ENERGY BALANCE FOR

NONREACTIVE PROCESSES
part 1
4.1 Elements of energy balance equations
a. Reference states
b. Hypothetical process paths
c. Procedure for energy balance calculations
4.2 Changes in pressure at constant temperature
4.3 Changes in temperature
a. Sensible heat and heat capacities
b. Heat capacity formulas
c. Estimation of heat capacities
d. Energy balance on single phase systems
1
4.1 Elements of energy balance equations
A common practice is to arbitrarily designate a reference
state for a substance at which U or H is declared to equal
zero.
Then tabulate U and/or H for the substance relative to
the reference state.
Reference
state
U and H are state properties of a species; their values
depend only on
the state of the species primarily on its temperature
and state of aggregation (solid, liquid or gas)
and, to a lesser extent, on its pressure (and for
mixtures of some species, on its mole fraction in the
mixture).
State
properties
Construct a hypothetical process path from the initial
state to the final state consisting of a series of steps.
When a species passes from one state to another, both
AU and AH for the process are independent of the path
taken from the first state to second one
Process path
2
Example
Compressing H
2
gas
from 1 atmto 300
atmat 25
o
C
Changes in P at constant
T and state of
aggregation
Melting ice at 0
o
C
and then heating
the liquid water to
30
o
C all
Phase changes at
constant T and P-
melting, solidifying,
vaporizing,
condensing,
sublimating
Changes in T at constant
P and state of
aggregation
Mixing sulfuric acid
and water at a
constant
temperature of
20
o
C and a constant
pressure 1 atm
Mixing of two liquids or
dissolving of a gas or a
solid in a liquid at
constant T and P
3
c. Procedure for energy balance
calculations
Perform all required
material balance
calculations
Write appropriate
form of the energy
balance (closed or
open system)
Choose a reference
state-phase, T, P- for
each of the species
involved in the
process
For a closed constant
volume system,
construct a table with
columns for initial and
final amounts of each
species and specific
internal energies
relative to the chosen
reference state.
For an open system,
construct a table with
columns for inlet and
outlet stream
component flow rates
and specific enthalpies
relative to the chosen
reference state.
Calculate all required
values of Ui or Hi and
insert values in the
appropriate places in
the table
Calculate Q for
open or close
system
Calculate any work, kinetic energy, or
potential energy terms that you have
not drop from the energy balance
Solve the energy balance
for whichever
4
4.2 Changes in pressure at constant
temperature
If the pressure of a solid or liquid changes at
constant T,
AU = 0
AH = [AU + A(PV)] = [AU + PAV + V AP] = [V AP]
Both U and H independent of pressure for ideal
gases may assume U = 0 and H = 0 for a gas
undergoing an isothermal pressure change unless
gas temperature below 0
0
C or
well above 1 atmare involved.
5
4.3 Changes in temperature
a. Sensible heat and heat capacities
The term sensible heat signifies that heat must be transferred to raise or
lower the temperature of a substance or mixture of substances.
The quantity of heat required to produce a temperature change:
Q = AU (closed system)
Q = AH (open system)
Heat capacity at constant volume C
v
. At constant volume:
6
( )dT T C U
T
T
v
^
}
= A
2
1
Suppose both temperature and the volume
of a substance change. To calculate AU
break the process into 2 steps ( a change in
V at constant T followed by a changes in T
and constant V):
7
( ) ( ) ( )
2 1
2 2 2 1 1 1
2 1
^ ^ ^
U U
U U U
V , T A V , T A V , T A
^ ^
A + A = A

A A

For ideal gas and (to a good
approximation) liquid and
solids, U depends only on T. In
step 1, T is constant, AU
1
= 0.
Step 2 V is constant:
8
( )dT T C U
T
T
v
}
= A
2
1
^
Ideal gas: Exact
Solid or liquid: good approximation
Non ideal gas: valid only if V is
constant
Heat capacity at constant pressure C
p
. At
constant pressure:
For first step refer section 8.2 (Felder), as T is
constant, AH
1
= 0 (for ideal gas), AH
1
= V AP
(for solid or liquid).
Step 2 P is constant:
9
( ) dT T C H
T
T
p

2
1
^
}
= A
( )dT T C P V H
T
T
p
}
+ A = A
2
1
^ ^

( )dT T C H
T
T
p
}
= A
2
1
^
Solid or liquid Ideal gas: Exact
Non ideal gas: valid only if P
is constant
b. Heat capacity formula
Heat capacities are functions of
temperature and frequently
expressed in polynomial form
(C
p
= a + bT + cT
2
+ dT
3
).
10
constant Gas : R
R C C : Gases Ideal
C C : Solids and Liquid
v p
v p
+ =
=
c. Estimation of heat capacity
Kopps rule
simple empirical
method for
estimating the
heat capacity of a
solid or liquid near
20
0
C.
For heat capacities
of certain mixture
may use these
rules:
Rules 1 : For a mixture of gases
or liquids, calculate the total
enthalpy change as the sum of
the enthalpy changes for the
pure mixture component
Rules 2 : For a highly dilute
solutions of solids or gases in
liquids, neglect the enthalpy
change of solute.
11
For heat capacities of certain mixture: (C
p
)
mix
(T)
For enthalpy calculation:
12
( ) ( ) ( )
( )
component i of capacity heat C
component i of f raction mole or mass y
mixture of capacity heat C
where
T C y T C
pi
i
mix
p
components
mixture
all
pi i
mix
p
=
=
=
=

( ) ( )
}
= A
2
1
T C
mix
p
^
T
T
dT H