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Chapter 4
Energy Balance-Part 1
Energy Balances
Energy
Balance
Energy &
Energy
Balance
Balance on
Nonreactive
Processes
Balance on
Reactive
Processes
2
TOPIC OUTCOMES
! Define the terms closed system and open system,
and write energy balance on closed and open
systems.
! Define the concept of a reference state and
choosing a reference state.
! Construct a hypothetical path from reference state
to the process state.
! Calculate internal energy (!U) and enthalpy
changes (!H) depends on changes in initial and
final states of a species.
! Perform energy balances on nonreactive process.
! Calculate the required heat transfer rate for
nonreactive process.

3
Energy
Balance
Energy &
Energy
Balance
Balance on
Nonreactive
Processes
Balance on
Reactive
Processes
4
2
The First Law of Thermodynamics
3 components of total energy of a system

1. Kinetic energy (E
k
)
! Energy due to motion of an object or flowing stream relative
to the surface of the earth.
! Unit: E
k
(J) or !
K
(J/s)
2. Potential energy (E
p
)
! Due to position in a gravitational or electromagnetic
potential field or due to height of center of mass of object
above a reference height).
! Unit: E
p
(J) or !
P
(J/s)
3. Internal energy (U)
! Sum of rotational, vibrational, and electromagnetic energies
of individual molecules, atoms & subatomic particles moving
around in a body of material or a flowing stream.
! Unit: U(J) or " (J/s) 5
Kinetic Energy
Definition
Energy of a moving object due to its motion
Formula
E
k
= ! mv
2
Where;

m = Mass (kg/g/Ibm )
v = Uniform velocity (m/s)
Units
Joules (J)
6
Potential Energy
Formula
E
p
= Mass x Free Fall Acceleration x Height
E
p
= mgz
Where;
m = Mass (kg/g/Ibm )
g = Acceleration of gravity(9.81 m/s
2
)
z = Height above a reference plane

7
Two forms of energy transfer between a system & its surroundings
Heat, Q
! Energy that flows as a result of temperature difference between a system
and its surroundings.
! Q as positive if heat flows to system from surroundings.

Work, W
! Energy that flows in response to any driving force other a temperature
difference, such as a force, a torque or a voltage.
! Work is defined as positive when it is done by the system on the
surroundings.
Heat & Work
E
TOT
= E
K
+ E
P
+ U
Energy can be transferred as heat (Q) or work (W)
+Q (Heat added)
+W (Work Done)
8
3
Energy transfer occur in :
Closed system
No mass is transferred
across the system
boundaries while the
process is taking place.
Example:
Batch process
Open system
Mass crosses
system
boundaries
Example:
Semi batch and
continuous
system
9
! A system is termed open or
closed according to whether or
not mass cross the system
boundary.
! Closed system: no mass crosses
system boundaries.
! Open system: mass crosses
system boundaries.
Energy Balances on
Closed Systems
10
Final Initial = Net energy transferred to the
System System system (Q W)
Energy Energy
!U+!E
k
+!E
p
= Q"W
" is used to signify
(Final Initial)
Initial System Energy: U
i
+ E
ki
+ E
pi
Final System Energy: U
f
+ E
kf
+ E
pf
Energy Transferred: Q!W
Energy Balances on Closed Systems
11
First law thermodynamics for a closed system is



Simplifying the first law for specific systems:
If No temperature change, no phase changes, no chemical
reaction occur and pressure changes < a few atmospheres,
then "U " 0
If system is not accelerating, !E
k
= 0
If system is not rising/falling, !E
p
= 0
If T
system
= T
surroundings
, Q = 0 (adiabatic)
If no moving parts /electrical currents at system
boundary (W=0)
We thus obtain:
Close System U Q ! =
Energy Balances on Closed Systems
!U+!E
k
+!E
p
= Q"W
12
4
Energy Balances on Closed System
! One important property for energy
balance on closed system is specific
internal energy, (kJ/kmol).
! ^ symbol is used to denote the specific
property (divided by mass or by mole).

!U = n

U
Final
"

U
Initial ( )
, where n = moles
!U = m

U
Final
"

U
Initial ( )
, where m = mass
13
! In closed system,

! The energy balance reduce to
Q!W = "U+"E
k
+"E
p
U Q ! =
Q= !U = n
i
final
"

U
i
# n
i
initial
"

U
i
Q= !U = m
i
final
"

U
i
# m
i
initial
"

U
i
Energy Balances on Closed System
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Energy Balances on Open System
! General Energy balance for open system:


where
U = Internal Energy
E
k
= Kinetic energy
E
p
= Potential Energy

Q = Heat
W = Work
" is used to signify
(Final-Initial).


!
Q!
!
W = "
!
U+"
!
E
k
+"
!
E
p
15
Work appearing in the equation is the combined flow work &
shaft work.




! Shaft work( W
s
)
All other work transmitted across system boundary by
moving parts (pistons, turbines, rotors, propellers,...),
electrical currents, radiation.
! Flow work (W
F
)
Also known as PV (pressure and volumetric flow rate) work.
Rate of work done by the fluid at the system outlet minus
the rate of work done on the fluid at the system inlet.

!
W =
!
W
s
+
!
W
F
Energy Balances on Open System
16
5
PROCESS
UNIT
(m
3
/s)
P
in
(N/m
2
)
(m
3
/s)
P
out
(N/m
2
)
V

In V

Out
Energy Balances on Open System
! The net flow work is determined as:
! The flow work is usually expressed in terms of pressure and
volumetric flow rate:

! If there is several input and output streams enter and leave the
system, the PV products for each streams must be summed:

!
W
F
=
!
W
F(Out )
!
!
W
F(In)
!
W
F
= P
Out
!
V
Out
! P
In
!
V
In
!
W
F
= P
Out
!
V
Out !
" P
In
!
V
In !
17
Definition of Enthalpy
! Thermodynamic Definition of Enthalpy (H):
H = U + PV
U = Internal energy of the system
P = Pressure of the system
V = Volume of the system
! Changes in enthalpy mainly when:
" Heating or cooling a solid, liquid or gas.
" Phase changes (evaporation,
condensation, freezing, and melting).
18
! It is known that the sum of Internal Energy, U and W
F
= PV is
equal to enthalpy, H therefore we obtain;

! The new energy balance equation now becomes
Energy Balances on Open System
!
H
Out
!
!
H
In
= "
!
H =
!
U
Out
+ P
Out
!
V
Out ( )
!
!
U
In
+ P
In
!
V
In ( )
= "
!
U+
!
W
F
!
Q!
!
W = "
!
U+"
!
E
k
+"
!
E
p
!
Q!
!
W
s
+
!
W
F ( )
= "
!
U+"
!
E
k
+"
!
E
p
!
Q!
!
W
s
= ("
!
U+
!
W
F
) +"
!
E
k
+"
!
E
p

!
Q!
!
W
s
= "
!
H +"
!
E
k
+"
!
E
p
19
! One important property for energy balance
on open system is specific enthalpy, # (kJ/
kmol).
! ^ symbol is used to denote the specific
property (divided by mass or by mole flow
rate).
Energy Balances on Open System
!
!
H = ! n

H
Out
"

H
In ( )
, where n = moles
!
!
H = ! m

H
Out
"

H
In ( )
, where m = mass
20
6
Simplifying the first law for specific systems:
# If there are no moving parts in the system and no energy is
transferred by electricity or radiation, W
s
=0;
# If no significant vertical distance separates the inlet and outlet
ports, $E
p
=0;
# If the system is not accelerating, $E
k
=0;
Then energy balance equation become:

H Q
! !
! =
!
Q!
!
W
S
= "
!
H +"
!
E
k
+"
!
E
p
Energy Balances on Open System
21
! In open system,


! The energy balance reduce to
p k s
E E H W Q
! ! ! ! !
! + ! + ! = "
H Q
! !
! =
!
Q= !
!
H = ! n
i
out
"

H
i
# ! n
i
in
"

H
i
!
Q= !
!
H = ! m
i
out
"

H
i
# ! m
i
in
"

H
i
Energy Balances on Open System
22
! In closed (batch) system,
! In open (continuous), steady state system,

where;

Energy Balances Equation
Q!W = "U+"E
k
+"E
p
p k s
E E H W Q
! ! ! ! !
! + ! + ! = "
!U = m
Out
output
streams
"

U
Out
# m
In
input
streams
"

U
In
!
!
H = ! m
Out
output
streams
"

H
Out
# m
In
input
streams
"

H
In
(where

H =

U+ P

V)
!
!
E
k
=
1
2
! m
Out
output
streams
" (u
Out
)
2
#
1
2
! m
In
input
streams
" (u
In
)
2
where u (m/s) = velocity [ ]
!
!
E
p
= ! m
Out
output
streams
" g z
Out
# ! m
In
input
streams
" g z
In
where z (m) = height [ ]
23 24
7
Reference States
What is a Reference State ?
! It is not possible to know the absolute value
of and # for pure species at a given state.
! However, the change in $ and $#
corresponding to a specified changes in
state (temperature, pressure, phase) can be
determined.
! In this regard, $ and $# are much like
altitude.
25
The altitude of a
mountain and the
altimeters on
airplanes are
referenced to
mean sea level.
A reference state is also needed when
tabulating the measured changes in U or H.
Reference States
26
! Convenient way is to
choose a temperature,
pressure and phase at
which either U or H is zero
as a reference state.
! Some enthalpy tables give
the reference state on
which the listed values of
# are based on (e.g Table
B.8 Elementary Principles
of Chemical Processes).
However some table do
not provide this reference
state.
Reference States
27
The enthalpy changes for CO going from a reference
state of 0C and 1 atm to two other states are
measured with following results.
Determine enthalpy changes of the process.

CO (g, 0
o
C, 1 atm) $ CO (g, 100
o
C, 1 atm)
: !#
1
= 2919 J/mol

CO (g, 0
o
C, 1 atm) $ CO (g, 500
o
C, 1 atm)
: !#
2
= 15060 J/mol
Example : Reference states and
states properties
28
8
# for CO at (g, 100C, 1 atm) and (g, 500C, 1 atm) cannot be known
absolutely.

CO (g, 0
o
C, 1 atm) $ CO (g, 100
o
C, 1 atm): !#
1
= 2919 J/mol

Assign value of specific enthalpy at a reference state, #
ref
= 0. Hence,
$#
1
= #
1
#
ref
= #
1
0 = #
1

$#
100
= #
100
0 = 2919 J/mol

Similarly for # for CO at (g, 500C, 1 atm)
CO (g, 0
o
C, 1 atm) $ CO (g, 500
o
C, 1 atm): !#
2
= 15060 J/mol
$#
500
= #
500
0 = 15060 J/mol

Since the reference state for both conditions is the same, the $# for CO from
State 1 (g, 100C, 1 atm) and State 2 (g, 500C, 1 atm) can be calculated by
$# = #
2
#
1
= 15060 2919 = 12141 J/mol
Example : Reference states and states properties
Reference State
29
1. If two different tables are used, make sure #
1
and #
2
are based
on the same reference state.
2. If another reference state had been used to generate the specific
enthalpy, #, they would have different values but the changes
(!#) still the same. Example :
30
Reference States
#
CO
(J/mol)
(Reference state 1 : g, 0
o
C, 1 atm)



15,060 @

2919 @

0 @
(Reference State)
#
CO
(J/mol)
(Reference state 2 : g, ?
o
C, ? atm)



@ 12,560

@ 419

@ 2500
(Not Reference State)
500
o
C, 1 atm

100
o
C, 1 atm

0
o
C, 1 atm
$# =
(15060 2919)
J/mol
= 12,141
J/mol
$# =
(12560 419)
J/mol
= 12,141
J/mol
Note that although the enthalpies values are different based on
the reference state, but !" would still be the same, 12,141 J/mol.
31
Water Phase Diagram
32
Water Phase Diagram
1. If Temperature and Pressure correspond to a point on the Vapor-Liquid
equilibrium curve for a substance, therefore;
P = Vapor pressure of the substance at specific T
T = Boiling point of the substance at a specific P
2. The boiling point of a substance at P = 1 atm is the normal boiling point
3. If Temperature and Pressure falls on the Solid-Liquid equilibrium curve,
T = Melting point or Freezing point at specific P
4. If Temperature and Pressure falls on Solid-Vapor equilibrium curve,
P = Vapor pressure of the solid at specific T
T = Sublimation point at specific P
5. The point at the temperature and pressure at which solid, liquid, and
vapor phases can all coexist is called the triple point of the substance.
6. The vapor-liquid equilibrium curve terminates at the Tc (Critical
Temperature) and Pc (Critical pressure)
9
Steam Tables
33
Table B.5
Properties of Saturated
Steam: Temperature Table
1. Properties of:
Saturated liquid water
Saturated steam
2. At T = 0.01 102
o
C
Table B.6: Properties of Saturated Steam: Pressure Table
1. Properties of:
Saturated liquid water
Saturated steam
2. 1
st
column for pressure and 2
nd
column for temperature.
3. Covers much broader of temperature and pressure.
Table B.7
Properties of Superheated
Steam
1. List of of water at
any T & P
2. Not just at the point on the
VLE curve
H U V

,

H U V

,

H U V

,

Steam Tables: Table B.5


34
Table B.5
Saturated Steam Tables
1. Properties of:
Saturated liquid water
Saturated steam
2. At T = 0.01 102
o
C
H U V

,

Steam Tables: Table B.6


35
Steam Tables: Table B.7
36
10
Mini Project Submission
Draft 2

Draft Submission For Mass
Balance is
TOMORROW (1/4/2014)

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