Bahir Dar University

College of Science
Department of Industrial Chemistry
2nd Year Industrial Chemistry Students
Chemical Engineering Thermodynamics(Iche2072)

Chapter one
Thermodynamic systems

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1.Thermodynamic systems
 Thermodynamics deals with the concepts of heat and temperature and the inter-conversion
of heat and other forms of energy. The four laws of thermodynamics govern the behavior of
these quantities and provide a quantitative description.
 Thermodynamic system: a quantity of fixed mass under investigation, or it is defined as
a fixed mass in a region of space under consideration to analyze a problem.

• Let also understand the terms system, surrounding, and boundary.

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Con…
• What is a System?
 The system is defined as the region or quantity of matter which is taken into consideration
for analysis.
• What is surrounding?
 Surroundings: Surrounding is the region located outside the system.
• There is a boundary between the surroundings and system which keeps them separated
from each other.
• What is Boundary?
 It is a surface in which the system is contained and separated from the surroundings. It can
be movable or fixed.

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• Types of thermodynamics system
 Systems in thermodynamics are classified as isolated, closed, or open based on the possible
transfer of mass and energy across the system boundaries.
1. An isolated system: is one that is not influenced in any way by the surroundings. This
means that no energy in the form of heat or work may cross the boundary of the system.
In addition, no mass may cross the boundary of the system.
Example: A thermos flask.
• When a liquid is poured inside the thermos flask whether it is hot or cold, the flask is built
in such a way that it maintains the temperature of the liquid present in it. It does not allow the
transfer of mass and energy because the lid is closed so nothing comes in and nothing goes out
of the flask. So, we can conclude that the thermos flask is an isolated system.

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2. A closed system: has no transfer of mass with its surroundings, but may have a transfer of
energy (either heat or work) with its surroundings.
For example, we have a piston-cylinder arrangement.
• The volume of gas is 1 m3, and the mass is 3 kg. The boundary is closed i.e. gas can’t escape
out of the cylinder into the atmosphere, When the cylinder is heated from below, the piston
moves upwards. The gas in the cylinder heats up and transfers work in the form of piston
movement. However, the mass remains constant as only expansion is taking place. Thus, we
can say that this is a closed system.

• Fig.1: Example of a thermodynamic system.

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3. An open system: is one that may have a transfer of both mass and energy with its
surroundings.
For example: Heating a pan.
When a pan containing water is kept on a stove and heated, water molecules get evaporated
and convert into steam. Thus, mass transfer is taking place. Water gets evaporated and water
can be added to the pan. Heat energy is transferred to the water by the gas flame and heat
energy is also lost to the surroundings. Hence, we can say that this is an open system.

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Thermodynamic equilibrium
• At a given state, all properties of a system have fixed values. Thus, if the value of even one
property changes, the system’s state changes to a different one.
• In a system that is in equilibrium, no changes in the value of properties occur when it is
isolated from its surroundings.
 When the temperature is the same throughout the entire system, we consider the system
to be in thermal equilibrium.
 When there is no change in pressure at any point of the system, we consider the system to
be in mechanical equilibrium.
 When the chemical composition of a system does not vary with time, we consider the
system to be in chemical equilibrium.
 Phase equilibrium in a two-phase system is when the mass of each phase reaches an
equilibrium level.
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Con…
• A thermodynamic system is said to be in thermodynamic equilibrium if it is in chemical
equilibrium, mechanical equilibrium and thermal equilibrium and the relevant parameters
cease to vary with time.
 For example the liquid inside a medical thermometer expands when it is first put into a
person’s mouth because at that point it is NOT in equilibrium.
• However, after a short period of time the liquid stops expanding as the thermometer
reaches equilibrium with the person (heat bath) with which it has been put into contact.
• Once this equilibrium has been reached the volume of the liquid inside the thermometer
does not change any further it settles down to a constant value.

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The Zeroth (0th) law of thermodynamics
 States that if two thermodynamic systems, each in thermal equilibrium with another
thermodynamic system, then they are in thermal equilibrium with each other.
 It can be used to compare the temperature of more than one object.
For example,
 two objects are in thermal equilibrium if heat passes through them but no heat is actually
being transmitted from one object to the other and vice versa.
• Consider going to a swimming pool, you can find out the temperature of the pool with a
thermometer and then check your own temperature. If the temperature of the pool and
your temperature are similar with the thermometer you are in thermal equilibrium with the
swimming pool

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Heat sink
• In thermo-dynamics are an environment or medium that absorbs heat from another in order to cool its temperature.

• Heat sink are common in electronic devices we use at home. heat sink help prevent overheating of electronic

devices by following the second law of thermo-dynamics whereby the temperature of the heat source falls as that of

the heat sink increases.

• In computers, heat sinks are used to cool CPUs, GPUs, and some chipsets and RAM modules. Heat sinks are used

with high-power semiconductor devices such as power transistors and optoelectronics such as lasers and light-

emitting diodes (LEDs), where the heat dissipation ability of the component itself is insufficient to moderate its

temperature.

• A heat sink is usually made out of aluminum or copper.

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Thermodynamic variables
• Thermodynamic variables are the quantities used to characterize a system.
1. Intensive Properties
A property which does not depend on the quantity of matter present in the system.
 Some examples of intensive properties are
 pressure,
 temperature,
 density, and
 Concentration.
 If the overall temperature of a glass of water (our system) is 20ºC, then any drop of water
in that glass has a temperature of 20ºC. Similarly if the concentration of salt, NaCl, in the
glass of water is 0.1 mole/litre, then any drop of water from the glass also has a salt
concentration of 0.1 mole/litre.

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2. Extensive Properties
A property that does depend on the quantity of matter present in the system.
 Some examples of extensive properties are
 Volume,
 number of moles,
 enthalpy,
 entropy, and
 Gibbs’ free energy.
• By definition, the extensive properties are additive while intensive properties are not.
 Let us consider the system ‘a glass of water’. If we double the mass of water, the volume is
doubled and so is the number of moles and the internal energy of the system.

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Thermodynamic processes
• when a thermodynamic system changes from one state to another, the operation is called a
Process. These processes involve the change of conditions (temperature, pressure and volume).
The various types of thermodynamic processes are:
(1) Isothermal Processes
Those processes in which the temperature remains fixed, are termed isothermal processes.
This is often achieved by placing the system in a thermostat (a constant temperature bath).
For an isothermal process dT = 0
(2) Adiabatic Processes
Those processes in which no heat can flow into or out of the system, are called adiabatic
processes.
• Adiabatic conditions can be approached by carrying the process in an insulated container
such as ‘thermos’ bottle. High vacuum and highly polished surfaces help to achieve thermal
insulation.
For an adiabatic process dq = 0
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(3) Isobaric Processes
Those processes which take place at constant pressure are called isobaric processes.
• For example, heating of water to its boiling point and its vaporization take place at the same
atmospheric pressure. These changes are, therefore, designated as isobaric processes and are
said to take place isobarically.
For an isobaric process dp = 0

Figure 2. ( a) Four basic thermodynamic processes; (b ) A cyclic process. 15

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(4) Isochoric Processes
Those processes in which the volume remains constant are known as isochoric processes. The
heating of a substance in a non-expanding chamber is an example of isochoric process.
For isochoric processes dV = 0.
(5) Cyclic Process
When a system in a given state goes through a number of different processes and finally
returns to its initial state, the overall process is called a cycle or cyclic process.
For a cyclic process dE = 0, dH = 0.

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 A thermodynamic cycle is a series of thermodynamic processes at the end of which the
system returns to its initial state. Properties depend only on the thermodynamic state
which varies during the operations of the process.

 The thermodynamic cycles are very essential for the power developing systems (such as
petrol engine, diesel engine, gas turbine etc.).

 These engines use a mixture of fuel and air for their operations.
 Since the mass of fuel used, as compared to the mass of air is
very small, thus the mixture may be assumed to obey the
properties of a perfect gas.

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Reversible and irreversible processes
• A thermodynamic reverse process is one that takes place infinitesimally slowly and its
direction at any point can be reversed by an infinitesimal change in the state of the system.
• When a process goes from the initial to the final state in a single step and cannot be
carried in the reverse order, it is said to be an irreversible process. Here the system is in
equilibrium state in the beginning and at the end, but not at points in between.

• Figure 3. (a) Reversible expansion occurs by decreasing the pressure on the piston by
infinitesimal amounts. (b ) Irreversible expansion occurs by sudden decrease of pressure
from P to P, when the gas expands rapidly in a single operation. 18
Con…
• Consider a certain quantity of a gas contained in a cylinder having a weightless and
frictionless piston. The expansion of gas can be carried by two methods illustrated in Fig.3.
• Let the pressure applied to the piston be P and this is equal to the internal pressure of the
gas. Since the external and internal pressures are exactly counterbalanced, the piston
remains stationary and there is no change in volume of the gas.
• Now suppose the pressure on the piston is decreased by an infinitesimal amount dP. Thus
the external pressure on the piston being P – dP , the piston moves up and the gas will
expand by an infinitesimal small amount. The gas will, therefore, be expanded infinitely
slowly i.e., by a thermodynamically reversible process. At all stages in the expansion of the
gas, dP being negligibly small the gas is maintained in a state of equilibrium throughout. If at
any point of the process the pressure is increased by dP, the gas would contract reversibly.

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Con…
• On the other hand, the expansion is irreversible (Fig. b) if the pressure on the piston is decreased suddenly. It moves upward
rapidly in a single operation. The gas is in equilibrium state in the initial and final stages only. The expansion of the gas, in this
case, takes place in an irreversible manner.
•

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Types of Thermodynamic Cycles
1. Carnot Cycle
 In a Carnot cycle, the work material is subjected to cyclic operation.
 Carnot cycle consists of two isothermal and adiabatic processes.
 The working substance is air in a cylinder in which the piston moves.
 The engine must operate between two sources of infinite capacity. One at high
temperature and the other at low temperature.
2. Stirling Cycle
 Stirling cycle was produced by Robert Sterling which includes the original Stirling engine.
 Stirling cycle is a modified version of the Carnot cycle.
 It consists of two isothermal processes and constant volume processes.
 The last two processes are performed with the help of a refrigerator to make this cycle
reversible.
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3. Ericson Cycle:
 The Ericson cycle is invented by John Ericson.
 This cycle is consists of two isothermal and constant pressure processes.
 It is thermodynamically reversible by the action of a regenerator.
 Ericson cycles are used in closed-cycle type gas turbines.
4. Joules cycle
 Joules Cycle is also known as the Brayton cycle.
 It is a thermodynamic cycle named after George Brayton.
 It describes the workings of a constant-pressure heat engine.
 It Consists of two constant pressure and two adiabatic processes.

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5. Otto Cycle
 An Otto cycle is a thermodynamic cycle that describes the working of a spark ignition
piston engine.
 The modern petrol engines operate on Otto cycle and generally found in automobile
engines.
6. Diesel Cycle
 The engine of heavy motor vehicles works mostly on the diesel cycle.
 Rudolf Diesel invented the diesel cycle in 1897.
 The diesel cycle differs from the Otto cycle in one case.
 This added constant pressure instead of constant volume.
 It comprises two adiabatic processes, one constant pressure heat addition process, and one
constant volume heat rejection process.

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7. Dual Combustion Cycle
 The dual combustion cycle is the combustion of Otto and diesel cycles.
 It is also called the semi-diesel cycle because semi-diesel engines work on this cycle.
 In this cycle, heat is absorbed partially at constant pressure.
 It has two adiabatic, two constant volume, and constant pressure processes.

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Important Terms for Thermodynamic Cycle
• There are many terms used in a thermodynamic cycle, yet the following are important from the
subject point of view;

1. Cylinder Bore:
• The diameter of the cylinder, in which the piston moves, is known as cylinder bore.
2. Stroke Length:
• The piston moves in the cylinder due to rotation of the crank. Its extreme positions are known as a
top dead center (TDC) and bottom dead center (BDC) respectively as shown in Fig. The distance
between the two extreme positions is known as stroke length or stroke.
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3. Clearance Volume:
• The volume occupied by the working fluid, when the piston reaches the top dead center, is known
as clearance volume. It is generally denoted by (VC).
4. Stroke Volume
• The volume swept by the piston when it moves between the two extreme positions is known as
swept volume, displacement volume, or stroke volume. Mathematically, swept volume,

5. Full Cylinder Volume:

• The volume occupied by the working fluid, when the piston is at the bottom dead center, is known
as full cylinder volume. Mathematically, the full cylinder volume is equal to the sum of clearance
volume and swept volume.
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6. Compression Ratio:
• The ratio of full cylinder volume to the clearance volume is known as the compression
ratio. It is an important term is an engine. Mathematically, compression ratio,

7. Mean Effective Pressure:

• In fact, pressure in the cylinder keeps on varies with the position of the piston. For all sorts
of calculations, we need the mean effective pressure, which may be defined as acting on the
piston during the working stroke.
• It will be able to do as much work as the actual varying pressures, generated during the
cycle. It is the ratio of work done to the displacement volume.
• Mathematically, mean effective pressure
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• The Efficiency of a Cycle:
• It is described as the ratio of work done to the heat supplied during a cycle. Mathematically,
the efficiency of a cycle.

• Since the work was done during a cycle is equal to heat supplied minus the heat rejected,
the efficiency of a cycle, therefore, it is expressed as

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Note:
• The above given efficiency is the theoretical efficiency of the cycle. Therefore it is known as
theoretical thermal efficiency.
• It does not take into account the practical damage done in the running of the engine.
• To compare the efficiency of a thermodynamic cycle, the air is considered to be the working
substance in the engine cylinder. Moreover, the air is allowed to act as a perfect gas. Thus, the
efficiency obtained is known as air standard efficiency. It is also known as ideal efficiency

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