.

Properties are considered to be either intensive or extensive.

Intensive properties: are those that are independent of the mass of a

system, such as temperature, pressure, and density.
Extensive properties: are those whose values
depend on the size—or extent—of the system.
Total mass, total volume, and total energy are
some examples of extensive properties.

Extensive properties per unit mass are called

specific properties. Some examples of specific
properties are specific volume (v = V/m), specific
internal energy (u = U/m), and specific total
energy (e = E/m).

Some of these properties are:

Density and specific volume

𝑚
Density, , is defined as mass per unit volume, 𝜌 = 𝑘𝑔⁄𝑚3
𝑉

𝑉
Specific volume v, is defined as volume per unit mass, 𝑣 = =
𝑚
1
𝑚3 ⁄𝑘𝑔
𝜌

Temperature and Zeroth Law of Thermodynamics

Although we are familiar with temperature as a measure of “hotness” or

“coldness,” it is not easy to give an exact definition for it. Others define
the temperature as the property that measures the heat (thermal) content
or the internal energy of the body.

Fortunately, several properties of materials change with temperature in a

repeatable and predictable way, and this forms the basis for accurate
temperature measurement. The commonly used mercury-in-glass
thermometer, for example, is based on the expansion of mercury with
temperature. Temperature is also measured by using several other
temperature-dependent properties.

Thermal equilibrium

When a body is brought into contact with another body that is at a

different temperature, heat is transferred from the body at higher
temperature to the one at lower
temperature until both bodies attain the
same temperature. At that point, the heat
transfer stops, and the two bodies are said
to have reached thermal equilibrium. The
equality of temperature is the only
requirement for thermal equilibrium.

The zeroth law of thermodynamics states that if two bodies are in

thermal equilibrium with a third body, they are also in thermal
equilibrium with each other. It serves as a basis for the validity of
temperature measurement. By replacing the third body with a
thermometer, the zeroth law can be restated as two bodies are in
thermal equilibrium if both have the same temperature reading even
if they are not in contact.
Temperature Scales

- Celsius scale (centigrade scale)

On this scale, the ice point (freezing point) and steam point (boiling
point) of water at 1 atm pressure were assigned the values of 0 and 100°
C, respectively.

- Thermodynamic temperature scale

In thermodynamics, it is very desirable to have a temperature scale that is

independent of the properties of any substance or substances. Such a
temperature scale is called a thermodynamic temperature scale, which
is developed later in conjunction with the second law of thermodynamics.

The thermodynamic temperature scale in the SI is the Kelvin scale or

absolute temperature scale with temperature unit is the kelvin, K. The
lowest temperature on the Kelvin scale is absolute zero, or 0 K.

The Kelvin scale is related to the Celsius scale by:

𝑇(𝐾) = 𝑇(𝐶°) + 273.15

Pressure

Pressure is defined as a normal force exerted by a fluid per unit area.

𝐹 𝑁
𝑃= = 2 = 𝑃𝑎𝑠𝑐𝑎𝑙 (𝑃𝑎)
𝐴 𝑚

The pressure unit pascal is too small for most pressures encountered in
practice. Therefore, its multiples:

1 𝑘𝑃𝑎 = 103 𝑃𝑎 1 𝑀𝑃𝑎 = 106 𝑃𝑎 1 𝑏𝑎𝑟 = 105 𝑃𝑎

There are two references by which the pressure can be expressed: The
zero absolute pressure (complete vacuum) and the local atmospheric
pressure.

Absolute pressure: It is the actual pressure at a given position. It is

measured relative to absolute vacuum (absolute zero pressure).

Gage pressure: Nearly, all measuring devices, however, are calibrated to

read zero in the atmosphere, and so they indicate the difference between
the absolute pressure and the local atmospheric pressure. This difference
is called the gage pressure.

The gage pressure can be positive (if the pressure is higher than the
atmospheric pressure) or negative (below atmospheric pressure). The
negative pressures are sometimes called vacuum pressures and are
measured by vacuum gages that indicate the difference between the
atmospheric pressure and the absolute pressure.

Absolute, gage, and vacuum pressures are related to each other by:

𝑃𝑔𝑎𝑔𝑒 = 𝑃𝑎𝑏𝑠 − 𝑃𝑎𝑡𝑚

 𝑃𝑣𝑎𝑐 = 𝑃𝑎𝑡𝑚 − 𝑃𝑎𝑏𝑠

In thermodynamic relations, the absolute pressure must be used.

State

The sum of properties the system has, constitutes

or describes the state of the system. At a given
state, all the properties of a system have fixed
values. For example, system at state (1), it has
properties P1, T1, V1, ….

If the value of even one property changes, the

state will change to a different one (state 2).
Process

The process is the change of state. If a system undergoes a change of sate

from state (1) to state (2), this is called
process and the series of states through which
a system passes during a process is called the
path of the process. To describe a process
completely, one should specify the initial and
final states of the process, as well as the path
it follows, and the interactions with the

surroundings.

Types of processes: The process may be,

- An isothermal process: a process during which the temperature T

remains constant
 - An isobaric process is a process during which the pressure P
remains constant
- An isochoric (or isometric) process is a process during which the
specific volume v remains constant.

Cycle

A system is said to have undergone a cycle if it returns to its initial state

at the end of some processes. That is, for a cycle the initial and final
states are identical. Least two processes can perform a cycle.

Two independent properties are required to completely identify the state.

Other properties can be determined from:
The equation law of state:

- For ideal gases 𝑃𝑉 = 𝑚𝑅𝑇

Or 𝑃𝑣 = 𝑅𝑇

P is the pressure kPa T is the temperature K

𝑉 is the volume m3 𝑣 is the specific volume 𝑚3 ⁄𝑘𝑔

𝑅𝑢
𝑅 is the gas constant 𝑅=
𝑀

𝑅𝑢 is the universal gas constant 𝑅𝑢 = 8.314 𝑘𝐽⁄𝑘𝑚𝑜𝑙𝑒. 𝐾

𝑀 is the molecular mass 𝑘𝑔⁄𝑘𝑚𝑜𝑙𝑒

M and R are determined from A1 table.

Most of gases (Air, Oxygen, Nitrogen, Heluim, ….) obey the ideal gas
relation especially at low pressures and high temperatures (gases at low
density).

- For real gases

𝑃𝑣 = 𝑍𝑅𝑇

𝑍 is the compressibility factor

Z=1 for ideal gases 𝑍 > 1 𝑜𝑟 < 1 for real gases

𝑍 depends on P and T of the gas (from chart)

- For pure substances with change of phase (water and refrigerants)

These substances are found in

three regions; compressed liquid,
saturated liquid-vapour mixture
and super-heated vapour.

The relations for these substances

are very complicated, These
relations (for each region) are
given in tables and charts.
- Compressed liquid state

The state is compressed if 𝑃 > 𝑃𝑠𝑎𝑡@𝑇 or

𝑇 < 𝑇𝑠𝑎𝑡@𝑃

The state is determined from compressed liquid

table (by P and T) or from saturated table as:

𝑣 = 𝑣𝑓@𝑇 𝑢 = 𝑢𝑓@𝑇 ℎ = ℎ𝑓@𝑇

- Liquid-vapour mixture state

During a vaporization process, a substance

exists as part liquid and part vapor. That is, it is
a mixture of saturated liquid and saturated
vapor. To analyze this mixture properly, we
need to know the proportions of the liquid and
vapor phases in the mixture. This is done by
defining a new property called the quality x
(or dryness fraction) as the ratio of the mass of
vapor to the total mass of the mixture:

𝑚𝑣𝑎𝑝𝑜𝑢𝑟
𝑥=
𝑚𝑡𝑜𝑡𝑎𝑙

Where 𝑚𝑡𝑜𝑡𝑎𝑙 = 𝑚𝑙𝑖𝑞𝑢𝑖𝑑 + 𝑚𝑣𝑎𝑝𝑜𝑢𝑟 = 𝑚𝑓 + 𝑚𝑔

𝑥=0 at saturated liquid line (state f) and 𝑥 = 1 at saturated vapor line

(state g). To analyze saturated mixtures, we need two independent
properties (P or T, they are not independent) and any other property in
order to determine the quality 𝑥. By T or P, we can determine the
saturated liquid state (state f) and saturated vapor state (state g) from the
saturated tables on the basis of temperature or on the basis of pressure.
The properties of the mixture are determined
from:

𝑣 = 𝑣𝑓 + 𝑥(𝑣𝑔 − 𝑣𝑓 ) = 𝑣𝑓 + 𝑥𝑣𝑓𝑔

𝑢 = 𝑢𝑓 + 𝑥(𝑢𝑔 − 𝑢𝑓 ) = 𝑢𝑓 + 𝑥𝑢𝑓𝑔

ℎ = ℎ𝑓 + 𝑥(ℎ𝑔 − ℎ𝑓 ) = ℎ𝑓 + 𝑥ℎ𝑓𝑔
- Super-heated vapour state

The state is super-heated if or 𝑇 > 𝑇𝑠𝑎𝑡@𝑃

From superheated tables, by the two independent P

and T, we can read other properties such as: 𝑣, 𝑢, h