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Chapter 7
Energy and Energy Balances
Name: _____________
Date: ______________
In Chapter 7, it will be shown how energy balances can be used to solve problems involving
chemical processes. Different types of problem including the types of energy and how it is
transferred in and out of a system, which can be either open or closed. The following
problems build upon the fundamentals covered in your text as applied to hydrogen
processing, hydrogen as an energy carrier, and the use of hydrogen in fuel cells.
Student View
P2 = 0.1 MPa
T2 = 400 K
moles
n H O,2 = 105
2
s
m
u 2 = 80
s
P1=1 MPa
T1=800 K
SOLID-OXIDE
FUEL CELL
n H
O,1
= 105
u1 = 50
moles
s
m
s
J
Q = 1.16 104
kg
Ws
= n H
H
H
2
1
The enthalpies of the steam entering and exiting the turbine can be found in Table 2-305 of
Perrys Chemical Engineers Handbook, 8th Edition.
P(MPa)
T(K)
800
(kJ/mol)
H
63.729
0.1
400
__________
Student View
s
mol
mol
= __________ kW
H
Since there is a difference in the velocity of the steam between the inlet and outlet streams,
the difference in the kinetic energy must be obtained as follows:
E k =
2
m
( u u12 )
2 2
Entering the mass flow rate and the velocities into this equation yields:
moles 1 kmol 18 kg
2
2
m
1 kJ
s 1000 moles kmol m
=
80 ________
2
s ________ J
s
= __________ kW
________
E k
E k
The potential energy is due to a difference in the height. Since both inlet and outlet streams
are at the same level, the term for the potential energy in the energy balance can be
neglected.
, which can be obtained
The only term that remains to be calculated is the heat loss term Q
J
by multiplying the mass flow rate by the heat loss in
:
kg
= mQ
Q
Now that all the terms in the energy balance are known, we can substitute these quantities
and solve for the shaft work Ws :
E E H
=Q
= __________ kW 3.69 kW ( __________ kW )
W
s
p
k
Ws = 1501.39 kW
Student View
T, K
P, kPa
Liquid
Liquid
Vapor
Vapor
285
315
330
345
8.2787
38.692
74.453
134.47
L
V,
mol
4.0125 x 10-2
4.1595 x 10-2
35.164
20.052
kJ
H,
mol
-4.4347
-1.9842
35.060
34.485
Calculate the changes in enthalpy and internal energy from 285 K to 315 K, and from 330 K
to 345 K.
Strategy
We need to use the values from the table and the definition of internal energy to find the
solution to this problem.
Solution
The change in the enthalpy will be given by the following equation:
=H
H
H
f
i
where:
= Enthalpy of methanol at the final temperature
H
f
H
= 1.9842
__________
285 K - 315 K
mol
mol
kJ
H
= __________
285 K - 315 K
mol
Student View
H
= __________
330 K - 345 K
H
= 0.575
330 K - 345 K
kJ
kJ
__________
mol
mol
kJ
mol
The values we just obtained for the changes in enthalpy will be used for calculating the
change in internal energy for methanol in both the liquid and vapor phases. The internal
energy definition is given by the following equation:
= H
(PV)
U
can be rewritten as follows
The term (PV)
= (P V
PV
)
(PV)
f f
i i
Where the sub index f refers to the final condition, and the sub index i to the initial condition
yields:
of methanol. Inserting this equation into the equation for U
= H
(P V
PV
)
U
f f
i i
We can insert the quantities from the table to determine the change in internal energy for the
liquid phase when increasing its temperature from 285 K to 315 K.
3
kJ
2 L 1 m
U
=
________
_________
kPa
4.1595
x
10
285K 315K
mol
mol 1000 L
L 1 m3
mol 1000 L
U
= ________
285K315K
kJ
mol
The same procedure is followed to difference in the internal energy of methanol in the vapor
phase from 330 to 345 K.
= 0.575
U
kJ
mol
L
L 1 m3
134.47
kPa
_______
_______
kPa
35.164
mol
mol 1000 L
U
= 0.6533
330K 345K
kJ
mol
Student View
Superheated Steam
T = 360C
P = 4.8 MPa
Strategy
The starting point for solving this problem will be the general energy balance equation. We
will also need the enthalpies of both the liquid water entering the boiler and the steam
produced.
Solution
We can start by applying the energy balance equation to this process:
W
+ E + E = Q
H
p
s
k
For the process taking place in this problem, the following assumptions can be made:
E k = 0
Since there is no information given about the velocities of the inlet and
outlet streams the velocity difference will be neglected
E p = 0
=0
W
s
Student View
1 MPa
300 K
303.15 K
400 K
_________
4.8 MPa
kJ
mol
2.1106
H
@T =303.15 K,P =1 MPa
9.6106
5 MPa
H
@T =303.15 K,P = 4.8 MPa
kJ
mol
kJ
mol
H
@T =303.15 K,P =5 MPa
_________
kJ
mol
Thigh Tlow
H
H
@T
@T
high
low
Entering the values from the table into this equation and solving for H
@T =303.15 K,P =1 MPa
yields:
kJ
kJ
kJ
303.15 K 300 K
H
=
_______
9.6106
+ _______
@T =303.15 K,P =1 MPa
mol
mol
mol
400 K 300 K
kJ
H
= _________
@T =303.15 K,P =1 MPa
mol
The same procedure is repeated at the temperature of 303.15 K, only that this time will be
done for the pressure of 5 MPa.
Tmid Tlow
Thigh Tlow
H
@ T =303.15 K,P=5 MPa H @ T
low
H
@T
high
H
@T
low
Entering the values from the table into this equation and solving for H
@T =303.15 K,P =5 MPa
yields:
kJ
kJ
kJ
303.15 K 300 K
H
=
2.1106
_________
+ 2.1106
@T =303.15 K,P =5 MPa
mol
mol
mol
400 K 300 K
Student View
H
= _______
@T =303.15 K,P =5 MPa
mol
Now, the only remaining step to be done is to obtain the value of the molar enthalpy of liquid
water at the temperature and pressure of the feed stream:
Pmid Plow
Phigh Plow
H
@ T =303.15 K,P=4.8 MPa H @ P
low
H
@P
high
H
@P
low
Substituting the values from the table into this equation, we can solve for
H
@T =303.15 K,P = 4.8 MPa to get:
kJ
kJ
_____ MPa 1 MPa
=
________
H
________
= _________
H
@T =303.15 K,P = 4.8 MPa
kJ
mol
1 MPa
300 K
303.15 K
400 K
kJ
mol
kJ
________
mol
kJ
9.6106
mol
4.8 MPa
________
5 MPa
kJ
mol
kJ
________
mol
kJ
________
mol
2.1106
________
kJ
mol
Student View
1 MPa
kJ
51.123
mol
4.8 MPa
5 MPa
kJ
49.734
mol
H
@T =633.15 K,P =1 MPa
H
@T =633.15 K,P = 4.8 MPa
H
@T =633.15 K,P =5 MPa
600 K
633.15 K
700 K
54.087
kJ
mol
53.286
kJ
mol
After doing the interpolation procedure and entering the values into the table, we get:
1 MPa
600 K
633.15 K
700 K
kJ
mol
kJ
________
mol
kJ
54.087
mol
4.8 MPa
51.123
5 MPa
kJ
mol
kJ
________
mol
kJ
53.286
mol
49.734
________
kJ
mol
Now we can determine the heat required to boil the feed water, by calculating the enthalpy
change:
= H
= n(H
)
out H
Q
in
= H
= 425 kg H 2 O 1 kmol H 2 O 1000 mol H 2 O 1 hr _______ kJ ______ kJ
Q
hr 18 kg H 2 O 1 kmol H 2 O ______ s
mol
mol
= ________ kW
Q
Student View
Strategy
We need to determine the unknown parameters by performing an energy balance on the
heater and use the information about the steam/methane ratio given in the problem statement.
Solution
The energy equation is given by:
W
+ E + E = Q
H
p
s
k
The changes in the kinetic and potential energies will be negligible since there are no
significant differences in the velocity and the height between the inlet and outlet streams.
Since there are no mechanical parts moving in the heater, the shaft work will be also
neglected. Thus, the equation is reduced to:
= H
Q
O, in
H
H
O,in
+ n CH
, in
H
CH
,in
Student View
O, in
H
H
O,in
+ n CH
, in
H
CH
,in
For the steam-methane reforming process, the ratio of the number of moles of steam to the
number of moles of methane is equal to 3. This can be described by the following equation:
n H
O, in
= 3n CH
, in
This equation can be used to determine the molar flow rate of the mixed gases exiting the
heater:
n out = n CH
, in
+ n H
O, in
= n CH
, in
+ 3n CH
, in
Substituting the last two equations in the general energy equation applied for this problem
gives:
= 4n
( ________ H
Q
H
+ n CH , in H
)
CH , in
mix
H O,in
CH ,in
4
Another quantity that remains unknown in this equation is the enthalpy of the mixture exiting
, which can be calculated as follows:
the heater H
mix
=y H
H
+ yH O H
CH
CH
H
mix
4
Since the only components present in the outlet stream are water and methane, and the ratio
of moles of steam to moles of methane is known, the molar fractions can be obtained as
follows:
y CH + y H
4
=1
y CH + 3y CH = 1
4
yCH = ________
4
moles CH 4
mol
and the molar fraction of water can be obtained by substituting the molar fraction into the
equation for the sum of the molar fractions:
yH
= 1 y CH = 1 ________
4
Student View
y H O = ________
2
moles H 2O
mol
Now the enthalpy of the mixture can be calculated by substituting the molar fractions and
enthalpies of methane and water to yield:
=y H
+ yH O H
H
CH
CH
H
mix
4
kJ
kJ
= _____ 26.393
+ ______ ________
mol
mol
= ________ kJ
H
mix
mol
Substituting the known enthalpies and the consumed power into the energy balance equation
allows us to solve for the molar flow rate of methane being fed to the heater:
2.5 kW = 4n CH
n CH
n CH
, in
, in
n CH
, in
, in
kJ
kJ
kJ
52.17
14.551
40.571
________
3n CH4 , in ________
+ n CH4 , in ________
mol
mol
mol
2.5 kW
52.17
kJ 40.571
kJ
kJ
14.551
________
4 ________ mol 3 ________
mol
mol
0.0345
= ________
124.28
= ________
mol 3600 s
s 1 hr
mol
hr
O, in
= 3n CH
, in
Entering the molar flow rate of methane into this equation gives:
n H
O, in
n H
O, in
mol
124.28
= 3 ________
hr
372.85
= ________
mol
hr
Student View
n 1 = 8.3 106
mol H 2O
hr
T = 260 C
P = 32.4 bar
H1=63.501
MIXING
POINT
kJ
mol
Steam/Syngas mixture
moles
n 3 ,
hr
T = 260 C
P = 27 bar
H3=41.698
= 41.698 kJ
H
3
mol
mol Syngas
hr
T = 260 C
P = 27 bar
= 18.344 kJ
H
2
mol
n 2 ,
Determine the unknown flow rates for the mixer operating at adiabatic conditions.
Strategy
In order to solve this problem, material balances must be done around the mixing point.
Since the compositions of each of the streams are unknown, we also need to perform an
energy balance on the system.
Solution
We can start by writing an overall material balance on the system:
Input = Output
n 1 + n 2 = n 3
As it can be seen in this equation, there are two unknown variables. Hence, we will need
another equation in order to be able to solve this problem.
There is no information given in the problem statement about the composition of the stream
but the enthalpies given in the process diagram can be used to perform an energy balance on
the system:
+ E + E
Q W = H
s
Student View
(adiabatic system)
Ws = 0
(the streams are just being added but there are no mechanical parts
moving)
E p = 0
E k = 0
The change in the enthalpy for this system will be given by:
=
H
n H n H
outlet
inlet
=0
= n H
________ + n H
=0
H
3 3
2 2
Now we have both the energy and material balance equations, which can be solved
simultaneously to determine the flow rates n 2 and n 3 . Solving for n 2 from the overall
material balance, we get:
n 2 = n 3 n 1
We can enter the quantities for all known variables in this equation to get:
kJ
kJ
mol
kJ
6 mol
n 3 _______
8.3 10
_______
+ n 3 _______
_______
=0
mol
hr
mol
hr
mol
Student View
hr
mol
mol
kJ
6 mol
8.3 10
________
hr
mol
n 3 =
kJ
________
mol
mol
n 3 = __________
hr
Now the value of the flow rate n 3 can be substituted into the material balance equation to
yield:
mol
mol
8.3 106
hr
hr
mol
n 2 = ____________
hr
n 2 = __________
Student View