Chemical Engineering Process

Thermodynamics I

CHE 345/325
(3 Units)

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

Grading/Assessment
Assignments/Tests = 30 marks
Examination = 70 marks
 Outline
1: INTRODUCTION
• Basic definitions & Revision
• PVT systems
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
4: Entropy
Origin
Mathematical Expression
Entropy Change Calculations
 MODULE ONE

INTRODUCTION
• Basic definitions & Revision
• PVT system
 Basic Definitions/Revision
Thermodynamics:
is the science of energy. It involves all aspects of
energy: energy storage, transformation &
transfer/transportation.
Energy is stored in one form of energy
It is transformed from one form of energy to
another.
It is transferred across a boundary as either
heat or work.
It is transported via media (fluids and conductors)
 In chemical engineering
thermodynamics, we are concerned with
energy in form of heat and work
(produced or consumed) in our processes
(energy producing processes and energy
requiring processes) evident across the
boundaries of systems. Examples of such
systems are: absorber, distillation
columns, humidifiers, extractors,
reactors, mixers, pumps, compressors,
refrigerators, heat pumps etc.
Classical Thermodynamics
is observation driven (macroscopic and empirical)
and focuses on bulk energy flow
(transfer/transformation/storage) and measurable.
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.
General Applications of Thermodynamics
• Conversion of chemical stored energy in fossil fuel
to Heat (burning) and Work (motion)

• Determination of properties of materials:

malleability, conductivity, elasticity, ductility,
plasticity, etc.
• Conversion of materials to useful products

• Monitoring of chemical reactions

 Applications of Thermodynamics in
Chemical Engineering
The main uses of thermodynamics in chemical
engineering are to:
 determine states of phase and chemical equilibrium
necessary for the design of separations processes
(distillation, absorption, extraction, etc.), mixing
processes, pumps, chemical reactors, grinders,
pressers, blowers, etc.
 determine the thermodynamic (2nd law) efficiency of
chemical processes/equipment.
 design power plants, heat pumps and refrigerators
with working fluids in focus
 control equilibrium operations
Some of The Benefits of Thermodynamics
• Better Industries/Home construction due to
reduction in the need of heating or cooling
system.
• Homes /Industries 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.
• Internet becomes predominant means of business
transactions.

• Wind, solar and other renewable technologies now

contribute significantly to nations’ electricity grids.

• Use of telecommuting and teleconferencing by

industries and institutions now very common.

ENERGY IS LIFE
System: portion/object to be studied (a whole
plant, part of plant, reactor, mixer, etc.)
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 with the
surroundings.
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 (T,
V, P, M, C, etc.)

State:
condition of a system when all its
properties do not change
Process: a series of changes experience by a system
from one state to another.
The path of successive stages 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.
Typical processes in chemical engineering
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
Assignment 1
Name and briefly discuss 2 examples, in each of
the typical processes above.
Exercise 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 (Heat).
Pressure exerted on the system
through the pump makes up-flow
of water possible (Work).
[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.
Cold water entering solar collector
interacts with the surroundings at the
surface of the collector and becomes hot
water Heat).
Hot water in the tank leaves the tank the
moment the water level rises to the top
under the influence of pump (work).
Exercise 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 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
[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
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
Assignment 2
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
needs.
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.
3. 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 (1 ton = 2000 ibf)
 PVT Systems
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
• 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 vapourization step
• A fluid existing at above TC is Supercritical fluid
PV Diagram (PV Phase Diagram) of a Pure
Substance
• The diagram shows the existence of regions
between two phases e.g. Solid/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).
• 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.
Assignment 3
Sketch a well labelled TV Diagram (TV Phase
Diagram) of pure water and summarize its salient
features.