11/29/2023

HARAMAYA UNIVERSITY
HARAMAYA INSTITUTE OF TECHNOLOGY
DEPARTMENT OF CHEMICAL ENGINEERING
CHEMICAL ENGINEERING THERMODYNAMICS I
BY
Melkiyas Diriba (MSc. In Chemical Process and Product Design)
2023/24
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 Basic terms and definitions

Thermodynamics can be defined as;

◦ It is a science, which deals with the relations among heat, work and properties

of system, which are in equilibrium.

 It describes state and changes in state of physical systems.

◦ The science of the regularities governing processes of energy conversion.

◦ It deals with the interaction between energy and material systems.

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 Application area of thermodynamics
 All activities in nature involve some interaction between energy and matter; thus, it is hard to imagine an area that

does not relate to thermodynamics in some manner.

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Four laws of thermodynamics:

The First law throws light on concept of internal energy.

The Zeroth law deals with thermal equilibrium and establishes a concept of

temperature.

The Second law indicates the limit of converting heat into work and introduces the

principle of increase of entropy.

The Third law defines the absolute zero of entropy.

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 Importance of dimensions and units

 Dimensions can characterize any physical quantity.

 The magnitudes assigned to the dimensions are called units.

Dimensions can be categorized into fundamental and derived dimensions.

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 Systems and Surroundings
 System: is a quantity of matter or a region in space chosen for study.

 Surroundings: is the mass or region outside the system.

 Boundary: is the real or imaginary surface that separates the system from its surroundings.

 the boundary has zero thickness

 it can neither contain any mass nor occupy any volume in space.

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 Types of thermodynamic system
Based on mass and energy transfer the thermodynamic system is divided into three types.

a. Closed system: Energy transfer but not mass.

Example: boiling of water in closed vessel.

b. Open system: both mass and energy exchange can takes place.

Example: boiling of water in open vessel.

c. Isolated system: neither energy nor mass

exchange takes place.

Example: Tea present in a thermos flask.

Open system
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 Control volume
 It is a volume which encloses the matter and the device inside a control surface.
 Not all open systems are control volume but control volumes are open systems.

 Most of the engineering devices, in general, represent an open system or control volume

 The mass of a control volume (open system) may or may not be fixed.

Example: heat exchanger, pump, etc.

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 Macroscopic and microscopic view of thermodynamics
S.No Macroscopic Approach Microscopic Approach

1 In this approach, a certain quantity of matter is considered The matter is considered to be comprised of a large number of tiny
without taking into account the events occurring at molecular particles known as molecules, which moves randomly in chaotic
level. fashion. The effect of molecular motion is considered.

2 Analysis is concerned with overall behavior of the system. The Knowledge of the structure of matter is essential in analyzing
the behavior of the system.
3 This approach is used in the study of classical This approach is used in the study of statistical thermodynamics.
thermodynamics.
4 A few properties are required to describe the system. Large numbers of variables are required to describe the system.

5 The properties like pressure, temperature, etc. needed to The properties like velocity, momentum, kinetic energy, etc. needed
describe the system, can be easily measured. to describe the system, cannot be measured easily.

6 The properties of the system are their average values. The properties are defined for each molecule individually.

7 This approach requires simple mathematical formulas for No. of molecules are very large so it requires advanced statistical
analyzing the system. and mathematical method to explain any change in the system.
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 Property of the system
 Property is defined as any characteristic of a system.

a. Intensive properties: are those that are independent of the size (mass) of a system.
 They are not additive.

Example: temperature, pressure, specific internal energy, and density

 Uppercase letters are used to denote extensive properties (except mass m)

b. Extensive properties: values that are dependent on size of the system.

 They are additive.

Example: mass, volume, enthalpy, entropy, and total energy U.

 Lower case letters are used for intensive properties (except pressure P, temperature T).
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 Difference between extensive and intensive properties

S.No Extensive property Intensive property

1 Its value depends on how a large portion of Its value remains constant whether we consider the
system are considered. whole system or part of it.

2 It depends on mass of system It is independent of mass of system

3 Energy, enthalpy, entropy, volume, area, Pressure, temperature, density, thermal

heat, etc. are its examples. conductivity and viscosity are its examples.

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 State and Equilibrium
 At a given state, all the properties of a system have fixed values.

 A system in equilibrium experiences no changes when it is isolated from its surroundings.

Thermal equilibrium: when the temperature is the same throughout the entire system.

Mechanical equilibrium: when there is no change in pressure at any point of the system.
 However, the pressure may vary within the system due to gravitational effects.

Phase equilibrium: in a two-phase system, when the mass of each phase reaches an equilibrium level.

Chemical equilibrium: when the chemical composition of a system does not change with time.
 no chemical reactions occur.

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 Processes and Cycles

Process: Any change a system undergoes from one equilibrium state to another.

Path: The series of states through which a system passes during a process.
Quasi‐equilibrium process: is an idealized process and is not
a true representation of the actual process

Prefix iso‐ is used to designate a process for which a particular property

is constant.

◦ Isothermal: is a process during which the temperature remains constant

◦ Isobaric: is a process during which the pressure remains constant

◦ Isometric: is process during which the specific volume remains constant.

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A system is said to have undergone a cycle if it returns to its initial state at the end of the process.

 The state of a system is Figure:

described
A fourby its properties
‐process cycle in a P‐V diagram.

 State postulate: The state of a simple compressible system is completely specified by two independent,
intensive properties.

 A system is called simple compressible system in the absence of electrical, magnetic, gravitational, motion, and

surface tension effects (external force fields).

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 Path and point functions

o Point function does not depend on the history (or path) of the system.

 It only depends on the state of the system.

o Examples of point functions are: temperature, pressure, density, mass, volume, enthalpy, entropy, internal energy etc.

o Path function depends on history of the system (or path by which system arrived at a

given state).

o Examples for path functions are work and heat.

o Path functions are not properties of the system, while point functions are properties of the system.

o Change in point function can be obtained by from the initial and final values of the function, whereas path has to

defined in order to evaluate path functions.

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

 Units: N/m2, Pa, Bar, atm, etc.

 The actual pressure at a given position is called the absolute pressure, and it is measured relative to absolute
vacuum (i.e., absolute zero pressure).

 Gage pressure: The difference between absolute and local atmospheric pressures.
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 Vacuum pressure: it is pressures below atmospheric pressure.
Measured by vacuum gages that indicate the difference between the atmospheric pressure and the absolute
pressure.

Relations:

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 Force

 It described as the product of mass m and acceleration a:

 The SI unit of force is the newton, symbol N.

 The newton is defined as the force which when applied to a mass of 1 kg produces an acceleration of

 Thus the newton is a derived unit representing 1 kg .

Example 1: An astronaut weighs 730 N in Houston, Texas, where the local acceleration of gravity is g =

9.792 . What are the astronaut’s mass and weight on the moon, where g = 1.67 ?

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 Work
 Work W is performed whenever a force acts through a distance.

Where; F is the component of force acting along the line of the displacement dl.

 When integrated, this equation yields the work of a finite process.

 The minus sign is required because the volume change is negative.

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 Energy
 It is the ability to do work.

Kinetic energy (Ek): When a body of mass m, acted upon by a force F, is displaced a distanced during a
differential interval of time dt.

= Ek
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Potential energy (Ep): The body by virtue of its elevation contains the ability or capacity to do the
work.

Example 2: An elevator with a mass of 2500 kg rests at a level 10 m above the base of an elevator shaft. It
is raised to 100 m above the base of the shaft, where the cable holding it breaks. The elevator falls freely to
the base of the shaft and strikes a strong spring. The spring is designed to bring the elevator to the rest
and, by the means of a catch arrangement, to hold the elevator at the position of maximum spring
compression. Assuming the entire process to be frictionless, and taking g = 9.8 , calculate;
a. The Ep of the elevator in its initial position relative to the base of the shaft.
b. The work done in raising the elevator.
c. The Ep of the elevator in its highest position relative to the base of the shaft.
d. The velocity and Ek of the elevator just before it strikes the spring.
e. The potential energy of the compressed spring.
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 Temperature and Zeroth law of thermodynamics

 Temperature is commonly measured with liquid-in-glass thermometers, wherein the liquid expands when heated.

 Thus a uniform tube, partially filled with mercury, alcohol, or some other fluid, can indicate degree of "hotness“
simply by the length of the fluid column.

 However, numerical values are assigned to the various degrees of hotness by arbitrary definition.

Figure. Relations among temperature scales

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Zeroth law of thermodynamics: The Thermodynamics Zeroth Law states that if two systems
are at the same time in thermal equilibrium with a third system, they are in equilibrium with each
other.

 If objects ‘A’ and ‘C’ are in thermal equilibrium with ‘B’, then object ‘A’ is in thermal equilibrium

with object ‘C’.

 Practically this means all three objects are at the same temperature and it forms the basis for

comparison of temperatures.

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