Introduction To Chemical

Engineering
Thermodynamics I

CHE 325
(3 Units)

Dr. F. B. ELEHINAFE
 Textbooks
1. Introduction To Chemical Engineering
Thermodynamics (J. M. Smith, H. C. Van Ness & M. M.
Abbot)
2. Thermodynamics: An Engineering Approach (Yunus A.
Cengel & Michael A. Boles)
3. Chemical and Process Thermodynamics (B. G. Kyle)
4. Any other relevant thermodynamics text

Grading
Assignments/Tests = 30 marks
Examination = 70 marks
 Modules
1: INTRODUCTION
• Basic definitions, aim and scope.
• PVT system, path dependency.

2: FIRST LAW OF THERMODYNAMICS

• Work and Heat.
• Adiabatic work.
• Internal Energy.
• Enthalpy.
• Heat Capacity.

3: SECOND LAW OF THERMODYNAMICS

• Inter-conversion of Work and Heat.
• Heat Engines and Cyclic processes.
• Refrigeration Cycle.
• Coefficient of Performance.
 MODULE ONE

BASIC DEFINITIONS OF
SOME TERMS
 Definition of Some Terms
Thermodynamics:
is the science of energy
involves all aspects of energy and energy
transformation.
involves the storage, transformation & transfer
of energy.
Energy is transformed from one form of energy
to another.
It is transferred across a boundary as either
heat or work.
 Definition of Some Terms
Classical Thermodynamics: is observation driven
(macroscopic) and focuses on bulk energy flow
(transfer/transformation/storage). It has its
applications mostly in Engineering fields.

Statistical Thermodynamics: is theory driven

(microscopic). Focuses on structure of matters and
molecules interaction. It has its applications mostly
in science fields (physics, chemistry).
 Applications of Thermodynamics in
Chemical Engineering
• Conversion of chemical stored energy in fossil fuel
to Heat and Work
• Transportation of materials
and goods
• Determination of properties of materials/systems
 Applications of Thermodynamics in
Chemical Engineering
• Conversion of materials to useful products

• Monitoring of chemical reactions

Some of The Future Benefits of Thermodynamics
• Better Industries/Homes construction due to
reduction in the need of heating or cooling
system.
• Homes /Industries will have systems that the
energy usage are electronically monitored and
regulated.
• Adoption of solar energy in every home.
• Improved railway system and the use of hybrid
vehicles that run on biofuels .
Some of the Future Benefits of Thermodynamics

• Internet becomes predominant means of business

transactions.

• Wind, solar and other renewable technologies will

contribute significantly to nation’s electricity grid.

• Use of telecommuting and teleconferencing by

industries and institutions will be very common.

ENERGY IS LIFE
 Revision
System: portion/object to be studied
Surroundings: everything external to the system
Boundary: what separates a system from its
surroundings.
Open System (control volume): a system that allows
mass and energy interaction.
 Revision
Closed System: a system with no
mass interaction between the system
and the surroundings
Properties:
What describe a system.
Macroscopic characteristics of
a system and can be assigned
numerical values

State:
condition of a system when all its
properties do not change
 Revision
Process: a series of changes experience by a system
from one state to another.
The path of successive states through which a system
passes when change from one state to another.
Reversible Process: a system undergoes reversible
process when it is restored to its initial state.

Equilibrium: state of balance, a system in equilibrium

experiences no changes when it is isolated from its
surroundings. No observable change in property
macroscopically.
 Revision
Isobaric process P
o P = constant
V
Isochoric process P
o V = constant
V
Isothermal process P
o T = constant

Adiabatic process P V
o Q=0

V
 Example 1
As shown in the figure, water which
circulates between a storage tank
and a solar collector is used for
domestic purposes. Identify
locations on the system boundary
where the system interacts with the
surroundings and describe events
that occur within the system, if the
system is
[a] solar collector
[b] solar collector, storage tank and
connecting pipes.
Solution
[a] The system (solar collector) is
an open system.
Warm water enters the system at
the base through the pump.
The water is heated up as a result
of heat radiation through the
surface of the system.
Hot water leaves the system at the
top.
Pressure exerted on the system
through the pump makes upflow
of water possible.
 Solution
[b] The system consisting of the solar
collector, the tank and pipes is an open
system.
Cold water enters the tank at the base and
get warm on mixing with hot water inside
the tank.
There is interaction between the
surroundings, surface of the tank, water
inside the tank.
Warm water entering solar collector
interacts with the surroundings at the
surface of the collector and becomes hot
water.
Hot water in the tank leaves the tank the
moment the water level rises to the top.
 Example 2
The Table below lists temperatures and specific volumes of water
vapor at two different pressures
p = 1.0 MPa p = 1.5 MPa
T (⁰C) v (m³/kg) T (⁰C) v (m³/kg)
200 0.2060 200 0.1325
240 0.2275 240 0.1483
280 0.2480 280 0.1627

Data encountered in solving problems often do not fall exactly on the

grid of values provided by property tables, and linear interpolation
between adjacent table entries become necessary. Using the data
provided here, estimate
a. the specific volume (in m³/kg) at T = 240 ⁰C and p = 1.25 MPa
b. the temperature (in ⁰C ) at p = 1.5 Mpa and v = 0.1555 m³/kg
c. the specific volume (in m³/kg) at T = 220 ⁰C and p = 1.4 MPa
 Solution
[a] At a temperature of 240ºC, 1.25MPa falls between
1.0 MPa and 1.5 MPa.
Finding slope will help
Slope =
𝑣 −0.1483 0.2275 −0.1483
=
1.5 −1.25 1.5 −1.0
0.5(v – 0.1483)
= 0.25 (0.0792)
0.5v = 0.0198 + 0.07415
v = 0.1879 m³/kg
 Solution
[b] p = 1.5 Mpa and v = 0.1555 m³/kg fall between
T = 240ºC and T = 280ºC.

Slope =
𝑇 −240
0.1555 −0.1483
280 −240
=
0.1627 −0.1483
⟹
T = 260ºC
 Solution
[c] At T = 220 ⁰C and p = 1.4 MPa, the specific volume
falls between 1.0 and 1.5 MPa and T = 220 ⁰C btw 200
and 240⁰C. Hence, double interpolation is required.
At 220 ⁰C, v at each pressure is the average over the
interval
0.2060 + 0.2275
At 1.0MPa, 220⁰C; v= = 0.21675 m³/kg
2
0.1325 + 0.1483
At 1.5MPa, 220⁰C; v= = 0.1404 m³/kg
2
so as calculated in [a]
𝑣 −0.1404 0.21675 −0.1404
= ⟹ v = 0.15567 m³/kg
1.5 −1.4 1.5 −1.0
PT Diagram (PT Phase
Diagram) of a Pure
Substance
PT Diagram (PT Phase Diagram) of a
Pure Substance

• Line 1-2: Solid/Vapour phase equilibrium,

• Line 2- C: Liquid/Vapour phase equilibrium,
• Line 2 -3: Solid/Liquid phase equilibrium
• Critical point: Highest value of P and T at
which chemical species of the pure
substance exist in liquid/vapour equilibrium.
• Triple point: Point at which the three phases
coexist in equilibrium
PT Diagram (PT Phase Diagram)
of a Pure Substance
• Isothermal Process is represented by vertical
line on the PT diagram
• Isobaric Process is represented by horizontal
line on PT diagram
• When any of these two lines crosses phase
boundary, there is immediate change of
properties and phase at constant T and P
• Transition from A to B is possible, it is gradual
and does not involve vapourisation step
• A fluid existing at above T is Supercritical
C

fluid
 PV Diagram (PV Phase
Diagram) of a Pure Substance
 PV Diagram (PV Phase
Diagram) of a Pure Substance
• PV diagram shows the existence of regions between two
phases e.g. Soild/Liquid region in equilibrium.
• Regions are separated by bounding curves that
represent single phases.
• At a fixed Temperature, a bounding curve is obtained.
• Lines labelled T1 and T2 are for subcritical temperatures,
each line consists of three segments.
• The horizontal segments of these lines represent
liquid/vapour mixture at equilibrium (i.e 100% liquid at
the extreme left, 100% vapour at the right end).
PV Diagram (PV Phase Diagram)
of a Pure Substance
• The locus of these end points forms a dome-shaped
curved, BCD.
• The left half (BC) represents single-phase liquids at
their vapourisation temperatures.
• The right half (CD) represents single-phase vapours at
their condensation temperatures.
• Liquids and vapours represented by BCD are said to be
saturated.
• Subcooled liquid region lies to the left of saturated
liquid curve, BC.
• Superheated vapour region lies to the right of
saturated vapour curve, CD.