Chemical Engineering

Thermodynamics
Thermodynamics 1 I

Chemical Engineering Department

Dr. Hadil Abu Khalifeh
Chemical Engineering
Abu Department
Dhabi University

ADU
Dr. Kathleen Haigh
Spring 2015
Assistant Professor
Basic Concepts
• System: A quantity of matter or a region in
space chosen for study.
• Surroundings: The mass or region outside the Reference 2

system
• Boundary: The real or imaginary surface that
separates the system from its surroundings.
• The boundary of a system can be fixed or
movable.
• Systems may be considered to be closed or
open.

The system’s thermodynamic state is defined by macroscopic properties

that can be measured (such as pressure).

The macroscopic properties are described in terms of fundamental

scientific dimensions: Length, time, mass, temperature etc.
 Closed and Open Systems

(a) Closed Systems: Moving

boundary
controlled (fixed) mass.
GAS

GAS 2 kg
2 kg 3 m3
1 m3

Closed
System mass NO Fixed
boundary
(m= constant)
energy YES

Reference 2
(b) Open system: controlled (fixed) volume

Control surface
Hot Water
Out
Water
Heater
(control
volume) Cold Water
IN

• Open system (control volume): A properly selected region in space.

• It usually encloses a device that involves mass flow such as a compressor,
turbine, or nozzle.
• Both mass and energy can cross the boundary of a control volume.
• Control surface: The boundaries of a control volume. It can be real or
imaginary.
Reference 2
 PROPERTIES OF A
SYSTEM
• Property: Any characteristic of a
system.
• Some familiar properties are pressure
P, temperature T, volume V, and mass
m.
• Properties are considered to be either
intensive or extensive.
• Intensive properties: Those that are
independent of the mass of a system,
such as temperature, pressure, and
density.
• Extensive properties: Those whose Reference 2

values depend on the size—or extent—

of the system.
• Specific properties: Extensive Criterion to differentiate intensive
properties per unit mass. and extensive properties.
STATE AND EQUILIBRIUM

• Thermodynamics deals with equilibrium

states.
• Equilibrium: A state of balance.
• In an equilibrium state there are no
unbalanced potentials (or driving
forces) within the system.
• Thermal equilibrium: If the
temperature is the same throughout Reference 2

the entire system.

• Mechanical equilibrium: If there is no A system at two different states.
change in pressure at any point of the
system with time.
• Phase equilibrium: If a system involves
two phases and when the mass of each
phase reaches an equilibrium level and
stays there.
• Chemical equilibrium: If the chemical
composition of a system does not
change with time, that is, no chemical Reference 2

reactions occur.

A closed system reaching thermal

equilibrium.
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.
To describe a process completely, one should specify the initial and final states, as well
as the path it follows, and the interactions with the surroundings.
Quasistatic or quasi-equilibrium process: When a process proceeds in such a manner
that the system remains infinitesimally close to an equilibrium state at all times.

Reference 2

Reference 2

Reference 2
• Process diagrams plotted by employing
thermodynamic properties as coordinates
are very useful in visualizing the
processes.
• Some common properties that are used
as coordinates are temperature T,
pressure 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: A Reference 2

process during which the specific volume

v remains constant. The P-V diagram of a compression
process.
• Cycle: A process during which the initial
and final states are identical.
Thermodynamic cycle: Processes as a result of which a system
returns to its original state, i.e., identical end states.

P (a) Two-process P (b) Four-process

cycle 3 cycle
2

4
2

1 1

V V
 Work
• Work: The energy transfer associated with a force acting through a distance.
• There are two requirements for a work interaction between a system
and its surroundings to exist:
– there must be a force acting on the boundary.
– the boundary must move.

When force is not constant

Work = Force  Distance

Reference 2

If there is no movement,
no work is done.
The work done is proportional to the force
applied (F) and the distance traveled (s).
 Work
1. Push-Pull work
work is done whenever a force acts through a distance

2. Pv work F = PA
A
W   F .dl
V l
dW  F .dl   P. A.d ( )   P.dV
A
V2

W    P.dV
V1

Note: V in these equations refers to total volume.

 A relation between P and V should be available to
determine the work (graphical or mathematical).
 W = area under the curve
 Sign convention:
 +W: work done by the surrounding on the system:
 -W: work done by the system on the surrounding
Graphical Representation of Compression and Expansion Processes
Compression: Expansion:
2 +ve work? 1 -ve work?

P P
1 2
W W
b V a b V a

For the compression process:


Opposite for
@ state 1; low pressure & high volume
expansion
@ state 2; high pressure & low volume process
 Example:
Gas contained in a cylinder:
Initial pressure and volume: P1 = 200 kPa
V1 = 0.04 m3
Determine the work done for the following cases:
a) The gas was heated under constant pressure until
the volume of the gas increase to V2 = 0.1 m2.
V2 V2

W  -  PdV t
 -P  dV t
= - P (V2-V1) = 200 kPa (0.1 – 0.04)m3 = -12 kJ
V1 V1
 Heat: The form of energy that is transferred between two systems (or a
system and its surroundings) by virtue of a temperature difference.

Reference 2

Energy can cross the

boundaries of a closed system
in the form of heat and work.
 Sign convention: Reference 2

Temperature difference is the driving

 +Q: heat done by the surrounding force for heat transfer. The larger the
on the system: temperature difference, the higher is the
 - Q: heat done by the system on rate of heat transfer.
the surrounding
A body never contains heat Heat is just crossing the boundary
(like electrical current)
 Heat is a transient phenomenon

 Temperature is the driving force for heat flow:

Rate of heat transfer  T

 Sign convention:
 +Q: heat done by the surrounding on the system:
 - Q: heat done by the system on the surrounding
 Heat like work, is a path function, 
2 T2

Q  Q
1
12   f (T )dT
T1
Heat vs. Work
• Both are recognized at the boundaries of a
system as they cross the boundaries. That
is, both heat and work are boundary
phenomena.
• Systems possess energy, but not heat or
work.
• Both are associated with a process, not a
state.
• Unlike properties, heat or work has no
meaning at a state.
• Both are path functions (i.e., their
magnitudes depend on the path
followed during a process as well as the Properties are point functions; but
end states). heat and work are path functions
(their magnitudes depend on the
path followed).
Kinetic Energy
If a body m, acted upon a force F, is displaced
F dl
a distance dl during a differential time dt. The m
u
work done is given by:
dW  Fdl but F  ma
du
dW  madl but a Where u is the velocity of the body
dl dt
du
dW  m dl  m du
dt dt u2
 u 22 u12 
or dW  mudu

W  m udu  m   
integration

u1  2 2 
mu 22 mu12  mu 2 
W  -    ½ mu2 is a kinetic energy
2 2  2  1
or E k  mu 2
• Work done on a body in accelerating it from 2
initial velocity u1 to a final velocity u2 is equal to
the change in kinetics energy of the body. Unit in SI system:
[Ek] = kg . m2/s2 or N.m = Joules
Potential Energy
If a body m is raised from an initial elevation Z1 to a final m
elevation Z2. The upward force exerted on the body is equal
mg dZ
to its weight. Work required to raise the body is:

dW  Fdl  mgdZ m

W  mg (Z 2  Z 1 )  mgZ 2 - mgZ 1  (mgZ )

 Work done on the body in raising it from Z1 to Z2 is equal to the change of the
quantity mgZ

 To lower the body, work should be done by the body which is also equal to the
change in mgZ.
 If the work done on a body in accelerating it or elevating it can be subsequently
recovered, then the body by virtue of its velocity or elevation has the ability to do
the work.

 Work accelerating a body is said to produce a change in its kinetic energy, or

 mu 2 
W  E K    
 2 

 Work done on a body in elevating it is said to produce a change in its potential

energy, or
W  E P    mgZ 
 Unit of EP in SI system: [EP] = kg . m/s2 . m = N . m = Joule
 Conservation of Energy
 If a body is given energy when it is elevated, then the body conserves or retains
this energy until it performs the work of which it is capable. An elevated body
allowed to fall freely gains in kinetic energy and loses potential energy.

Potential energy is converted into kinetic energy; or its capability for

doing work remains unchanged, or:
Total W = EK + EP = 0

1 1
Or mu 2  mu12  mgZ 2  mgZ 1  0
2

2 2
 Other types of mechanical energies: Compression of spring by external force,
energy is stored in the spring; later when the spring expands, it performs this work
or releases this energy by a resisting force  spring has capability for doing work.
Exercise (2):
A gas is confined in a 0.47-m-diameter cylinder by a piston, on which rests a
weight. The mass of the piston and weight together is 150 kg. The local
acceleration of gravity is 9.813 m s-2, and atmospheric pressure is 101.57 kPa.

(a) What is the force in newtons exerted on the gas by the atmosphere, the
piston, and the weight, assuming no friction between the piston and
cylinder?
(b) What is the pressure of the gas in kPa?
(c) If the gas in the cylinder is heated, it expands, pushing the piston and
weight upward. If the piston and weight are raised 0.83 m, what is the
work done by the gas in kJ?
What is the change in potential energy of the piston and weight?
Solution:

1-23
• Energy can exist in numerous forms such as thermal, mechanical, kinetic,
potential, electric, magnetic, chemical, and nuclear, and their sum constitutes
the total energy, E of a system.
• Thermodynamics deals with the change of the total energy.
• Macroscopic forms of energy: Those a system possesses as a whole with
respect to some outside reference frame, such as kinetic and potential
energies.

• Kinetic energy, KE: The energy

that a system possesses as a result
of its motion relative to some
reference frame.
• Potential energy, PE: The energy
Reference 2

that a system possesses as a result The macroscopic energy of an

of its elevation in a gravitational object changes with velocity and
field. elevation.
Microscopic forms of energy: Those related to the molecular structure of a
system and the degree of the molecular activity.
Internal energy, U: The sum of all the microscopic forms of energy.
 Kinetic energy

Kinetic energy
per unit mass

Potential energy

Potential energy
per unit mass

Conservation of energy principle: During an

interaction, energy can change from one form to
another but the total amount of energy remains
constant. Reference 2

Energy cannot be created or destroyed.

Total energy
of a system
 Microscopic forms of energy: Those related to the molecular structure of a
system and the degree of the molecular activity.
Internal energy, U: The sum of all the microscopic forms of energy.
It accounts for internal motions of the molecules which move around with some
velocity (transnational motion), vibrate about each other (Vibrational motion),
and rotate about an axis during their random motion (rotational motion) .

Sensible energy: The portion of the internal

Reference 2
The various forms of
microscopic
energies that make
up sensible energy.
energy of a system associated with the kinetic
energies of the molecules.
Latent energy: The internal energy associated
with the phase of a system.
Chemical energy: The internal energy
associated with the atomic bonds in a molecule.
Nuclear energy: The tremendous amount of
energy associated with the strong bonds within
the nucleus of the atom itself.
 The Steady-Flow Process

• The term steady implies no

change with time. The
opposite of steady is unsteady,
or transient.
• A large number of engineering During a steady-
devices operate for long flow process, fluid
periods of time under the properties within
same conditions, and they are the control
classified as steady-flow volume may
devices. change with
• Steady-flow process: A process position but not
during which a fluid flows with time. Reference 2

through a control volume

steadily.
• Steady-flow conditions can be
closely approximated by
devices that are intended for
continuous operation such as
turbines, pumps, boilers,
condensers, and heat
exchangers or power plants or Under steady-flow conditions, the mass
refrigeration systems. and energy contents of a control volume
remain constant.
References:
Cengel, Y. A. and Boles, A. B. Thermodynamics: An Engineering
Approach, Third Edition, McGraw-Hill (1998).

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