Introduction To Chemical

Engineering
Thermodynamics II

CHE 415
(2 Units)

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

Grading
Assignments/Tests = 30 marks
Examination = 70 marks
 MODULE ONE

INTRODUCTION TO
CHEMICAL
ENGINEERING
THERMODYNAMICS
 MODULE ONE: INTRODUCTION
Definition of Some Terms
Thermodynamics:
It is derived from the greek word therme (heat) and
dynamis (dynamic/power).
It is the science of energy that deals with:
energy forms,
energy storage,
energy transformation
energy transfer and
energy utilisation.
 Definition of Some Terms
Thermodynamics:

It is 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.

Energy 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 energy stored in fossil fuel
to Heat and Work

Determination of properties of materials/systems

Applications of Thermodynamics in
Chemical Engineering
 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 for heating or cooling
system.
Homes /Industries will have systems with energy
usage which 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 nations electricity grid.

Use of telecommuting and teleconferencing by

industries and institutions will be very common.

THERMODYNAMICS ENHANCES ENERGY EFFICIENCY

 Definition of Some Terms
System:
portion/object to be studied
It is any object of interest that is being studied in
thermodynamics.
any designated region of a continuum of fixed
mass.
It can be classified
as isolated, closed
(control mass) or
open system (control
volume).
 Definition of Some Terms
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
surroundings.
 Definition of Some Terms
Closed System: a system with no mass
interaction between the system and
the surroundings.
Properties:
What describe (behaviour/performance of) a system.
Macroscopic characteristics of
a system and can be assigned
numerical values. E.g. T, V, P.

State:
condition or position of a system
due to change in properties
 Definition of Some Terms
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. Condition of constant property.
 Definition of Some Terms
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 (C) v (m/kg) T (C) v (m/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 m/kg) at T = 240 C and p = 1.25 MPa
b. the temperature (in C ) at p = 1.5 Mpa and v = 0.1555 m/kg
c. the specific volume (in m/kg) at T = 220 C and p = 1.4 MPa
 Solution
[a] At a temperature of 240C, 1.25MPa falls between
1.0 MPa and 1.5 MPa.
Finding slope will help
Slope =
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 m/kg
 Solution
[b] p = 1.5 Mpa and v = 0.1555 m/kg fall between
T = 240C and T = 280C.

Slope =
240
0.1555 0.1483
280 240
=
0.1627 0.1483

T = 260C
 Solution
[c] At T = 220 C and p = 1.4 MPa, the specific volume
falls between 1.0 and 1.5 MPa and T = 220 C btw 200
and 240C. Hence, double interpolation is required.
At 220 C, v at each pressure is the average over the
interval
0.2060 + 0.2275
At 1.0MPa, 220C; v= = 0.21675 m/kg
2
0.1325 + 0.1483
At 1.5MPa, 220C; v= = 0.1404 m/kg
2
so as calculated in [a]
0.1404 0.21675 0.1404
= v = 0.15567 m/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
= 0 [1 + ( 0 )]
where 0 is the resistance, in ohms (), measured at
reference temperature 0 (C) and is a material constant
with units of (C)1 . The following data are obtained for a
particular resistance thermometer.
0 (C) ()
Test 1 (0 ) 0 0 = 51.39
Test 2 91 51.72

What temperature would correspond to a resistance of

51.47 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
122 in to L
778.17 ft.ibf to kJ
100 hp to kW
1000 ib/h to kg/s
29.392 ibf/in to bar
650 J to Btu
0.135 kW to ft.ibf/s
304 kPa to ibf/in
2500 ft/min to m/s
1 ton to N
 PT BEHAVIOR OF PURE SUBSTANCES

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 and P
Transition from A to B is possible, it is gradual
and does not involve vapourisation step
PV Diagram
Compressed liquid or a
subcooled liquid: A liquid
that is not about to
vaporize.
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
vapor that is not about to
condense
PV Diagram
Compressed liquid region

Saturated liquid line at boiling temperature

Superheated vapor region

Saturated vapor line at condensation

temperature
 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
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
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
 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, 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
(Energy of the System) + (Energy of the
Surroundings) = 0 1
where change
 WORK, W
is a transfer of energy between the system and
surroundings.
It can only be transferred, but not stored
Work is done by a system on its surroundings if the
sole effect on everything external to the system
could have been the raising of a weight
W is not a point function, but path function
(magnitude depends on the path).
2 2
W= 1
F dS = 1
p dv
 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
 Forms of Energy
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)
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, U.
 Forms of Energy
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).
 Other Forms of Energy: Enthalpy, H
Enthalpy is defined using combination of properties.
The enthalpy, H, is defined as:
H 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 ***
Recall also that
the product P x V has energy units.
Q = nH = nCpdT ****
Read Textbooks for more information on Enthalpy and Heat
Capacity
Study Example 2.1 2.14 in Introduction To Chemical Engineering
Thermodynamics (J. M. Smith, H. C. Van Ness & M. M. Abbot).
 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 1 is now written as
(Energy of the Surroundings) = Q W 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 3
Equation 1 becomes
(Energy of the System) + [ Q W ] = 0
(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 ( ) of the system.
so
= Q + W 4
For differential change, = dQ + dW
 Examples 3
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

water and that the local acceleration of gravity is 9.8 2 , 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 3

Mwt = 35 kg, g = 9.8 2 , z = 5 m


[a] Work, W = F.d = Mwt . g . z = 35 kg x 9.8 x5m
2
W = 1715 J = 1.715 kJ
[b] Change in Internal Energy, Ut
No energy loss, (Q = 0)
= 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 3
1.715 = 35 x 4.18 x (T2 - 20)
hence
= 20.01 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 4
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 U /J Q /J W /J
12 -200 - -6000
23 - -3800 -
34 - -800 300
41 4700 - -
12341 - - -1400
Solution To Example 4
A Thermodynamic Cycle

1
2

4
3
 Solution To Example 4

For a closed system, U t = Q + W

Step 1 2: U12 = Q12 + W12
-200 = Q12 + (-6000)
Q12 = 5,800 J

Step 3 4: U34 = Q34 + W34

U34 = -800 + 300
U34 = -500 J
 Solution To Example 4
For a closed system, Ut = 0
U = 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 4
Step 4 1: U = Q + W
41 41 41

4700 = 200 + W 41

W = 4500 J
41

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

0 = -200 + U - 500 + 4700 23

U = -4000 J
23
 Solution To Example 4
Step 2 3: U = Q + W
23 23 23

-4000 = -3800 + W 23

W = -200 J
23

Hence the table becomes

Step U /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 5
1 kg of liquid water at 250 C:
a) Experience a temperature increase of 1 K. What is
Ut , in J?
b) Experience a change in elevation, Z. The change
in potential energy Epe is the same as Ut for part
(a). What is Z, in meters?
c) Is accelerated from rest to final velocity, v. the
change in kinetic energy Eke is the same as Ut 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 5
m = 1kg
a) T = 1 K,
Q = m x C x T = mC
Hence Ut = mC = C [ m= 1]

U = 4.18 kJ = 4180 J
b) Z = ?
Epe = Ut
Epe = m x g x Z = C
g Z = C [m = 1]
Z = 4180/9.8 = 426.5 m
 Solution To Example 5
c) v = ?
Eke = Ut
1
Eke = mv 2 = C
2
1 2
v = 4180 (m = 1)
2
2
v =8360
v = 8360
v = 91.43 m/s
 Example 6
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 6
1 2
d = 2.5cm d = 5cm
v = 2 m/s v=?
For an incompressible fluid, = constant
a] mass balance:
d2
= (A = )
4
so v1 d21 = v2 d2 2
v2 = 2 x 0.0252 /0.052
= 0.5 m/s
 Solution To Example 6
b]
1
Eke = mv 2
2
1
= m[v 2 2 v 21 ]
2
1 2
Eke/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 U and H 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