01 Chapter 01 (Compiled)

CHAPTER 1
Mohd Asmadi Bin Mohammed Yussuf

Faculty of Chemical Engineering
Universiti Teknologi Malaysia, 81310 UTM
Johor, Johor Bahru, Malaysia
Chemical Reaction Engineering Group, Universiti Teknologi Malaysia
Introduction to Chemical
Engineering Thermodynamics
N02 2-6, 11.00 1.00P.M Feb 10, 2013 (Mon)
Week Topic Topic Outcomes
1 Introduction to Chemical
Engineering Thermodynamics

Overview of thermodynamic
application in chemical
industry

Application of thermodynamic
properties and equations in
chemical process
It is expected that students are
able to:

Describe the importance of
chemical engineering
thermodynamics in chemical
engineering profession.

Apply the thermodynamics
properties in the chemical process
simulators.
Topic Outcomes
Scope of Lecture
Overview of thermodynamic application
in chemical industry

Application of thermodynamic properties
and equations in chemical process
Thermodynamic Applications
Definition
The study of the effects of work, heat and energy on the
system).
Only concerned with large scale observations.
Ref: NASA. Available from: http://www.grc.nasa.gov/WWW/k-12/airplane/thermo.html. (Accessed 8 Feb, 2013).
0
th
Law:
Thermodynamic
equilibrium, temperature
1
st
Law:
Work, heat, energy
2
nd
Law:
Entropy
3
rd
Law:
As the T of a substance
approaches absolute zero
its entropy approaches zero
Applications of Thermodynamics
Types of process applications of thermodynamics, namely:
Ref: Edmister W C (1945) Applications of Thermodynamics to the Process Industries. Journal of Chemical Education. pp13 - 19
Combustion
Heat balances
Power
Phase equilibrium
Chemical reaction equilibrium
Chemical Engineer & Thermodynamics
Why is thermodynamics useful to chemical engineers?
Heat transfer
Mass transfer
Separation process
Chemical reactions
Ref: Girard-Lauriault P-L. Chemical Engineering Thermodynamics CHEE220. (Accessed 8 Feb, 2013); Selis . KMU 220 -
Chemical Engineering Thermodynamics (Accessed 8 Feb, 2013)
Calculation of heat and work requirements for physical and
chemical processes.
Transfer of chemical
species between phases
Determination of
equilibrium conditions
Physical processes
(e.g. distillation)
Chem. Engineer & Thermo. (Cont.)
Thermodynamics permits
to determine how far
processes will proceed.
Chemical kinetics
helps evaluate how
fast.
The 2 concepts are at the base of many of the
considerations of Chemical Engineers.
Ref: Girard-Lauriault P-L. Chemical Engineering Thermodynamics CHEE220. (Accessed 8 Feb, 2013); Selis . KMU 220 -
Chemical Engineering Thermodynamics (Accessed 8 Feb, 2013)
Deals with driving force
Does not deal with RATEs of
physical or chemical phenomena.
Examples
Manufacture of Ethylene Glycol
Desired reaction
H
2
C C H
2
1 / 2 O
2
C a t a l y s t
H
2
C C H
2
O
+
AH = 24.7 kcal/gmole
Need to be heated to 250 C before enter the reactor
To design the preheater
MUST KNOW HOW MUCH HEAT IS TRANSFERRED
CATALYTIC OXIDATION REACTION
Most effective when carried out at T 250 C
T

Undesired Reaction
H
2
C C H
2
3 O
2
+
2 C O
2
+ 2 H
2
O
AH = 320 kcal/gmole
Combustion reaction
Tend to raise the temperature
Heat is removed from reactor
T does not rise much above 250 C
To design the reactor
REQUIRES KNOWLEDGE OF THE RATE OF HEAT TRANSFER
Hydrolysis Reaction
H
2
C CH
2
O
+
H
2
O HOCH
2
CH
2
OH
Recovered by distillation,
vaporization & condensation
Heat evolved because of
Phase change
Dissolution process
Hydration reaction between the
dissolved ethylene oxide and H
2
O
CSTRs with Heat Exchanger
Ref: Fogler H S (1999). Chapter 8: Elements of Chemical Reaction Engineering, 3
rd
Ed. Prentice Hall. Pp 426 477; CSTR:
Continuous stirred-tank reactor.

Continuous-flow reactors

out out in in
E F E F W Q
dt
E d
+ =

0 H F H F W Q
i
n
1 i
i i0
n
1 i
i0 s
= +

= =

At steady state,
CSTR with heat exchange
( )
( ) | | ( )
=
= +
n
1 i
i0 pi i R p R
o
RX
A0
a
T - T C T T C ) ( T H X
F
T T UA ~
( )
( )
( ) | |
R P R RX
i0 pi i
A0
a
EB
T T C ) ( T H
T T C
F
T T UA
X
+
+
~
Determination of X & T
5. Energy Balance (Calculate X
EB
)

6. Calculate X
MB
Elementary irreversible liquid phase reaction A B
Non-adiabatic
RX
0 PA A0 a
EB
H
) T ( T C ) /F T UA( T
X

+
=
~
A0
A0
0
MB
F
VC
V
;
.k 1
.k
X = =
+
= t
t
t
E/RT
Ae k

=
7. Plot X vs. T
X

T
X
EB
X
MB
Ref: Fogler H S (1999). Chapter 8: Elements of Chemical Reaction Engineering, 3
rd
Ed. Prentice Hall. Pp 426 477; X: Conversion,
T: Temperature; EB: Energy balance; MB: Mole balance.
Algorithm

1. Design equation
2. Rate law
3. Stoichiometry
4. Combining
Properties & Equations
Thermodynamic Properties
The thermodynamic properties required for the many
fluids handled in the process industries include:
Densities
Vapor pressures
Critical state
Fugacities
Entropies
Enthalpies
Free energies
Some of these properties
experimentally determined
Others are computed from basic
experimental data
thermodynamic equations.
Some Basic Relations in Thermodynamics
First law:
Second law:
Phase equilibrium relations:
Chemical reaction equilibrium:
( ) ( ) gen E flow E W Q E
t
+ + + =
( ) ( ) gen S flow S
T
Q
S
t
+ + =
t | o
i i i
f f f

= = =
G RTlnK=
i
v
0
i
i
f
f
[
|
|
.
|
\
|
=

K
Dimensions & Units
Dimension SI Unit English Unit
Time second, s
Distance meter, m
foot, ft
(1 ft = 0.3048 m)
(1 m = 3.28084 ft)
Mass kilogram, kg
pound mass, Ib
m
(1 Ib
m
= 0.4536 kg)
(1 kg = 2.2046 Ib
m
Temperature Kelvin, k
Rankine, R
T(R) = 1.8T(K)
Amount of substance gram mole, g mole
pound mole, Ib mol
(1 Ib mol = 453.59 g mol)
Note: Appendix A: Table A.1, Conversion factors
Prefixes for SI Units
Multiple Prefix Symbol Multiple Prefix Symbol
10
15
femto f 10
2
hecto h
10
12
pico p 10
2
kilo k
10
9
nano n 10
6
mega M
10
6
micro 10
9
giga G
10
3
milli m 10
12
tera T
10
2
centi c 10
15
peta P
Note: Appendix A: Table A.1, Conversion factors
Measures of Amount & Size
3 basic measures
Mass, m (kg)
Number f moles, n (mol)
Total volume, V
t
(m
3
)v
4 derivatives
Specific volume,
Molar volume,
Specific density,
Molar density,
( ) /kg m
m
V
V
3
t
( ) /mol m
n
V
V
3
t
( )
3
t
kg/m
V
1
V
=
m
( )
3
t
mol/m
V
1
V
=
n

Force (Newton 2
nd
Law)
SI units:
English units:
ma F=
ma
g
1
F
c
=
Force (N = kg ms
-2
), defined as that force
which accelerates 1 kg mass 1.0 ms
-2
Mass (kg)
Acceleration (ms
-2
), 1 ms
-2
= 3.20808 (ft)(s)
-2
The acceleration of gravity a = g = 9.81ms
-2
Force (Ib
f
), 1 Ib
f
represents the force that
accelerates 1 Ib
m
at a = 32.1740 (ft)(s
-2
)

Mass (Ib
m
)
Acceleration (ft)(s)
-2
32.1740 (Ib
m
)(ft)(Ib
f
)
-1
(s)
-2

Temperature
Temperature scale
The Celsius Scale : 0C & 100C correspond to the ice point (freezing
point) & the steam point (boiling point) of pure water
at standard atmospheric pressure.

The Fahrenheit scale : T (F) = 1.8T (C) + 32 or T (C) = [T (F) 32]5/9

The Kelvin scale
(absolute T)
: T (K) = T (C) + 273.15
The Rankine scale : T (R) = 1.8 T (K)
T (R) = T (F) + 459.67
Relationship Among T Scales
Celsius Fahrenheit Kelvin Rankine
Steam point
Ice point
Absolute zero
Pressure
Defined as the normal force exerted by a fluid on a
surface per unit area of the surface.
SI units : N/m
2
= Pascal (Pa)

English units : (lb
f
)/(in)
2
= pound force per square inch (psi).
1 psi = 6894.8 Pa
1 atm = 101325 Pa
1 atm = 14.7 psi
Measurement Method
Dead-Weight Gauge Manometer
To pressure
source
h
Weight
Pan
Piston
Cylinder
Oil
To pressure
source
A
mg
A
F
P = =
( )
g h
A
g Ah
A
mg
A
F
P
= = = =
m -the mass of the piston, pan and weights;
g - the local acceleration of gravity;
A - the cross-sectional area of the piston.
h - the relative height of the fluid;
- the fluid density;
g - the local acceleration of gravity.
Pressure (Cont.)
Gauge Pressure vs. Absolute Pressure
Different SI units for Pressure
Readings from most pressure gauges and the manometers correspond
to gauge pressures which are the difference between the pressure of
interest and the pressure of the surrounding atmosphere.
P (absolute) = P (gauge) + P (barometric)
1 kPa = 10
3
Pa
1 MPa = 10
6
Pa
1 torr = 1 mm Hg = 133.32 Pa
1 atm = 101325 Pa
= 101.325 kPa = 0.101325 MPa
= 760 mm Hg = 760 torr
= 14.7 psi
1 bar = 10
5
Pa = 0.986923 atm
Work
Push-Pull Work
dl F dW=
SI units : Joule (J), 1 J = 1 N m = 1 Pa. m
3

English units : (Ib
f
)(ft), 1 (Ib
f
)(ft) = (4.4482 N)(0.3048) =1.3558 J
}
=
2
1
l
l
Fdl W
Work done by the force F
over the distance of (l
2
l
1
)

Sign of the work:
+ve when the displacement dl is in the same direction as the
applied force.
-ve when they are in opposite directions.
Work (Cont.)
PV Work
( )
t
t
pdV
A
V
d PA dl F dW = = =
}
=
2
1
V
V
t
PdV W
Sign of the work:
+ve for compression
-ve for expansion.
Calculation of PV Work
Graphical method
}
=
2
1
V
V
t
PdV W
Relationship
between P and V
Area W =
Energy
Energy is something that a body can store, and
which it can receive or give away as work or heat.

Thus, energy, work and heat are closely related.
Work and heat are energy in transit, and are
never regarded as residing in a body.

Energy, work and heat have the same units:
Joule (SI) or lb ft (English)
Kinetic Energy (E
K
)
Consider a body of mass m, acted upon by a force F, is displaced a
distance dl during a time interval of dt, when it gains in velocity from u
1
The work done by the F is,

SI system : E
K
1/2mu
2
Units of Joule or N.m or kgm
2
s
-2
English system : E
K
mu
2
/2g
c
Units of (Ib
f
)(ft),
where g
c
= 32.1740 (Ib
m
)(ft)(Ib
f
)
-1
(s)
-2
( ) mudu du
dt
dl
m dl
dt
du
m dl ma Fdl dW = =
|
.
|
\
|
= = =
( )
K
u
u
u
u
E
mu u u
m udu m mudu dW W A =
|
.
|
\
|
A =
|
|
.
|
\
|
= = = =
} } }
2
2
1
2
2
2 2 2
2
1
2
1
Potential Energy (E
P
)
Consider a body of mass m, acted upon by a force F =
mg, is raised from position z = z
1
to z = z
2
.

The total work done by the F is

( ) ( )
( )
p
z
z
z
z
E
mgz mgz mgz dl mg Fdl W
A =
A = = = =
} }

1 2
2
1
2
1
SI system : E
P
mgz

Units of Joule or N.m or kgm
2
s
-2
English system : E
p
mgz/g
c
Units of (Ib
f
)(ft),
where g
c
= 32.1740 (Ib
m
)(ft)(Ib
f
)
-1
(s)
-2
Energy Conservation
Consider a body of mass m, falls freely from position z
= z
1
to z = z
2
, where the body gains in velocity u
1
u
2
.

( ) ( )
2 1 2 1
2
1
2
2
2 2
mgz mgz z z mg Fl W
mu mu
E
K
= = = =
|
|
.
|
\
|
= A
In this process, the body gains in kinetic energy is
the work done by the force of gravity, i.e.,

While in this process, the change in the bodys
potential energy is AE
P
= A(mgz) = (mgz
2
mgz
1
)

Thus, AE
K
+ AE
P
= (mgz
1
mg
2
) + (mgz
2
mgz
1
)

Therefore, for purely mechanical processes without
friction, the energy conserves, i.e.,

0 = A + A
K K
E E
2
2
2
1
2
1
2 2
mgz
mu
mgz
mu
+ = + or
Heat
Heat (Q) always transfers from a high temp. body to a lower temp. one.

The rate of heat transfer ( ) is proportional to the temp. difference T

Like work, heat exists only as energy in transit from one body to another
or between a system and its surroundings.

When energy in the form of heat is added to a system, this part of
energy is stored NOT as heat, but as kinetic and potential energy of
atoms/molecules in the system.
Q
Units of heat
SI system : Joule (J)
Calorie (Cal), 1 Cal = 4.184 J

British system : (Ib
f
)(ft), 1 (Ib
f
)(ft) = 1.3558 J
British thermal Unit (Btu), 1 (Btu) = 1055.04 J

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CHAPTER 1

Mohd Asmadi Bin Mohammed Yussuf

Chemical Reaction Engineering Group, Universiti Teknologi Malaysia

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