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Introduction To Chemical

Thermodynamics I

CHE 325
(3 Units)

Lecturer: Dr. AYOOLA A. A.

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. Any other relevant thermodynamics text

Mode of Grading
Assignments/Tests = 30 marks
Examination = 70 marks
• Basic definitions, aim and scope.
• PVT system, path dependency.


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


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


Basic Terms in Chemical

Engineering Thermodynamics
• the science of energy
• the science that seeks to predict the amount
of energy needed to bring about a change of
state of a system from one equilibrium state
to another.
• involves the forms, storage, transformation
and transfer of energy.
It focuses on Energy
Giving a general definition of Energy is a difficult task
due to its wide areas of application.
Simple definitions of Energy include the followings:
• Energy is the strength or vitality required for
sustained physical or mental activities (work).
• Energy is the power derived from the utilisation of
physical or chemical resources to provide light,
work or heat.
• Energy is a property of matter that can be
converted into work, heat or radiation
Classical Thermodynamics: is observation driven
(macroscopic) and focuses on bulk energy flow.
It has its applications mostly in Engineering fields.

Statistical Thermodynamics: is theory driven

(microscopic) and focuses on structure of matters
and molecules interaction.
It has its applications mostly in science fields
(Physics, Chemistry).
Applications of Thermodynamics in
Chemical Engineering
Some of the operations of Chemical Engineers
(separation, reactions etc.) are based on the
principles of thermodynamics.
• Optimisation of Energy usage and improved Energy
efficiency (Pinch technology & Energy balance)
• Promotion of cost-effective design
• Budgeting of energy costs for the future
• It guides in the choice of energy efficient equipment
and process technology
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 Applications of
Thermodynamics in Engineering
• Efficient heating or cooling system in Industries
and homes.

• Good Accessibility to solar energy (and other

renewable energy forms) in homes/industries.
• Improved railway system and the use of hybrid
vehicles that run on biofuels .
Some of the Applications of
Thermodynamics in Engineering
• Internet service as a predominant means of
business transactions.

• Significant contribution of wind, solar and other

renewable technologies to the nation’s
electricity grid.

• Adoption of the use of telecommuting and

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

Condition/position of a system
due to change in properties
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 following same manner.
Cyclic process: a system undergoes
thermodynamic cyclic 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.
It is a condition of constant property.
Isobaric process P
P = constant
Isochoric process P
V = constant
Isothermal process P
T = constant
Adiabatic process P

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.
[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
Pressure exerted on the system
through the pump makes upflow
of water possible.
[b] The system consisting of the solar
collector, the tank and pipes is an open
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
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
[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
[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
[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
0.2060 + 0.2275
At 1.0MPa, 220⁰C; v= = 0.21675 m³/kg
0.1325 + 0.1483
At 1.5MPa, 220⁰C; v= = 0.1404 m³/kg
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
1. Over a limited temperature range , the relation between
electrical resistance R and temperature T for a resistance
temperature detector is
𝑅 = 𝑅0 [1 + 𝛼(𝑇 − 𝑇0 )]
where 𝑅0 is the resistance, in ohms (Ώ), measured at
reference temperature 𝑇0 (⁰C) and 𝛼 is a material constant
with units of (⁰C)−1 . The following data are obtained for a
particular resistance thermometer.
𝑇0 (⁰C) 𝑅 (Ώ)
Test 1 (𝑇0 ) 0 𝑅0 = 51.39
Test 2 91 51.72

What temperature would correspond to a resistance of

51.47Ώ on this thermometer?
2. As illustrated in the
figure, water circulates
through a piping system,
servicing various household
Considering the water
heater as a system, identify
locations on the system
boundary where the system
interacts with its
surroundings and describe
significant occurrence
within the system. repeat
for the dishwasher and for
the shower.
Perform the following unit conversion
a) 122 in³ to L
b) 778.17 ft.ibf to kJ
c) 100 hp to kW
d) 1000 ib/h to kg/s
e) 29.392 ibf/in² to bar
f) 650 J to Btu
g) 0.135 kW to ft.ibf/s
h) 304 kPa to ibf/in²
i) 2500 ft³/min to m³/s
j) 1 ton to N
PT Diagram of a Pure Substance

Critical point – highest

combination of pressure and
temperature where the fluid
exist in liq-vap equilibrium

The 2-C line, also known as

vaporization curve is where
liquid-vapor is in equilibrium

The 1-2 line, also known

Triple point, three The 2-3 line, also known as
as sublimation curve is
phases exist in fusion curve is where solid-liquid
where solid & vapor are
equilibrium (F=0) is in equilibrium
in equilibrium
PT 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 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 or P
• Transition from A to B is possible, it is gradual and
does not involve vapourisation step
• A fluid existing at above TC is Supercritical fluid
eg. Atmospheric Air.
PV Diagram
 Compressed liquid or a
subcooled liquid: A liquid
that will not vaporize easily.
 Saturated liquid: A liquid
that is about to vaporize.
 Saturated vapor: A vapor
that is about to condense.
 Saturated liquid-vapor
mixture: the liquid and
vapor phases coexist in
 Superheated vapor: A dry
vapor that will not
condense easily
PV Diagram
Compressed liquid region

Saturated liquid line at boiling temperature

Superheated vapor region

Saturated vapor line at condensation

PV Diagram
• 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
• 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
• 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.
TV Diagram