Introduction To Chemical

Engineering
Thermodynamics I

CHE 325
(3 Units)

Lecturer: Dr. AYOOLA A. A.

 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. Any other relevant thermodynamics text

Mode of Grading
Assignments/Tests = 30 marks
Examination = 70 marks
 Module
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

INTRODUCTION:

Basic Terms in Chemical

Engineering Thermodynamics
 INTRODUCTION
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
 INTRODUCTION
Thermodynamics:
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
 INTRODUCTION
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.
 INTRODUCTION
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 between the system and
its surroundings.
 INTRODUCTION
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/position of a system
due to change in properties
 INTRODUCTION
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.
 INTRODUCTION
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.
 INTRODUCTION
Isobaric process P
P = constant
V
Isochoric process P
V = constant
V
Isothermal process P
T = constant
V
Adiabatic process P
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
 Assignment
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?
 Assignment
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.
 Exercises
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
 P-T 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.
P-V 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
equilibrium.
 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

temperature
 P-V Diagram
• P-V 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).
 P-V 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.
T-V Diagram
 MODULE TWO

FIRST LAW OF THERMODYNAMICS

• Work and Heat.
• Internal Energy.
• Enthalpy.
• Heat Capacity.
 First law of Thermodynamics

Although energy assumes many forms, the

total quantity of energy is constant, and
when disappears in one form it appears
simultaneously in other forms.

………that is during an interaction between a system and its

surroundings, 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.
 First law of Thermodynamics
The law implies that
• There are different forms of energy
• There is conservation of energy
• Total energy between a system and its
surroundings is constant (no change in total
energy between a system and its surroundings)
The last expression can be written as
Δ(Energy of the System) + Δ(Energy of the
Surroundings) = 0 2.1
where Δ ≡ change
 WORK, W
• Work is a form of energy transferred between the
system and surroundings.
• It can only be transferred, but not stored (transient
energy)
• Work can done by a system on its surroundings and
work can be done by surroundings on a system.
+ve sign is assigned when work is done on the system
-ve sign is assigned when work is done by the system
• W is not a point function, but path function (i.e. its
magnitude depends on the process path).
•
 WORK, W
2
• For finite process, W = 1
F dS
• For infinite process, dW = F dS
• In Engineering thermodynamics, the
predominant type of work involves expansion
and contraction of a fluid
2
W= 1
p dv
 WORK, W
In a piston-cylinder arrangement, and the piston is
withdrawn in such a way that the pressure remains
constant. The initial pressure and volume are 10 kPa
and 0.1m³, respectively. Calculate the work done by
the gas on the piston, if expands to 0.3m³ .
Solution
2
W= 1
p dv
2
W= p 1 dv
W = p [v2 - v1 ] = 10 (0.3 – 0.1)
= 2 kJ
 Heat, Q
• 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.
• Energy interaction is heat only if it takes place
because of temperature difference.
• 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
 Internal Energy, U
• Internal Energy, U, is the macroscopic
measure of molecular and atomic energies of
a system.
• It is a state function.
• It can not be measured directly, but it can be
calculated in terms of measurable properties
such as P, V, T.
• Change in internal Energy, ∆U, is expressed
2
as ∆U = 1
CV dT
 Enthalpy, H
• Enthalpy is defined using combination of properties.
The enthalpy, H, is defined as:
H Ξ U + PV and *
∆H = ∆U + ∆(PV) **
where U is Internal Energy, P is Pressure and V is
volume.
• For a constant P and V process,
∆H = ∆U ***
also
Q = n∆H = n∫CpdT ****
 Energy Balance For A Closed System
• For a closed system, no form of energy is
transported between the system & surroundings.
• The only forms of energy that may be transferred
are Heat (Q) and Work (W).
• The second term of Equation 2.1 can be written as
Δ(Energy of the Surroundings) = ±Q ±W 2.2
• Q and W denote Heat and Work of the system.
• The sign used depends on the nature of the energy
and convention adopt, +ve sign is taken as energy to
the system
 Energy Balance For A Closed System
Hence,
Q surr. = -Q, Wsurr. = -W 2.3
Equation 2.1 becomes
Δ(Energy of the System) + [ – Q – W ] = 0
Δ(Energy of the System) = Q + W
i.e. Change in Total Energy of a closed system equals net
energy transferred to it in form of heat and Work.

Total Energy of a closed system is represented as Total

Internal Energy (𝐔 𝐭 ) of the system.
so
Δ𝐔𝐭 = Q + W 2.4
For differential change, 𝒅𝑼𝒕 = dQ + dW
Example 2.1: A system is changed from state a to
b, as shown below. 100 J of heat flows into the system
along aeb path and the system does 40 J of work.
a) How much heat flows into the system along path
aeb if the work done by the system is 20 J
b) The system returns
from b to a along bda.
If the work done on
the system is 30 J, does
the system absorb or
liberate heat? How
much?
a) From Δ𝐔 𝐭 = Q + W
t
ΔUab = Q acb + Wacb = 100 – 40 = 60 J
Considering the path aed,
ΔUab t = 60 = Q aeb + Waeb = Q aeb – 20
hence Q aeb = 80 J
b) For path bda,
ΔUba t = - ΔUab t = - 60
= Q bda + Wbda = Q bda + 30
hence Q bda = - 90 J
90 J of heat is transferred from the system to the
surroundings
 Examples 2.2
A non-conducting container filled with 25 kg of water at 200 C is fitted
with a stirrer which is made to turn by gravity acting on a weight of mass
35 kg. The weight falls slowly through a distance of 5 m in driving the
stirrer. Assuming that all work done on the weight is transferred to the
𝑚
water and that the local acceleration of gravity is 9.8 𝑠2 , determine
a) the amount of work done on the water
b) the internal energy change of the water
kJ
c) the final temperature of the water, for which Cp = 4.18 kg 0 C
d) the amount of heat that must be removed from the water to return
it to its initial temperature
e) the total energy change of the universe because of
i. the process of lowering the weight
ii. the process of cooling the water back to its initial temperature
iii. both processes together.
 Solution to Example 2.2
𝑚
Mwt = 35 kg, g = 9.8 2 , Δz = 5 m
𝑠
𝑚
[a] Work, W = F.d = Mwt . g . Δz = 35 kg x 9.8 x5m
𝑠2
W = 1715 J = 1.715 kJ
[b] Change in Internal Energy, ΔUt
No energy loss, (Q = 0)
∴ Δ𝑼𝒕 = W = 1.715 kJ
[c] Final Temperature of water, T2
At constant P and V, [using *** and ****]
∆U = ∆H = Mwt ∫CpdT = Mwt x Cp x T2 - T1
 Solution to Example 2.2
1.715 = 35 x 4.18 x (T2 - 20)
hence
𝐓𝟐 = 20.01𝟐𝟎 C, Final Temperature
[d] Heat removed, Q, to restore (cool) water to T1
Q = - ∆U = -1.715 kJ
[e] No change in total energy of the universal in each
of the three cases (because both the system and its
surroundings make up the universe)
….……..1st law of thermodynamics
 Example 2.3
One mole of gas in a closed system undergoes a
four-step thermodynamic cycle. Use the data
given in the following table to determine
numerical values for the missing quantities.
Step ΔU /J Q /J W /J
12 -200 - -6000
23 - -3800 -
34 - -800 300
41 4700 - -
12341 - - -1400
Solution To Example 2.3
A Thermodynamic Cycle

1
2

4
3
 Solution To Example 2.3

For a closed system, ΔU t = Q + W

Step 1 – 2: ΔU12 = Q12 + W12
-200 = Q12 + (-6000)
⟹ Q12 = 5,800 J

Step 3 – 4: ΔU34 = Q34 + W34

ΔU34 = -800 + 300
ΔU34 = -500 J
 Solution To Example 2.3
For a closed system, ΔUt = 0
ΔU = 0 = Q + W
1234 1234 12343

⟹ Q = -W = 1400 J
1234 1234

Q =Q +Q +Q +Q
1234 12 23 34 41

Q =Q -Q - Q - Q
41 1234 12 23 34

= 1400 – 5800 + 3800 + 800

Q = 200 J
41
 Solution To Example 2.3
Step 4 – 1: ΔU = Q + W
41 41 41

4700 = 200 + W 41

⟹ W = 4500 J41

ΔU = 0 = ΔU + ΔU + ΔU + ΔU
1234 12 23 34 41

0 = -200 + ΔU - 500 + 4700 23

⟹ ΔU = -4000 J
23
 Solution To Example 2.3
Step 2 – 3: ΔU = Q + W
23 23 23

-4000 = -3800 + W 23

⟹ W = -200 J
23

Hence the table becomes

Step ΔU /J Q /J W /J
12 -200 5,800 -6000
23 -4000 -3800 -200
34 -500 -800 300
41 4700 200 4500
12341 0 1400 -1400
 Example 2.4
1 kg of liquid water at 250 C:
a) Experience a temperature increase of 1 K. What is
ΔUt , in J?
b) Experience a change in elevation, ΔZ. The change
in potential energy ΔEpe is the same as ΔUt for part
(a). What is ΔZ, in meters?
c) Is accelerated from rest to final velocity, v. the
change in kinetic energy ΔEke is the same as ΔUt for
part (a). What is v, in m/s?
kJ m
Given that C = 4.18 and g = 9.8
kg K s2
 Solution To Example 2.4
m = 1kg
a) ΔT = 1 K,
Q = m x C x ΔT = mC
Hence ΔUt = mC = C [ m= 1]
𝒕
ΔU = 4.18 kJ = 4180 J
b) ΔZ = ?
ΔEpe = ΔUt
ΔEpe = m x g x ΔZ = C
g ΔZ = C [m = 1]
ΔZ = 4180/9.8 = 426.5 m
 Solution To Example 2.4
c) v = ?
ΔEke = ΔUt
1
ΔEke = mΔv 2 = C
2
1 2
v = 4180 (m = 1)
2
2
v =8360
v = 8360
v = 91.43 m/s
 Example 2.5
4. An incompressible liquid flows steadily through a
conduit of circular cross-section and increasing
diameter. At location 1, the diameter is 2.5 cm
and the velocity is 2 m/s; at location 2, the
diameter is 5 cm.
a] What is the velocity at location 2?
b] What is the kinetic energy change (J/kg) of
the fluid between locations 1 and 2?
 Solution To Example 2.5
1 2
d = 2.5cm d = 5cm
v = 2 m/s v=?
For an incompressible fluid, 𝜌 = constant
a] mass balance:
d2
𝐯𝟏 𝐀𝟏 𝝆𝟏 = 𝐯𝟐 𝐀𝟐 𝝆𝟐 (A = π)
4
so v1 d21 = v2 d2 2
v2 = 2 x 0.0252 /0.052
𝐯𝟐 = 0.5 m/s
 Solution To Example 2.5
b]
1
ΔEke = mΔv 2
2
1
= m[v 2 2 − v 21 ]
2
1 2
ΔEke/m = [v 2 − v 21 ]
2
1
= [0.52 − 22 ]
2
= - 1.875 J/kg
N.B: -ve implies loss of KE
 Exercises
1. Heat in the amount of 7.5 kJ is added to a closed system
while its internal energy decreases by 12 kJ. How much
energy is transferred as work? For a process causing the same
change of state but for which the work is zero, how much
heat is transferred?
2. Liquid water at 1800 C and 1,002.7 kPa has an internal
energy (on an arbitrary
3
scale) of 762 kJ/kg and a specific
cm
volume of 1.128 .
g
a) What is its enthalpy?
b) The water is brought to the vapour state at
3000 C and 1,500 kPa, where its internal energy is
cm3
2,784.4 kJ/kg and its specific volume is 169.7 .
g
Calculate ΔU and ΔH for the process.
 Exercises
3. A hydro-turbine operates with a head of 50 m of
water. inlet and outlet conduits are 2 m in diameter.
Estimate the mechanical power developed by the turbine
for an outlet velocity of 5 m/s.

4. A steel casting weighing 2 kg has an initial temperature

of 5000 C; 40 kg of water initially at 250 C is contained in a
perfectly insulated steel tank weighing 5 kg. The casting is
immersed in the water and the system is allowed to come
to equilibrium. What is its final temperature? Ignore
effects of expansion or contraction, and assume constant
kJ kJ
specific heats of 4.18 for water and 0.50 for steel.
kg K kg K
 Exercises
5. A stream of warm water is produced in a
steady flow mixing process by combining 1kg/s
of cool water at 250 C with 0.8 kg/s of hot water
at 750 C. During mixing, heat is lost to the
surroundings at the rate of 30 kJ/s. What is the
temperature of the warm water stream?
Assume the specific heat of water constant at
kJ
4.18
kg K