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THERMODYNAMICS

Definitions of Thermodynamics:
can be defined as the science of ENERGY

ENERGY :
might be difficult to define precisely, but
we can view it as AN ABILITY TO
CAUSE CHANGES

Covenant University, Dept. of Chemical


11/3/2017 1
Engineering, Thermodynamics (GEC 221)
Thermodynamics stems from the greek word
therme (heat) and dynamis (dynamic/power)
Heat Power

Early interpretation described it as EFFORTS TO


CONVERT HEAT INTO POWER

Modern times broadly interpreted it to include all


aspects of energy and energy transformation;
including power generation, refrigeration, and
relationships among the properties of matter.

Covenant University, Dept. of Chemical


11/3/2017 2
Engineering, Thermodynamics (GEC 221)
One of the fundamental law of nature is
Conservation of energy principle

that during an interaction, energy can


change from one form to another but the total
amount of energy remains constant, that is,
energy can neither be created nor destroyed.

Covenant University, Dept. of Chemical


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Engineering, Thermodynamics (GEC 221)
Example 1: A rock on a cliff
PE = 10 units picks up speed as its P.E.
KE = 0
changes to K.E. as it falls to
the ground.

PE = 7 units
KE = 3 units

Covenant University, Dept. of Chemical


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Engineering, Thermodynamics (GEC 221)
Example 2:

A person that has greater energy input (food)


than energy output (exercise) will gain weight
(stores energy in form of fat), and a person
who has smaller energy input than output
looses weight

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Engineering, Thermodynamics (GEC 221)
It follows then that:
The change in energy content of a body or any
other system is equal to the difference between
the energy input and the energy output, and the
energy balance is given as
Human being, 1
unit energy storage

Ein Eout = E Energy in, Energy out,


5 units 4 units

The 1 unit stored energy is used


to grow fatter
Covenant University, Dept. of Chemical
11/3/2017 6
Engineering, Thermodynamics (GEC 221)
The Two Laws of Thermodynamics
The 1st law expresses the conservation of
energy principle, and it assets that energy is a
thermodynamic property
The 2nd law asserts that energy has quality as
well as quantity, and actual processes occur in
the direction of decreasing quality of energy.

Covenant University, Dept. of Chemical


11/3/2017 7
Engineering, Thermodynamics (GEC 221)
An example of the second law is a cup of hot
coffee left on a table which eventually cools,
but a cup of cool coffee in the same room
never gets hot by itself.

Hot cold
decreasing quality

Covenant University, Dept. of Chemical


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Engineering, Thermodynamics (GEC 221)
At high temp., energy of coffee is degraded
(transformed into a less useful form at a lower
temp.) once it is transferred to the surrounding
air.
The 1st and 2nd laws emerged simultaneously
in 1850s from the works of William Rankine,
Rudolph Clausius, Lord Kelvin.

Covenant University, Dept. of Chemical


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Engineering, Thermodynamics (GEC 221)
NOTE
Substances consists of large number of
particles called MOLECULES. The properties
of the substance naturally depend on the
behaviour of these particles (the molecules).
e.g. The pressure of a gas in a container is the
result of momentum transfer between the
molecules and the walls of the container. It
will be sufficient to attach a pressure gauge to
the container to determine the pressure in the
container rather than trying to know the
behaviour of the gas particles to determine the
pressure.
Covenant University, Dept. of Chemical
11/3/2017 10
Engineering, Thermodynamics (GEC 221)
Approaches to Thermodynamics
Classical Thermodynamics
It is the macroscopic approach that does not
require a knowledge of the behaviour of
individual particle.
It is observation driven
Focus is on bulk energy flow
Interest includes: energy transfer, energy
transformation and energy storage
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Engineering, Thermodynamics (GEC 221)
Approaches to Thermodynamics
Statistical Thermodynamics
It is a more elaborate approach, based on the
average behaviour of large groups of
individual particles.
It is a microscopic approach.
Focus includes structures of matter and
molecular interaction
It is theory driven
Covenant University, Dept. of Chemical
11/3/2017 12
Engineering, Thermodynamics (GEC 221)
Application Areas of Thermodynamics
1. Human Existence

Food, drink Body heat


Human Body
(rejection)
(Heart)

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Engineering, Thermodynamics (GEC 221)
Heart pumps blood continuously to all parts of
the body.
Energy conversions occur in trillions of body
cells.
Body heat generated is constantly rejected to
the environment.
The body comfort is closely tied to the rate of
this metabolic heat rejection.
We control the heat transfer rate by adjusting
our clothing to the environmental conditions.

Covenant University, Dept. of Chemical


11/3/2017 14
Engineering, Thermodynamics (GEC 221)
Application Areas of Thermodynamics

2. Household utensils and applications : are


designed in whole or in part by using the
principles of thermodynamics e.g. heating or
air conditioning systems, the refrigerator, the
humidifiers, the pressure cooker, the water
heater, the shower, the iron.

Covenant University, Dept. of Chemical


11/3/2017 15
Engineering, Thermodynamics (GEC 221)
Application Areas of Thermodynamics

On a larger scale , thermodynamics play a


major role in the design and analysis of
automobile engines, rockets, jet engines,
conventional or nuclear power plant, and
design of vehicles from ordinary car to
airplanes.

Covenant University, Dept. of Chemical


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Engineering, Thermodynamics (GEC 221)
DIMENSIONS AND UNITS
Any physical quantity can be characterised by
dimensions.
The magnitude (size) assigned to the
dimensions are called units.
Basic dimensions : mass (m), length (L), time
(t) and Temperature (T) are selected as
primary or fundamental units.

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11/3/2017 17
Engineering, Thermodynamics (GEC 221)
Velocity (V), energy (E), and volume (V) are
expressed in terms of the primary dimensions
and are called secondary dimensions or
derived dimensions.

Covenant University, Dept. of Chemical


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Engineering, Thermodynamics (GEC 221)
Common Unit Systems in Science and
Engineering

English system : no apparent systematic


numerical base, various units in the system
are related to each other rather arbitrarily
12 inch = 1 ft.
1 mile = 5280 ft.
4 quint = 1 gallon

Covenant University, Dept. of Chemical


11/3/2017 19
Engineering, Thermodynamics (GEC 221)
The metric SI system : This is a simple and
logical system based on a decimal relationship
between various units.

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Engineering, Thermodynamics (GEC 221)
Dimensions SI units
Length metre, m
Mass kilogram, (kg)
Time Second, (s)
Temperature kelvin (K)
Electric current ampere (A)
Amount of matter mole, (mol)
Amount of light (luminous intensity) Candela (cd)

Covenant University, Dept. of Chemical


11/3/2017 21
Engineering, Thermodynamics (GEC 221)
Convention in Writing Units
Do not capitalise fundamental units like
metre, kilogram, and second : 20 M is wrong,
instead 20 m, 20 kg NOT 20 Kg, 20 Min
instead, write 20 min
Units having proper names e.g. SI unit of force
named after Sir Isaac Newton is 20 newton
(not Newton) but if you abbreviate, you write
20 N

Covenant University, Dept. of Chemical


11/3/2017 22
Engineering, Thermodynamics (GEC 221)
Dont write 5 ms but you can write 5 metres.
Also is wrong to write 5 metre, but 5 m is
correct.
No full stop after writing the unit e.g. 5 m not
5 m.
There is always a space between the number
and unit
e.g. 5 m not 5m

Space

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11/3/2017 23
Engineering, Thermodynamics (GEC 221)
SI units English system
kg Ibm (pound-mass)
m ft (foot)
s s (second)
O.45359 kg 1 Ibm
0.3048 m 1 ft

Covenant University, Dept. of Chemical


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Engineering, Thermodynamics (GEC 221)
Note that weight is a force, it is the gravitational
force applied to a body, and its magnitude is
determined from Newtons 2nd law
W = mg (N)
The mass of a body remains the same regardless
of its location in the universe. Its weight, however
changes with a change in gravitational
acceleration.
A body weighs less on top of a mountain since g,
decreases with altitude.
On the surface of the moon, an astronaut weighs
about 1/6th of what she or he normally weighs on
earth
Covenant University, Dept. of Chemical
11/3/2017 25
Engineering, Thermodynamics (GEC 221)
At locations below sea level, the value of g
(gravitational acceleration) increases with
distance from the sea level, reaches a
maximum at about 4500 m, and then starts
decreasing.
g, varies with location from 9.8295 m/s2 at
4500 m below sea level to 7.3218 m/s2 at
100,000 m above sea level.
At altitude up to 30,000 m variation of g from
the sea level value of 9.807 m/s2 is less than
1%
Covenant University, Dept. of Chemical
11/3/2017 26
Engineering, Thermodynamics (GEC 221)
Exercises
Read about prefixes for multiples of various
units e.g. tera, giga, deci, nano, pico.
What is the difference between pound-mass
and pound-force.
Determine the mass and the weight of the air
contained in a room whose dimensions are 6 m
x 6 m x 8 m. Assume the density of the air is
1.16 kg/m3.
Convert 100 Ibf/in2 to N/m2. Given that 1 Ibf =
4.4482 N, 1 m = 39.37 in

Covenant University, Dept. of Chemical


11/3/2017 27
Engineering, Thermodynamics (GEC 221)
Dimensional Homogeneity
In science and engineering, all equations must
be dimensionally homogeneous ( every term
in an equation must have the same unit)

e.g. John + lettuce + olives + mayonaise + eba +


fufu + pickles = stomach upset.
Checking dimensions can serve as a valuable
tool to spot errors in engineering analysis.
Covenant University, Dept. of Chemical
11/3/2017 28
Engineering, Thermodynamics (GEC 221)
Basic Concepts of Thermodynamics
System
A system is a region in space, delineated
(chosen) for study.

Surroundings
The mass or region outside the system.

Boundary
The real or imaginary surface that separates
the system from its surroundings.
Covenant University, Dept. of Chemical
11/3/2017 29
Engineering, Thermodynamics (GEC 221)
NOTE
The boundary is the contact surface shared by
both the system and the surroundings.
Mathematically speaking, the boundary has zero
thickness, and thus it can neither contain any
mass nor occupy any volume in space.
SURROUNDINGS

BOUNDARY

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Engineering, Thermodynamics (GEC 221)
Types of System
1. Closed system (also known as control mass):
Consists of a fixed amount of mass, and no
mass can cross its boundary, i.e. no mass can
enter or leave a closed system.
But energy, in the form of heat or work, can
cross the boundary; and the volume of a closed
system does not have to be fixed.
2. If, as a special case, even energy is not
allowed to cross the boundary, that system is
called an Isolated system.
Covenant University, Dept. of Chemical
11/3/2017 31
Engineering, Thermodynamics (GEC 221)
3. Open system (a control volume): Is 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.
Most engineering problems involve mass flow
in and out of the system and, therefore, are
modelled as control volumes. A water heater, a
car radiator, a turbine, a compressor all involve
mass flow and should be analysed as control
volumes (open systems) instead of as control
masses (closed systems)
Covenant University, Dept. of Chemical
11/3/2017 32
Engineering, Thermodynamics (GEC 221)
Open
Isolated

E, M
X E, M

E
Closed
X M

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Engineering, Thermodynamics (GEC 221)
Properties of a system
Something that describes a system. Any
characteristic of a system is called a property.
Examples are pressure P, temperature T,
volume V, and mass m.
Less familiar ones include such as viscosity,
thermal conductivity, modulus of elasticity,
thermal expansion coefficient, electric
resistivity, and even velocity and elevation.

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Engineering, Thermodynamics (GEC 221)
Properties are considered to be either
Intensive or Extensive
Properties that are independent of the mass
of a system are intensive properties e.g.
temperature, pressure, density, heat/energy in
transit, heat capacity (Cv and Cp). They are
also called thermodynamic properties or state
properties.
Extensive properties are those whose values
depend on the size (or extent ) of the system
e.g. total mass, total volume, total
momentum.
Covenant University, Dept. of Chemical
11/3/2017 35
Engineering, Thermodynamics (GEC 221)
Extensive properties per unit mass are called
specific properties, e.g., specific volume (V/m)
and specific total energy (E/m).

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Engineering, Thermodynamics (GEC 221)
Volume: A measure of size, on the same basis
as mass and mole.
Total volume: is a defined quantity given as
the product of three lengths. Total volume
may be divided by the mass or number of
moles of the system to yield specific volume
Specific volume: is the volume of a unit mass.
Mass: Is a primitive, without definition but
well understood.

Covenant University, Dept. of Chemical


11/3/2017 37
Engineering, Thermodynamics (GEC 221)
Specific volume
V Vt/m or Vt = mV 1

Molar volume
V = Vt/n or Vt = nV 2

Specific molar density,


= V-1 3

Covenant University, Dept. of Chemical


11/3/2017 38
Engineering, Thermodynamics (GEC 221)
V (specific volume), , Temperature, pressure
and composition are examples of intensive
properties that are independent of size.

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11/3/2017 39
Engineering, Thermodynamics (GEC 221)
Pressure
It is defined as a normal force exerted by a
fluid per unit area. We speak of pressure only
when we deal with a gas or a liquid. In solids
we talk of normal stress.
P = F/A = (Fxl)/ (Axl) 4
= W/V 5
P (pressure), F (Force), A (Area), l (Length), W
(Work), V (Specific volume)

Covenant University, Dept. of Chemical


11/3/2017 40
Engineering, Thermodynamics (GEC 221)
But work W, is a form of energy E,
Therefore, P = E/V 6
Equation 6 defines pressure as energy
required to introduce a fluid into a space of
specific volume, V. Equation 6 can also be
written as
PV = E 7
Implying that at a given value of pressure P,
energy will vary with specific pressure.
.

Covenant University, Dept. of Chemical


11/3/2017 41
Engineering, Thermodynamics (GEC 221)
Equation 6 also implies that an addition of a
given specific volume of a fluid V, using energy
E, will lead to a given increase of pressure,
each time. This is the principle of pumping of
liquids or compression of vapour and gases.

Covenant University, Dept. of Chemical


11/3/2017 42
Engineering, Thermodynamics (GEC 221)
A gauge for measuring pressure in a
reaction vessel
Gauge

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11/3/2017 43
Engineering, Thermodynamics (GEC 221)
Heat
Heat is a form of energy which, when
transferred to or from a system makes it
hotter or colder, respectively.
Heat and work are energy in transit, between
a system and its surroundings.
Heat is the most primordial (earliest) form of
energy. Friction between any two matters,
even electrons transform to heat.
Energy interaction is heat only if it takes place
because of temperature difference.
Covenant University, Dept. of Chemical
11/3/2017 44
Engineering, Thermodynamics (GEC 221)
There cannot be any heat transfer between two
systems that are at the same temperature.
Heat is recognized only as it crosses the
boundary of a system.
For example, a hot baked potato contains
energy, but the energy is heat transfer only as it
passes through the skin of the potato (system
boundary) to reach the air. Once in the
surroundings, the transferred heat becomes
part of the internal energy of the surroundings.

Covenant University, Dept. of Chemical


11/3/2017 45
Engineering, Thermodynamics (GEC 221)
In other words, in thermodynamics, the term
heat means heat transfer. A process during
which there is no heat transfer is called an
adiabatic process.
2 kJ thermal NOTE: Energy is
SURROUNDING AIR
energy recognized as heat
HEAT
transfer only as it
crosses the system
2 kJ boundary
Heat

BAKED (HOT) POTATO


2 kJ thermal
energy System boundary

Covenant University, Dept. of Chemical


11/3/2017 46
Engineering, Thermodynamics (GEC 221)
System boundary

Q=0
ADIABATIC
AA
SYSTEM
Insulation

During an adiabatic process, a system


exchanges no heat with its surroundings
Covenant University, Dept. of Chemical
11/3/2017 47
Engineering, Thermodynamics (GEC 221)
Heat Capacity
Everybody has capacity (ability) for heat, as it
(heat) passes through it.
The smaller the temperature change in a body
resulting from the transfer of a given quantity
of heat, the greater its capacity, C. Thus, the C
can be defined by Eq 8,
C = dQ/dT 8

Covenant University, Dept. of Chemical


11/3/2017 48
Engineering, Thermodynamics (GEC 221)
Specific Heat
Like the relationship between total volume
and specific volume, specific and molar heat
are heat per unit mass or per unit mole,
respectively. It can be at constant pressure or
constant volume

Covenant University, Dept. of Chemical


11/3/2017 49
Engineering, Thermodynamics (GEC 221)
Temperature
It is defined as a measure of its thermal state
considered in reference to its power to
transfer heat to or from other bodies.
By analogy, from Eq. 6, we can write

T = E/Cp 8a

Covenant University, Dept. of Chemical


11/3/2017 50
Engineering, Thermodynamics (GEC 221)
where Cp is the thermal capacity per unit
mass per unit temperature, at constant
pressure
Equation 8a can be seen to imply that an
addition of a unit quantity of Cp to a system
increases its temperature by one unit of
temperature

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11/3/2017 51
Engineering, Thermodynamics (GEC 221)
Other Concepts

Energy
Energy is difficult to define. Many define it as
ability to do work. It is beyond this. Suffice to
say that energy exists as heat, mechanical
(potential, volume, kinetic), chemical,
magnetic, nuclear, and electrical forms.

Covenant University, Dept. of Chemical


11/3/2017 52
Engineering, Thermodynamics (GEC 221)
The sum of these numerous forms of energy
constitutes the total energy, E of a system.
In thermodynamics, we consider the various
forms of energy that make up the total
energy of a system in two groups:
1. Macroscopic : forms of energy a system
possesses as a whole with respect to some
outside reference frame, such as kinetic and
potential energies (the macroscopic energy of
an object changes with velocity and elevation)

Covenant University, Dept. of Chemical


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Engineering, Thermodynamics (GEC 221)
2. Microscopic forms of energy are those related
to the molecular structure of a system and
the degree of the molecular activity, and the
are independent of outside reference frames.
The sum of all the microscopic forms of
energy is called the internal energy of a
system.

Covenant University, Dept. of Chemical


11/3/2017 54
Engineering, Thermodynamics (GEC 221)
The macroscopic energy of a system is related
to motion and the influence of some external
effects such as gravity, magnetism, electricity,
and surface tension.
The energy that a system possesses as a result
of its motion relative to some reference frame
is called kinetic energy (KE).
The energy that a system possesses as a result
of its elevation in a gravitational field is called
potential energy (PE).

Covenant University, Dept. of Chemical


11/3/2017 55
Engineering, Thermodynamics (GEC 221)
Sensible heat
At the molecular level, the portion of the
internal energy of a system associated with
the kinetic energies of the molecules is called
sensible heat.
The average velocity and the degree of activity
of the molecules are proportional to the
temperature of, for example, a gas. Therefore,
at higher temperatures, the molecules
possess higher kinetic energies, as a result
the system has a higher internal energy
Covenant University, Dept. of Chemical
11/3/2017 56
Engineering, Thermodynamics (GEC 221)
Equilibrum
The kinetic theory states that matter is in
continuous state of motion, as a result of
inherent energy.
However, when the relative motion of the
component matter in a system is in exact
balance and there is no tendency to change,
equilibrium is attained.
Under this condition, T and P are uniform in
the system and only infinitesimally different
from those of its surroundings.
Covenant University, Dept. of Chemical
11/3/2017 57
Engineering, Thermodynamics (GEC 221)
Types of equilibrium
Thermodynamics deals with equilibrium states.
The word equilibrium implies a state of balance.
There are many types of equilibrium, and a
system is not in thermodynamic equilibrium
unless the conditions of all the relevant types of
equilibrium are satisfied.
The condition of a system in which all
competing influences are balanced.

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Engineering, Thermodynamics (GEC 221)
Examples on Equilibrium

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Engineering, Thermodynamics (GEC 221)
Covenant University, Dept. of Chemical
11/3/2017 60
Engineering, Thermodynamics (GEC 221)
Thermal equilibrium : temperature is the
same throughout the entire system. That is,
the system involves no temperature
differential, which is the driving force for heat
flow.
Before After

50oC 23oC
33oC 33oC
40oC 30oC
35oC 33oC 33oC
33oC
44oC 20oC

A closed system reaching thermal equilibrium

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11/3/2017 61
Engineering, Thermodynamics (GEC 221)
Mechanical equilibrium
This is related to pressure, and a system is in
mechanical equilibrium if there is no change
in pressure at any point of the system with
time.
However, pressure may vary within the system
with elevation as a result of gravitational
effects.
The variation of pressure as a result of gravity
in most thermodynamic systems is relatively
small and usually disregarded.
Covenant University, Dept. of Chemical
11/3/2017 62
Engineering, Thermodynamics (GEC 221)
wall

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Engineering, Thermodynamics (GEC 221)
Phase equilibrium
A system involving two phases reaches
equilibrium when the mass of each phase
reaches an equilibrium level and stays there.

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11/3/2017 64
Engineering, Thermodynamics (GEC 221)
Chemical equilibrium
A system is in chemical equilibrium if its
chemical composition does not change with
time, that is, no chemical reaction occurs.

NOTE: A system will not be in equilibrium unless all the


relevant equilibrium criteria are satisfied.
Covenant University, Dept. of Chemical
11/3/2017 65
Engineering, Thermodynamics (GEC 221)
Reversibility
Reversibility conceives of a closed system
process whose direction can be reversed at
any point by an infinitesimal change in
external conditions. It means both the system
and the surroundings are returned to their
initial states at the end of the reverse
process.
It means the process can be reversed without
leaving any trace on the surroundings.

Covenant University, Dept. of Chemical


11/3/2017 66
Engineering, Thermodynamics (GEC 221)
The process in which the system and surroundings can be restored
to the initial state from the final state without producing any
changes in the thermodynamics properties

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11/3/2017 67
Engineering, Thermodynamics (GEC 221)
Reversible processes

Quasi-equilibrium expansion
and compression of a gas
Frictionless pendulum

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11/3/2017 68
Engineering, Thermodynamics (GEC 221)
A reversible process is possible only if the net
heat and net work exchange between the
system and the surroundings is zero for the
combined (original and reverse) process.
Processes that are not reversible are called
irreversible processes. Once a cup of hot
coffee cools, it will not heat up by retrieving
the heat it lost from the surroundings. If it
could, the surroundings, as well as the system
(coffee), would be restored to their original
condition, and this would be a reversible
process.
Covenant University, Dept. of Chemical
11/3/2017 69
Engineering, Thermodynamics (GEC 221)
Friction
Causes the transformation of mechanical
energy to internal energy --- Resident energy
Note that transformations other than
mechanical to heat occur.
For example as heat flows when a
temperature difference exists, electricity flows
under an electromotive force, chemical
reactions occur because of a chemical
potential exists.

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11/3/2017 70
Engineering, Thermodynamics (GEC 221)
In summary, a reversible process ;
Is frictionless.
Traverses a succession of equilibrium states.
Is driven by forces whose imbalance is
differential in magnitude.
Can be reversed at any point by a differential
change in external conditions.
When reversed, retraces its forward path, and
restores the initial state of system and
surroundings.
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11/3/2017 71
Engineering, Thermodynamics (GEC 221)
The reversible process is ideal in that it
provides the best results. The reversible work
as a limiting value can be combined with an
appropriate efficiency to yield a reasonable
approximation to the work of an actual
process.
Note that friction renders a process
irreversible. Other factors include
unrestrained expansion, mixing of two fluids,
heat transfer across a finite temperature
difference, electric resistance, inelastic
deformation of solids, and chemical reactions.
Covenant University, Dept. of Chemical
11/3/2017 72
Engineering, Thermodynamics (GEC 221)
Enthalpy
Its a combination property. The enthalpy, H,
defined as:
H U + PV 9
where H, U and V are molar or unit mass values.
Gotten from the Greek word enthalpien
( which means to heat).
Recall that the product P x V has energy units.

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11/3/2017 73
Engineering, Thermodynamics (GEC 221)
Q = nH = nCpdT and W = -nPdV
Only for mechanically reversible, constant
pressure conditions.

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11/3/2017 74
Engineering, Thermodynamics (GEC 221)
Conservation
Conservation is a very general concept. It states
that when any change takes place, the overall
effect is zero, i.e. the total quantity of matter
and energy, before and after any change
remains constant. It applies to :
Single matter or/and surroundings
Isolated, closed or open systems
Single or multistep processes
Single or multi-component processes/ system
Units
Covenant University, Dept. of Chemical
11/3/2017 75
Engineering, Thermodynamics (GEC 221)
Under any of these conditions, the total
amount of matter or/and energy remain
constant, for a process or/and system as
changes take place from one state to the
other.

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11/3/2017 76
Engineering, Thermodynamics (GEC 221)
Application to system

B
SYSTEM
A C
A+CB=0 10
By convention, input to system is +ve
and output is ve.
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11/3/2017 77
Engineering, Thermodynamics (GEC 221)
Technical Definition of Thermodynamics
On the basis of the our discussions so far,
thermodynamics can be defined as the
science that considers the relationship
between a quantity of energy that causes/
accompanies a change of state from 1 to 2,
and the properties in State 1 and State 2.
(E) = f( P1, P1, P1 P2, P2, P2) 11

where the difference operator signifies


finite (countable) changes in the quantities
enclosed in brackets.
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The First Law of Thermodynamics
It is usually expressed in many forms:
1. Although energy assumes many forms, the
total quantity of energy is constant, and
when energy disappear in one form, it
appears simultaneously in other forms. It
applies to a system and its surrounding.

(Energy of system) + (Energy of


Surroundings) = 0 12

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Energy containable and storable in the system
may be internal, potential or/ and kinetic.
Work and heat energy are said to be energy
in transit, across the boundary dividing the
system and its surroundings.
Writing each energy term in Eq. 12 in terms
of its properties, it turns out in the form of Eq.
11.
On these bases, Eq. 12 will be developed for
various practical applications:

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Energy Balance for Closed Systems
In a closed system, only energy in transit can
cross the boundary of the system.
Since matter cannot cross the boundary,
energy associated with matter internal
energy, potential and kinetic energy also can
not cross.
Therefore all energy exchange between a
closed system and its surroundings are only
heat and work. Thus the second term in Eq 12
may be replaced by
Covenant University, Dept. of Chemical
11/3/2017 81
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Heat (Energy of Surroundings) = Q W
Heat and work always refer to the system,
and the choice of signs used with these
quantities depends on which direction the
energy is transferred, with respect/reference
to the system.
When it is to or out of the system, it is positive
(+) or negative (-) respectively.

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Q into system is +ve
Q out of system is ve
W into system is +ve
W out of system is ve

That is, When heat and work are transferred


into the system from the surroundings:

Qsurr is -Q and Wsurr is W

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NOTE:
Heat and Work are path functions (their
magnitude depends on the path followed
during a process as well as the end states; e,g
states 1 to 2).
Path functions have inexact differential (in
our case designated as d e.g. dW or dQ, and
also as delta)
State properties are point functions (they
depend on the state only, and not how a
system reaches that state). They are exact
differentials (designated as )
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Therefore, the second term of Eq. 12 may be
replaced by;
(Energy of surroundings) = Qsurr + Wsurr
=-Q-W
which makes Eq 12 become
(Energy of system) = Q + W 13

Covenant University, Dept. of Chemical


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The interpolation of Eq. 13 is that total energy
change of a closed system equals the net
energy transferred into it as heat and work.
But closed systems undergo processes during
which only the internal energy of the system
changes. For such processes Eq. 13 reduces to:

Ut = Q + W 14

where Ut = mU or Ut = nU
Equation 14 is for a finite closed system
Covenant University, Dept. of Chemical
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For differential changes:
dUt = dQ + dW 15
For closed system of n moles, Eq. 14 and Eq. 15
may be written as
(nU) = n U = Q + W 16
d(nU) = ndU = dQ + dW 17
Note that Q and W are extensive properties and
not thermodynamic properties. They depend
on their history. Thermodynamic properties
are unique, not ambiguous i.e. not dependent
on path. dW and not W
Covenant University, Dept. of Chemical
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What makes Eq. 17 a thermodynamic
equation is that the LHS of the equation is a
thermodynamic property - the beginning and
end conditions are specified irrespective of
the paths.
The fact that the factors on the RHS are not
thermodynamic properties implies that the
specific conditions have to be specified for
thermodynamic states to be met.

Covenant University, Dept. of Chemical


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When n =1, Eq. 16 and Eq. 17 become;
U = Q + W and dU = dQ + dW, for the
intensive state of the system.
Equation 17 is the ultimate source of all
property relations that connect the internal
energy to measurable quantities.

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It is also important to note that;
The differential of a state function represents
an infinitesimal change in its value. Integration
of such a differential results in finite difference
between two of its values, e.g.

= P2 P1 = P and

= V2 V1 = V

Covenant University, Dept. of Chemical


11/3/2017 90
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The differentials of heat and work are not
changes, but are infinitesimal amounts.
When integrated, these differentials give not
finite changes, but finite amounts. Thus,
dQ = Q and dW = W

i.e. the integral of dW is not W2 W1 , since


work is not a property and systems do not
possess work at a state.

Study and understand Examples 2.2, 2.3, and 2.4 in


Smith, Van Ness and Abbott.
Covenant University, Dept. of Chemical
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For a closed system undergoing the same
change in state by several processes,
experience shows that the amounts of heat
and work required differ for differential
processes, but that the sum of Q + W is the
same for all processes.
This is the basis for identification of internal
energy as a state function. The same amount
of Ut is given by equation 14 regardless of
the process, provided only that the change in
the system is between the same initial and
final states.
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Phases of a pure substance
A substance that has a fixed chemical
composition throughout is called a pure
substance. Water, nitrogen, helium, and
carbon dioxide, for example, are all pure
substances.
A mixture of various chemical elements or
compounds also qualifies as a pure substance
as long as the mixture is homogeneous.

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Substances exist in different phases (at room
temperature, copper is solid, mercury is liquid,
and nitrogen is gas). Under different
conditions, each may appear in a different
phase.
A substance may also have several phases
within a principal phase, each with a different
molecular structure. For example, carbon may
exist as graphite or diamond in the solid
phase.
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A phase is identified as having a distinct
molecular arrangement that is homogeneous
throughout and separated from the others by
easily identifiable boundary surfaces. The two
phases of H2O in ice water represent an
example.

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The state of a pure homogeneous fluid is
fixed whenever two intensive thermodynamic
properties are set at specific values.
In contrast, when two phases are in
equilibrium, the state of the system is fixed
when only a single property is specified. For
example a mixture of steam and liquid water,
in equilibrium at 101.33 kPa can exist only at
100 oC.

Covenant University, Dept. of Chemical


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For multi phase systems, the number of
independent variables that must be arbitrarily
fixed to establish its intensive state is given by
Gibbs phase rule equation,
F = 2+N 18
= number of phases
N = Number of chemical species
F = Degrees of freedom of the system
Equ. 18 holds only for non-reacting systems at
equilibrium.
Covenant University, Dept. of Chemical
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A phase is a homogeneous region of matter.
Examples are;
Mixture of gas
A liquid or liquid solution
Bubbles of gas dispersed in a liquid
Fine particles dispersed in gas or liquid
Liquid droplets dispersed in another
Liquid with which its immiscible

Covenant University, Dept. of Chemical


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For solutions, note that the compositions are
not independent; for these, the phase rule
gives the minimum number of variables from
the set of fractional compositions, that must
be fixed.
Study and understand
Examples 2.5 in Smith,
Van Ness and Abbott.

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11/3/2017 99
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Constant V and Constant P Processes
For a homogeneous fluid contained in a closed
system, the energy balance is
d (nU) = dQ + dW 17
dW = -P d (nV) 19
dW = F dl = P A dl
= P A d (V/A)
=P dV for constant A
Combination of Eqs. 17 and 19 give
d (nU) = dQ - Pd (nV) 20
Covenant University, Dept. of Chemical
11/3/2017 100
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Constant V Process
For constant volume
0
d(nU)= dQ-Pd(nV) OR
dQ = d (nU)v 21
and Q = n U 22

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Constant P Process
Making dQ subject in Eq. 17 yields
dQ = d (nU) + P d (nV)
for constant pressure
dQ = d (nU) + d (nPV)
= d [ n (U + PV)]
But H = U + PV 9
dQ = d (nH) constant P 23

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and Q = n H constant P 24
From Eq. 9,
dH = dU + d (PV) 25
and H = U + (PV) 26

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Heat Capacity at Constant Volume
Heat capacity, as defined by equation 8 is not
a thermodynamic property, since Q (process
dependent), is not a thermodynamic property.
However heat capacity at constant volume is a
thermodynamic property.
Relating Eq. 22 with Eq. 8 suggest the constant
volume heat capacity as;
Cv 27

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C applied to both molar and specific cases. For
the particular case of closed system Equation
27 can be written as;
dU = Cv dT ( constant V) 28
Integration yields

U = (constant V) 29

This result, with Eq. 22 for a mechanically


reversible, constant volume process gives:
Q = nU = n (constant V)
30
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The specific, here, of mechanical reversibility
is essential since, that is what makes Q = n U.
This establishes the fact that;
For the calculation of property changes, an
actual process may be replaced by any other
process which accomplishes the same change
in state.

Covenant University, Dept. of Chemical


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Heat Capacity at Constant Pressure
The constant pressure heat capacity is
defined as:
Cp 31

The definition accommodates both molar and


specific heat capacities just as we have for Cv,
corresponding with the specification of H.

Covenant University, Dept. of Chemical


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For a constant pressure, closed system,
Equation 31 translates to
dH = Cpdt (constant p) 32

and H = ( constant P) 33

For a mechanically reversible, constant P


process, this result may be combined with
Equation 24

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Q = nH = n (constant P) 34

Study and understand Examples 2.9 and 2.10


in Smith, Van Ness and Abbott.

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Mass and Energy Balances for Open Systems
The closed system is a special type of open
system
Measures of Flow
Mass flow rate
Molar flow rate
Volumetric flow rate q
Velocity u

= M , q = uA 35
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= uA 36
= uA 37
A = cross sectional area, = density.
Although velocity is a vector quantity, its scalar
magnitude, u is used as the average speed of a
stream in the direction normal to A.
Note that all the flow rates represent measure
of quantity per unit time, however, u does not
suggest the magnitude of flow.

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MASS BALANCE FOR OPEN SYSTEMS

1 CONTROL VOLUME
dmcv/dt

CONTROL
2
SURFACE

Accumulation and flow streams


in control volume
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The application of the law of conservation
for mass in this system is mass balance.
For Figure 1, it is

38

is the accumulation
(if depletion, its negative) of mass.

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fs represents the following streams.
The conservation applied is in +ve for inflows,
-ve for outflows, with respect to the system.
On basis the second term in Eq. 38 is

=
When is written in terms of Eqs. 36, 37 and
38 becomes

Covenant University, Dept. of Chemical


11/3/2017 114
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39
This is the CONTINUITY EQUATION.
At steady state, there is neither accumulation
nor consumption while flows are still taking
place, by which

= 0 40

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Therefore ( )fs = 0
With only one single entrance and outlet, with
equal in both

= Constant = 41 =

In terms of volumetric flow rate, equation 41


can be written as:
= = = 42
This form of continuity equation is frequently
used.
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THE GENERAL ENERGY BALANCE
The law of conservation is as equally applicable
to energy as it is for mass.
For a fluid in motion as in Figure 2 below:

E1 E2

Figure 2: Energy Balance for a Fluid in Motion


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The total energy, E, for mass of fluid is given by the
equation.

43

The total energy of a simple compressible


system consists of three parts for a non-
flowing fluid (U, K.E., P.E.) and four parts for a
flowing fluid (flow energy/ flow work : Pv, U,
K.E.,P.E). v, is volume/mass

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From Figure 2, consider some fluid flowing from
Point 1 to Point 2.
Between these two points, let an amount of
heat energy, Q, be added to the fluid as
shown.
Let an amount of work W1 be done on the
fluid and the fluid do an amount of work W2
on its surrounding.

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An energy balance can be written for fluid either
as;

Or as 44
If no work, in form of pumping say, is done on
the system, a combination of Equations 43
and 44 yields;
m -m

= Q - (PV) m 45
Covenant University, Dept. of Chemical
11/3/2017 120
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H = U + PV, Eq. 45 becomes
46
This equation is applicable to a situation of
steady state flow (the fluid properties at an
inlet or exit remain constant, i.e. do not
change with time), with internal friction in the
fluid but no shaft work done.
Eq. 46 may have been obtained from over
simplification of the conditions applied in
Figure 2
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For more practical purposes, other types of
work such as stirring, etc. may have gone into
the system. With stirring, for example Eq. 46
becomes

Furthermore, if changes in potential and


kinetic energies become negligible with
respect to enthalpy changes, we may have,

Covenant University, Dept. of Chemical


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= + 48
And unit mass basis

48
Where are on unit mass basis.

Study and understand Examples 2.12 to 2.14 in


Smith, Van Ness and Abbott.

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Examples of steady-flow engineering devices
Nozzles and Diffusers

V1 Nozzle V2 >> V1 V1 Diffuser V2 << V1

Nozzles and diffusers are shaped so that they


cause large changes in fluid velocities and thus
kinetic energies
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A nozzle is a device that increases the velocity
of a fluid at the expense of pressure.
A diffuser is a devise that increases the
pressure of a fluid by slowing it down.
It follows that nozzles and diffusers perform
opposite tasks. They are commonly utilized in
jet engines, rockets, spacecraft, and even
garden hoses.

Covenant University, Dept. of Chemical


11/3/2017 125
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Other examples include;
Turbine and Compressors
Throttling Valves
Mixing Chambers, Heat Exchangers
Pipe and Duct flow

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A FLOW CALORIMETER FOR ENTHALPY MEASUREMENTS

all the thermodynamic properties so far used


such as P, T, V, etc can be measured either
directly with meters or indirectly.
non thermodynamic properties such as Q,
W etc. can also be measured indirectly using a
calorimeter and a tachometer respectively.
W can also be measured directly with a
dynamometer.

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However, properties such as enthalpy, entropy
etc. can only be obtained by relating them
with some other directing measurable
parameters such as P, V and T.
An experimental set up such as presented in
Figure 3 below can be arranged for the
measurement of enthalpy.

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Flow calorimeter

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The essential features are
an electric resistance heater immersed in a
flowing fluid
minimal velocity and elevation changes from
section 1 to section 2, implying minimal
changes in kinetic and potential energy.
With no shaft work entering the system, Eq.
48

reduces to

Covenant University, Dept. of Chemical


11/3/2017 130
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49
The rate of heat transfer to the fluid is
determined from the resistance of the heater
and the current passing through it.
Measurements of the heat rate and flow rate
allow calculation of the change between
sections 1 and 2.
The constant temperature water bath is filled
with a mixture of crushed ice and water to
maintain a temperature of 0 oC

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The temperature and pressure at section 2 are
measured by suitable instruments.
From Eq. 49; H = Q, values of water for
various conditions at section 2 are given by

H2 = H1 + Q where

Q is the heat added per unit mass of water


flowing and H1 is assumed, for practical
purposes to remain as a constant value, with
the stipulated conditions.

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NOTE: Absolute values of enthalpy or internal
energy are unknown. Absolute value is actual
value at a given position, e.g. we have
absolute pressure, absolute temperature.
Therefore, an arbitrary value may be assigned
to H1 as the basis for all other enthalpy values.

For example, setting H1 = 0 for liquid water 0 oC


makes
H2 = H1 + Q = 0 + Q = Q

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11/3/2017 133
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On this basis, enthalpy values can be obtained
for a range of temperatures and pressures
existing at section 2.
Similarly, specific volumes measurements
made at these conditions may be used to
calculate values of internal energy, U, from Eq.
9, H = U + PV

In this way, tables of thermodynamic properties


are compiled over the entire useful range of
conditions.
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The most widely used of such tabulations for
water and is known as the Steam Tables. Tables
for various other substances are found in the
literature.
Property tables such as steam tables provide very
accurate information about the properties, but
they are bulky and vulnerable to typographical
errors.
A more practical and desirable approach is to
have some simple relations among the properties
that are sufficiently general and accurate.
Study and understand Examples 2.15 to 2.17 in
Smith, Van Ness and Abbott.

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SUMMARY
measurement and real understanding of the
meaning of total volume
and specific or molar volume,
pressure and temperature have been
presented.

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the application of Phase Rule to the definition
of thermodynamics, as presented in Eq. 11,
gives the least complex model/equation
relating pressure, molar volume and
temperature as

PV = RT 50
The equation is for an ideal gas. This is the
simplest best known equation of state for
substances in the gas phase. The equation
predicts the P-v-T behaviour of a gas quite
accurately within some properly selected
region.
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11/3/2017 137
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However, industrial processes for which
thermodynamics are intended for applications go
beyond ideal gases to pure and mixture of gases,
liquids and solids.
They also go beyond PVT relations to others from
which properties such as enthalpy, H, entropy, S
etc can be obtained.
Accordingly, equations of state, which Eq. 50
represents, can be developed for virtually all
industrial conditions.
The variations of properties during phase-change
processes are best studied and understood with
the help of property diagrams/relations.
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138
Engineering, Thermodynamics (GEC 221)
PVT Behaviour of Pure Substances
1.P-T Relation (Figure 4)

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The P-T relation is often called the phase diagram
since all three phases are separated from each
other by three lines.
Sublimation line separates the S-V regions.
Vaporization line separates the L-V regions.
Fusion/melting line separates S-L regions.
The three lines meet at the triple point, where all
three phases coexist in equilibrium.
The vapourization line ends at the critical point
because no distinction can be made between
liquid and vapour phases above the critical point.
Substances that expand and contract on freezing
differ only in the melting line on the P-T diagram
Covenant University, Dept. of Chemical
11/3/2017 140
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P-V relation for a pure substance (Figure 5)

Covenant University, Dept. of Chemical


11/3/2017 141
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From Figure 5b (P-V with constant T),
BC is saturated liquid line
C is the critical point
CD is saturated vapour line
The doom, i.e. BCD is the saturated L-V region.
Beyond the dash lines is the superheated
vapour region.
The left side of the doom is the compressed
liquid region.
Figure 5a is the general P-V relation which is for
a substance that contracts on freezing
Covenant University, Dept. of Chemical
11/3/2017 142
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PT at specific constant V (Figure 6)

Covenant University, Dept. of Chemical


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Single phase region
It was pointed out that we should be able to
calculate all the properties of a system at any
state once two independent, intensive
properties are available.
For properties that cannot be measured
directly such as internal energy, enthalpy, and
entropy, we can get them measured from the
knowledge of the intensive properties.
The calculation of these properties from
measurable ones depends on the availability
of simple and accurate relations between the
two groups.
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PVT relations in each of the single phases in
Figures 5 and 6 is relatively simpler than
between any of two phases.
This suggests that relatively simple PVT
equations can be established for each of the
single phase regions.
For example, an equation of state can be
formulated for any of P, V or T as subject, with
the other two as variable, in accordance with
the phase rule.

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11/3/2017 145
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51
In practice, each of the partial derivatives has
physical meaning.

volume expansivity (also called coefficient


of volumetric expansion is a measure of
the change in volume with temperature
at constant pressure)
53 is

Isothermal compressibility
Covenant University, Dept. of Chemical
11/3/2017 146
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A combination of Eqs. 51, 52 and 53 yields

Examination of isotherms for liquid phase in


Figure 5 shows that they are almost straight
down and are very close pack. This means that
V is relatively invariant with T and P, hence
the usual idealistic claim that liquids are
incompresssible.

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and with this assumption, from equ 54 after
integration,

= 55

Study and understand


Examples 3.1 in Smith, Van
Ness and Abbott.

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EQUATIONS OF STATE
Any equation that relates the pressure, temperature,
and specific volume of a substance is called an
equation of state.
There are several equations of state, some simple
and others complex.
The simplest and best known equation of state for
substances in the gas phase is the ideal-gas
equation of state.
It predicts the PVT behaviour of a gas quite
accurately within some properly selected region.
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11/3/2017 149
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VIRIAL EQUATIONS OF STATE
Examination of Figure 5b shows that P is
inversely proportional to V, such that the
product PV for a given T should be about
constant and can be represented as a function
of P.
It also suggests that PV for an isotherm can be
represented by a power series in P:
PV = a + bP + cp2 + .

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If b = aBI, c = aCI, etc then
PV = a(1 + BIP + CIp2 + DIp3 + ..) 56
where a, BI, CI .. are constants for a given
temperature and a given chemical species.
The coefficients can be determined experimentally
or theoretically from statistical mechanics.
As the pressure approaches zero, all the virial
coefficients will vanish and the equation will
reduce to an ideal gas equation of state.

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The PVT behaviour of a substance can be
represented accurately with the virial
equation of state over a wider range by
including a sufficient number of terms.

In principle, the term on the RHS of Eq. 56 is


an infinite series. However, experience shows
that at low pressures, truncation after two
terms often provides satisfactory results.

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Ideal Gas Temperatures; Universal Gas Constant
It has been established empirically that while
parameters BI, CI etc are functions of
temperature and species, parameter, a, is a
function only of temperature for all chemical
species ( in some text, a is replaced with RT).
This is demonstrated by the plot of PV versus P
for four chemical species as in Figure 7, where
the limiting value of PV as P 0 is the same
for all the gases. In this limit (denoted by
asterisk), Eq. 56 becomes
Covenant University, Dept. of Chemical
11/3/2017 153
Engineering, Thermodynamics (GEC 221)
Covenant University, Dept. of Chemical
11/3/2017 154
Engineering, Thermodynamics (GEC 221)
This property of gases is the basis for
establishing an absolute temperature scale.
What is required is to arbitrarily assign the
functional relationship and also assign a value
for a single point on the scale. The procedure
assigned is that which defines the Kelvin scale
and
Makes (PV)* directly proportional to T, with R
as the constant of proportionality
57
Covenant University, Dept. of Chemical
11/3/2017 155
Engineering, Thermodynamics (GEC 221)
Assigns the value of 273.16K to the
temperature of the triple point of water
(denoted by subscript t):
= R .. 58
Division of Eq. 57 by Eq. 58 gives:
or

59

Covenant University, Dept. of Chemical


11/3/2017 156
Engineering, Thermodynamics (GEC 221)
Eq. 59 established the Kelvin temperature
scale throughout the temperature range for
which values of (PV)* are experimentally
accessible.
The state of a gas at the limiting condition
where P 0 ,
The molecules become so far apart
The unit molecular volume became
negligible in comparison with the total volume
occupied by a unit mass of the gas.
Intermolecular forces approach zero.

Covenant University, Dept. of Chemical


11/3/2017 157
Engineering, Thermodynamics (GEC 221)
These conditions define the ideal gas state
and Eq. 59 establishes the ideal gas
temperature scale.
The proportionality constant, R, is defined as
the universal gas constant. Its numerical value
is given by Eq. 58 from experimental PVT data:

Covenant University, Dept. of Chemical


11/3/2017 158
Engineering, Thermodynamics (GEC 221)
In reality, this data is difficult to measure. This
notwithstanding, the internationally accepted
value of is 22,711.8cm3 bar mol-1
leading to the following value of R:

= 83.1447c K-1

Covenant University, Dept. of Chemical


11/3/2017 159
Engineering, Thermodynamics (GEC 221)
Two Forms Of The Viral Equation
Modification of eq. 56 introduces a property
as

And its replacement with a = RT (Eq. 57),


transforms Eq. 56

1 + BIP + CIp2 + DIp3 + .. 61


An alternative expression for is also in
common use,
Covenant University, Dept. of Chemical
11/3/2017 160
Engineering, Thermodynamics (GEC 221)
= 1 + +

The factor defined by Eq. 60 is called the


compressibility factor. Eq. 61 and 62 are also
called virial equations and the parameters BI,
CI, DI etc. and B, C, D, etc. are called virial
coefficients. BI and B are second virial
coefficients, CI and C are third virial
coefficients, etc.

Covenant University, Dept. of Chemical


11/3/2017 161
Engineering, Thermodynamics (GEC 221)
For a given gas, the virial coefficients are
functions of temperature only.
The two sets of coefficients in Eq. 61 and 62
are related as follows:
BI = .. 63

CI = 64

DI = 65

Covenant University, Dept. of Chemical


11/3/2017 162
Engineering, Thermodynamics (GEC 221)
Many other equations of state have been
proposed for gases, but the virial equations
are the only ones firmly based on statistical
mechanics, which provide physical significance
to the virial coefficients.

Covenant University, Dept. of Chemical


11/3/2017 163
Engineering, Thermodynamics (GEC 221)
Thus, for the expansion in , the term arises
on account of interactions between pairs of
molecules, the , on account of three-body
interactions, etc.
Because two-body interactions are many times
more common than three-body interactions
and three-body interactions are many time
more numerous than four-body interactions,
etc. the contributions to of the successively
higher-ordered terms decrease rapidly.

Covenant University, Dept. of Chemical


11/3/2017 164
Engineering, Thermodynamics (GEC 221)
The terms etc. of the virial expansion
(Eq. 62), arise by reason of molecular
interactions. Otherwise the virial coefficients
B,C, etc. would be zero in the absence of such
interactions and the virial expansion would
reduce to
or PV = RT
In reality, molecular interactions do exist and
influence the observed behavior of real gases.
However, as pressure is reduced at constant
temperature, V increases and the
contributions of the terms
in Eq. 62 decrease 165
For P0, approaches unity, not because of
any change in virial coefficients, but because V
becomes infinite.
Thus in the limit, as P0, the equation of
state reduces to the same simple form as for
the hypothetical case of B = C = = 0,
that is
or PV = RT

Covenant University, Dept. of Chemical


11/3/2017 166
Engineering, Thermodynamics (GEC 221)
From the phase rule, that internal energy of a real
gas is a function of pressure and temperature.
This pressure dependency varies from molecular
interactions of the gas. In the absence of
molecular interactions, internal energy would
depend on temperature only and no energy
would be required to bring about pressure and
volume changes. These concepts of the behavior
of a hypothetical gas in which no intermolecular
forces exist and of a real gas in the limit as
pressure approaches zero lead to the definition of
an ideal gas as one whose macroscopic behavior
is characterized by

Covenant University, Dept. of Chemical


11/3/2017 167
Engineering, Thermodynamics (GEC 221)
The equation of state
PV = RT (ideal) ...66
An internal energy that is a function of
temperature only
U = U(T) (ideal gas) 67

Covenant University, Dept. of Chemical


11/3/2017 168
Engineering, Thermodynamics (GEC 221)
Equations For Process Calculations For Ideal Gases
It has been noted earlier that very common
parameters required in any process are heat
and work.
Further, for a mechanically reversible closed
system process
dW = - PdV 19
And for an ideal gas
dQ + dW = CVdT .17, 28

Covenant University, Dept. of Chemical


11/3/2017 169
Engineering, Thermodynamics (GEC 221)
substituting for dW and solution for dQ yields
an equation valid for an ideal gas in any
mechanically reversible closed-system
process.
dQ = CVdT + PdV . 67
This equation contains the variables P, V and T,
only two of which are independent.
Working equations are obtained by using the
equation to reduce the Eq. 67 to just
two independent variables.

Covenant University, Dept. of Chemical


11/3/2017 170
Engineering, Thermodynamics (GEC 221)
With

dQ = CVdT + 68
Substituting 68 into 17,

dW = - RT . 69

with

Covenant University, Dept. of Chemical


11/3/2017 171
Engineering, Thermodynamics (GEC 221)
dQ = Cp dT - . 70

and dW = - R dT + RT . 71

with
work is simply
dW = - P dV and

dQ = dP + P dV . 72

Covenant University, Dept. of Chemical


11/3/2017 172
Engineering, Thermodynamics (GEC 221)
These equations (68, 70, and 72) may be applied
for ideal gases to various kinds of processes
that are closed and mechanically reversible, as
follows:
Isothermal Processes
At constant temperature,
U = = 0

and H = = 0
Similarly write Eqs. 68 and 70,
Covenant University, Dept. of Chemical
11/3/2017 173
Engineering, Thermodynamics (GEC 221)
=

and write Eqns. 69 and 71

=
Note that Q = -W, a result which also follows
from Eq. 14
Q = -W =

(const. T)
11/3/2017
.. 73
Covenant University, Dept. of Chemical
174
Engineering, Thermodynamics (GEC 221)
Isobaric Process
From previous equations
U = and H =

and following from Eqs. 70 and 71,


Q = and W = -R(T2 T1)

Note that Q = H
Q = H = (const. P) .. 74

Covenant University, Dept. of Chemical


11/3/2017 175
Engineering, Thermodynamics (GEC 221)
Isochoric Process (Constant V)
From previous equations
U = and H =

Following from Eq. 68 and the basic work


equation,
Q = and W = - PdV = 0
Note that Q = H,

Q = U = Const. V . 75
Covenant University, Dept. of Chemical
11/3/2017 176
Engineering, Thermodynamics (GEC 221)
Adiabatic Process; Constant Heat Capacities
An adiabatic process is one for which there is
no exchange of heat between the system and
the surroundings,

i.e dQ = 0, following which Eqs. 68, 70 and 72


may therefore be set to zero. Integration with
and constant gives,
From Eq. 68, =-

Integrating with constant gives


Covenant University, Dept. of Chemical
11/3/2017 177
Engineering, Thermodynamics (GEC 221)
=

Similarly Eq. 70 and 72 lead to


=

and =

These equations may also be written as


= constant . 76a

Covenant University, Dept. of Chemical


11/3/2017 178
Engineering, Thermodynamics (GEC 221)
= constant .. 76b
and = constant .. 76c

given that .. 77

Covenant University, Dept. of Chemical


11/3/2017 179
Engineering, Thermodynamics (GEC 221)
2nd Law of Thermodynamic
The 1st law was applied to processes involving
closed and open systems.
It was shown that a process must satisfy the
first law to occur. However, to further our
discussions, satisfying the first law alone does
not ensure that the process will actually take
place.
We know that the amount of heat loss by a
hot cup of coffee is equal to amount of heat
gain by the surrounding air.
Covenant University, Dept. of Chemical
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But the hot coffee getting hotter in a cooler
room as a result of heat transfer from the
room air never takes place.
Doing the reverse of the process would not
violate the first law as long as the amount of
energy lost by the air is equal to the amount
gained by the coffee.
Therefore, it is cleared that processes proceed
in a certain direction and not in the reverse
direction.

Covenant University, Dept. of Chemical


11/3/2017 181
Engineering, Thermodynamics (GEC 221)
The 1st law places no restriction on the
direction of a process, but satisfying the first
law does not ensure that the process can
occur.
The inadequacy of the first law to identify
whether a process can take place is corrected
by another general principle, the 2nd law of
thermodynamics.
The reverse process of hot cup of coffee
getting hotter from cold air violates the
second law of thermodynamics.

Covenant University, Dept. of Chemical


11/3/2017 182
Engineering, Thermodynamics (GEC 221)
The violation is easily detected by a property
called entropy.
It follows therefore that a process must satisfy
both the first and second laws of
thermodynamics to proceed.
The 2nd law is not limited in identifying the
direction of processes. It also asserts that
energy has quality as well as quantity. The 1st
law is concerned with the quantity of energy
and the transformation of energy from one
form to another with no regard to its quality.
Covenant University, Dept. of Chemical
11/3/2017 183
Engineering, Thermodynamics (GEC 221)
Preserving the quality of energy is a major
concern to engineers, and the second law
provides the necessary means to determine
the quality as well as the degree of
degradation of energy during a process.
The second law is also used in determining the
theoretical limits for the performance of
commonly used engineering systems, such as
heat engines and refrigerators, as well as
predicting the degree of completion of
chemical reactions.
Covenant University, Dept. of Chemical
11/3/2017 184
Engineering, Thermodynamics (GEC 221)
Thermal energy reservoir (or just a reservoir)
It is a hypothetical (assumed) body with a
relatively large thermal energy capacity (mass
x specific heat).
It can absorb or supply finite amounts of heat
without undergoing any change in
temperature.
Large bodies of water such as oceans, lakes,
and rivers as well as atmospheric air can be
modeled accurately as thermal energy
reservoir because of their large thermal
energy storage capabilities or thermal masses.
Covenant University, Dept. of Chemical
11/3/2017 185
Engineering, Thermodynamics (GEC 221)
The atmosphere does not warm up as a result
of heat losses from residential buildings
during winter.
A body does not have to be very large to be
considered a reservoir.
Any physical body whose thermal capacity is
large relative to the amount of energy it
supplies or absorbs can be modeled as a
reservoir.

Covenant University, Dept. of Chemical


11/3/2017 186
Engineering, Thermodynamics (GEC 221)
experience shows that;
Whereas work can be transformed to heat
with 100% efficiency, the reverse is not the
same.
Heat can be transformed from a hot body to a
cold body, but the reverse is not true.
These suggest that different forms of energy
may possess different quality. In this case,
work is of a higher quality than heat and
further, heat at a higher temperature is at a
higher quality than heat at a lower
temperature.
Covenant University, Dept. of Chemical
11/3/2017 187
Engineering, Thermodynamics (GEC 221)
The second law of thermodynamics are
expressed in the following statements;
Statement 1 : No apparatus can operate in
such a way that its only effect
-that being the only thing happening (in
system and surroundings) is to convert heat
absorbed by a system completely into work
done by the system.
OR

Covenant University, Dept. of Chemical


11/3/2017 188
Engineering, Thermodynamics (GEC 221)
Statement 1a; It is impossible by a cyclic
process to convert the heat absorbed by a
system completely into work done by a
system.
Statement 2: No process is possible which
consists solely (at being the only thing
happening) in the transfer of heat from one
temperature level to a higher one.

Covenant University, Dept. of Chemical


11/3/2017 189
Engineering, Thermodynamics (GEC 221)
These observations are addressed by the
second law of thermodynamics and they are
very well demonstrated by the principles and
practice of heat engine and heat pump.

Covenant University, Dept. of Chemical


11/3/2017 190
Engineering, Thermodynamics (GEC 221)
A reservoir that supplies energy in the form of
heat is called a SOURCE, and one that absorbs
energy in the form of heat is called a SINK.
Thermal energy reservoirs are often referred
to as heat reservoir since they supply or
absorbs energy in the form of heat.

Covenant University, Dept. of Chemical


11/3/2017 191
Engineering, Thermodynamics (GEC 221)
Thermal energy
SOURCE

HEAT

HEAT

Thermal energy
SINK

Figure 8. A source supplies energy in the form of heat, and a sink


absorbs it Covenant University, Dept. of Chemical
11/3/2017 192
Engineering, Thermodynamics (GEC 221)
Heat engines
Work can easily be converted to other forms
of energy, but converting other forms of
energy to work is not that easy
Work No Work

Heat

WATER Heat WATER

Figure 9. Work can always be converted to heat directly and


completely, but the reverse is not true
Covenant University, Dept. of Chemical
11/3/2017 193
Engineering, Thermodynamics (GEC 221)
The mechanical work done by the shaft as
shown is first converted into internal energy of
the water.
This energy may then leave the water as heat.
Attempt to reverse this process will fail.
Transferring heat to the water does not cause
the shaft to rotate.
From this we conclude that work can be
converted to heat directly and completely, but
converting heat to work requires the use of
some special devises. These devises are called
heat engines Covenant University, Dept. of Chemical
11/3/2017 194
Engineering, Thermodynamics (GEC 221)
Heat Engines (HE)

Covenant University, Dept. of Chemical


11/3/2017 195
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Heat Engines differ considerably from one another.
They are all can be characterized by the following
They receive heat from a high-temperature
source (solar energy, oil furnace, nuclear
reactor, etc)
They convert part of this heat to work (usually
in the form of a rotating shaft).
They reject the remaining waste heat to a low-
temperature sink (the atmosphere, rivers, etc)
They operate in a cycle.

Covenant University, Dept. of Chemical


11/3/2017 196
Engineering, Thermodynamics (GEC 221)
TH
QH

Qc

Tc
Figure 10. The principle of heat engines
Covenant University, Dept. of Chemical
11/3/2017 197
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A heat engine is a system which converts heat QH
drawn from a higher temperature TH, to work, W,
and discharges residual heat Qc, at a lower
temperature Tc.
The principle of the heat engine is illustrated in
Figure 10.
The practice of a heat engine requires that a heat
exchanger brings about heat exchange between a
reservoir at each of hot and cold ends, where the
heat exchange takes place through a fluid called a
working fluids, as presented in Figure 11.

Covenant University, Dept. of Chemical


11/3/2017 198
Engineering, Thermodynamics (GEC 221)
Heat engines and other cyclic devices usually
involve a fluid to and from which heat is
transferred while undergoing a cycle. This fluid
is called the working fluid.

Covenant University, Dept. of Chemical


11/3/2017 199
Engineering, Thermodynamics (GEC 221)
QH
Heat engine
Boiler

W Pump Turbine W

Condenser
Figure 11. Practice of heat engines Qc
Covenant University, Dept. of Chemical
11/3/2017 200
Engineering, Thermodynamics (GEC 221)
Thermodynamic representation of Heat Engine
P

1 2
Constant Entropy & Enthalpy
Constant Entropy

4 3

Figure 12 H
Covenant University, Dept. of Chemical
11/3/2017 201
Engineering, Thermodynamics (GEC 221)
The term heat engine is often used in broader
sense to include work producing devices that do
not operate in a thermodynamic cycle.
Engines that involve internal combustion such as
gas turbines and car engines fall into this
category. These devises operate in a mechanical
cycle but not in a thermodynamic cycle since the
working fluid (the combustion gases) does not
undergo complete cycle. Instead of being cooled
to the initial temperature, the exhaust gases are
purged and replace by fresh air-and-fuel mixture
at the end of the cycle.
Covenant University, Dept. of Chemical
11/3/2017 202
Engineering, Thermodynamics (GEC 221)
The work producing device that best fit into
the definition of a heat engine is the steam
power plant, which is an external combustion
engine. That is, combustion takes place
outside the engine, and the thermal energy
released during the process is transferred to
the steam as heat.
Schematic of a basic steam power plant is
shown in figure 11.

Covenant University, Dept. of Chemical


11/3/2017 203
Engineering, Thermodynamics (GEC 221)
Figure 12 represents the Rankine cycle of the
system just described in Figure 11, on a
pressure enthalpy diagram for the said fluid.
Point 1 on the diagram represents a sub-
cooled liquid entering the boiler in Figure 11.
step 1 2 represents the isothermal boiling of
the fluid.
point 2 representing saturated vapour coming
out of the boiler.
The quantity of heat QH absorbed by the
boiler is given by
Covenant University, Dept. of Chemical
11/3/2017 204
Engineering, Thermodynamics (GEC 221)
QH = H2 H1 , Where H is the enthalpy.
Step 2 3 represents the operation in the
turbine, in which saturated steam at point 2
expands from a high to low pressure at
constant entropy.
The quantity of work W, yielded is represented
by
W = H2 H3

Covenant University, Dept. of Chemical


11/3/2017 205
Engineering, Thermodynamics (GEC 221)
Step 3 4 represents isothermal condensation
where the quantity of heat Qc removed for
this purpose is given by
Qc = H3 H4
Thus operation is at isothermal condition at Tc
The lifting of saturated liquid from point 4 to 1
is isentropic, i.e. constant entropy and
enthalpy.

Covenant University, Dept. of Chemical


11/3/2017 206
Engineering, Thermodynamics (GEC 221)
Thermal Efficiency of Heat Engine
The net work output of a heat engine is always
less than the amount of heat input.
It means only part of the heat transferred to
the heat engine is converted to work.
The fraction of the heat input that is
converted to net work output is a measure of
the performance of a heat engine and is called
the thermal efficiency.

Covenant University, Dept. of Chemical


11/3/2017 207
Engineering, Thermodynamics (GEC 221)
It is important to note that the system obeys
the first law.
For example, from figure 11,
W = Q H Qc
But the thermal efficiency of the engine, is
given as
= =

= =

Covenant University, Dept. of Chemical


11/3/2017 208
Engineering, Thermodynamics (GEC 221)
Qc and QH are defined as magnitudes and
therefore are positive quantities.
The thermal efficiency of a heat engine is
always less than unity since both Qc and QH
are defined as positive quantities.
Thermal efficiency is a measure of how
efficiently a heat engine converts heat that it
receives to work.
Engineers are constantly trying to improve
the efficiencies of these devices since
increased efficiencies means less fuel
consumption and thus lower fuel bills and less
pollution. Covenant University, Dept. of Chemical
11/3/2017 209
Engineering, Thermodynamics (GEC 221)
The thermal efficiencies of work producing
devices are relatively low. Ordinary spark-
ignition automobile engines have a thermal
efficiency of 25%. That is, an automobile
engine converts about 25% of the chemical
energy of the gasoline to mechanical work. In
diesel engines and large gas-turbine plants it is
40%. For large combined gas-steam plants it is
as high as 60%.
Therefore, for most efficient heat engines
available today almost one-half of the energy
supplied ends up in the rivers, lakes, or the
atmosphere as wastes or useless energy.
Covenant University, Dept. of Chemical
11/3/2017 210
Engineering, Thermodynamics (GEC 221)
Furnace
TH
QH = 100 MJ

HEAT W = 55 MJ
ENGINE

Qc = 45 MJ

Tc The atmosphere
The most efficient heat engines reject almost one-half of the
energy they receive as waste heat.
Covenant University, Dept. of Chemical
11/3/2017 211
Engineering, Thermodynamics (GEC 221)
For to be unity, i.e. net work produced be
equal to the heat responsible for the
production of the work, i.e. efficiency 100%,
Qc must be zero!
No engine has ever been built that
approaches this result; heat is always rejected
to the cold reservoir.
This observation from engineering experience
is the basis for statement 1 and 1a of the
second law.

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11/3/2017 212
Engineering, Thermodynamics (GEC 221)
If a thermal efficiency of 100% is not possible
for heat engines, what then determines the
upper limit? A heat engine operating in a
completely reversible mode the Carnot
engine should serve this purpose.
NOTE: A heat engine cycle cannot be
completed without rejecting some heat to a
low temperature sink. That is, cyclic devices
such as steam power plants cannot run
continuously unless the cycle is completed.

Covenant University, Dept. of Chemical


11/3/2017 213
Engineering, Thermodynamics (GEC 221)
The theoretical heat engine that operates on
the Carnot cycle is called Carnot heat engine.
The Carnot engine is composed of four
reversible processes. Two isothermal and two
adiabatic. These can be executed either in
closed or a steady flow system.
The net work, thus the cycle efficiency of a
heat engine, can be maximized by using
processes that require the least amount of
work and deliver the most, that is, by
reversible processes.
Covenant University, Dept. of Chemical
11/3/2017 214
Engineering, Thermodynamics (GEC 221)
Carnot Cycle
The four steps that make up a Carnot cycle are as
follows
Step 1-2: Reversible Isothermal Expansion
Isothermal reversible process when the system
absorbs heat QH from the reservoir at TH.

Step 2-3: Reversible Adiabatic Expansion


A reversible adiabatic process that brings the
temperature back to Tc
Covenant University, Dept. of Chemical
11/3/2017 215
Engineering, Thermodynamics (GEC 221)
Step 3-4: Reversible Isothermal Compression
A reversible isothermal process while the
system maintains contact with the cold
reservoir at temperature Tc, that returns the
system to its initial state with rejection of heat
Qc.

Step 4-1: Reversible Adiabatic Compression


A reversible adiabatic process from a cold
reservoir at Tc to a hot reservoir at TH .

Covenant University, Dept. of Chemical


11/3/2017 216
Engineering, Thermodynamics (GEC 221)
This set of processes can in principle be
performed on any kind of system and some of
practical interest will be described.
In overall,
W = QH Qc

Covenant University, Dept. of Chemical


11/3/2017 217
Engineering, Thermodynamics (GEC 221)
Carnot Theorem
In general the thermal efficiency of a Carnot
engine depends only on the temperature
levels and upon neither the working
substance nor the hard wares of the engine
i.e.

and as a result

Covenant University, Dept. of Chemical


11/3/2017 218
Engineering, Thermodynamics (GEC 221)
Two conclusions pertain to the thermal efficiency
of reversible and irreversible heat engines, and they
are known as the Carnot principles expressed as
follows:
1. The efficiency of an irreversible heat engine is
always less than the efficiency of a reversible
one operating between the same two reservoir.
2. The efficiencies of all reversible heat engines
operating between the same two reservoirs are
the same.
These two statements can be proved by
demonstrating that the violation of either
statement results in the violation of the 2nd law.
Covenant University, Dept. of Chemical
11/3/2017 219
Engineering, Thermodynamics (GEC 221)
1 2 3
Irrev. Rev. Rev.
HE HE HE

1<2 2=3

11/3/2017 The Carnot


Covenant principles
University, Dept. of Chemical
Engineering, Thermodynamics (GEC 221)
220
ENTROPY
It is of great interest to compare the quantities
of heat transferred from and into the two
reservoirs, in the Carnot engine thus

But enters the system, while leaves the


system.
Covenant University, Dept. of Chemical
11/3/2017 221
Engineering, Thermodynamics (GEC 221)
Thus, by convention, and are considered
positive and negative respectively.
Thus,

= 0

This means that for the complete cycle of


a Carnot engine, the two quantities Q/T
associated with the absorption and rejection
of heat by the working fluid of the engine sum
to zero
Covenant University, Dept. of Chemical
11/3/2017 222
Engineering, Thermodynamics (GEC 221)
The working fluid of a cyclic engine
periodically returns to its initial state, and its
properties e.g. temperature, pressure, and
internal energy, return to their initial values,
being a primary characteristic of a property.
Thus for a Carnot cycle, Eg. T suggests the
existence of a property whose changes are
given by the quantities Q/T. The property is
called entropy.

Covenant University, Dept. of Chemical


11/3/2017 223
Engineering, Thermodynamics (GEC 221)
For reversible Carnot heat engine systems
operated in small (differential) steps,
=

or = and

Covenant University, Dept. of Chemical


11/3/2017 224
Engineering, Thermodynamics (GEC 221)
Question
A steam engine, using water as working fluid,
operates between boiler and condenser temperatures
of 2800C and 1200C, respectively.
[a] Illustrate the system with indications of areas of
energy intakes and rejections and the corresponding
conditions of operation on a P H diagram for a
Rankine cycle.
[b] What is the temperature drop in the system.
[c] Calculate the Rankine thermal efficiency of the
heat engine.
[d] Calculate the Carnot thermal efficiency of the
engine.
[e] Calculate the effectiveness of the heat engine,
with respect to a Carnot heat engine. 225
Solution
[a]

QH
P TH
1 Isothermal Boiling 2

Isenthalpy & Isentropy Isentropic Expansion

W
4 Isothermal Condensation 3 3I
Tc
QH
11/3/2017
Covenant University, Dept. of Chemical
Engineering, Thermodynamics (GEC 221)
H 226
Solution
[b] The temperature drop of the heat engine is the
temperature difference between the boiler and condenser
2800C 1200C = 1600C
[c] The Rankine thermal efficiency, , of the system,
work done H2 H3
= = where
heat obtained H2 H1
H is enthalpy of water
Figure subscripts indicate points in the engines cycle of
operation
H2 = saturation enthalpy of water vapour at 2800C
S2 = saturation entropy (S) of water vapour at 2800C
Since operation 2 3 is isentropic, S3 = S2.
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solution
H4 = the saturation enthalpy of liquid water at 1200C
Since Operation 4 1 is isenthalpic, H4 = H1.
S3I = entropy of saturated vapour at point 3I (1200C).
From Steam tables,
H2 = 2780.4 kJ/kg
S2 = 5.8586 kJ/kg.K
S3 = 5.8586 kJ/kg.K
H4 = 503.7 kJ/kg
H1 = 503.7 kJ/kg
S3I = 7.1293 kJ/kg.K
S4 = 1.5276 kJ/kg.K
H3I = 2706 kJ/kg
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Solution
Calculation of H3
If an enthalpy balance is to be carried out along the
equilibrium temperature of 1200C, i.e 4 3 3I, on
the Heat Engine cycle, the vapour or water quality
of the wet vapour at point 3 is not known.
However, the entropies at points 3 and 3I and 4 are
known. Thus, an entropy balance, will give the
quality of the vapour at point 3,

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solution
Thus if the vapour quality at point 3 is x
S3 = xS3I + (1 x)S4
S3 = xS3I + S4 xS4

x =

5.8586 1.5276
=
7.1293 1.5276
4.331
=
5.6017
= 0.77316
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solution
Enthalpy balance
H3 = x H3I + (1 - x) H4
= 0.77316(2706) + (1 - 0.77316)503.7
= 2092.17 + 114.259
= 2206.429 kJ/kg
H2 H3 2780.4 2206.43
= =
H2 H1 2780.4 503.7
573.97
=
2276.7
= .
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Solution
[d] Carnot Efficiency depends on temperature only, thus

=

273.1 + 280 120 + 273.1
=
273.1 + 280
553.1 393.1
=
553.1
160
=
553.1
= .
[e] Heat Engine Effectiveness (HEE), Carnot (HEE)C

(HEE)C =

0.252
=
0.289
= .
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Engineering, Thermodynamics (GEC 221)
Example
The data listed below are claimed for a power cycle
operating between reservours at 527 C and 27 C. In
each case determine if any principles of
thermodynamics would be violated
a) QH = 700 kJ, Wcycle = 400 kJ, QC = 300 kJ
b) QH = 640 kJ, Wcycle = 400 kJ, QC = 240 kJ
c) QH = 640 kJ, Wcycle = 400 kJ, QC = 200 kJ
Solution
TH = 527 C = (527 + 273) K = 800 K
TC = 27 C = (27 + 273) K = 300 K
Principles of thermodynamics would be violated once the
efficiency is greater than that of Carnot engine or conservation
of energy principle is violated
a) Q H = 700 kJ, Wcycle = 400 kJ, Q C = 300 kJ

= 1 where

300
=1 = 0.625
800
400
= = = 0.5714
700
Since , principle of thermodynamics is
not violated
solution
b) QH = 640 kJ, Wcycle = 400 kJ, QC = 240 kJ

= 1 where

300
=1 = 0.625
800
400
= = = 0.625
640
Since = obtained, principle of
thermodynamics is violated
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Engineering, Thermodynamics (GEC 221)
solution
c) Q H = 700 kJ, Wcycle = 400 kJ, Q C = 200 kJ
The principle of energy conservation says
Q H = Wcycle + Q
but
700 kJ 400 kJ + 200 kJ
hence
The principle of thermodynamics is violated

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Exercise
Obtain the Heat Engine Effectiveness (HEE) of the
given Rankine cycle
QH
P TH = 26 C
1 Isothermal Boiling 2

Isenthalpy & Isentropy Isentropic Expansion

W
4 Isothermal Condensation 3 3I

Tc = 1 C
QH
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Engineering, Thermodynamics (GEC 221)
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