ALAWI UNIVERSITY OF SCIENCE AND TECHNOLO

CHEMICAL ENGINEERING
THERMODYNAMICS 1 (CTDY-221)

• Basic Concepts Of Thermodynamics

THERMODYNAMICS
The science of thermodynamics was developed in the 19th century as a result
of the need to describe the basic operating principles of the newly invented
steam engine and to provide a basis for relating the work produced to the
heat supplied. Thus the name itself denotes power generated from heat.
From the study of steam engines, there emerged two of the primary
generalizations of science: the First and Second Laws of Thermodynamics
SYSTEMS
• Thermodynamic system: A
quantity of matter or a region in
space chosen for study
• Surroundings: The mass or
region outside the system
• Boundary: The real or imaginary
surface that separates the
system from its surroundings
• Can be fixed or movable
 • There are many different systems one
Consider the Rankine Cycle might define in the Rankine cycle:
• The entire cycle
• Any single piece of equipment e.g.
turbine, pump, boiler or
condenser
• Two sequential pieces of
equipment, e.g. the pump and the
boiler.

Schematic description of the Rankine cycle

 CLOSED AND OPEN SYSTEMS
• Systems may be considered to be closed or open, depending on
whether a fixed mass or a fixed volume in space is chosen for study.
• A closed system consists of a fixed amount of mass and no mass may
cross the system boundary
• The closed system boundary may move
• Heat and work (energy) can cross the boundary
• volume does not have to be fixed
• Examples of closed systems:
• Sealed tanks
• Piston cylinder device
• An open system, or control volume, has mass as well as energy
crossing the system boundary (called a control surface).
• Control surface: The boundaries of a control volume

An open system (control

volume) with one inlet and one
exit
Control surface
• The control surface can be real or imaginary, fixed or moving

A control volume with real and imaginary A control volume with fixed and moving
boundaries boundaries
• Examples of open systems
from the Rankine cycle?
• Boiler
• Turbine
• Pump
• Condenser

• Examples of closed systems

from the Rankine cycle?
• The whole cycle
PROPERTIES OF A SYSTEM
• Property: Any characteristic of a system
• P, T, V, mass m, viscosity, thermal conductivity,
velocity
• Intensive properties: Properties that are
independent of the mass of a system e.g.?
• T, P, ρ
• Extensive properties: Properties whose
values depend on the size or extent of the
system e.g.?
• mass, volume
• Specific properties: Extensive properties
per unit mass
• Criterion to differentiate intensive
and extensive properties
STATE AND EQUILIBRIUM
• The state of a system is its
condition as described by a set
of relevant properties e.g. T, P, v
• Equilibrium: a static condition or
the absence of change.
• A system at equilibrium exists
under conditions such that no
change in state can occur.
• Thermodynamics deals with
equilibrium states
A system at two different states
Types of equilibrium
• 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 with time
• Phase equilibrium: in a two phase
system, when the mass of each
phase reaches an equilibrium level A closed system reaching thermal
• Chemical equilibrium: when the equilibrium
chemical composition of a system
does not change with time i.e. no
chemical reactions occur
PROCESSES AND CYCLES
• Process: Any change that a system undergoes
from one equilibrium state to another.
• Path: The series of states through which a
system passes during a process.

• A system is said to have undergone a cycle if it

returns to its initial state at the end of the
process.

A process between states 1 and 2 and

the process path
• Process diagrams plotted by employing
thermodynamic properties as coordinates are
very useful in visualizing the processes.
• Some common properties that are used as
coordinates include T, P, and volume V (or
specific volume v)
• The prefix iso- is often used to designate a
process for which a particular property remains
constant.
Isothermal process:
• A process during which the temperature T
remains constant.
Isobaric process:
• A process during which the pressure P remains
constant.
Isochoric (or isometric) process:
The P-V diagram of a compression
• A process during which the specific volume v process of a gas
remains constant.
 FIRST LAW OF
THERMODYNAMICS
• First law of thermodynamics
(the conservation of energy
principle):
• Energy can neither be created
nor destroyed during a process;
it can only change forms.
FIRST LAW OF
THERMODYNAMICS
• The conservation of energy principle can be expressed as:
The net change (increase or decrease) in the total energy of a system
during a process is equal to the difference between the total energy
entering and the total energy leaving the system during that process

OR
FORMS OF ENERGY
• Energy can exist in numerous forms e.g. thermal, mechanical, kinetic,
potential, electric, chemical, and their sum constitutes the total
energy, E, of a system.
• The total energy of a system on a unit mass basis is denoted by e and
is expressed as:
(kJ/kg)
• Thermodynamics deals with the change of the total energy i.e. .
ENERGY FORMS IN THERMODYNAMIC
SYSTEMS
• Various energy forms can exist in thermodynamic systems.
• In some systems they may all be present while in other systems only
some may be present.
• Various forms of energy appearing in thermodynamic systems include:
• Kinetic energy
• Potential energy
• Internal energy
• Heat
• Work
• Displacement or flow energy (discussed in open system analysis)
Kinetic energy (KE):
• The energy that a system possesses as a result of its motion relative
to some reference frame.
(kJ)
Where:
• C is the velocity of the system
• m is the mass of the system
• For unit mass,

Specific kinetic energy, ke

Potential energy (PE):
• The energy that a system possesses as a result of its elevation in a
gravitational field.
(kJ)
Where:
• g is the gravitational acceleration
• is the height of the object above a reference plane at which PE
• m is the mass of the system
• For unit mass,

Specific potential energy pe

Internal energy (U):
• Energy resulting from the motion of atoms or molecules
• Due to their ceaseless motion, all molecules possess kinetic energy of
translation; kinetic energy of rotation and kinetic energy of internal
vibration.
• Internal energy is the sum of all these forms of energy
Heat transfer, Q
• Heat is defined as the form of energy that is transferred between two
systems (or a system and its surroundings) by virtue of a temperature
difference
• Heat transfer to a system (heat gain) increases the energy of the molecules
and thus the internal energy of the system
• Heat transfer from a system (heat loss) decreases the energy of the
molecules
• An energy interaction is heat only if it takes place because of a
temperature difference
• There cannot be any heat transfer between two systems that are at the
same temperature.
• A process during which there is no heat transfer is called an adiabatic
process
Work Transfer, W
• An energy interaction that is not caused by a temperature difference
between a system and its surroundings is work.
• Work done on or by a system is accomplished by movement of the system
boundary against a resisting force.
• If there is no motion along the system boundary, then there is no work
transfer to or from the system.
• A rising piston, a rotating shaft, and an electrical wire crossing the system
boundaries are all associated with work interactions.
• Work transfer to a system (i.e., work done on a system) increases the energy
of the system.
• Work transfer from a system (i.e., work done by the system) decreases the
energy of the system
• energy transferred out as work comes from the energy contained in the
system
ENERGY BALANCE FOR CLOSED
SYSTEM
In a closed systems, no streams enter or leave a closed system,
no energy associated with matter is transported across the
boundary that divides the system from its surroundings.
All energy exchange between a closed system and its
surroundings is in the form of heat or work, and the total energy
change of the surroundings equals the net energy transferred to
or from it as heat and work.

Heat Q and work W always refer to the system, and the choice of sign for
numerical values of these quantities depends on which direction of energy
transfer with respect to the system is regarded as positive.
When Energy is transferred to the system

When Energy is transferred to the surrounding

Closed systems often undergo processes during which only the internal energy of
the system changes. For such processes
Where Ut is the total internal energy of the system. The equation applies to
processes of finite change in the internal energy of the system. For differential
changes in Ut:

The symbols Q, W, and Ut pertain to the entire system, which may be of any size,
but must be clearly defined. All terms require expression in the same energy
units. In the SI system the unit is the joule.
Total volume Vt and total internal energy Ut depend on the quantity of material
in a system, and are called extensive properties.

For a homogeneous system, an alternative means of expression for the extensive

properties, such as Vt and Ut, is:
Where the plain symbols V and U represent the volume and internal energy of a
unit amount of material, either a unit mass or a mole.

For a closed system of n moles

In this form, these equations show explicitly the amount of substance comprising
the system. The equations of thermodynamics are often written for a
representative unit amount of material, either a unit mass or a mole.
Thus, for n = 1,

The basis for Q and W is always implied by the mass or number of moles
associated with the left side of the energy equation.
Example 1
The Niagara river, separating the United States from Canada, flows from Lake
Erie to Lake Ontario. These lakes differ in elevation by about 100 m. Most of this
drop occurs over Niagara Falls and in the rapids just above and below the falls,
creating a natural opportunity for hydroelectric power generation. The Robert
Moses hydroelectric power plant draws water from the river well above the falls
and discharges it well below them. It has a peak capacity of 2,300,000 kW at a
maximum water flow of 3,100,000 kg·s-1. In the following, take 1 kg of water as
the system.
• (a) What is the potential energy of the water flowing out of Lake Erie,
relative to the surface of Lake Ontario?
• (b) At peak capacity, what fraction of this potential energy is converted to
electrical energy in the Robert Moses power plant?
• (c) If the temperature of the water is unchanged in the overall process,
how much heat flows to or from it?
SOLUTION
Example 2
Solution
Example 3
A horizontal piston/cylinder arrangement is placed in a constant-temperature
bath. The piston slides in the cylinder with negligible friction, and an external
force holds it in place against an initial gas pressure of 14 bar. The initial gas
volume is 0.03 m3. The external force on the piston is reduced gradually, and the
gas expands isothermally as its volume doubles. If the volume of the gas is
related to its pressure so that PVt is constant, what is the work done by the gas
in moving the external force?
Solution